WO2022207590A1

WO2022207590A1 - Washing or cleaning agents

Info

Publication number: WO2022207590A1
Application number: PCT/EP2022/058190
Authority: WO
Inventors: Till Frey; Michael Kreis; Peter Schmiedel; Antje Gebert-Schwarzwaelder
Original assignee: Henkel Ag & Co. Kgaa
Priority date: 2021-03-30
Filing date: 2022-03-29
Publication date: 2022-10-06
Also published as: EP4314223A1; DE102021203178A1

Abstract

The invention relates to special washing or cleaning agents, comprising at least one gel, preferably a gel that is solid at room temperature (20 °C), based in each case on the total weight of the gel, 3 to 40 wt.%, preferably 4 to 20 wt.%, in particular 5 to 18 wt.%, PVOH and/or the derivatives thereof; and a. at least one component having a parameter r <= 15.3 MPa^1/2 and b. at least one component having a parameter r >= 16.3 MPa^1/2; and c. optionally at least one additional active substance, preferably selected from dyes, glass corrosion inhibitors, perfumes, pH regulators and additional process auxiliaries; wherein at least one of the components according to a) or b) is liquid at 20 °C.

Description

, detergents or cleaning agents”

The invention relates to cleaning agents, preferably dishwashing agents, in particular machine dishwashing agents, comprising at least one gel, preferably a gel that is solid at room temperature (20° C.), based in each case on the total weight of the gel, 3 to 40% by weight, preferably 4 to 20% by weight %, in particular 5 to 18% by weight, PVOH and/or its derivatives; as well as a. at least one component with a parameter r <= 15.3 MPa ^1/2 and b. at least one component with a parameter r >= 16.3 MPa ^1/2 ; as well as c. optionally at least one further active ingredient, preferably selected from dyes, glass corrosion inhibitors, perfumes, pH adjusters and other processing auxiliaries; where at least one of the components according to a) or b) is liquid at 20° C., and with the proviso that the following applies to the mixture of the components (number n) according to a) and b) or a), b) and c). :

With

and

(dD _Mix - dD ₀ ) ² + ( dP _Mix - dP ₀ ) ² + ( dH _Mix - dH ₀ ) ² = r ² where dD ₀ = 16.05 MPaz dP ₀ = 20.31 MPaz dH ₀ = 36.86 MPaz And r= 14.0 to 18.5 MPa ^1/2 .

Detergents or cleaning agents, preferably dishwashing agents, in particular machine dishwashing agents, are usually in solid form (for example as tablets) or in liquid form (or else as a flowing gel). Liquid cleaning agents in particular are enjoying increasing popularity with consumers. Pre-portioned forms of presentation are popular with consumers because they are easier to dose. In this context, pre-portioned flowing gels are often problematic because they tend to leak, for example when packaged in single-chamber or multi-chamber bags. At the same time, it is necessary for such gels to have good cleaning and rinsing performance.

The object of the present invention is to provide a system that provides particularly suitable gel formulations comprising PVOH and / or its derivatives, as well as the provision of cleaning agents, preferably dishwashing detergents, in particular automatic dishwashing detergents, which can be produced easily and cost-effectively, a good Have storage stability and also have good cleaning and / or rinsing performance.

A first subject matter of the present invention relates to washing or cleaning agents, preferably dishwashing agents, in particular machine dishwashing agents, comprising a gel, preferably a gel which is solid at room temperature (20° C.), comprising 3 to 40% by weight, based in each case on the total weight of the gel. %, preferably 4 to 20% by weight, in particular 5 to 18% by weight, PVOH and/or its derivatives; as well as a. at least one component with a parameter r <= 15.3 and b. at least one component with a parameter r >= 16.3; as well as c. optionally at least one further active ingredient, preferably selected from dyes, glass corrosion inhibitors, perfumes, pH adjusters and other processing auxiliaries; where at least one of the components according to a) or b) is liquid at 20° C., and with the proviso that for the mixture of the components (number n) according to a) and b) or a), b) and c) the following is applicable:

and

Polyvinyl alcohol can thicken various solvents, thereby forming gels. Here, the PVOH is stabilized by non-covalent intermolecular interactions. The Hansen solubility parameters are based on a semi-empirical concept developed by Charles M. Hansen. Each substance can be analyzed using the three Hansen parameters, disperse/van der Waals forces (dD); Dipolar interactions (dP) and the ability to form hydrogen bonds (dH) can be characterized.

These variables span a three-dimensional space, the Hansen space, with which regions with good solubility and gelling regions can be found for a defined gelator. The Hansen parameters for specific substances can be determined by testing their solubility in reference solvents with known Hansen parameters. Based on such data it is then possible to determine the location of this substance in the Hansen space (Hansen Parameters Users Handbook, 2nd Edition, June 15, 2007)

The Hansen parameters for the mixture of different substances (dD _Mix , dP _Mix , dHiwx) result from the linear combination of the Hansen parameters of the components in the mixture according to Equation 1 below. PVOH is not taken into account in this equation. The sum of all substances adds up to 1 (equation 2).

(equation 1)

With

S?= _i ^c _ί = 1 (equation 2)

The appropriate section of the Hansen space (three-dimensional space spanned by dD, dP and dH), in which gelation and solubility are given, is fitted by a spherical function with radius r, for which Equation 3 applies.

(dD _Mix - dD ₀ ) ² + {dP _Mix - dP ₀ ) ² + (dH _Mix - d// ₀ ) ² = r ² (Equation 3)

It has now been found that gels comprising PVOH and/or its derivatives in an amount, based in each case on the total weight of the gel, from 3 to 40% by weight, preferably from 4 to 20% by weight, in particular from 5 up to 18% by weight, have particularly advantageous properties if they also meet the following parameters. dD ₀ = 16.05 MRάϊ dP ₀ = 20.31 MPc dH ₀ = 36.86 MPc and r = 14.0 to 18.5 MPa ^1/2 .

At r > 18.5 the gel shows unfavorable syneresis, i.e. leakage of solvent, on storage, while at r < 14.0 the gel becomes too soft and no longer has the desired properties in terms of strength and dimensional stability.

Solutions of Equation 3 in which the radius r is r=15.0 to 17.5 are particularly preferred.

It is of particular advantage to control preferred properties of the gel, in particular the storage stability and / or setting time, if at least one component with a parameter r _a <= 15.3 MPa ⁰⁵ , and at least one component with a parameter rb>= 16.3 MPa ⁰⁵ and optionally at least one other active ingredient, preferably selected from dyes, glass corrosion inhibitors, perfumes, pH adjusters and other processing aids that satisfy the above equations.

Components according to a) are substances whose coordinates in the Hansen space are on or within the spherical function according to Equation 3 with the proviso dD ₀ = 16.05 MPc dP ₀ = 20.31 MPc dH ₀ = 36.86 MPc with r _a <= 15.3 MPa ⁰⁵ are located.

Components according to b) are substances whose coordinates in the Hansen space are on or outside the spherical function according to Equation 3 with the proviso dD ₀ = 16.05 MPc dP ₀ = 20.31 MPc dH ₀ = 36.86 MPc with rb>= 16 .3 MPa ⁰⁵ are located.

As described above, the Hansen parameters (dD, dP, dH) for the individual components can be determined experimentally by testing their solubility in reference solvents with known Hansen parameters.

It is preferred that at least one of the components according to a) or b) is liquid at 20.degree.

This function enables the person skilled in the art to determine combinations of components (both in terms of the substances in the component mixture and their proportions by weight) which produce a particularly suitable gel formulation.

The mixture preferably has no separation of the mixture of the individual components at 80° C. in a period of 10 minutes, preferably 20 minutes, after the components have been mixed.

According to the invention, a gel or a gel-like phase, also referred to below as a gel phase, means a composition (or phase) which has an internally structuring network. This internal structuring (spatial) network is formed by the dispersion of a solid but distributed substance with long or highly branched particles and/or gelling agent, here polyvinyl alcohol and/or its derivatives, in at least one liquid (the at least one liquid is liquid at 20° C) formed. Such gel phases behave thermoreversibly. The washing or cleaning agent, preferably dishwashing detergent, in particular machine dishwashing detergent, can have one, two, three, four or more gels or gel phases. The gels/gel phases can be the same or different. In the case of several gels or gel phases, these can preferably be distinguished spatially, optically or on the basis of their ingredients. If the gels/gel phases are different, they can have different dyes and different additions of active ingredients.

The gel is dimensionally stable. During production, the polyvinyl alcohol and/or its derivatives are brought into contact with glycerol. This gives a flowable mixture which can be brought into a desired shape. After a certain period of time, a gel/a gel phase is obtained which remains in the specified form, i.e. is dimensionally stable. This period of time, the setting time, is preferably 15 minutes or less, preferably 10 minutes or less, particularly preferably 5 minutes or less. The gel gives way under pressure, but does not deform as a result, but returns to its original state after the pressure is removed. The gel is preferably elastic, in particular linear-elastic.

The gel is preferably a shaped body. A molded body is a single body that stabilizes itself in its imposed shape. This dimensionally stable body is formed from a molding compound (e.g. a composition) by deliberately bringing this molding compound into a predetermined shape, e.g. by pouring a liquid composition into a mold and then curing the liquid composition, e.g. as part of a sol-gel process.

Certain minimum requirements are placed on formulations of the at least one gel phase. As already stated, the gel must solidify within the shortest possible time. Long solidification times would lead to a long production time and thus to high costs. According to the invention, the setting time means the period of time during which the gel changes from a flowable to a non-flowable, dimensionally stable state at room temperature during production. Room temperature is understood to mean a temperature of 20°C. Where temperatures are mentioned herein, unless otherwise noted, they are to be understood as measured at a pressure of 1013 mbar.

The gel is a solid gel phase. It is preferably cut-resistant. It can, for example, be cut with a knife after it has solidified without being destroyed further, except at the point where the cut was made.

A phase within the meaning of the present invention is a spatial area in which physical parameters and the chemical composition are homogeneous. A phase differs from another phase by various characteristics, such as ingredients, physical properties, external appearance, etc. Different phases can preferably be distinguished visually.

Thus, the at least one gel phase can be clearly distinguished from other phases (solid, preferably granular, liquid or gel-like) for the consumer. If the washing or cleaning agent according to the invention, preferably dishwashing detergent, in particular machine dishwashing detergent, has more than one gel phase, these can also be distinguished from one another with the naked eye because they differ from one another, for example in terms of color. The same applies if two or more gel phases are present. In this case, too, an optical differentiation of the phases is possible, for example on the basis of a difference in color or transparency. Phases within the meaning of the present invention are therefore self-contained areas which the consumer can visually distinguish from one another with the naked eye. The individual phases can have different properties when used, such as the speed with which the phase dissolves in water and thus the speed and sequence of release of the ingredients contained in the respective phase.

In addition, the gel is preferably translucent (translucent) or transparent, which results in a good optical impression. The transmittance of the gel phase (without dye) is preferably in a range between 100% and 20%, between 100% and 30%, in particular between 100% and 40%. To measure the light transmittance (transmission), the permeability was determined in % at 600 nm against water as a reference at 20 °C. For this purpose, the mass was poured into the 11 mm round cuvettes provided and, after a storage time of 12 h at room temperature, measured in a LICO 300 color measuring system according to Lange.

The detergents or cleaning agents according to the invention, preferably dishwashing detergents, in particular machine dishwashing detergents, contain polyvinyl alcohol and/or its derivatives in an amount of 3 to 40% by weight, in particular 4 to 30% by weight, particularly preferably in an amount of 5 to 18% by weight %, in each case based on the total weight of the gel.

Polyvinyl alcohols are thermoplastics that are usually produced as a white to yellowish powder by the hydrolysis of polyvinyl acetate. Partially hydrolyzed polyvinyl alcohol which still has amounts of up to 30 mol % of non-hydrolyzed acetyl groups is to be understood as polyvinyl alcohol in the context of the invention. Polyvinyl alcohol (PVOH) is resistant to almost all anhydrous organic solvents. Polyvinyl alcohols with a molar mass of 30,000 to 60,000 g/mol are preferred.

Particularly preferred are polyvinyl alcohols, which are available as yellowish-white powders or granules with degrees of polymerization in the range from about 100 to 2500 (molecular weights from about 4000 to 100,000 g/mol) and degrees of hydrolysis from 80 to 99 mol%, preferably from 85 to 90 mol%, in particular from 87 to 89 mol%, for example 88 mol%, which accordingly still contain a residual content of acetyl groups.

According to a preferred embodiment, the gel comprises PVOH (polyvinyl alcohol). The gels or gel phases produced in this way have a particularly high melting point, are dimensionally stable (even at 40° C.) and do not change their shape, if at all, only insignificantly, even during storage. In particular, they are also not very reactive with regard to a direct negative interaction with components of a granular mixture, in particular an additional powder phase. PVOH can produce both water-containing and water-poor or water-free gel phases. When using PVOH as a polymer for the gel, low-viscosity melts result at 80-90 °C or 110-120 °C, which are particularly easy to process. In particular, the gel phase can be filled into the water-soluble coating quickly and precisely , without sticking or the amount being dosed imprecisely. Furthermore, these gel phases adhere particularly well to the water-soluble coating, in particular if this is also made from PVOH. This is also a visual advantage. Due to the rapid solidification of the at least one gel phase with PVOH, the further processing of the gel phases can take place particularly quickly. Furthermore, the good solubility of the gel phases produced is particularly favorable for the overall solubility of the washing or cleaning agent. In addition, gel phases with such short setting times are advantageous in the event that a solid, preferably granular phase dosed thereon, comprising granular mixtures, in particular powder, does not sink into the gel that is not yet completely solidified or is too soft. This leads to visually unappealing washing or cleaning agent portions.

Particular preference is given to polyvinyl alcohols, which are available as white-yellowish powders or granules with degrees of polymerization in the range from about 100 to 2500 (molar masses from about 4000 to 100,000 g/mol) and degrees of hydrolysis from 80 to 99 mol%, preferably from 85 to 90 mol %, in particular from 87 to 89 mol%, for example 88 mol%, which accordingly still contain a residual content of acetyl groups.

PVOH powders with the properties mentioned above, which are suitable for use in the at least one gel phase, are marketed, for example, by Kuraray under the name Mowiol® or Poval®. Exceval® AQ4104 from Kuraray, for example, is also suitable. Particularly suitable are Mowiol C30, the Poval® qualities, in particular the qualities 3-83, 3-88, 6-88, 4-85, and particularly preferably 4-88, very particularly preferably Poval 4-88 S2 and Mowiol® 4- 88 by Kuraray.

According to the invention, preferred derivatives of PVOH are copolymers of polyvinyl alcohol with other monomers, in particular copolymers with anionic monomers. As anionic Monomers are preferably suitable vinylacetic acid, alkyl acrylates, maleic acid and their derivatives, in particular monoalkyl maleates (especially monomethyl maleate), dialkyl maleates (especially dimethyl maleate), maleic anhydride, fumaric acid and their derivatives, especially monoalkyl fumarate (especially monomethyl fumarate), dialkyl fumarate (especially dimethyl fumarate), fumaric anhydride, itaconic acid and derivatives thereof, in particular monomethyl itaconate, dialkyl itaconate, dimethyl itaconate, itaconic anhydride, citraconic acid (methylmaleic acid) and derivatives thereof, monoalkyl citraconic acid (especially methyl citraconic acid), dialkyl citraconic acid (dimethyl citraconic acid), citraconic acid anhydride, mesaconic acid (methyl fumaric acid) and derivatives thereof, monoalkyl mesaconate, dialkyl mesaconate, mesaconic acid anhydride, glutaconic acid and their derivatives derivatives, monoalkyl glutaconate,

Dialkyl glutaconate, glutaconic anhydride, vinyl sulfonic acid, alkyl sulfonic acid, ethylene sulfonic acid, 2-acrylamido-1-methylpropanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-methylacrylamido-2-methylpropanesulfonic acid, 2-sulfoethyl acrylate and combinations thereof and the alkali metal salts or esters of the abovementioned monomers.

Particularly preferred derivatives of PVOH are those selected from copolymers of polyvinyl alcohol with a monomer selected in particular from the group of monoalkyl maleates (especially monomethyl maleate), dialkyl maleates (especially dimethyl maleate), maleic anhydride, and combinations thereof, and the alkali metal salts or esters of the above mentioned monomers. The values given for the polyvinyl alcohols themselves apply to the suitable molar masses. In the context of the present invention, it is preferred that the gel comprises a polyvinyl alcohol and/or derivatives thereof, preferably polyvinyl alcohol, the degree of hydrolysis of which is preferably 70 to 100 mol %, in particular 80 to 90 mol %, particularly preferably 81 to 89 mol %. % and especially 82 to 88 mol%.

The water solubility of polyvinyl alcohol can be changed by post-treatment with aldehydes (acetalization) or ketones (ketalization). These are also to be understood as derivatives of polyvinyl alcohol. Polyvinyl alcohols which are acetalized or ketalized with the aldehyde or keto groups of saccharides or polysaccharides or mixtures thereof have proven to be particularly preferred and particularly advantageous due to their extremely good solubility in cold water. The reaction products of polyvinyl alcohol and starch can be used extremely advantageously. Furthermore, the water solubility can be changed by complexing with Ni or Cu salts or by treatment with dichromates, boric acid, borax and thus adjusted to desired values.

Optionally, at least one further active ingredient, preferably selected from dyes, perfumes, pH adjusters and other processing auxiliaries, can be used. The gel according to the invention preferably comprises less than 1% by weight, in particular less than 0.5% by weight, particularly preferably less than 0.1% by weight, of at least one benzylidene alditol compound of the formula (I),

wherein

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

R1, R2 and R3 independently represent a hydrogen atom, a halogen atom, a C1-C4-alkyl group, a cyano group, a nitro group, an amino group, a carboxyl group, a hydroxy group, a group -C(=0)-NH-NH2, a group -NHC(=

0)-(C2-C4-alkyl), a C1-C4-alkoxy group, a C1-C4-alkoxy-C2-C4-alkyl group, two of the radicals together with the remainder molecule form a 5- or 6-membered ring,

R4, R5 and R6 independently represent a hydrogen atom, a halogen atom, a C1-C4-alkyl group, a cyano group, a nitro group, an amino group, a carboxyl group, a hydroxy group, a group -C(=0)-NH-NH2, a group -NHC(=

0)-(C2-C4-alkyl), a C1-C4-alkoxy group, a C1-C4-alkoxy-C2-C4-alkyl group, two of the radicals together with the remainder molecule form a 5- or 6-membered ring.

In particular, the gel according to the invention comprises less than 1% by weight, in particular less than 0.5% by weight, particularly preferably less than 0.1% by weight, of the compounds selected from 1,3:2,4-Di-O -benzylidene-D-sorbitol; 1,3:2,4-di-0-(p-methyl-benzylidene)-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-Q-(p- ethylbenzylidene)-D-sorbitol; 1,3:2,4-di-0-(3,4-dimethylbenzylidene)-D-sorbitol or mixtures thereof.

According to a preferred embodiment, the gel according to the invention comprises polyvinyl alcohol as the only gel former, as described above. Gel formers other than PVOH are preferably not contained in the gel.

According to a preferred embodiment, the gel contains at least one component according to a), which is liquid at 20° C., i.e. a component with a parameter _ra less than or equal to 15.3 MPa ⁰⁵ , preferably less than 15.3 MPa ⁰⁵ , particularly preferably less than 15 2 MPa ⁰⁵ , very particularly preferably less than 15.0 MPa ⁰⁵ . This improves the ability of the PVOH gelling agent to dissolve, making the gel easier to process.

According to a particularly preferred embodiment, the gel contains at least one component according to a) which is liquid at 20° C., ie a component with a parameter rb greater than or equal to 16.3, and at least one component according to b) which is liquid at 20° C. As a result, the setting of the parameters, in particular with regard to the ability to dissolve and the gel-forming properties, in particular the setting time and hardness of the gel, can be controlled even better.

According to a particularly preferred embodiment, the gel contains at least one component according to a), preferably one component according to a) which is liquid at 20° C. and at least two components according to b), preferably two components according to b) which are liquid at 20° C. This makes it much easier to set and control the particularly important gelation parameters with regard to storage stability and setting time.

According to a particularly preferred embodiment, component a) is selected from the group consisting of water, glycerol and the oligomeric or polymeric carboxylates, preferably polycarboxylates as described in detail below, particularly preferably polyacrylates, very particularly preferably polyacrylates containing sulfonic acid groups.

At least one of the components according to a), preferably two or more, in particular three or more, of the components according to a) is present in the gels according to the invention.

Particular preference is given to components a) which are liquid at 20° C. are glycerol or water and mixtures thereof.

The gel preferably comprises oligomers or polymeric carboxylates, such as citrates, amino carboxylates and/or polycarboxylates, as described in detail below. Examples which may be mentioned are acrylate homopolymers or acrylate copolymers, e.g Maleic acid-acrylic acid copolymer sodium salt or sulfopolymers. These can act either as builders and/or as a thickening polymer. A copolymeric polyacrylate, preferably a sulphopolymer, preferably a copolymeric polysulfonate, preferably a hydrophobically modified copolymeric polysulfonate, is preferably used as the polycarboxylate. The copolymers can have two, three, four or more different monomer units. In addition to monomer(s) containing sulfonic acid groups, preferred copolymers polysulfonates contain at least one monomer from the group of unsaturated carboxylic acids.

According to a particularly preferred embodiment, the gel-like phase contains as one of the components according to a), ie a component with a Hansen parameter r less than or equal to 15.3, a polymer comprising at least one sulfonic acid-containing monomer.

The unsaturated carboxylic acid(s) used is/are particularly preferably unsaturated carboxylic acids of the formula R ¹ (R ² )C═C(R ³ )COOH, in which R ¹ to R ³ independently represent —H, —CH 3 , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, alkyl or alkenyl radicals substituted with -NH2, -OH or -COOH as defined above or for -COOH or- COOR ⁴ where R ⁴ is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.

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, methylenemalonic acid, sorbic acid, cinnamic acid or mixtures thereof. Of course, the unsaturated dicarboxylic acids can also be used.

In the case of the sulfonic acid group-containing monomers, preference is given to those of the formula R ⁵ (R ⁶ )C═C(R ⁷ )—X—SO 3 H, in which R ⁵ to R ⁷ independently 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 -NH2, -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 -(CH2)n- with n = 0 to 4, -COO-(CH2)k - with k = 1 to 6, -C(0)-NH-C(CH3)2-, - C(0)-NH-C(CH ₃ )2-CH ₂ - and -C(0)-NH- CH(CH3 ₎ _-CH2 -.

Preferred among these monomers are those of the formulas H ₂ C=CH-X-S0 ₃ H, H ₂ C=C(CH 3 )-X-S0 ₃ H or H0 ₃ SX-(R ⁶ )C=C(R ⁷ ) -X-S0 ₃ H, in which R ⁶ and R ⁷ are independently selected from -H, -Chh, -CH2CH3, -CH2CH2CH3 and -CH(CH ₃ )2 and X is an optionally present spacer group selected from -(CH2)n- with n = 0 to 4, -COO-(CH2)k- with k = 1 to 6, -C(0)-NH-C(CH3)2-, -C(0)-NH-C(CH ₃ ) 2-CH ₂ - and -C(0)-NH-CH(CH ₃ )-CH ₂ -.

According to a particularly preferred embodiment, the gel/gel phase contains a polymer comprising acrylamidopropanesulfonic acids, methacrylamidomethylpropanesulfonic acids or acrylamidomethylpropanesulfonic acid as the monomer containing sulfonic acid groups.

Particularly preferred sulfonic acid group-containing monomers 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-hydroxy-propanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3-(2-propenyloxy)propanesulfonic acid, 2-methyl-2-propenesulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate , sulfomethacrylamide, sulfomethylmethacrylamide and mixtures of the acids mentioned or their water-soluble salts. In the polymers, some or all of the sulfonic acid groups can be present in neutralized form, ie the acidic hydrogen atom of the sulfonic acid group in some or all of the sulfonic acid groups can be exchanged for metal ions, preferably alkali metal ions and in particular sodium ions. The use of partially or fully neutralized copolymers containing sulfonic acid groups is preferred according to the invention.

The monomer distribution of the copolymers preferably used according to the invention in the case of copolymers which only contain carboxylic acid group-containing monomers and sulfonic acid group-containing monomers is preferably 5 to 95% by weight in each case, and the proportion of the sulfonic acid group-containing monomer is particularly preferably 50 to 90% by weight. % and the proportion of the carboxylic acid group-containing monomer is 10 to 50% by weight; the monomers are preferably selected from those mentioned above. The molar mass of the sulfo-copolymers preferably used according to the invention can be varied in order to adapt the properties of the polymers to the desired application. Preferred detergents or cleaning agents, preferably dishwashing detergents, in particular automatic dishwashing detergents, are characterized in that the copolymers have molecular weights of 2000 to 200,000 g mol ^-1 , preferably 4000 to 25,000 g mol ^-1 and in particular 5000 to 15,000 g mol ^-1 .

In a further preferred embodiment, the copolymers also comprise at least one nonionic, preferably hydrophobic, monomer in addition to monomer containing carboxyl groups and monomer containing sulfonic acid groups. By using this hydrophobically modified polymers, it was possible in particular to improve the rinsing performance of dishwashing detergents according to the invention.

The gel particularly preferably also comprises an anionic copolymer, a copolymer comprising i) carboxylic acid group-containing monomers ii) sulfonic acid group-containing monomers iii) nonionic monomers, in particular hydrophobic monomers, being used as anionic copolymer.

The nonionic monomers used are preferably monomers of the general formula R ¹ (R ² )C═C(R ³ )—XR ⁴ , in which R ¹ to R ³ independently represent —H, —Ch or —C2H5, X represents one optionally present spacer group, which is selected from -CH2-, -C(0)0- and -C(0)-NH-, and R ⁴ represents a straight-chain or branched saturated alkyl radical having 2 to 22 carbon atoms or an unsaturated, preferably aromatic radical having 6 to 22 carbon atoms.

Particularly preferred nonionic monomers are butene, isobutene, pentene, 3-methylbutene, 2-methylbutene, cyclopentene, hexene, 1-hexene, 2-methylpentene-1, 3-methylpentene-1, cyclohexene, methylcyclopentene, cycloheptene, methylcyclohexene, 2,4 ,4-trimethylpentene-1, 2,4,4-trimethylpentene-2,2,3-dimethylhexene-1, 2,4-dimethylhexene-1, 2,5-dimethylhexene-1, 3,5-dimethylhexene-1 , 4,4-dimethylhexane-1, ethylcyclohexyne, 1-octene, α-olefins having 10 or more carbon atoms such as 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene and C22 α-olefin, 2-styrene , a-methylstyrene, 3-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 1-vinylnaphthalene, 2-vinylnaphthalene, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, methyl methacrylate , A/-(methyl)acrylamide, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, A/-(2-ethylhexyl)acrylamide,

Octyl acrylate, octyl methacrylate, A/-(octyl)acrylamide, lauryl acrylate, lauryl methacrylate, A/-(lauryl)acrylamide, stearyl acrylate, stearyl methacrylate, A/-(stearyl)acrylamide, behenyl acrylate, behenyl methacrylate and N-(behenyl)acrylamide or their Mixtures, in particular acrylic acid, ethyl acrylate, 2-acrylamido-2-methylpropanesulfonic acid (AMPS) and mixtures thereof.

According to a preferred embodiment, the polymers containing sulfonic acid groups are present in the gel in an amount of 0 to 30% by weight, in particular 0 to 20% by weight.

According to a particularly preferred embodiment, the at least one component b) is independently selected from the group consisting of organic solvents, whose coordinates in the Hansen space have the value of rb greater than or equal to 16.3 MPa ⁰ · ⁵ at dD ₀ = 16.05 MPc dP ₀ = 20.31 MPc dH ₀ = 36.86 MPc, as well as nonionic surfactants and organic metal salts.

According to a particularly preferred embodiment, the washing or cleaning agent according to one of the preceding claims, characterized in that component b) in the gel is selected from the group formed by polyalkylene glycols (especially polyethylene glycols, polypropylene glycols), carbonate esters (especially glycerol carbonates, propylene carbonates, Ethylene carbonates, diethyl carbonates, dimethyl carbonates), 3-methyl-1,3-butanediol, fatty alcohol alkoxylates (possibly end-capped), acetates and zinc salts, in particular zinc acetates, in particular zinc acetate.

As a further component according to b), the gel preferably contains polypropylene glycol, preferably in an amount of 0.1 to 30% by weight. Mixtures of different polypropylene glycols can of course be used. These are commercially available, for example, under the trade name Pluriol® (BASF).

According to a preferred embodiment, the average molecular weight of the propylene glycol is from 500 to 10,000 g/mol, in particular from 1000 to 6000 g/mol.

According to a particularly preferred embodiment, polypropylene glycol is contained in an amount of 0.6 to 25% by weight, preferably in an amount of 1 to 15% by weight, based in each case on the total weight of the gel.

Preferred components according to b) are carbonate esters (in particular glycerol carbonate (glycerol carbonate, 4-hydroxymethyl-1,3-dioxolan-2-one), propylene carbonate (4-methyl-1,3-dioxolan-2-one), ethylene carbonate ( 1,3-dioxolan-2-one), diethyl carbonate, dimethyl carbonate).

Glycerol carbonate, propylene carbonate and/or ethylene carbonate are particularly preferred.

According to the invention, the gel phase preferably contains at least one polyethylene glycol.

Polyethylene glycols with an average molar mass of between about 100 and 8000 are particularly suitable. Mixtures thereof can also be used. The abovementioned polyethylene glycols are particularly preferred in amounts of 1 to 40% by weight, preferably 5 to 35% by weight, in particular 10 to 30% by weight, for example 12 to 25% by weight, preferably based on the total weight of the gel phase or .of the gel used; 12 to 18.5% by weight of polyethylene glycol, in particular 13.5 to 16.5% by weight of polyethylene glycol, preferably polyethylene glycol, are very particularly preferably present in the gel. The polyethylene glycols used are preferably liquid at 20° C. and 1 bar. According to the invention, preference is given to using polyethylene glycol(s) with an average molar mass of 200 to 600 g/mol in the at least one gel phase or the gel phases. In this case, in combination with polyvinyl alcohol, polyethylene glycols with an average molar mass of between about 200 and about 600 g/mol, preferably between 300 and 500 g/mol, particularly preferably between 350 and 450 g/mol, for example around 400 g/mol INCI: PEG400) deployed. Washing or cleaning agents according to the invention, preferably dishwashing detergents, in particular machine dishwashing detergents, are thus characterized in that they contain polyethylene glycol(s) with an average molar mass of 300 to 500 g/mol, in particular 350 to 450 g/mol.

Surprisingly, it has been shown that the addition of polyethylene glycols, especially those with an average molar mass of 200 to 600 g/mol, to the at least one gel phase, especially in the case of gel phases comprising polyvinyl alcohol, accelerates the setting time of the gel phases. Values of a few minutes and even less than a minute can be achieved. This is of great advantage in particular for the production processes, since the further processing of the gel phases in the solidified state can be carried out much more quickly and therefore generally more cost-effectively. It has surprisingly been found that the presence of polyethylene glycol(s) with an average molar mass of 200 to 600 g/mol in combination with polyvinyl alcohol and/or its derivatives makes a decisive contribution to reducing the solidification times. Without being bound to theory, it is assumed that such polyethylene glycols, in particular those with a molar mass of 350 to 450 g/mol, increase the sol-gel temperature, in particular by 400 g/mol.

In a particularly preferred embodiment, the amount of polyethylene glycol(s) with an average molar mass of 350 to 450 g/mol, for example around 400 g/mol, is 10 to 22% by weight, based on the total weight of the gel.

According to a further embodiment, in addition to the polyethylene glycols mentioned with an average molecular weight of 200 to 600 g/mol, further polyethylene glycols, in particular further polyethylene glycols, with an average molecular weight between about 800 and 8000 can be contained in the at least one gel phase. The abovementioned polyethylene glycols are particularly preferably used in amounts of 1 to 40% by weight, preferably 5 to 35% by weight, in particular 10 to 30% by weight, for example 15 to 25% by weight, based on the total weight of the gel .

Nonionic surfactants, as described in detail below, can also be used as preferred components according to b). All nonionic surfactants known to those skilled in the art can be used as nonionic surfactants. To be favoured low-foaming nonionic surfactants used, in particular alkoxylated fatty acid alkyl ethers (fatty acid polyalkylene glycols). Particularly preferred nonionic surfactants are specified in more detail below as being particularly preferred.

At least one water-soluble zinc salt is preferably present as a further component according to b).

In addition to the effect of such zinc salts as glass corrosion inhibitors, it has been found that the presence of zinc salts in the gel phase contributes to stabilizing the gel and improving processability.

According to a further preferred embodiment of the present invention, detergents or cleaning agents, preferably dishwashing agents, in particular automatic dishwashing agents, which are packaged as washing or cleaning agent portions, preferably dishwashing agent portions, in particular automatic dishwashing agent portions, which preferably contain the active ingredients necessary for a cleaning cycle, are packaged as the total amount of the water-soluble zinc salts , in particular zinc sulphate and/or zinc acetate, in particular zinc acetate, in the washing or cleaning agent portion, preferably dishwashing agent portion, in particular automatic dishwashing agent portion, preferably 0.0004 to 0.5 g, preferably 0.001 to 0.2 g, in particular 0.02 to 0.06 g .

This means that the individual detergent or cleaning agent portion, preferably dishwashing agent portion, in particular machine dishwashing agent portion, which is used to carry out a single cleaning cycle, in particular in a cleaning cycle of a machine dishwasher, is 0.0005 to 1 g, preferably 0.01 to 0 5 g, in particular 0.02 to 0.06 g of water-soluble zinc salts, in particular zinc sulfate and/or zinc acetate, in particular zinc acetate.

Particularly preferably, an individual detergent or cleaning agent portion according to the invention, preferably a dishwashing detergent portion, in particular an automatic dishwashing detergent portion, which is added in particular to a cleaning cycle of an automatic dishwasher, contains 0.001 to 0.5 g, in particular 0.02 to 0.05 g, of water-soluble zinc salts, in particular zinc sulfate and/or zinc acetate, in particular zinc acetate, based on the total amount of the detergent or cleaning agent, preferably dishwashing detergent, in particular automatic dishwashing detergent.

The zinc salt to be used with preference according to the invention is water-soluble, which means that it has a solubility in water of more than 100 mg/l, preferably more than 500 mg/l, particularly preferably more than 1 g/l and in particular more than 5 g/l (all solubilities at 20° C water temperature). 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 of zinc acetate, zinc acetylacetonate, zinc PCA (zinc 5-oxopyrrolidine-2-carboxylate), zinc benzoate, zinc chloride, zinc formate, zinc lactate, zinc gluconate, zinc ricinoleate , zinc abietate, zinc valerate and zinc p-toluenesulfonate.

In a particularly preferred embodiment according to the invention, the water-soluble zinc salt used is zinc chloride, zinc acetate or zinc sulfate, in particular anhydrous zinc salt (anhydrate), particularly preferably zinc acetate (anhydrate).

Another component according to b) is preferably at least one water-soluble zinc salt, in particular zinc sulfate and/or zinc acetate, in particular zinc acetate, in an amount of from 0.05 to 5% by weight, in particular from 0.1 to 2.0% by weight. , very particularly preferably from 0.2 to 1.0% by weight, based on the total weight of the gel.

The zinc salt is present in the gel phase preferably in an amount of from 0.05% to 3% by weight, more preferably in an amount of from 0.1% to 2.4% by weight, especially in a Amount of 0.2% by weight to 1.0% by weight, based on the total weight of the gel phase.

Zinc salts can also be contained in a solid phase that may be present. In this case, the zinc salt in agents according to the invention is preferably in an amount of 0.01% by weight to 5% by weight, particularly preferably in an amount of 0.05% by weight to 3% by weight, in particular in an amount of 0.1% by weight to 2% by weight, based on the total weight of the detergent or cleaning agent, preferably dishwashing detergent, in particular automatic dishwashing detergent.

According to a particularly preferred embodiment, the gel comprises at least one other ingredient according to component c), which is selected from dyes, glass corrosion inhibitors, and other processing aids, in particular perfume, pH adjusters.

According to a particularly preferred embodiment, the water content of the gel is from 0 to 55% by weight, preferably from 1 to 50% by weight, based on the total weight of the gel.

According to a particularly preferred embodiment, the gel comprises less than 5% by weight, preferably less than 3% by weight, in particular less than 1% by weight, of a component with 15.3<r<16.3. According to a further, very particularly preferred embodiment, the gel comprises less than 5% by weight, preferably less than 3% by weight, in particular less than 1% by weight, of 1,3-propanediol. The absence of 1,3-propanediol makes it possible to set the critical gel parameters, such as hardness of the gel, setting time, syneresis and/or storage stability, by combining the components according to a) and the components according to b).

Propanediols, in particular 1,3-propanediol, also lead to interactions with water-soluble coatings and/or other components, in particular coated components, with unsightly discolorations being able to form on the coated components, the discolored appearance of which is then perceived by the end user as unattractive or even harmful Part is considered to be no longer perfectly usable. The coating can also be softened in the presence of propanediols, so that the protective effect of the coating for the encapsulated active ingredient may no longer be available.

1,3 propanediol has clear disadvantages in large-scale production, since some of it evaporates when the gel is dosed and quickly condenses again in the environment. This makes it difficult to suck off this solvent. Contamination of other surfaces of plants or other product components (e.g. a water-soluble film) with 1,3-propanediol as a result of evaporation should be avoided as far as possible in order to prevent negative interactions.

According to another, particularly preferred embodiment, the proportion of 1,3-propanediol and 1,2-propanediol, based on the total weight of the gel, is preferably <5% by weight, preferably less than 3% by weight, in particular less than 1% by weight based on the total weight of the gel.

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. Each feature from one aspect of the invention can be used in any other aspect of the invention. Furthermore, it should be 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 stated. Numeric ranges given in the format "from x to y" include the stated values. Where multiple preferred numeric ranges are given in this format, it is understood that any ranges resulting from the combination of the different endpoints are also included. "At least one" as used herein means 1 or more, ie 1, 2, 3, 4, 5, 6, 7, 8, 9 or more. With regard to an ingredient, the information refers to the type of ingredient and not to the absolute number of molecules. “At least one bleach catalyst” thus means, for example, at least one type of bleach catalyst, ie it can mean one type of bleach catalyst or a mixture of several different bleach catalysts. Together with weight information, the information relates to all compounds of the specified type that are contained in the composition/mixture, ie the composition does not contain any other compounds of this type beyond the specified amount of the corresponding compounds.

When reference is made herein to molar masses, this information always relates to the number-average molar mass M _n , unless explicitly stated otherwise. The number average molar mass can be determined, for example, by means of gel permeation chromatography (GPC) in accordance with DIN 55672-1:2007-08 with THF as the eluent. The mass-average molar mass M can also be determined by means of _GPC , as described for Mn.

Unless explicitly stated otherwise, all percentages given in connection with the compositions described herein relate to % by weight, in each case based on the mixture or phase in question.

Furthermore, the gel must be storage-stable under normal storage conditions. The gel phase according to the invention is a component of a washing or cleaning agent, preferably a dishwashing detergent, in particular a machine dishwashing detergent. Such detergents or cleaning agents are usually stored in a household for a certain period of time. They are usually stored near the washing machine or dishwasher. For such storage, the gel should be stable. Thus, the gel should be stable even after a storage time of, for example, 4 to 12 weeks, especially 10 to 12 weeks or longer at a temperature of up to 40°C, especially at 30°C, especially at 25°C or at 20°C be and do not deform during this time or otherwise change in consistency.

If the gel and a solid, in particular a powder phase are in direct contact with one another, the gel penetrates into the interstices of the immediately underlying powder phase by a maximum of 1 mm during the storage period of 4 weeks at 25°C.

A change in volume or shrinkage during storage would be disadvantageous, since this would result in poor acceptance of the product by consumers. Escape of liquid or exudation of components from the gel phase is also undesirable. On the one hand, the visual impression is also relevant here. The stability of the gel phase can be affected by the escape of liquid, such as solvents, so that the components cannot are contained more stably and thereby the washing or cleaning effect can be influenced.

The detergents or cleaning agents, preferably dishwashing agents, in particular machine dishwashing agents, preferably dishwashing agents, in particular machine dishwashing agents, are in particular not films. Rather, they represent moldings that have a non-film-like thickness. They therefore have a layer thickness of at least 0.3 mm, preferably at least 0.7 mm, in particular at least 1.0 mm, very particularly preferably at least 1.2 mm. The layer thickness is measured in the plane with the smallest expansion.

Another subject of the present invention relates to a detergent or cleaning agent portion, comprising at least one gel as described above, in a water-soluble casing.

According to a further particularly preferred embodiment, the washing or cleaning agents, preferably dishwashing agents, in particular machine dishwashing agents, are a washing or cleaning agent portion, preferably dishwashing agent portion, in particular machine dishwashing agent portion, in a water-soluble casing. This can have one or more chambers/compartments.

The washing or cleaning agent, preferably dishwashing agent, in particular machine dishwashing agent, is preferably packaged as a single portion washing or cleaning agent, so that it is used to carry out a dishwasher cycle and is (largely) essentially or completely consumed.

The water-soluble cover is preferably formed from a water-soluble film material which is selected from the group consisting of polymers or polymer mixtures. The cover can be formed from one or from two or more layers of the water-soluble film material. The water-soluble film material of the first layer and the further layers, if any, can be the same or different.

It is preferred that the water-soluble coating contains polyvinyl alcohol or a polyvinyl alcohol copolymer. Water-soluble coatings that contain polyvinyl alcohol or a polyvinyl alcohol copolymer have good stability with sufficiently high water solubility, especially cold water solubility.

Suitable water-soluble films for producing the water-soluble envelope are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer whose molecular weight is in Range from 10,000 to 1,000,000 gmol ¹ , preferably from 20,000 to 500,000 gmol ¹ , particularly preferably from 30,000 to 100,000 gmol ^-1 and in particular from 40,000 to 80,000 gmol ^-1 .

Polyvinyl alcohol is usually produced by hydrolysis of polyvinyl acetate, since the direct synthesis route is not possible. The same applies to polyvinyl alcohol copolymers which are correspondingly produced from polyvinyl acetate copolymers. It is preferred if at least one layer of the water-soluble coating comprises 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 %.

In a preferred embodiment, the water-soluble packaging consists of at least 20% by weight, more preferably at least 40% by weight, very preferably at least 60% by weight and in particular at least 80% by weight of a polyvinyl alcohol whose Degree of hydrolysis is 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%.

A polyvinyl alcohol-containing film material suitable for producing the water-soluble casing can also have a polymer selected from the group consisting of (meth)acrylic acid-containing (co)polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters, polyethers, polylactic acid or mixtures of the above Polymers can be added. A preferred additional polymer are polylactic acids.

In addition to vinyl alcohol, preferred polyvinyl alcohol copolymers include dicarboxylic acids as further monomers. Suitable dicarboxylic acids are itaconic acid, malonic acid, succinic acid and mixtures thereof, with itaconic acid being preferred. Polyvinyl alcohol copolymers which are also preferred include, in addition to vinyl alcohol, an ethylenically unsaturated carboxylic acid, its salt or its ester. Such polyvinyl alcohol copolymers particularly preferably contain, in addition to vinyl alcohol, acrylic acid, methacrylic acid, acrylic acid esters, methacrylic acid esters or mixtures thereof.

It can be preferred that the film material contains further additives. The film material can contain, for example, plasticizers such as dipropylene glycol, ethylene glycol, diethylene glycol, propylene glycol, glycerol, sorbitol, mannitol or mixtures thereof. Further additives include, for example, release aids, fillers, crosslinking agents, surfactants, antioxidants, UV absorbers, anti-blocking agents, anti-adhesive agents or mixtures thereof.

Suitable water-soluble films for use in the water-soluble wrappers of the water-soluble packaging according to the invention are films available from MonoSol LLC, for example under the designation M8720, M8630, M8312, M8440, M7062, C8400 or M8900 to be expelled. Films sold by Nippon Gohsei under the name SH2601, SH2504, SH2707 or SH2701 are also suitable. Other suitable films include films with the designation Solublon® PT, Solublon® GA, Solublon® KC or Solublon® KL from Aicello Chemical Europe GmbH or films VF-HP from Kuraray.

The water-soluble coating preferably at least partially has a bitter substance with a bitterness between 1,000 and 200,000, in particular those selected from quinine sulfate (bitter value=10,000), naringin (bitter value=10,000), sucrose octaacetate (bitter value=100,000), quinine hydrochloride and mixtures thereof. In particular, the outer surface of the water-soluble casing is at least partially coated with a bitter substance with a bitterness between 1,000 and 200,000. In this context, it is particularly preferable that the water-soluble coating is coated to an extent of at least 50%, preferably at least 75% and very particularly preferably at least 90% with the bitter substance with a bitterness value between 1,000 and 200,000. The application of the bitter substance with a bitter value between 1,000 and 200,000 can be done, for example, by printing, spraying or brushing.

According to the invention, the water-soluble casing preferably has at least one continuous circumferential sealing seam, which essentially lies in one plane. This is favorable in terms of process technology, since only a single sealing step, possibly using only a single sealing tool, is necessary for a circumferential sealing seam which lies essentially in one plane. The continuously circumferential sealing seam leads to a better closure compared to such casings with several sealing seams and an excellent tightness of the sealing seam and thus of the casing itself. Leaking of product from the casing, e.g. on the surface of the portion would be disadvantageous, since the consumer would then be exposed to the product came into contact. However, this is precisely what should be avoided as far as possible in the case of a detergent or cleaning agent portion, preferably a dishwashing agent portion, in particular a machine dishwashing agent portion, with a water-soluble coating.

The water-soluble casing can preferably be made from at least 2 packaging parts. The at least two packaging parts are preferably water-soluble, so that no packaging parts remain in the dishwasher, which could then lead to problems in the dishwasher. It is not necessary for the at least two packaging parts to be different. They can preferably be made from the same material and in the same way. In a preferred embodiment, these are two parts of a water-soluble film, in particular two parts of a water-soluble film of the same composition.

In a further embodiment, the at least two packaging parts made of different materials, for example different films or material with two different properties (e.g. hot and cold water soluble film). In this embodiment, it is preferable that a water-soluble film and another packaging member made by injection molding are combined.

According to a particularly preferred embodiment of the present invention, the water-soluble cover comprises at least one at least partially plastically deformed film. In particular, this plastic deformation of the film can be produced by methods known to those skilled in the art, such as deep drawing (with and without applying a vacuum), blow molding or stamping. In particular, the water-soluble covering comprises at least one at least partially plastically deformed film that was produced by deep-drawing.

According to a particularly preferred embodiment, the water-soluble coating has a layer thickness of from 30 to 100 μm, in particular from 40 to 800 μm.

The at least one solid, preferably granular phase and the gel can be arranged within the water-soluble envelope in any combination with one another. A solid, preferably granular phase can be arranged on or next to a gel phase. In this embodiment, the washing or cleaning agent according to the invention, preferably dishwashing detergent, in particular machine dishwashing detergent, has a solid, preferably granular phase and a gel phase or gel. It is also conceivable that a solid, preferably granular phase is surrounded by gel phases. Embedding one phase in another is also included according to the invention. In a further particularly preferred arrangement, the gel is in cast form, for example in the form of a gel core surrounded by a solid phase. There can also be 2 or more separate cavities that are filled with at least one gel phase. In this embodiment, the washing or cleaning agent, preferably dishwashing detergent, in particular machine dishwashing detergent, comprises two gel phases, it being possible for the two gel phases to have different compositions.

According to a preferred embodiment, there are 3, 4, 5 or 6 or more separate cavities which are filled with one or more of the gel phases. Such detergents or cleaning agents, preferably dishwashing detergents, in particular machine dishwashing detergents, preferably comprise 3, 4, 5 or 6 or more gel phases, it being possible for these gel phases to have the same or also different compositions.

A preferred subject of the present invention is a detergent or cleaning agent, preferably dishwashing detergent, in particular automatic dishwashing detergent, which, in addition to the at least one gel phase, at least one solid, in particular particulate phase and optionally at least one other liquid / gel-like or solid, preferably granular phase includes. “Solid” in this context means that the composition is in solid form under standard conditions (temperature 25°C, pressure 1013 mbar). Suitable solid, preferably granular phases are, on the one hand, granular mixtures of a solid composition, such as, for example, powder and/or granules, in particular pulverulent phases. Also suitable according to the invention are solid compositions/phases which have greater dimensional stability than the loose powder, for example powder or granulate preparations which have been compacted by compression before or after being enclosed in the film, e.g. by restoring forces of the film after deep-drawing or directly compressed compositions such as compresses or tablets. This at least one solid, preferably granular phase can be in direct contact with the gel-like phase. According to the invention are also detergent or cleaning agent portions, preferably dishwashing detergent portions, in particular machine dishwashing detergent portions, in particular multi-chamber bags, in which the solid and the gel/the gel phase are present in close proximity but separate from one another. The two chambers can be separated, for example, by a film, in particular a water-soluble film, or by a sealed seam (preferably a sealed seam of 3 mm or less). According to the invention, chambers of a multi-chamber pouch are arranged one above the other or next to one another. Furthermore, mixtures of single or multi-chamber bags, which comprise a gel-like phase according to the invention and separately from it at least one solid, preferably granular phase, which can be arranged, for example by folding and fixing a pouch, or by storage at a distance of less than 3 mm come into contact, for example in a packaging bag or a device for portioned dosing, according to the invention.

A granular mixture is to be understood as a powdery phase within the meaning of the present invention, which is formed from a large number of loose, solid particles, which in turn comprise so-called grains. According to the invention, the term powdery phase includes powders and/or granules according to the following definition.

A grain is a designation for the particulate components of powders (grains are the loose, solid particles), dusts (grains are the loose, solid particles), granules (loose, solid particles are agglomerates of several grains) and other granular mixtures. A preferred embodiment of the granular mixture of the composition of the solid phase is the powder and/or the granulate, if “powder” or “granulate” is mentioned here, it also includes mixtures of different powders or different granulates . Correspondingly, powder and granules also mean mixtures of different powders with different granules. Said solid particles of the granular mixture in turn preferably have a particle diameter X (volume average) of 10 to 1500 μm, more preferably of 200 μm to 1200 μm, particularly preferably of 600 μm to 1100 μm. These particle sizes can by sieving or by means a particle size analyzer Camsizer from Retsch. The granular mixture of the solid composition of the present invention, which serves as the solid, preferably granular phase, is preferably in a free-flowing form (particularly preferably as a free-flowing powder and/or free-flowing granules). The agent of the portion according to the invention thus comprises at least one solid, preferably granular phase of a free-flowing, granular mixture of a solid composition, in particular a powder, and at least one gel phase, as defined above.

A particularly preferred subject of the present invention are detergents or cleaning agents, preferably dishwashing agents, in particular automatic dishwashing agents, in particular a portion of washing or cleaning agent, preferably dishwashing agent portion, in particular automatic dishwashing agent portion, in which the gel/the gel phase is in direct contact, for example in a chamber, is included with the at least one solid phase.

Furthermore, it is preferred that the at least one solid, preferably granular phase and the gel are in direct contact with one another. In this case there should be no negative interaction between the solid phase and the gel phase. No negative interaction means here, for example, that no ingredients or solvents pass from one phase to the other or that the stability, in particular storage stability, preferably at 4 weeks and 30 °C storage temperature, and / or the aesthetics of the product in any form, for example by Color change, the formation of edges that appear moist, the boundary between the two phases becoming blurred, or the like.

Surprisingly, it has been shown that by formulating a gel phase, preferably dimensionally stable gel phase, comprising at least one polypropylene glycol, preferably having an average molecular weight of 1000 to 6000 g/mol, preferably in an amount of 1 to 15% by weight, which with a granular mixture of a solid composition, in particular a powdered phase is combined, this goal can be achieved. It is particularly suitable if the granular mixture of a solid composition, in particular the powdery phase, is free-flowing, since a more targeted filling of the water-soluble covering can be achieved as a result of the process, in particular when filling a cavity produced by deep drawing. In addition, the visual appearance of the granular mixture of a solid composition, in particular the powder, can be changed better compared to a compressed tablet, in particular differences in texture, such as coarse and fine particles as well as particles or areas with different colors, overall or as colored speckles, can thus be Improving a visually appealing appearance are used. The granular mixture of the solid The composition, in particular the powder, also offers improved solubility compared to compressed tablets, even without the addition of disintegrants.

Particularly in the case of the multi-phase single-use portions according to the invention with at least one solid phase, it is important that the gel is dimensionally stable so that as few interactions as possible can take place between the solid and the gel phase.

The at least one solid, preferably granular phase of the present invention comprises a granular mixture of a solid composition, in particular it is in powdered and free-flowing form. The washing or cleaning agent according to the invention, preferably dishwashing detergents, in particular machine dishwashing detergents, thus comprises at least one solid powdery and free-flowing phase, and at least one gel phase, the at least one water-soluble zinc salt, in particular zinc sulfate and/or zinc acetate, in particular zinc acetate, and at least one polyvinyl alcohol, at least PVOH and/or derivatives thereof, particularly preferably at least PVOH, and glycerol as gel formers.

The pourability of a granular mixture, in particular of a powdery solid, of the powdery phase, preferably of the powder and/or granulate, relates to its ability to pour freely under its own weight. The pourability is determined by measuring the flow time of 1000 ml of detergent or cleaning agent, preferably dishwashing detergent, in particular automatic dishwashing powder, from a standardized flow test funnel that is initially closed in its outlet direction and has an outlet diameter of 16.5 mm by measuring the time it takes for it to flow out completely of the granular mixture, in particular the powdery phase, preferably the powder and/or granules, e.g. the powder is measured after opening the outlet and compared with the outlet speed (in seconds) of a standard test sand, the outlet speed of which is defined as 100%. The defined sand mixture for calibrating the trickle apparatus is dry sea sand. Sea sand with a particle diameter of 0.4 to 0.8 mm is used, available for example from Carl Roth, Germany CAS no. [14808- 60-7] Before the measurement, the sea sand is dried for 24 h at 60 °C in a drying cabinet on a plate with a maximum layer height of 2 cm.

Preferred embodiments of the solid phases according to the invention have an angle of repose/repose of 26 to 35, 27 to 34, 28 to 33, the angle of repose according to the method mentioned below after 24 hours after the preparation of the granular mixture of the solid composition, in particular the powdery solid phase, preferably the powder and/or granules and storage at 20° C., is determined. Such angles of repose have the advantage that the cavities can be filled with the at least one solid phase comparatively quickly and precisely. To determine the angle of repose (or also known as the angle of repose) of the at least one solid, preferably granular phase, a powder funnel with a capacity of 400 ml and an outlet with a diameter of 25 mm is hung straight on a tripod. The hopper is moved upwards at a speed of 80 mm/min using a manually operated knurled wheel, so that the granular mixture, in particular the powdered phase, preferably the powder and/or granules, eg the powder, trickles out. This forms a so-called material cone. The height of the cone of repose and the diameter of the cone of repose are determined for the individual solid phases. The angle of repose is calculated from the quotient of the heap of repose and the diameter of the cone of repose * 100.

Particularly suitable are such granular mixtures of a solid composition, in particular such powdery phases, preferably the powders and/or granules, e.g. the powders which have a flowability in % of the standard test material specified above of greater than 40%, preferably greater than 50, in particular greater than 55 %, particularly preferably greater than 60%, particularly preferably between 63% and 80%, for example between 65% and 75%. Particularly suitable are those granular mixtures of a solid composition, in particular those powders and/or granules, which have a pourability in % of the standard test substance specified above of greater than 40%, preferably greater than 45%, in particular greater than 50%, particularly preferably greater than 55 %, particularly preferably greater than 60%, the pourability being measured 24 hours after the powder has been produced and stored at 20°C.

Lower values for the pourability are rather unsuitable since, from the point of view of process technology, precise dosing of the granular mixture, in particular the powdered phase, preferably the powder and/or granules, for example the powder, is necessary. In particular, the values greater than 50%, in particular greater than 55%, preferably greater than 60% (the flowability being measured 24 h after the production of the powder and storage at 20° C.) have proven to be advantageous because the good dosability the granular mixture, in particular the pulverulent phases, preferably the powder and/or granules, eg powder, result in only slight fluctuations in the metered quantity or the composition. The more precise dosing leads to a constant product performance, economic losses due to overdosing are thus avoided. Furthermore, it is advantageous that the granular mixture, in particular the pulverulent phase, preferably the powder and/or granulate, eg the powder, can be easily dosed, so that the dosing process runs more quickly. Furthermore, such a good flowability better prevents the granular mixture, in particular the powdery phase, preferably the powder and/or granules, e.g. the powder, from getting onto the part of the water-soluble cover that is intended for the production of the sealed seam and is therefore possible should remain granule-free, in particular powder-free. The granular mixture of the solid composition of the present invention, which serves as the solid, preferably granular phase, is preferably in a free-flowing form (particularly preferably as a free-flowing powder and/or free-flowing granules). The means of the portion according to the invention thus comprises at least one solid, preferably granular phase of a free-flowing, granular mixture of a solid composition, in particular a powder, and at least one previously defined gel phase.

The washing or cleaning agent according to the invention, preferably dishwashing detergents, in particular machine dishwashing detergents, preferably comprises at least one surfactant. This surfactant is selected from the group of anionic, nonionic and cationic surfactants. The washing or cleaning agent according to the invention, preferably dishwashing detergents, in particular machine dishwashing detergents, can also contain mixtures of two or more surfactants selected from the same group.

According to the invention, the at least one solid, preferably granular phase and/or the gel comprise at least one surfactant. It is possible for only the at least one solid, preferably granular phase or only the gel to comprise at least one surfactant. If both phases comprise a surfactant, they are preferably different surfactants. However, it is also possible for the solid and gel phases to have the same surfactant or surfactants. At least one solid and/or gel phase according to the invention preferably contains at least one nonionic surfactant. All nonionic surfactants known to those skilled in the art can be used as nonionic surfactants. Low-foaming nonionic surfactants are preferably used, in particular alkoxylated, especially ethoxylated, low-foaming nonionic surfactants, such as, for example, alkyl glycosides, alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, polyhydroxy fatty acid amides or amine oxides. Particularly preferred nonionic surfactants are specified in more detail below.

Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

Particular preference is given to ethoxylated nonionic surfactants obtained from C6-20 monohydroxyalkanols or C6-20 alkylphenols or C16-20 fatty alcohols and more than 12 moles, preferably more than 15 moles and in particular more than 20 moles of ethylene oxide per mole of alcohol, deployed. A particularly preferred nonionic surfactant is obtained from a straight-chain fatty alcohol having 16 to 20 carbon atoms (Ci6-20 alcohol), preferably a cis alcohol, and at least 12 moles, preferably at least 15 moles and in particular at least 20 moles of ethylene oxide. Among these, the so-called “narrow range ethoxylates” are particularly preferred. Surfactants to be used with preference come from the groups of alkoxylated nonionic surfactants, in particular ethoxylated primary alcohols and mixtures of these surfactants with structurally complex surfactants such as polyoxypropylene/polyoxyethylene/polyoxypropylene ((PO/EO/PO) surfactants). Such (PO/EO/PO) nonionic surfactants are also distinguished by good foam control.

In the context of the present invention, particularly preferred nonionic surfactants have been found for the low-foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units. Among these, preference is in turn given to surfactants with EO-AO-EO-AO blocks, in which case one to ten EO or AO groups are bonded to one another before a block of the other groups follows. Here are nonionic surfactants of the general formula

preferably in which R ¹ is a straight-chain or branched, saturated or one or more times unsaturated C6-24 _-alkyl or - alkenyl radical; each group R ² or R ³ is independently selected from -CH3, -CH2CH3, -CH2CH2-CH3, -CH(CH ₃ ) ₂ and the indices w, x, y, z are independently integers from 1 to 6 .

Preferred nonionic surfactants of the above formula can be prepared from the corresponding alcohols R ¹ —OH and ethylene or alkylene oxide by known methods. The radical R ¹ in the above formula can vary depending on the origin of the alcohol. If native sources are used, the radical R ¹ has an even number of carbon atoms and is usually unbranched, with the linear radicals from alcohols of natural origin having 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, are preferred. Alcohols obtainable from synthetic sources are, for example, the Guerbet alcohols or a mixture of methyl-branched or linear and methyl-branched radicals in the 2-position, such as are usually present in oxo alcohol radicals. Regardless of the type of alcohol used to produce the nonionic surfactants contained in the agents, nonionic surfactants are preferred in which R ¹ in the above formula is an alkyl radical with 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 to 11 carbon atoms.

A suitable alkylene oxide unit, which is present in the preferred nonionic surfactants alternating with the ethylene oxide unit, is, in addition to propylene oxide, in particular butylene oxide. However, other alkylene oxides in which R ² or R ³ are independently selected from -CH2CH2-CH3 or -CH(CH3)2 are also suitable. Preference is given to using nonionic surfactants of the above formula in which ^R.sup.2 or ^R.sup.3 is a --CH.sub.3 radical, w and x are independently 3 or 4, and y and z are independently 1 or 2.

Other nonionic surfactants preferably used in the solid phase are nonionic surfactants of the general formula R ¹ 0(Alk0) _x M(0Alk) _y 0R ² , where

R ¹ and R ² independently represent a branched or unbranched, saturated or unsaturated, optionally hydroxylated alkyl radical having 4 to 22 carbon atoms; Alk represents a branched or unbranched alkyl group having 2 to 4 carbon atoms; x and y independently represent values between 1 and 70; and M is an alkyl radical from the group CH ₂ , CHR ³ , CR ³ R ⁴ , CH2CHR ³ and CHR ³ CHR ⁴ , where R ³ and R ⁴ are independently branched or unbranched, saturated or unsaturated alkyl radicals having 1 to 18 carbon atoms.

Nonionic surfactants of the general formula are preferred here

R ¹ -CH(0H)CH ₂ -0(CH ₂ CH ₂ 0)xCH ₂ CHR(0CH ₂ CH ₂ )y -CH ₂ CH(0H)-R ² where R, R ¹ and R ² are independently an alkyl radical or alkenyl radical with 6 to 22

carbon atoms; x and y independently represent values between 1 and 40.

Particular preference is given here to compounds of the general formula R ¹ -CH(0H)CH ₂ -0(CH ₂ CH ₂ 0)xCH ₂ CHR(0CH ₂ CH ₂ )y0-CH ₂ CH(0H)-R ² in which R is a linear, saturated alkyl radical having 8 to 16 carbon atoms, preferably 10 to 14 carbon atoms, and n and m independently have values of 20 to 30. Corresponding compounds can be obtained, for example, by reacting alkyl diols HO-CHR-CH2-OH with ethylene oxide, followed by a reaction with an alkyl epoxide to close the free OH functions with formation of a dihydroxy ether.

Preferred nonionic surfactants here are those of the general formula R ¹ -CH(OH)CH ₂ 0-(A0)w-(A0)x-(A"0) _y- (A'"0)zR ² , in which

- R ¹ is a straight-chain or branched, saturated or mono- or polyunsaturated _C6-24 alkyl or alkenyl radical;

- R ² represents hydrogen or a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;

- A, A', A" and A'" independently represent a radical from the group _-CH2CH2 , -CH2CH2- _CH2 , -CH2-CH(CH3), _-CH2 -CH2-CH2-CH2, -CH2 -CH(CH ₃ )-CH ₂ -, -CH ₂ -CH(CH ₂ -CH ₃ ),

- w, x, y and z stand for values between 0.5 and 120, where x, y and/or z can also be 0.

By adding the aforementioned nonionic surfactants of the general formula R ¹ -CH(OH)CH2O-(AO)w-(A′O)x-(A″O)y-(A″O) _z -R ² , also referred to below as “hydroxy mixed ether”, can surprisingly improve the cleaning performance Preparations according to the invention are significantly improved, both in comparison to surfactant-free systems and in comparison to systems that contain alternative nonionic surfactants, for example from the group of polyalkoxylated fatty alcohols.

The use of these nonionic surfactants having one or more free hydroxyl groups on one or both terminal alkyl radicals can significantly improve the stability of the enzymes contained in the detergents or cleaning agents according to the invention, preferably dishwashing detergents, in particular machine dishwashing detergents.

Preference is given in particular to those end-capped poly(oxyalkylated) nonionic surfactants which, according to the following formula

in addition to a radical R ¹ , which is a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical having 2 to 30 carbon atoms, preferably having 4 to 22 carbon atoms, also a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R ² with 1 to 30 carbon atoms, where n is between 1 and 90, preferably between 10 and 80 and in particular between 20 and 60. Particular preference is given to surfactants of the above formula in which R ¹ is C7 to C13, n is an integer from 16 to 28 and R ² is Cs to C12.

Particularly preferred are surfactants of the formula R ¹ 0 [CH ₂ CH (CH 3) 0] x [CH ₂ CH ₂ 0] _y CH ₂ CH (OH) R ² , in which R ¹ is a linear or branched aliphatic hydrocarbon radical having 4 bis 18 carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x has values between 0.5 and 1.5 and y has a value of at least 15. The group of these nonionic surfactants includes, for example, the C2-26 fatty alcohol (PO)i-(EO)i5- ₄₀ -2-hydroxyalkyl ethers, in particular also the Ce-io fatty alcohol (PO)i-(EO) ₂₂ -2-hydroxydecyl ether .

Particular preference is also given to end-capped poly(oxyalkylated) nonionic surfactants of the formula R ¹ 0[CH ₂ CH ₂ 0]x[CH ₂ CH(R ³ )0] _y CH ₂ CH(0H)R ² , in which R ¹ and R ² is independently a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical having 2 to 26 carbon atoms, R ³ is independently selected from -CH3, -CH2CH3, -CH2CH2-CH3, -CH(CH3)2 , but preferably represents -CH3, and x and y independently represent values between 1 and 32, where nonionic surfactants with R ³ = -Chh and values for x from 15 to 32 and y from 0.5 to 1.5 are very particularly preferred.

Other preferably usable nonionic surfactants are the end-capped poly(oxyalkylated) nonionic surfactants of the formula R ¹ 0[CH ₂ CH(R ³ )0]x[CH ₂ ] _k CH(0H)[CH ₂ ]j0R 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. When the value of x > 2, each R ³ in the above formula R ¹ 0[CH ₂ CH(R ³ )0]x[CH ₂ ] _k CH(0H)[CH ₂ ]j 0R 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, radicals having 8 to 18 carbon atoms being particularly preferred. H, -CH3 or -CFhCF are particularly preferred for the radical R ³ . Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.

As described above, each R ³ in the above formula can be different when x>2. This allows the alkylene oxide unit in the square brackets to be varied. For example, when x is 3, the R ³ group may be selected to form ethylene oxide (R ³ = H) or propylene oxide (R ³ = CH 3 ) moieties which may be joined in any order, e.g. (EO)(PO )(EO), (EO)(EO)(PO), (EO)(EO)(EO), (PO)(EO)(PO), (PO)(PO)(EO) and (PO)(PO )(PO). The value 3 for x was selected here as an example and can certainly be larger, with the range of variation increasing with increasing x values and including, for example, a large number of (EO) groups combined with a small number of (PO) groups, or vice versa .

Particularly preferred endcapped poly(oxyalkylated) alcohols of the above formula have values of k=1 and j=1 such that the above formula translates to R ¹ 0[CH ₂ CH(R ³ )0] _X CH ₂ CH(0H )CH ₂ 0R ² simplified. In the latter formula, R ¹ , R ² and R ³ are as defined above and x is a number from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Surfactants in which the radicals R ¹ and R ² has 9 to 14 carbon atoms, R ³ is H and x has values from 6 to 15. Finally, the nonionic surfactants of the general formula R ¹ --CH(OH)CH ₂ 0-(A0) _W --R ² have proven to be particularly effective

- R ¹ is 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 from 2 to 26 carbon atoms; - A is a radical from the group CH2CH2, CH2CH2CH2, CH2CH(CH3), preferably CH2CH2, and

- w represents values between 1 and 120, preferably 10 to 80, in particular 20 to 40.

The group of these nonionic surfactants includes, for example, the C4-22 fatty alcohol (EO) io-8o-2-hydroxyalkyl ethers, in particular the C8-12 fatty alcohol (EO) ₂₂ -2-hydroxydecyl ether and the C4- 22 fatty alcohol (EO) ₄₀ -80-2-hydroxyalkyl ether.

Preferably, the at least one solid and/or the gel contains at least one nonionic surfactant, preferably a nonionic surfactant from the group of hydroxy mixed ethers, with the proportion by weight of the nonionic surfactant based on the total weight of the gel preferably being 0.5% by weight to 30% by weight. , preferably 5% by weight to 25% by weight and in particular 10% by weight to 20% by weight.

In a further preferred embodiment, the nonionic surfactant of the solid and/or gel phase is selected from nonionic surfactants of the general formula R ¹ -0(CH ₂ CH ₂ 0) _x CR ³ R ⁴ (0CH ₂ CH ₂ )y0-R ² , in which R ¹ and R ² independently represent an alkyl group or alkenyl group having 4 to 22 carbon atoms; R ³ and R ⁴ are independently H or an alkyl or alkenyl group having from 1 to 18 carbon atoms and x and y are independently from 1 to 40.

In this connection, particular preference is given to compounds of the general formula R ¹ -0(CH ₂ CH ₂ 0)xCR ³ R ⁴ (0CH ₂ CH ₂ ) _y 0-R ² , in which R ³ and R ⁴ represent H and the indices x and y independently assume values from 1 to 40, preferably from 1 to 15.

Particular preference is given in particular to compounds of the general formula R ¹ -0(CH ₂ CH ₂ 0) x CR ³ R ⁴ (0CH ₂ CH ₂ ) _y 0-R ² , in which the radicals R ¹ and R ² are, independently of one another, saturated alkyl radicals with 4 represent up to 14 carbon atoms and the indices x and y independently assume values from 1 to 15 and in particular from 1 to 12.

Preference is also given to compounds of the general formula R ¹ -0(CH ₂ CH ₂ 0)xCR ³ R ⁴ (0CH ₂ CH ₂ ) _y 0-R ² in which one of the radicals R ¹ and R ² is branched.

Compounds of the general formula are very particularly preferred

R ¹ -0(CH ₂ CH ₂ 0) _x CR ³ R ⁴ (0CH ₂ CH ₂ )y0-R ² in which the indices x and y assume values from 8 to 12 independently of one another.

The given carbon chain lengths and degrees of ethoxylation or alkoxylation of the nonionic surfactants represent statistical mean values, which can be a whole or a fractional number for a specific product. Due to the manufacturing process, commercial products of the formulas mentioned usually do not consist of an individual representative, but of mixtures, which means that both the C chain lengths and the Degrees of ethoxylation or degrees of alkoxylation can result in mean values and fractional numbers as a result.

Of course, the aforementioned nonionic surfactants (nonionic surfactants) can be used not only as individual substances but also as surfactant mixtures of two, three, four or more surfactants.

Nonionic surfactants which have a melting point above room temperature are particularly preferred in the at least one solid, preferably granular phase. Nonionic surfactant(s) with a melting point above 20°C, preferably above 25°C, more preferably between 25 and 60°C and especially between 26.6 and 43.3°C is/are particularly preferred .

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

The nonionic surfactant which is solid at room temperature preferably has propylene oxide units (PO) in the molecule. Such PO units preferably make up up to 25% by weight, particularly preferably up to 20% by weight and in particular up to 15% by weight, of the total molar mass of the nonionic surfactant. Particularly preferred nonionic surfactants are ethoxylated monohydroxy alkanols or alkyl phenols which additionally have polyoxyethylene-polyoxypropylene block copolymer units. The alcohol or alkylphenol part of such nonionic surfactant molecules makes up preferably more than 30% by weight, particularly preferably more than 50% by weight and in particular more than 70% by weight of the total molar mass of such nonionic surfactants. Preferred agents are characterized in that they contain ethoxylated and propoxylated nonionic surfactants in which the propylene oxide units in the molecule make up up to 25% by weight, preferably up to 20% by weight and in particular up to 15% by weight of the total molar mass of the nonionic identify surfactants.

Other nonionic surfactants to be used particularly preferably in the solid phase with melting points above room temperature contain 40 to 70% of a polyoxypropylene/polyoxyethylene/polyoxypropylene block polymer blend which contains 75% by weight of a reverse block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25% by weight of a block copolymer of polyoxyethylene and polyoxypropylene initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.

In a preferred embodiment, the proportion by weight of the nonionic surfactant in the total weight of the solid, preferably granular phase is from 0.1 to 20% by weight, particularly preferably from 0.5 to 15% by weight, in particular from 2.5 to 10% by weight %.

All anionic surface-active substances are suitable as anionic surfactants in the agents.

These are characterized by a water-solubilizing, anionic group such as. B. a carboxylate, sulfate or sulfonate group and a lipophilic alkyl group having about 8 to 30 carbon atoms. In addition, the molecule can contain glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups. Suitable anionic surfactants are preferably in the form of the sodium, potassium and ammonium and the mono-, di- and trialkanolammonium salts with 2 to 4 carbon atoms in the alkanol group, but also zinc, manganese (II), magnesium, calcium or Mixtures of these can serve as counterions. Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids having 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule.

Instead of the surfactants mentioned or in combination with them, cationic and/or amphoteric surfactants such as betaines or quaternary ammonium compounds can also be used. However, it is preferred that no cationic and/or amphoteric surfactants are used.

According to a particularly preferred embodiment, the gel contains at least one further nonionic surfactant, preferably in an amount of 0.1 to 80% by weight.

Particularly suitable nonionic surfactants are described above. Substances from the Plurafac® LF (BASF) series are particularly suitable, as are the end-capped or non-capped non-ionic surfactants described above as hydroxy mixed ethers or fatty alcohol polyalkylene glycols.

Preferred washing or cleaning agents according to the invention, preferably dishwashing detergents, in particular machine dishwashing detergents, are further characterized in that they contain less than 1.0% by weight and in particular less than 0.1% by weight, preferably no anionic surfactant.

According to a particularly preferred embodiment, the washing or cleaning agents according to the invention, preferably dishwashing agents, in particular machine dishwashing agents, characterized in that the gel comprises less than 1% by weight, in particular less than 0.5% by weight, in particular less than 0.1% by weight, of anionic surfactant, based in each case on the total weight of the gel. The gel is preferably essentially free of anionic surfactants. Substantially free means that the gel contains less than 0.05% by weight of anionic surfactant, based on the total weight of the gel.

In this context, it has been shown that the presence of 1% by weight of anionic surfactant in the at least one gel phase leads to poorer foaming behavior and poorer rinsing behavior of the composition as a whole. Furthermore, higher amounts of anionic surfactants have a negative effect on curing. According to a particularly preferred embodiment, the gel contains less than 1% by weight, preferably less than 0.5% by weight, in particular less than 0.05% by weight, of fatty acid salts or soaps.

In another embodiment, the gel may include sugars. According to the invention, sugars include sugar alcohols, monosaccharides, disaccharides and oligosaccharides. In a preferred embodiment, the gel comprises at least one sugar alcohol other than glycerol, preferably at least one monosaccharide or disaccharide sugar alcohol. Mannitol, isomalt, lactitol, sorbitol, threitol, erythritol, arabitol and xylitol are particularly preferred. Particularly preferred monosaccharide sugar alcohols are pentitols and/or hexitols. Xylitol and/or sorbitol is very particularly preferred.

In a further embodiment the gel may comprise disaccharides, in particular sucrose. The proportion of sucrose is 0% by weight to 30% by weight, in particular 5% by weight to 25% by weight, particularly preferably 10% by weight to 20% by weight, based on the weight of the gel phase . In higher amounts, the sugar does not completely dissolve in the gel phase and causes the same to become cloudy. The use of sugar, in particular in a proportion of 10% by weight to 15% by weight, reduces moisture development and thus improves adhesion to at least one solid phase.

According to a particularly preferred embodiment, the at least one additional phase, preferably a solid, granular phase, comprises at least one, preferably several ingredients, which are selected from which are selected from the group consisting of builders (preferably carbonates, citrates, aminopolycarboxylates and/or Amino carboxylates, preferably MGDA and/or GLDA or salts thereof, and/or bleaches (particularly percarbonate), and/or bleach activators and/or bleach catalysts, and/or silver protectants, and/or enzymes (preferably protease(s) and/or amylase (n)), and/or nonionic surfactants and/or other processing aids. The use of builders (builders) such as silicates, aluminum silicates (in particular zeolites), salts of organic di- and polycarboxylic acids and mixtures of these substances, preferably water-soluble builders, can be advantageous.

In an embodiment which is particularly preferred according to the invention, the use of phosphates (including polyphosphates) is largely or completely dispensed with. In this embodiment, the agent preferably contains less than 5% by weight, particularly preferably less than 3% by weight, in particular less than 1% by weight, of phosphate(s). In this embodiment, the agent is particularly preferably completely phosphate-free, i.e. the agents contain less than 0.1% by weight of phosphate(s).

The builders include, in particular, carbonates, citrates, phosphonates, organic builders and silicates. The proportion by weight of the total builders in the total weight of agents according to the invention is preferably 15 to 80% by weight and in particular 20 to 70% by weight.

Organic builders suitable according to the invention are, for example, the polycarboxylic acids (polycarboxylates) which can be used in the form of their sodium salts, polycarboxylic acids/polycarboxylates being understood as meaning those carboxylic acids which have more than one, in particular two to eight acid functions, preferably two to six, in particular two, three, four or carry five acid functions throughout the 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 can also carry other functional groups, such as hydroxyl or amino groups. For example, these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, saccharic acids (preferably aldaric acids, for example galactaric acid and glucaric acid), iminocarboxylic acids, aminocarboxylic acids, in particular aminodicarboxylic acids, aminotricarboxylic acids, aminotetracarboxylic acids such as nitrilotriacetic acid (NTA), glutamine-N ,N-diacetic acid (also referred to as N,N-bis(carboxymethyl)-L-glutamic acid or GLDA), methylglycine diacetic acid (MGDA) and their derivatives and mixtures of these. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, GLDA, MGDA and mixtures of these.

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. In addition to their builder effect, the free acids typically also have the property of an acidifying component. Particular mention should be made here of citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures of these.

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

Particular preference is also given to using 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 from 10 to 30% by weight, very particularly preferably 10 to 24% by weight, based in each case on the weight of the agent.

Particularly preferred washing or cleaning agents according to the invention, preferably dishwashing detergents, in particular machine dishwashing detergents, are characterized in that they contain at least two builders from the group of silicates, phosphonates, carbonates, aminocarboxylic acids and citrates, the proportion by weight of these builders, based on the total weight of the washing or cleaning agent according to the invention, preferably dishwashing detergent, in particular machine dishwashing detergent, is preferably 5 to 70% by weight, preferably 15 to 60% by weight and in particular 20 to 50% by weight. The combination of two or more builders from the group mentioned above has proven advantageous for the cleaning and rinsing performance of washing or cleaning agents according to the invention, preferably dishwashing detergents, in particular machine dishwashing detergents. In addition to the builders mentioned here, one or more other builders can also be present.

Preferred detergents or cleaning agents, preferably dishwashing detergents, in particular machine dishwashing detergents, are characterized by a builder combination of citrate and carbonate and/or bicarbonate. In a very 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% by weight, in particular from 10 to 35% by weight, very particularly preferably from 15 to 30% by weight. and the amount of citrate preferably from 5 to 35 wt machine dishwashing detergent, the total amount of these two builders preferably being 20 to 65% by weight, in particular 25 to 60% by weight, preferably 30 to 50% by weight. In addition, one or more other builders can also be included.

The detergents or cleaning agents according to the invention, preferably dishwashing detergents, in particular machine dishwashing detergents, can contain phosphonates in particular as a further builder, to the extent permitted by regulations. A hydroxyalkane and/or aminoalkane phosphonate is preferably used as the phosphonate compound. Among the hydroxyalkanephosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance. Aminoalkanephosphonates are preferred

Ethylenediamine tetramethylene phosphonate (EDTMP), diethylene triamine pentamethylene phosphonate (DTPMP) and their higher homologues in question. Phosphonates are present in agents according to the invention, to the extent permitted by regulations, preferably in amounts of 0.1 to 10% by weight, in particular in amounts of 0.5 to 8% by weight, very particularly preferably 2.5 to 7.5% by weight .- %, based on the total weight of the agent.

The combined use of citrate, (hydrogen) carbonate and phosphonate is particularly preferred. These can be used in the amounts mentioned above. In this combination, in particular, amounts of, in each case based on the total weight of the agent, 10 to 25% by weight of citrate, 10 to 30% by weight of carbonate (or bicarbonate) and 2.5 to 7.5% by weight

phosphonate used.

Further particularly preferred detergents or cleaning agents, preferably dishwashing detergents, in particular machine dishwashing detergents, are characterized in that they contain at least one further phosphorus-free builder in addition to citrate and (hydrogen) carbonate and, if appropriate, phosphonate. In particular, this is selected from the aminocarboxylic acids, with the further phosphorus-free builder preferably being selected from methylglycine diacetic 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.

The percentage by weight of the further phosphorus-free builder, in particular of the MGDA and/or GLDA, is preferably 0 to 40% by weight, in particular 5 to 30% by weight, in particular 7 to 25% by weight. The use of MGDA or GLDA, in particular MGDA, as granules is particularly preferred. MGDA granules that contain as little water as possible and/or have a lower hygroscopicity (water absorption at 25° C., normal pressure) than non-granulated powder are advantageous. The combination of at least three, in particular at least four, builders from the group mentioned above has proven to be preferred for the cleaning and rinsing performance of washing or cleaning agents according to the invention Dishwashing detergents, in particular machine dishwashing detergents, proved to be advantageous.

Other builders can also be included.

Polymeric polycarboxylates are also suitable as organic builders, for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular mass of 500 to 70,000 g/mol. Suitable polymers are, in particular, polyacrylates, which preferably have a molecular weight of 1000 to 20,000 g/mol. Because of their superior solubility, the short-chain polyacrylates which have molar masses from 1100 to 10000 g/mol, and particularly preferably from 1200 to 5000 g/mol, may in turn be preferred from this group.

The content of (homo)polymeric polycarboxylates in the washing or cleaning agents according to the invention, preferably dishwashing detergents, in particular machine dishwashing detergents, is preferably 0.5 to 20% by weight, preferably 2 to 15% by weight and in particular 4 to 10% by weight. %.

Detergents or cleaning agents according to the invention, preferably dishwashing detergents, in particular machine dishwashing detergents, can also contain crystalline layered silicates of the general formula NaMSi _x 0 _2x+i y H2O as a builder, in which M represents sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, where particularly preferred values for x are 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20. Amorphous sodium silicates with an Na2O:S1O2 modulus of 1:2 to 1:3.3, preferably of 1:2 to 1:2.8 and in particular of 1:2 to 1:2.6, which are preferably delayed in dissolution, can also be used and have secondary washing properties.

In addition to the aforementioned builders, the washing or cleaning agents according to the invention, preferably dishwashing detergents, in particular machine dishwashing detergents, can also contain alkali metal hydroxides. These alkali carriers are used in the detergents or cleaning agents, preferably dishwashing detergents, in particular machine dishwashing detergents and in particular in the at least one gel phase, preferably only in small amounts, preferably in amounts below 10% by weight, preferably below 6% by weight, preferably below 5 Wt. Alternative washing or cleaning agents according to the invention, preferably dishwashing agents, in particular machine dishwashing agents, are free from alkali metal hydroxides.

Washing or cleaning agents according to the invention, preferably dishwashing detergents, in particular machine dishwashing detergents, contain at least one solid as a further component and/or the at least one gel phase, preferably enzyme(s). These include in particular proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases or oxidoreductases, and preferably mixtures thereof. These enzymes are in principle of natural origin; Based on the natural molecules, improved variants are available for use in detergents or cleaning agents, preferably dishwashing agents, in particular machine dishwashing agents, which are correspondingly preferably used. Detergents or cleaning agents according to the invention, preferably dishwashing detergents, in particular machine dishwashing detergents, preferably contain enzymes in total amounts of 1×10 ^-6 % by weight to 5% by weight, based on active protein. The protein concentration can be determined using known methods, for example the BCA method or the Biuret method.

Among the proteases, those of the subtilisin type are preferred. Examples of this are the subtilisins BPN' and Carlsberg and their further developed forms, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase, which can be assigned to the subtilases, but no longer to the subtilisins in the narrower sense, Proteinase K and the proteases TW3 and TW7.

Examples of amylases which can be used according to the invention are the α-amylases from Bacillus licheniformis, from B. amyloliquefaciens, from B. stearothermophilus, from Aspergillus niger and A. oryzae and the further developments improved for use in detergents or cleaning agents, preferably dishwashing agents, in particular machine dishwashing agents the aforementioned amylases. Furthermore, the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948).

Lipases or cutinases can also be used according to the invention, in particular because of their triglyceride-splitting activities, but also in order to generate peracids in situ from suitable precursors. These include, for example, the lipases originally available from Humicola lanuginosa (Thermomyces lanuginosus) or further developed, in particular those with the amino acid exchange in positions D96LT213R and/or N233R, particularly preferably all of the exchanges D96L, T213R and N233R.

It is also possible to use enzymes which are summarized under the term hemicellulases. These include, for example, mannanases, xanthan lyases, pectin lyases (=pectinases), pectinesterases, pectate lyases, xyloglucanases (=xylanases), pullulanases and ß-glucanases. According to the invention, 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 to increase the bleaching effect. Advantageously, preferably organic, particularly preferably aromatic, compounds that interact with the enzymes are additionally added in order to increase the activity of the relevant oxidoreductases (enhancers) or to ensure the flow of electrons in the case of greatly differing redox potentials between the oxidizing enzymes and the soiling (mediators). A protein and/or enzyme can be protected against damage such as, for example, inactivation, denaturation or decomposition, for example due to physical influences, oxidation or proteolytic cleavage, particularly during storage. In the case of microbial production of the proteins and/or enzymes, inhibition of proteolysis is particularly preferred, particularly if the agents also contain proteases. Detergents or cleaning agents, preferably dishwashing detergents, in particular machine dishwashing detergents, can contain stabilizers for this purpose; the provision of such means represents a preferred embodiment of the present invention.

Cleaning-active proteases and amylases are generally not provided in the form of the pure protein but rather in the form of stabilized preparations that can be stored and transported. These ready-made preparations include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, particularly in the case of liquid or gel-like preparations, solutions of the enzymes, advantageously as concentrated as possible, low in water and/or mixed with stabilizers or other auxiliaries.

Alternatively, the enzymes for the at least one solid and/or the gel 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 in a set gel or in those of the core-shell type, in which an enzyme-containing core is coated with a water, air and/or chemical impermeable protective layer. Additional active substances, for example stabilizers, emulsifiers, pigments, bleaching agents or dyes, can also be applied in superimposed layers. Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes. Advantageously, such granules, for example due to the application of polymeric film formers, produce little dust and are stable in storage due to the coating.

Furthermore, it is possible to formulate two or more enzymes together, so that a single granulate has several enzyme activities. As can be seen from the above, the enzyme protein forms only a fraction of the total weight of conventional enzyme preparations. Protease and amylase preparations used according to the invention contain between 1 and 40% by weight, preferably between 2 and 30% by weight, particularly preferably between 3 and 25% by weight, of the enzyme protein. Preference is given in particular to detergents or cleaning agents, preferably dishwashing detergents, in particular machine dishwashing detergents, which, based on their total weight, contain from 0.1 to 12% by weight, preferably from 0.2 to 10% by weight and in particular from 0.5 to 8% by weight of the respective enzyme preparations.

In addition to the ingredients mentioned so far, the at least one solid and/or the gel of the washing or cleaning agent according to the invention, preferably dishwashing detergent, in particular automatic dishwashing detergent, can contain other ingredients. These include, for example, anionic, cationic and/or amphoteric surfactants, bleaches,

Bleaching activators, bleaching catalysts, other solvents, thickeners, sequestering agents, electrolytes, corrosion inhibitors, in particular silver preservatives, glass corrosion inhibitors, foam inhibitors, dyes, fragrances (in particular in the at least one solid phase), additives to improve drainage and drying behavior, to adjust viscosity, to Stabilization, UV stabilizers, preservatives, antimicrobial active ingredients (disinfectants), pH adjusters in amounts of usually not more than 5% by weight.

Agents according to the invention preferably contain at least one alkanolamine as a further solvent. The alkanolamine is preferably selected from the group consisting of mono-, di-, triethanol- and -propanolamine and mixtures thereof. The alkanolamine is preferably contained in agents according to the invention in an amount of 0.5 to 10% by weight, in particular in an amount of 1 to 6% by weight. In preferred detergents or cleaning agents, preferably dishwashing detergents, in particular machine dishwashing detergents, the gel is essentially free of alkanolamine, i.e. the gel contains less than 1% by weight, in particular less than 0.5% by weight, preferably less than 0 1% by weight, particularly preferably less than 0.05% by weight, of alkanolamine and the alkanolamine is contained only in the at least one solid phase.

In addition to the zinc salts mentioned above, 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% by weight, in particular 0.01 to 2% by weight .

Polymers suitable as additives are in particular maleic acid-acrylic acid copolymer Na salt (for example ^Sokalan® CP 5 from BASF, Ludwigshafen (Germany)), modified polyacrylic acid Na salt (for example ^Sokalan® CP 10 from BASF, Ludwigshafen (Germany)), modified polycarboxylate sodium salt (for example Sokalan ^® HP 25 from BASF, Ludwigshafen (Germany)), polyalkylene oxide, modified heptamethyltrisiloxane (for example Silwet ^® L-77 from BASF, Ludwigshafen (Germany)), polyalkylene oxide, modified heptamethyltrisiloxane (e.g. Silwet ^® L-7608 from BASF, Ludwigshafen (Germany)) and polyether siloxanes (copolymers of polymethyl siloxanes with ethylene oxide/propylene oxide segments (polyether blocks)), preferably water-soluble linear polyether siloxanes with terminal polyether blocks such as Tegopren ^® 5840, Tegopren ^® 5843, ^Tegopren® 5847, ^Tegopren® 5851, ^Tegopren® 5863 or ^Tegopren® 5878 from Evonik, Essen (Germany). Builder substances suitable as additives are, in particular, sodium polyaspartic acid salt, ethylenediamine triacetate coconut alkylacetamide (for example ^Rewopol® CHT 12 from Evonik, Essen (Germany)), sodium trimethylglycine diacetic acid salt and acetophosphonic acid. In the case of Tegopren ^® 5843 and Tegopren ^® 5863, mixtures with surfactant or polymer additives show synergisms. However, the use of Tegopren types 5843 and 5863 is less preferred when used on hard surfaces made of glass, in particular glassware, since these silicone surfactants can be absorbed by glass. In a particular embodiment of the invention, the additives mentioned are omitted.

A preferred washing or cleaning agent, preferably a dishwashing detergent, in particular a machine dishwashing detergent, preferably also comprises a bleach, in particular an oxygen bleach and optionally a bleach activator and/or bleach catalyst.

If present, these are contained exclusively in the at least one solid phase.

Detergents or cleaning agents according to the invention, preferably dishwashing detergents, in particular machine dishwashing detergents, contain an oxygen bleaching agent from the group consisting of sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate as a preferred bleaching agent. Other usable bleaches are, for example, peroxypyrophosphates, citrate perhydrates and H2O2-supplying peracid salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloimino peracid or diperdodecanedioic acid. Bleaching agents from the group of organic bleaching agents can also be used. Typical organic bleaches are the diacyl peroxides, such as dibenzoyl peroxide. Other typical organic bleaches are the peroxyacids, examples being the alkylperoxyacids and the arylperoxyacids. Sodium percarbonate is particularly preferred because of its good bleaching performance. A particularly preferred oxygen bleach is sodium percarbonate.

Bleach activators which can be used are compounds which, under perhydrolysis conditions, produce aliphatic peroxocarboxylic acids having preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and/or optionally substituted perbenzoic acid. Substances which contain 0- and/or N-acyl groups with the number of carbon atoms mentioned and/or optionally carry substituted benzoyl groups. Polyacylated alkylenediamines are preferred, with tetraacetylethylenediamine (TAED) having proven to be particularly suitable.

The bleach catalysts are bleach-boosting transition metal salts or transition metal complexes such as, for example, 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 and Co, Fe, Cu and Ru ammine complexes can also be used as bleach catalysts. Complexes of manganese in the oxidation state II, III, IV or IV, which preferably contain one or more macrocyclic ligand(s) with the donor functions N, NR, PR, O and/or S, are particularly preferably used. Ligands which have nitrogen donor functions are preferably used. It is particularly preferred to use bleaching catalyst(s) in the agents according to the invention which contain, as macromolecular ligands, 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). Suitable manganese complexes are, for example, [Mh ^ip ₂ (m-0)i(m-0AC) ₂ (TACN)2](CI0 ₄ )2, [Mn ^m Mn ^lv ^-0)2^-0Ac)i(TACN)2 ](BPh4)2, [Mn ^lv ₄ (p-0)6(TACN) ₄ ](CI0 ₄ ) ₄ , [M ^hiii 2(mO)i(m-OA0)2(Mb-TAΰN) ₂ ](ΰIO ₄ )2, [Mn ^IM Mn ^lv (p-0)i(p-0Ac)2(Me-TACN)2](CI0 ₄ )3, [M ^hin ₂ (m-0) ₃ (Me-TACN) ₂ ](PF6)2 and [Mn ^lv 2^-0)3(Me/Me-TACN)2](PF ₆ )2 (with OAc = 0C(0)CH ₃ ).

According to a preferred embodiment, the detergent or cleaning agent portion comprises, in addition to at least one gel or a gel phase, at least or more additional phase(s) which is/are selected from a liquid phase, gel-like phase and/or solid, preferably granular, in particular particulate, preferably free-flowing, solid phase.

The washing or cleaning agent according to the invention, preferably dishwashing detergent, in particular machine dishwashing detergent, preferably comprises at least one gel or one gel phase and at least one solid, preferably granular phase. The detergent or cleaning agent, preferably dishwashing detergents, in particular machine dishwashing detergents, can have one, two, three or more solid, preferably granular phases; it can also have one, two, three, four or more different gel phases. The washing or cleaning agent according to the invention, preferably dishwashing detergents, in particular machine dishwashing detergents, preferably comprises a solid, preferably granular phase and a gel phase.

The washing or cleaning agent, preferably dishwashing detergent, in particular machine dishwashing detergent, particularly preferably comprises two solid, preferably granular phases and a gel phase. It preferably comprises two solid, preferably granular, phases and two gel phases. Also preferred is an embodiment in which the washing or cleaning agent, preferably dishwashing detergent, in particular machine dishwashing detergent, comprises three solid, preferably granular phases and one or two gel phases. The weight ratio of all of the at least one solid phase to all of the at least one gel phase is generally 40:1 to 2:1, in particular 20:1 to 4:1, preferably 14:1 to 6:1, for example 12:1 to 8:1 . The total weight of all phases in a detergent or cleaning agent portion, preferably dishwashing agent portion, in particular machine dishwashing agent portion, can be between 8 and 30 g, in particular 10 to 25 g, preferably 12 to 21 g, for example 13 to 17 g per washing or cleaning agent portion, preferably dishwashing agent portion , In particular machine dishwashing detergent portion amount. This weight ratio results in a good concentration of the respective ingredients of the solid or gel phase in a cleaning process.

According to the invention, the at least one solid, preferably granular phase and the gel adjoin one another over the whole or part of the surface. It is preferred that the two phases directly adjoin one another.

If the at least one solid, preferably granular phase and the gel directly adjoin one another over the whole or part of the surface, the stability is important in addition to the shortest possible setting time of the at least one gel phase. Stability here means that the components contained in the gel phase do not migrate into the at least one solid, preferably granular phase, but rather that the at least one solid, preferably granular phase and the gel are optically separate from one another even after prolonged storage and do not interact with one another, such as diffusion of liquid components from one phase to another or reaction of components in one phase with those in the other phase.

Another subject of the present application is a method for cleaning hard surfaces, in particular dishes, in which the surface is treated in a manner known per se using a detergent or cleaning agent according to the invention, preferably dishwashing detergent, in particular automatic dishwashing detergent. In particular, the surface is brought into contact with the washing or cleaning agent according to the invention, preferably dishwashing detergent, in particular machine dishwashing detergent. The cleaning takes place in particular with a cleaning machine, preferably with a dishwasher.

A further subject of the present invention is also the use of a washing or cleaning agent, preferably dishwashing agent, in particular automatic dishwashing agent, as described above, for cleaning hard surfaces, in particular dishes, in particular in automatic dishwashers. For the use or the process, the specific disclosures made above for the detergents or cleaning agents, preferably dishwashing agents, in particular machine dishwashing agents, apply accordingly.

Insofar as it is stated in the present application that the washing or cleaning agent according to the invention, preferably dishwashing detergent, in particular automatic dishwashing detergent, as a whole or in the gel, comprises something, it is also to be regarded as disclosed that washing or cleaning agent, preferably dishwashing detergent, in particular automatic dishwashing detergent , or the respective phase can consist of it. In the exemplary embodiment below, the preferred dishwashing agent according to the invention, in particular automatic dishwashing agent, is described in a manner that does not limit cleaning agents.

Items provided by this application include:

1 . Detergents or cleaning agents, comprising at least one gel, preferably one

Room temperature (20°C) solid gel comprising, based in each case on the total weight of the gel, 3 to 40% by weight, preferably 4 to 20% by weight, in particular 5 to 18% by weight, PVOH and/or its derivatives; as well as a. at least one component with a parameter r <= 15.3 MPa ^1/2 and b. at least one component with a parameter r >= 16.3 MPa ^1/2 ; as well as c. optionally at least one further active ingredient, preferably selected from dyes, glass corrosion inhibitors, perfumes, pH adjusters and other processing auxiliaries; where at least one of the components according to a) or b) is liquid at 20 °C, and with the proviso that for the mixture of components (number n) according to a) and b) or a), b) and c) applies :

With

and

And where dD ₀ = 16.05 MPc dP ₀ = 20.31 MPc dH ₀ = 36.86 MPa And r = 14.0 to 18.5 MPa ^1/2 .

2. Detergent or cleaning agent according to point 1, characterized in that the radius r is r=15.0 to 17.5. Detergent or cleaning agent according to one of the above points, characterized in that <5% by weight, preferably <3% by weight, in particular <1% by weight, of a component with

15.3<r<16.3 is included. Detergent or cleaning agent according to one of the above points, characterized in that it contains <5% by weight, preferably <3% by weight, in particular <1% by weight, of 1,3-propanediol. Detergent or cleaning agent according to one of the above points, characterized in that <5% by weight, preferably <3% by weight, in particular <1% by weight, of 1,3-propanediol and/or

1,2-propanediol is included. Detergent or cleaning agent according to one of the above points, characterized in that at least one component according to a) which is liquid at 20°C is present. Detergent or cleaning agent according to one of the above points, characterized in that at least one component according to a) which is liquid at 20°C and at least one component according to b) which is liquid at 20°C are present. Detergent or cleaning agent according to one of the above points, characterized in that at least one component according to a), preferably one component a) which is liquid at 20°C, and at least two components, preferably two components according to b) which are liquid at 20°C, are present . Detergent or cleaning agent according to one of the above points, characterized in that component a) is selected from the group consisting of water, glycerol and polyacrylates, in particular polyacrylates containing sulfonic acid groups. Detergent or cleaning agent according to one of the above points, characterized in that component b) is selected independently from the group consisting of organic solvents, nonionic surfactants and organic metal salts. Detergent or cleaning agent according to one of the above points, characterized in that component b) is independently selected from polyalkylene glycols (particularly polyethylene glycols, polypropylene glycols), carbonate esters (particularly glycerol carbonates, propylene carbonates, ethylene carbonates, diethyl carbonates, dimethyl carbonates), 3-methyl -1,3-Butanediol, fatty alcohol alkoxylates (possibly end-capped) and acetates, in particular zinc acetate. Detergent or cleaning agent according to one of the above points, characterized in that the gel has a layer thickness of at least 0.3 mm, preferably at least 0.7 mm, in particular of at least 1.0 mm, very particularly preferably of at least 1.2 mm. Detergent or cleaning agent according to one of the above points, characterized in that as component according to c) at least one zinc salt, preferably zinc chloride, zinc sulfate and/or zinc acetate, in particular zinc acetate, particularly preferably zinc acetate anhydrate, in an amount of 0.05 to 5 % by weight, preferably in an amount of 0.1 to 2.0% by weight, in particular 0.2 to 1% by weight, based on the total weight of the gel. Detergent or cleaning agent portion comprising at least one gel according to one of points 1 to 11 in a water-soluble envelope, preferably comprising polyvinyl alcohol, in particular a film comprising polyvinyl alcohol. Detergent or cleaning agent portion according to point 11 or 12, characterized in that it comprises at least one additional phase which is selected from a liquid phase, a gel phase and/or a particulate, preferably free-flowing, solid phase. Detergent or cleaning agent portion according to point 13, characterized in that at least one additional phase comprises at least one, preferably several ingredients selected from the group consisting of builders (preferably carbonates, citrates, amino carboxylates, preferably MGDA and/or GLDA or their Salts,) and/or bleaching agents (in particular percarbonate), and/or bleach activators and/or bleaching catalysts, and/or silver protectants, and/or enzymes (preferably protease(s) and/or amylase(s)), and/or nonionic surfactants and/or other processing aids. Detergent or cleaning agent according to one of points 1 to 14, characterized in that it is a dishwashing detergent, in particular a dishwashing detergent for machine cleaning of dishes. Use of a cleaning agent according to one of points 1 to 16 for machine cleaning of dishes, in particular for cleaning stubborn, greasy or greasy and protein-rich leftovers, eg fried bacon or gratinated cheese. Method for machine cleaning of dishes, characterized in that a cleaning agent according to one of points 1 to 16 is used in a dishwasher. Examples:

Cleaning agents according to the invention, preferably dishwashing detergents, in particular machine dishwashing detergents, were produced which comprised a solid, preferably granular phase and a gel phase. Different geometries were realized here. Furthermore, detergents, preferably dishwashing detergents, in particular machine dishwashing detergents, were produced which comprised two solid, preferably granular phases and a gel phase. Cleaning agents, preferably dishwashing agents, in particular machine dishwashing agents, were also produced, which comprised a solid, preferably granular phase and 3, 4 and 5 gel phases (of the same or different composition). The following information relates to % by weight of active substance based on the total weight of the phase in question (unless otherwise stated).

Table 1: The solid, granular mixtures of a solid composition, in particular powdery and free-flowing phases, had the following preferred composition:

Table 2: The gels have compositions that are preferably in the following ranges (data based on the total amount of the gel phase):

Table 3: Particularly preferred gels have the following compositions.

The solid granular phases and the gel could be combined with one another as desired. The spatial configuration of the gel phase, which was liquid after mixing the ingredients and dimensionally stable within a maximum setting time of 5 minutes, was determined by the spatial configuration of the solid phase and by commercially available or self-designed forms. A water-soluble cover in the form of an open pouch was produced by deep-drawing a film containing PVOH. A liquid composition was poured into this open cavity, which gave the gel after curing, then solid phases in the form of a free-flowing solid were filled into a pouch comprising polyvinyl alcohol and the open pouch was then sealed by placing a second film and sealing by heat sealing.

Table 4: Examples

(*1) Fatty alcohol alkoxylate, preferably 20-40 EO, endcapped

For E1, the value r is calculated as follows (Table 5): Table 5:

This results in with

(dD Mix dD ₀ ) ² + ( _dPMix dP ₀ ) ² + ( dHMix dH ₀ ) ² = r ²

And dD ₀ = 16.05 MPc dP ₀ = 20.31 MPc dH ₀ = 36.86 MPc a value for r= 15.0.

According to Table 3, the gel formulations were prepared.

The gels were stirred at elevated temperature (80-90°C for water-containing gels, 110-120°C for low-water gels). These gel phases were then poured into castings as described under Table 2. It was found that the gel phases produced in this way, even without 1,3 propanediol, had particularly good processing properties with setting times of less than 10 minutes.

Surprisingly, it was found that these gels work particularly well on stubborn deposits on hard surfaces, in particular on items to be washed. A particularly positive cleaning performance is achieved with greasy or greasy-protein residues as well as burnt and/or baked-on food residues. Surprisingly, good rinsing performance is also found.

Claims

Patent Claims:

1 . Detergents or cleaning agents, comprising at least one gel, preferably one

With

and

( dD _Mix - dD ₀ ) ² + ( dPMix - dP ₀ ) ² + ( dHMix - dH ₀ ) ² = r ² where dD ₀ = 16.05 MPa dP ₀ = 20.31 MPc dH ₀ = 36.86 MPc

And r= 14.0 to 18.5 MPa ^1/2 .

2. Detergent or cleaning agent according to 1, characterized in that the radius r is r=15.0 to 17.5.

3. Detergent or cleaning agent according to one of the preceding claims, characterized in that at least one component according to a) which is liquid at 20° C. is present.

4. Detergent or cleaning agent according to one of the preceding claims, characterized in that at least one component according to a) which is liquid at 20° C. and at least one component according to b) which is liquid at 20° C. are present.

5. Detergent or cleaning agent according to one of the preceding claims, characterized in that at least one component according to a), preferably one component a) which is liquid at 20° C., and at least two components, preferably two components which are liquid at 20° C. according to b) are included.

6. Detergent or cleaning agent according to one of the preceding claims, characterized in that component a) is selected from the group consisting of water, glycerol and polyacrylates, in particular polyacrylates containing sulfonic acid groups.

7. Detergent or cleaning agent according to one of the preceding claims, characterized in that component b) is selected independently from the group consisting of organic solvents, nonionic surfactants and organic metal salts.

8. Detergent or cleaning agent according to one of the preceding claims, characterized in that component b) is independently selected from polyalkylene glycols (in particular polyethylene glycols, polypropylene glycols), carbonate esters (in particular glycerol carbonates, propylene carbonates, ethylene carbonates, diethyl carbonates, dimethyl carbonates), 3 -Methyl-1,3-butanediol, fatty alcohol alkoxylates (possibly end-capped) and acetates, in particular zinc acetate.

9. Detergent or cleaning agent according to one of the preceding claims, characterized in that the gel comprises less than 5% by weight, preferably less than 3% by weight, in particular less than 1% by weight, of 1,3-propanediol.

10. Detergent or cleaning agent according to one of the preceding claims, characterized in that the gel has a layer thickness of at least 0.3 mm, preferably at least 0.7 mm, in particular at least 1.0 mm, very particularly preferably at least 1 2mm.

11. Detergent or cleaning agent portion comprising at least one gel according to any one of claims 1 to 10 in a water-soluble envelope, preferably comprising polyvinyl alcohol, in particular a film comprising polyvinyl alcohol.

12. Detergent or cleaning agent portion according to claim 10 or 11, characterized in that it comprises at least one additional phase which is selected from a liquid phase, a gel phase and/or a particulate, preferably free-flowing, solid phase.

13. Detergent or cleaning agent portion according to claim 12, characterized in that at least one additional phase has at least one, preferably several ingredients which are selected from the group formed from builders (preferably carbonates, citrates, aminopolycarboxylates, preferably MGDA and/or GLDA or their salts) and/or bleaches (especially percarbonate), and/or bleach activators and/or bleach catalysts, and/or or silver protectants, and/or enzymes (preferably protease(s) and/or amylase(s)), and/or nonionic surfactants and/or other processing aids.

14. Detergent or cleaning agent according to one of claims 1 to 13, characterized in that it is a dishwashing detergent, in particular a dishwashing detergent for machine cleaning of dishes.

15. Use of a detergent or cleaning agent according to one of Claims 1 to 14 for machine cleaning of dishes, in particular for cleaning stubborn, greasy or greasy and protein-rich food residues, e.g. fried bacon or gratinated cheese.