EP3749738A1

EP3749738A1 - Viscoelastic, solid surfactant composition

Info

Publication number: EP3749738A1
Application number: EP19702201.5A
Authority: EP
Inventors: Anna KLEMMER; Peter Schmiedel; Filiz Yapici; Boris Nachtsheim; Dominik Göbel
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 2018-02-06
Filing date: 2019-01-21
Publication date: 2020-12-16
Also published as: DE102018201830A1; WO2019154612A1

Abstract

The invention relates to a viscoelastic, solid surfactant composition for treating textiles, the composition comprising, based on the total weight thereof, (i) a total amount of 0.1 to 70 wt% of at least one surfactant and (ii) at least one organic compound having a molecular weight of < 1000 g/mol, a solubility in water of less than 0.1 g/L (20 °C, pH 7) and a structure containing a) at least two groups selected from -OH, -NH- or mixtures thereof, and b) at least one carbocyclic structural unit having at least two endocyclic double bonds, in particular at least one carbocyclic, aromatic structural unit, and c) at least one additional cyclic structural unit that comprises at least two carbonyl groups, and (iii) water. The viscoelastic, solid surfactant composition is a readily soluble, aesthetically pleasing and storage-stable form of a solid composition for preparing surfactant-containing liquors.

Description

"Viscoelastic, solid surfactant composition"

The present invention relates to the technical field of the fixed-shaped

Surfactant compositions, in particular for the provision of surfactant-containing liquors for textile treatment or for cleaning hard surfaces such as dishes, ceramics, glass, wood or plastic, in particular for cleaning textiles.

Many detergents are in solid form (for example as powders or tablets) or in liquid form (or else as flowing gel). In particular, liquid washing or

Detergents are becoming increasingly popular with consumers.

Solid substrate treatment agents have the advantage that, in contrast to liquid substrate treatment agents, they do not require preservatives and contain the same

Ingredients (such as bleaches or enzymes) can be more stable incorporated. Liquid supply forms are increasingly gaining acceptance on the market, in particular due to their rapid solubility and the associated rapid availability of the active ingredients contained.

Consumers have resorted to a convenient dosing of pre-portioned

Substrate treatment agents, such as detergent pouches or dishwashing tablets, for machine substrate treatment accustomed and use these products in the form of tablets or in the form of bags (also: pillows or pouches), which are usually filled with at least one liquid composition. However, in addition to the aforementioned advantages, the use of liquids has the disadvantage, for example, that leakages in the sachet of the portion cause the liquid composition to run out.

Disposable portions in water-soluble bags enjoy popularity with the consumer also because of the attractive appearance of the disposable portion. The appearance of the dosage form is becoming more important. In addition to a good cleaning performance and a sufficient storage stability, a good appearance is one of the reasons for choosing a product. In particular, transparent products are perceived by the consumer as visually appealing. For the

Textile cleaning used solid surfactant compositions are usually opaque. It is therefore also an object to translucent to transparent solid surfactant compositions

provide.

From the point of view of the consumer, it is also desirable to combine the advantages of the forms of solid and liquid preparations and an improved dosage form, especially for liquid or liquid detergents, which is better than the prior art

To provide cleaning agents. For this purpose, a one-time portioning of the contained Components are possible and at the same time a visually appealing appearance for the consumer, in particular transparency or translucency, can be achieved.

In particular, when using solid moldings which have to be dissolved or dispersed for application to a substrate in an aqueous medium, it is particularly important that the solid dissolves well in water. With co-dosage of disposable portions and substrate, e.g. the laundry, in the same room of the machine, e.g. the drum of the washing machine, the disposable portion must be quickly incorporated into the aqueous, liquid liquor. Otherwise, the substrate (e.g., fabric) directly in contact with the portion will most likely be damaged by a sustained over-concentration of the surfactant composition on the substrate. It is therefore the object of the invention to provide solid-form surfactant compositions, in particular as a single-use portion in the form of a particulate shaped body, which dissolve readily in water or can be dispersed therein upon contact with water.

From the publication WO 02/086074 A1 are viscoelastic, festförmige

Surfactant compositions with a storage modulus of 40,000 to 800,000 Pa known. The viscoelastic surfactant compositions disclosed therein are liquid crystalline

Surfactant phases. The preparation of the viscoelastic surfactant compositions of the prior art is dependent on the phase behavior of the respective surfactants present, which is the

Freedom of formulation with regard to the selection of surfactants and their amounts used

limited.

Another object was thus to provide solid-form surfactant compositions which have a viscoelastic behavior independently of the phase behavior of the surfactants used.

Surprisingly, it has been found that by formulating a composition containing at least one surfactant and at least one specific organic compound, this object can be achieved.

A first subject of the invention is therefore a viscoelastic, festförmige

Surfactant composition (especially as a washing or cleaning agent), containing based on their total weight

(i) a total amount of 0.1 to 70% by weight of at least one surfactant and

(ii) at least one organic compound having a molecular weight of <1000 g / mol, a solubility in water of less than 0.1 g / L (20 ° C, pH 7) and a structure containing a) at least two groups from -OH, -NH-, or mixtures thereof, and

b) at least one carbocyclic structural unit having at least two

endocyclic double bonds, in particular at least one carbocyclic, aromatic structural unit,

and

c) at least one further cyclic structural unit having at least two carbonyl groups

and

(iii) water.

Particularly preferred as a second embodiment of the first subject of the invention is a viscoelastic, solid surfactant composition (in particular as a washing or cleaning agent), based on their total weight

(i) a total amount of from 0.1 to 70% by weight of at least one surfactant

and

b) at least one carbocyclic structural unit having at least two

and

(iii) water,

with the proviso that the composition has a storage modulus between 10 ³ Pa and 10 ⁸ Pa, preferably between 10 ⁴ Pa and 10 ⁸ Pa and a loss modulus (each at 20 ° C, a deformation of 0.1% and a frequency of 1 Hz) and the memory module in the frequency range between 10 ³ Hz and 10 ² Hz is at least twice greater than the loss modulus. More preferably, the composition has a storage modulus in a range of 10 ⁵ Pa to 10 ⁷ Pa.

To further optimize the stability properties of the said composition, it is preferred if the storage modulus is at least five times greater than the loss modulus, more preferably at least ten times greater than the loss modulus (in each case at 20 ° C., a deformation of 0.1%). and a frequency of 1 Hz). All definitions and preferred embodiments below, unless otherwise defined, apply equally to the first embodiment and the second embodiment.

The viscoelastic, solid surfactant composition combines all the advantages of a liquid composition with its solid form, providing an aesthetic product form with a good dissolution profile in the context of textile treatment with an outstanding performance profile on the substrate.

The viscoelastic solid surfactant composition of the present invention is storage and dimensionally stable. The said viscoelastic, solid surfactant composition exhibits almost no syneresis even after prolonged storage.

A substance (e.g., a composition) is solid according to the definition of the invention when in the solid state at 20 ° C and 1013 mbar.

As is known and therefore according to the invention, a fabric (e.g., a composition) is viscoelastic and solid when at 20 ° C the storage modulus of the fabric is greater than the loss modulus present. When subjected to a mechanical force on the substance, it exhibits both the properties of an elastic solid and exhibits a viscosity similar to that of a liquid. The terms of the storage modulus and the loss modulus, as well as the determination of the values of these modules, are notoriously familiar to the person skilled in the art (see Christopher W. Macosco, "Rheology Principles, Measurements and Applications", VCH, 1994, pp. 121 ff or Gebhard Schramm , "Introduction to Rheology and Rheometry", Karlsruhe, 1995, p. 156 ff. Or WO 02/086074 A1, p. 2, third paragraph to p. 4, end of the first paragraph).

The rheological characterization is in the context of this invention with a

Rotationsrheometer, for example, TA Instruments, type AR G2, Malvern "Kinexus", carried out using a cone-plate measuring system with 40 mm diameter and 2 ° opening angle at a temperature of 20 ° C. This is

shear stress controlled rheometer. However, the determination can also be made with others

Instruments or measurement geometries of comparable specifications.

The measurement of the memory module (abbreviation: G ') and the loss modulus (abbreviation: G ")

(each unit: Pa) was carried out with the equipment described above in an experiment with oscillating deformation. For this purpose, the linear viscoelastic region is first determined in a stress sweep experiment. Here, at a constant frequency of e.g. 1 Hz, the shear stress amplitude increased. The modules G 'and G "are in one

plotted log log plot. On the x-axis can optionally the

Shear stress amplitude or the (resulting) deformation amplitude can be plotted. The memory module G 'is below a certain shear stress amplitude or Deformation amplitude constant, above it collapses. The break point is suitably determined by applying tangents to the two curve sections. The corresponding deformation amplitude or shear stress amplitude is usually referred to as "critical deformation" or "critical shear stress".

To determine the frequency dependence of the modules, a frequency ramp, e.g. moved between 0.001 Hz and 100 Hz at a constant deformation amplitude. The

Deformation amplitude must be chosen so that it is in the linear range, i. below the o.g. critical deformation lies. In the case of the invention

Compositions has a deformation amplitude of 0.1% proved suitable. The modules G 'and G "are plotted against the frequency in a log-log plot.

A substance (e.g., a composition) is liquid according to the definition of the invention when in the liquid state at 20 ° C and 1013 mbar.

A chemical compound is an organic compound when the molecule of the chemical compound contains at least one covalent bond between carbon and hydrogen.

A chemical compound is, inversely to the definition of the organic compound, an inorganic compound when the molecule of the chemical compound does not contain a covalent bond between carbon and hydrogen.

An "endocyclic double bond" is a double bond in a ring of a cyclic compound. The double bond is thus completely formed by atoms that form the ring.

For the purposes of the invention, a compound or a structural unit is "aromatic" if it or a structural fragment thereof satisfies the Hückel rule. Polycyclic, aromatic

Hydrocarbons, i.e. aromatic compounds with fused ring systems are explicitly covered by this definition.

In the context of this application for polymeric ingredients specified mean

Molar masses are always, unless explicitly indicated otherwise

weight-average molar masses M _w , which can be determined in principle by means of gel permeation chromatography with the aid of an RI detector, wherein the measurement is expediently carried out against an external standard.

A "surfactant-containing liquor" in the context of the invention is a liquid preparation obtainable by use of a surfactant-containing dilution with at least one solvent (preferably water) for the treatment of a substrate. As a substrate tissue or textiles (such as clothing), as well as hard surfaces (such as dishes, ceramics, plastic, metal) come into question. The surfactant compositions according to the invention are preferred for providing a surfactant-containing liquor used in the context of mechanical cleaning processes, such as those performed by a washing machine for textiles or a dishwasher. The surfactant compositions according to the invention can preferably also be used as cleaners for hard surfaces, such as ceramics, toilets or glass. The surfactant compositions according to the invention can be used in particular as toilet cleaners. The surfactant-containing liquor is here preferably applied by a toilet bowl on the toilet rim on the rinse or glued directly to the inner surface of the toilet bowl and distributed over the rinse.

"At least one" as used herein refers to 1, 2, 3, 4, 5, 6, 7, 8, 9 or more. In the context of ingredients of the compositions described herein, this indication does not refer to the absolute amount of molecules but to the nature of the ingredient. Thus, "at least one inorganic base" means, for example, one or more different inorganic bases, i. one or more different types of inorganic bases. The amounts given, together with quantities, refer to the total amount of the corresponding type of ingredient.

If, in the context of the application, numerical ranges are defined from one number to another number, then the limit values are included in the range.

If, in the context of the application, numerical ranges are defined between a number and another number, the limits do not include the range.

The viscoelastic, solid surfactant composition according to the invention is preferably transparent or translucent. A mixture according to the invention in the spectral range between 380 nm and 780 nm has a residual light power related to the reference measurement

(Transmission) of at least 20%, it is considered transparent in the context of the invention.

The transparency of the surfactant composition according to the invention can be determined by various methods. The nephelometric turbidity unit (NTU) is often used as a measure of transparency. It is a e.g. in the

Water treatment unit used for turbidity measurements e.g. in liquids. It is the unit of turbidity measured with a calibrated nephelometer. High NTU values are measured for cloudy surfactant compositions, while low values are determined for clear, transparent surfactant compositions.

The HACH Turbidimeter 2100Q turbidimimeter from Hach Company, Loveland, Colorado (USA) is used with the calibration probes StabICal Solution HACH (20 NTU), StabICal Solution HACH (100 NTU) and StabICal Solution HACH (800 NTU). , all can also be ordered from Hach Company. The measurement is in a 10 ml cuvette with cap filled with the composition to be examined and the measurement is carried out at 20 ° C.

At an NTU value (at 20 ° C.) of 60 or more, surfactant compositions which can be recognized by the naked eye in the sense of the invention have a perceptible haze. Therefore, it is preferred that the surfactant compositions of the invention have an NTU (at 20 ° C) of at most 120, more preferably at most 1 10, more preferably at most 100, most preferably at most 80.

In the context of the present invention, the transparency of the solid-state agents according to the invention was determined by a transmission measurement in the visual light spectrum over a wavelength range from 380 nm to 780 nm at 20 ° C. For this purpose, a reference sample (water, deionized) is first measured in a photometer (Messrs. Specord S 600 from Analytik Jena) with a cuvette which is transparent in the spectrum to be examined (layer thickness 10 mm). Subsequently, the cuvette with a sample of the invention

Filled surfactant composition and measured again. The sample is filled in the liquid state and solidified in the cuvette and then measured.

It is preferred if the transparent surfactant composition according to the invention has a transmission (20 ° C.) of particularly preferably at least 25%, more preferably at least 30%, more preferably at least 40%, in particular at least 50%, very particularly preferably at least 60%.

It is very particularly preferred if the transparent according to the invention

Surfactant composition has a transmission (at 20 ° C) of at least 30% (in particular of at least 40% more preferably of at least 50%, more preferably of at least 60%) and an NTU value (at 20 ° C) of at most 120 (more preferably at most 1) 10, more preferably at most 100, more preferably at most 80).

The viscoelastic, solid-form surfactant composition according to the invention contains, based on its total weight, a total amount of from 0.1 to 70% by weight of surfactant. Suitable surfactants according to the invention are preferably anionic surfactants, nonionic surfactants, zwitterionic surfactants, amphoteric surfactants or cationic surfactants.

Preferred surfactant compositions contain, based on their total weight, a total amount of from 5 to 70% by weight, more preferably from 5 to 65% by weight, more preferably from 5 to 60% by weight, more preferably from 10 to 70% by weight, more preferably from 10 to 65% by weight, more preferably from 10 to 60% by weight, more preferably from 15 to 70% by weight, more preferably from 15 to 65% by weight, more preferably from 15 to 60% by weight, most preferably from From 20 to 70% by weight, more preferably from 20 to 65% by weight, more preferably from 20 to 60% by weight, most preferably from 25 to 70 Wt .-%, more preferably from 25 to 65 wt .-%, more preferably from 25 to 60 wt .-%, further preferably from 30 to 70 wt .-%, more preferably from 30 to 65 wt .-%, more preferably from 30 to 60% by weight of at least one surfactant. These surfactant compositions are particularly suitable for textile treatment, but especially for use in a washing machine for the

Textile washing. In this case, it is again particularly preferred if the surfactant composition contains at least one anionic surfactant and optionally additionally at least one nonionic surfactant.

Preferred embodiments of a surfactant composition according to the invention as

Dishwashing agents, in particular for use in a dishwasher, each contain, based on the weight of the composition, 0.1 to 5.0 wt .-%, in particular 0.2 to 4.0 wt .-%, of at least one surfactant.

An inventively preferred viscoelastic, solid-form surfactant composition is characterized in that it contains at least one anionic surfactant. Surfactant compositions according to the invention with anionic surfactant are particularly suitable for washing textiles, particularly preferably for use in a washing machine for textile washing. Preferred surfactant compositions which are suitable as dishwashing agents (in particular for use in a dishwashing machine) contain in each case, based on the weight of the composition, 0 to 1% by weight, in particular 0 to 0.5% by weight, particularly preferably 0 to 0, 25% by weight, anionic surfactant.

When the surfactant composition of the invention contains anionic surfactant and is used as a laundry detergent, it is preferred that based on the total weight of the composition, anionic surfactant be present in a total amount of from 5 to 70% by weight, more preferably from 5 to 60% by weight, more preferably from 10 to 70 wt .-%, in particular 10 to 60 wt .-%, particularly preferably from 10 to 40 wt .-%, more preferably from 25 to 40 wt .-%, is contained.

Regardless of the field of application of the surfactant composition according to the invention, preference is given to using sulfonates and / or sulfates as the anionic surfactant.

As surfactants of the sulfonate type are preferably C9 -i3-alkylbenzenesulfonates,

Olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as obtained for example from Ci2-i8 monoolefins with terminal or internal double bond by sulfonating with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation, into consideration. Also suitable are C 12-18 alkanesulfonates and the esters of α-sulfo fatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids. Particularly preferred surfactant compositions according to the invention, in particular

Textile detergents containing as anionic surfactant at least one compound of formula (T-1),

+

Y

(T-1),

in the

R ^' and R ^"are independently H or alkyl and together contain 9 to 19, preferably 9 to 15 and especially 9 to 13 C atoms, and Y ^{+ is} a monovalent cation or the nth part of an N-valent cation (especially Na ⁺ ).

Alk (en) ylsulfates are the alkali metal and in particular the sodium salts of

Sulfuric acid half esters of C 12 -18 fatty alcohols, for example from coconut fatty alcohol,

Tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half-esters of secondary alcohols of these chain lengths. Of washing technology interest, the Ci2-Ci6-alkyl sulfates and Ci ₂ -Ci5-alkyl sulfates and Ci ₄ -Ci5-alkyl sulfates are preferred. 2,3-alkyl sulfates are also suitable anionic surfactants.

Also fatty alcohol ether sulfates, such as the Schwefelsäuremonoester the ethoxylated with 1 to 6 moles of ethylene oxide chain or branched C7 _2i alcohols such as 2-methyl-branched C9-11- alcohols containing on average 3.5 mol ethylene oxide (EO) or Ci2-is- Fatty alcohols with 1 to 4 EO are suitable.

Other suitable anionic surfactants are soaps. Suitable are saturated and unsaturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, (hydrogenated) erucic acid and behenic acid and, in particular, soap mixtures derived from natural fatty acids, for example coconut, palm kernel, olive oil or tallow fatty acids.

The anionic surfactants and the soaps may be in the form of their sodium, potassium or

Magnesium or ammonium salts are present. Preferably, the anionic surfactants are in the form of their ammonium salts. Preferred counterions for the anionic surfactants are the protonated forms of choline, triethylamine, monoethanolamine or methylethylamine.

In a very particularly preferred embodiment, the inventive

Surfactant composition, in particular as a laundry detergent, a monoethanolamine-neutralized alkylbenzenesulfonic acid, in particular C9 -i3-alkylbenzenesulfonic acid, and / or a monoethanolamine-neutralized fatty acid.

A preferred surfactant composition of the invention contains at least one anionic surfactant selected from the group consisting of Cs -is-alkylbenzenesulfonates, olefin-sulfonates, C 12-18 alkanesulfonates, ester sulfonates, alkyl sulfates, alkenyl sulfates, fatty alcohol ether sulfates and mixtures thereof.

In a preferred embodiment, the inventive

Surfactant composition, in particular as a washing or cleaning agent, at least one nonionic surfactant.

The at least one nonionic surfactant may be any known nonionic surfactant suitable for the purpose of this invention.

In a preferred embodiment, the surfactant composition contains at least one nonionic surfactant.

Preferred embodiments of a surfactant composition according to the invention as

Dishwashing agents, in particular for use in a dishwasher, each contain, based on the weight of the composition, 0.1 to 5.0 wt .-%, in particular 0.2 to 4.0 wt .-%, of at least one nonionic surfactant.

Preferred embodiments of a surfactant composition according to the invention as

Textile detergents, in particular for use in a washing machine, each contain, based on the weight of the composition, 1, 0 to 25 wt .-%, preferably 2.5 to 20.0 wt .-%, more preferably 5.0 to 18.0 Wt .-%, of at least one nonionic surfactant.

In a preferred embodiment of the invention, those described herein contain

Surfactant compositions as nonionic surfactant at least one fatty alcohol alkoxylate represented by the following formula (T-2),

R ^' -O- (XO) m H (T-2)

wherein R ^'is a linear or branched Cs-C-is-alkyl radical, an aryl radical or alkylaryl radical, XO is independently an ethylene oxide (EO) or propylene oxide (PO) grouping and m is an integer from 1 to 50. In the above formula, R ^'is a linear or branched, substituted or unsubstituted alkyl radical. In a preferred

Embodiment of the present invention R 'is a linear or branched alkyl radical having 5 to 30 carbon atoms, preferably having 7 to 25 carbon atoms and especially having 10 to 19 carbon atoms. Preferred radicals R ^' are selected from decyl, undecyl, dodecyl, Tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and mixtures thereof, with the even number of carbon atoms being preferred. Particularly preferred radicals R ^' are derived from fatty alcohols having 12 to 19 carbon atoms, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or oxo alcohols having 10 to 19 carbon atoms.

XO of the formula (T-2) is an ethylene oxide (EO) or propylene oxide (PO) grouping,

preferably an ethylene oxide moiety.

The subscript m of the formula (T-2) is an integer of 1 to 50, preferably 2 to 20, and preferably 2 to 10. In particular, m is 3, 4, 5, 6 or 7. The present invention

Surfactant composition may include mixtures of nonionic surfactants having different degrees of ethoxylation.

In summary, particularly preferred fatty alcohol alkoxylates are those of the formula (T-3)

(T-3)

with k = 9 to 17, m = 3, 4, 5, 6, or 7. Very particularly preferred representatives are fatty alcohols having 10 to 18 carbon atoms and 7 EO (k = 1 1 to 17, m = 7).

Such fatty alcohol ethoxylates are available under the brand names 45-7 Dehydol LT7 ^® (BASF) Lutensol ^® A07 (BASF) Lutensol ^® M7 (BASF), and Neodol ^® (Shell Chemicals).

With particular preference, the surfactant compositions according to the invention contain nonionic surfactants from the group of the alkoxylated alcohols. The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as they are usually present in Oxoalkoholresten. In particular, however, preferred are alcohol ethoxylates having linear radicals of alcohols of native origin having 12 to 18 carbon atoms, for example coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 moles of EO per mole of alcohol. Preferred ethoxylated alcohols include, for example, Ci ₂ -i ₄ alcohols containing 3 EO or 4 EO, Cs-n-alcohol with 7 EO, Cs alcohols containing 3 EO, 5 EO, 7 EO or 8 EO, C 12 18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C12-14 alcohol with 3 EO and Ci2-is-alcohol with 5 EO. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow rank ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used, in particular as automatic dishwashing detergents. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

Particular preference is given to ethoxylated nonionic surfactants which have been obtained from C 6-20 monohydroxyalkanols or C 6-2 o -alkylphenols or C 16-20 fatty alcohols and more than 12 mol, preferably more than 15 mol and in particular more than 20 mol of ethylene oxide per mol of alcohol, used. A particularly preferred nonionic surfactant is selected from a straight chain fatty alcohol having 16 to 20

Carbon atoms (C 16-20 alcohol), preferably a C-is-alcohol and at least 12 moles, preferably at least 15 moles and especially at least 20 moles of ethylene oxide. Of these, the so-called "narrow ranks ethoxylates" are particularly preferred.

Preferably used surfactants come from the groups of alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols and mixtures of these surfactants with structurally complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene ((PO / EO / PO) surfactants). Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control.

Particularly preferred nonionic surfactants, in particular for machine dishwashing detergents, have been found in the context of the present invention to be the low-foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units. Among these, in turn, surfactants with EO-AO-EO-AO blocks are preferred, wherein in each case one to ten EO or AO groups are bonded to each other before a block of the other groups follows. Here are nonionic surfactants of the general formula (T-4)

R1-0- (0 H ₂ -CH ₂ -0) - (CH ₂ -C H-0) - (CH ₂ -CH ₂ -0) - (CH ₂ C H 0) -H

R2 R3

(T-4)

preferably, R ¹ ₂₄ alkyl or-alkenyl stands for a straight-chain or branched, saturated or inclusion as polyunsaturated C6; each group R ² or R ^{3 is} independently selected from -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ -CH ₃ , -CH (CH ₃ ) ₂ and the indices w, x, y, z independently represent integers from 1 to 6 ,

Preferred nonionic surfactants of the above formula can be prepared by known methods from the corresponding alcohols R ¹ -OH and ethylene or alkylene oxide. The radical R ¹ in the above formula may vary depending on the origin of the alcohol. When native sources are used, the radical R ^{1 has} an even number of carbon atoms and is usually unbranched, the linear radicals being selected from alcohols of native origin having 12 to 18 carbon atoms. Atoms, for example from coconut, palm, tallow or oleyl alcohol, are preferred. Examples of alcohols which are accessible from synthetic sources are the Guerbet alcohols or methyl-branched or linear and methyl-branched radicals in the 2-position, such as are usually present in oxo alcohol radicals. Irrespective of the type of alcohol used to prepare the nonionic surfactants contained in the surfactant composition, preference is given to nonionic surfactants in which R ¹ in the above formula is an alkyl radical having 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 to 1 1 carbon atoms.

As the alkylene oxide unit which is contained in the preferred nonionic surfactants in alternation with the ethylene oxide unit, in particular butylene oxide is considered in addition to propylene oxide. However, other alkylene oxides in which R ² or R ^{3 are} independently selected from - CH 2 CH 2 -CH 3 or -CH (CH 3) 2 are suitable. Preference is given to using nonionic surfactants of the above formula in which R ² or R ^{3 is} a radical -CH 3, w and x are independently of one another values of 3 or 4 and y and z are independently of one another values of 1 or 2.

Further preferred nonionic surfactants, in particular for automatic dishwashing detergents, are nonionic surfactants of the general formula (T-5)

R ¹ 0 (Alk0) x M (OAlk) _y 0R ² (T-5) where R ¹ and R ² independently of one another represent a branched or unbranched, saturated or unsaturated, optionally hydroxylated alkyl radical having 4 to 22 carbon atoms; Alk is a branched or unbranched alkyl radical 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, CH 2 CHR ³ and CHR ³ CHR ^4, wherein R ³ and R ⁴ independently represent a branched or unbranched, saturated or unsaturated alkyl radical having 1 to 18 Carbon atoms.

Nonionic surfactants of the general formula (T-6) are preferred here.

R ¹ -CH (OH) CH ₂ -O (CH ₂ CH ₂ O) x CH ₂ CHR (OCH ₂ CH ₂ ) y-CH ₂ CH (OH) -R ² (T-6) where R, R ¹ and R ² independently represent an alkyl group or alkenyl group having 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 (T-7)

R ¹ -CH (OH) CH ₂ -O (CH ₂ CH ₂ O) x CH ₂ CHR (OCH ₂ CH ₂ ) y O -CH ₂ CH (OH) -R ² (T-7) in which R is a linear, saturated alkyl radical having 8 to 16 carbon atoms, preferably 10 to 14 carbon atoms, and R ¹ and R ² independently represent an alkyl radical or alkenyl radical having 6 to 22 carbon atoms, and n and m independently of one another have values of 20 to 30 have. Corresponding compounds can be obtained, for example, by reaction of alkyldiols HO-CHR-CH 2 -OH with ethylene oxide, followed by reaction with an alkyl epoxide to close the free OH functions to form a dihydroxy ether.

Preferred nonionic surfactants here are, in particular for automatic dishwashing detergents, those of the general formula (T-8)

R ¹ -CH (OH) CH ₂ O- (AO) w- (A0) x- (A "0) y- (A"'0) _z -R ² (T-8) in the

R ^{1 represents} a straight-chain or branched, saturated or mono- or polyunsaturated C 6- ₂₄ -alkyl or -alkenyl radical;

R ^{2 is} hydrogen or a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;

- A, A ', A "and A'" independently of one another are radicals from the group -CH ₂ CH ₂ , -CH ₂ CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ), -CH ₂ -CH ₂ -CH ₂ -CH ₂ , -CH ₂ - CH (CH ₃ ) -CH ₂ -, -CH ₂ -CH (CH ₂ -CH ₃ ),

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

By the addition of the aforementioned nonionic surfactants of the general formula (T-8) R ¹ -CH (OH) CH ₂ O- (AO) w- (AO) x- (A "0) _y - (A" O) z R ² (T-8) hereinafter also referred to as "hydroxy mixed ether", can surprisingly be

Cleaning performance of inventive preparations can be significantly improved and indeed compared to systems containing alternative nonionic surfactants, for example from the group of polyalkoxylated fatty alcohols.

By using these nonionic surfactants having one or more free hydroxyl groups on one or both terminal alkyl radicals, the stability of the enzymes optionally additionally present in the surfactant compositions according to the invention can be markedly improved. Preferred end-capped poly (oxyalkylated) nonionic surfactants which, according to the following formula (T-10), are preferred, in particular for machine dishwashing detergents.

in addition to a radical R ¹ which is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 2 to 30 carbon atoms, preferably having 4 to 22 carbon atoms, furthermore a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R ² having from 1 to 30 carbon atoms, wherein n stands for values between 1 and 90, preferably for values between 10 and 80 and in particular for values between 20 and 60. Especially preferred are surfactants of the above formula in which R ^{1 is} Cz to C ₁₃ , n is an integer from 16 to 28 and R ^{2 is} Cs to C ₁₂ .

Particularly preferred, in particular for automatic dishwashing detergents, are surfactants of the formula R ¹ O [CH ₂ CH (CH 3) O] x [CH ₂ CH ₂ O] _y CH ₂ CH (O) R ² ,

in which R ^{1 is} a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms or mixtures thereof, R ^{2 is} a linear or branched one

Hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x for values between 0.5 and 1, 5 and y is a value of at least 15 stands. The group of these non-ionic surfactants include for example the C2-26 fatty alcohol (PO) i- (EO) -2- i5 ₄₀ hydroxyalkyl ethers, in particular the Cs -io fatty alcohol (PO) i- (EO) ₂₂ -2-hydroxydecylether ,

Particular preference is furthermore given, in particular for automatic dishwashing detergents, to such end-capped polyoxyalkylene nonionic surfactants of the formula RO [CH ₂ CH ₂ O] x [CH ₂ CH (R ³ ) O] _y CH ₂ CH (O) R ² .

in which R ¹ and R ² independently of one another are a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical having 2 to 26 carbon atoms, R ^{3 is} independently selected from -CH 3, -CH 2 CH 3, -CH 2 CH 2 -CH 3, -CH (CH3) 2, but preferably -CFh, and x and y independently represent values between 1 and 32, with nonionic surfactants having R ³ = -CFhund values for x of 15 to 32 and y of 0.5 and 1 , 5 are very particularly preferred.

Further preferred nonionic surfactants, in particular for machine dishwashing detergents, are the end-capped poly (oxyalkylated) nonionic surfactants of the formula RO [CH ₂ CH (R ³ ) O] x [CH ₂ ] k CH (OH) [CH ₂ ] _j OR ² , in which R ¹ and R ^{2 are} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{3 is} H or a methyl, ethyl, n-propyl, iso-propyl, n Is butyl, 2-butyl or 2-methyl-2-butyl radical, x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5. If the value x> 2, each R ³ in the above formula

RO [CH ₂ CH (R ³ ) O] x [CH ₂ ] _k CH (OH) [CH ₂ ] _j 0R ^{2 be} different. R ¹ and R ² are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic

Hydrocarbon radicals having 6 to 22 carbon atoms, with radicals having 8 to 18 carbon atoms being particularly preferred. For the radical R ³ , H, -CF or -CH ₂ CH ³ are particularly preferred. Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.

As described above, each R ³ in the above formula may be different if x> 2. As a result, the alkylene oxide unit in the square bracket can be varied. For example, when x is 3, the radical R ³ can be selected to form ethylene oxide (R ³ = H) or propylene oxide (R ³ = CH ³ ) units which may be joined in any order, for example (EO) (PO ) (EO), (EO) (EO) (PO), (EO) (EO) (EO), (PO) (EO) (PO),

(PO) (PO) (EO) and (PO) (PO) (PO). The value 3 for x has been selected here by way of example and may well be greater, with the range of variation increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,

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

R ¹ 0 [CH ₂ CH (R ³ ) O] _X CH ₂ CH (OH) CH ₂ 0R ² simplified. In the latter formula, R ¹ , R ² and R ^{3 are} as defined above and x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Particularly preferred are surfactants in which the radicals R ¹ and R ^{2 has} 9 to 14 C atoms, R ^{3 is} H and x assumes values of 6 to 15. Finally, the nonionic surfactants of the general formula R ¹ -CH (OH) CH ₂ O- (AO) _W -R ^{2 have} proved to be particularly effective, in which

R ^{2 is} a linear or branched hydrocarbon radical having 2 to 26

Carbon atoms;

A is a radical from the group CH ₂ CH ₂ , CH ₂ CH ₂ CH ₂ , CH ₂ CH (CH 3), preferably CH ₂ CH ₂ , and

w stands for values between 1 and 120, preferably 10 to 80, in particular 20 to 40. The group of these non-ionic surfactants include for example the C4-22 fatty alcohol (EO) io-8o-2-hydroxyalkyl ethers, in particular the C8-12 fatty alcohol (EO) ₂₂ -2-C4 hydroxydecylether and 22 fatty alcohol (EO) ₄₀ -80-2-hydroxyalkyl ether.

Further, the surfactant composition of the present invention may contain, as a nonionic surfactant, amine oxide. As amine oxide are in principle all established in the art for this purpose amine oxides thus compounds having the formula R ¹ R ² R ³ NO, wherein each R ¹ , R ² and R ³ independently of the other an optionally substituted hydrocarbon chain with 1 to 30 carbon atoms, can be used. Particularly preferred amine oxides are those in which R ^{1 is} alkyl of 12 to 18 carbon atoms and R ² and R ^{3 are} each independently alkyl of 1 to 4 carbon atoms, especially alkyl dimethylamine oxides of 12 to 18 carbon atoms. Exemplary representatives of suitable amine oxides are N-cocoalkyl-N, N-dimethylamine oxide, N-tallowalkyl-N, N-dihydroxyethylamine oxide, myristyl / cetyldimethylamine oxide or

Lauryl dimethyl.

Suitable nonionic surfactants are, for example, alkyl glycosides of the general formula RO (G) x in which R is a primary straight-chain or methyl-branched, in particular 2-methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose. The degree of oligomerization x, the distribution of monoglycosides and

Indicating oligoglycosides, is any number between 1 and 10; preferably x is 1, 2 to 1, 4.

Another class of preferred nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated

Fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain.

Further suitable surfactants are the polyhydroxy fatty acid amides known as PHFA.

Other usable nonionic surfactants may be, for example

polyol

alkoxylated triglycerides,

alkoxylated fatty acid alkyl esters of the formula R ³ CO- (OCH ² CHR ⁴ ) _w OR ⁵ ,

in which R ³ CO is a linear or branched, saturated and / or unsaturated acyl radical having 6 to 22 carbon atoms, R ^{4 is} hydrogen or methyl and R ^{5 is} linear or branched alkyl radicals having 1 to 4 carbon atoms and w is 1 to 20,

hydroxy mixed, Sorbitan fatty acid esters and adducts of ethylene oxide with sorbitan fatty acid esters such as the polysorbates,

Sugar fatty acid esters and addition products of ethylene oxide with sugar fatty acid esters, addition products of ethylene oxide onto fatty acid alkanolamides and fatty amines,

Fatty acid N-alkyl glucamides.

The surfactant compositions of the invention described herein may also contain several of the nonionic surfactants described above.

According to the invention, particularly preferred viscoelastic, solid-form surfactant compositions, in particular as textile detergents, contain in each case based on the total weight a total amount of

From 10 to 60% by weight, in particular from 25 to 40% by weight, of at least one anionic surfactant and

- 2 to 35 wt .-%, in particular 18 to 28 wt .-%, of at least one nonionic surfactant.

Very particular preferred viscoelastic, solid-form surfactant compositions according to the invention (especially as laundry detergents) contain, in addition to water and said organic compound of component (ii), at least one surfactant combination as described below for compositions (A) to (D):

(A) Viscoelastic, solid-form surfactant composition containing, as surfactant, in each case at least in each case a total amount of, based on the total weight of the composition

From 10 to 60% by weight of at least one anionic surfactant, wherein at least one C9 -i3-alkylbenzenesulfonate is present as the anionic surfactant, and

2 to 35% by weight of at least one nonionic surfactant, containing as nonionic surfactant at least one alkoxylated alcohol having 8 to 18 carbon atoms and an average of 4 to 12 moles of ethylene oxide (EO) per mole of alcohol.

(B) Viscoelastic, solid surfactant composition containing as surfactant in each case based on the total weight of the composition at least in each case a total amount of

10 to 60 wt .-% of at least one anionic surfactant, wherein as anionic surfactant at least 5 to 60 wt .-% of at least one C9 -i3-alkylbenzenesulfonate is contained, and

From 2 to 35% by weight of at least one nonionic surfactant, wherein as nonionic surfactant at least 2 to 35% by weight of at least one alkoxylated alcohol having 8 to 18

Carbon atoms and an average of 4 to 12 moles of ethylene oxide (EO) per mole of alcohol is included.

(C) Viscoelastic, solid-form surfactant composition containing, as surfactant, in each case at least in each case a total amount of, based on the total weight of the composition - 25 to 40 wt .-% of at least one anionic surfactant, wherein as anionic surfactant at least one C9 -i3-alkylbenzenesulfonate is contained, and

18 to 28 wt .-% of at least one nonionic surfactant, wherein as nonionic surfactant at least one alkoxylated alcohol having 8 to 18 carbon atoms and an average of 4 to 12 moles of ethylene oxide (EO) per mole of alcohol is included.

(D) Viscoelastic, solid-form surfactant composition containing, as surfactant, in each case at least in each case a total amount of, based on the total weight of the composition

- 25 to 40 wt .-% of at least one anionic surfactant, wherein as anionic surfactant at least 25 to 40 wt .-% of at least one C9 -i3-alkylbenzenesulfonate is contained, and

18 to 28 wt .-% of at least one nonionic surfactant, wherein as nonionic surfactant at least 18 to 28 wt .-% of at least one alkoxylated alcohol having 8 to 18

When all of the aforementioned surfactant compositions with a specific amount of selected surfactant are provided, the amounts of the individual surfactant components are, of course, to be selected within the given quantitative ranges of the individual surfactant components such that the predetermined total amount of surfactant is maintained.

It is preferred according to the invention if the viscoelastic, solid-form surfactant composition according to the invention (in particular as a laundry detergent) contains at least one polyalkoxylated polyamine in addition to the surfactant.

The polyalkoxylated polyamine in the context of the present invention and its individual aspects is a polymer having an N-atom-containing backbone which carries polyalkoxy groups on the N atoms. The polyamine has at the ends (terminus and / or side chains) primary amino functions and internally preferably both secondary and tertiary amino functions; if appropriate, it may also have only secondary amino functions on the inside, so that the result is not a branched-chain but a linear polyamine. The ratio of primary to secondary amino groups in the polyamine is preferably in the range from 1: 0.5 to 1: 1.5, in particular in the range from 1: 0.7 to 1: 1. The ratio of primary to tertiary amino groups in the polyamine is preferably in the range from 1: 0.2 to 1: 1, in particular in the range from 1: 0.5 to 1: 0.8. Preferably, the polyamine has an average molecular weight in the range of 500 g / mol to 50,000 g / mol, in particular from 550 g / mol to 5000 g / mol. The N atoms in the polyamine are separated from one another by alkylene groups, preferably by alkylene groups having 2 to 12 C atoms, in particular 2 to 6 C atoms, wherein not all alkylene groups must have the same C atom number. Particularly preferred are ethylene groups, 1, 2-propylene groups, 1, 3-propylene groups, and their Mixtures. Polyamines bearing ethylene groups as said alkylene group are also referred to as polyethyleneimine or PEI. PEI is an inventively particularly preferred polymer with N-atom-containing backbone.

The primary amino functions in the polyamine can carry 1 or 2 polyalkoxy groups and the secondary amino functions 1 polyalkoxy group, although not every amino function

Must be alkoxy group-substituted. The average number of alkoxy groups per primary and secondary amino function in the polyalkoxylated polyamine is preferably from 1 to 100, in particular from 5 to 50. The alkoxy groups in the polyalkoxylated polyamine are preferably polypropoxy groups which are bonded directly to N atoms, and / or Polyethoxy groups which are attached to any existing propoxy and N atoms which do not carry propoxy groups.

Polyethoxylated polyamines are obtained by reacting polyamines with ethylene oxide (EO for short). The polyalkoxylated polyamines containing ethoxy and propoxy groups are preferably accessible by reaction of polyamines with propylene oxide (abbreviated to PO) and subsequent reaction with ethylene oxide.

The average number of propoxy groups per primary and secondary amino function in the polyalkoxylated polyamine is preferably 1 to 40, in particular 5 to 20,

The average number of ethoxy groups per primary and secondary amino function in the polyalkoxylated polyamine is preferably 10 to 60, especially 15 to 30.

If desired, the terminal OH function polyalkoxy substituents in the polyalkoxylated polyamine may be partially or completely etherified with a C 1 -C 10, in particular C 1 -C 3, alkyl group.

Polyalkoxylated polyamines which are particularly preferred according to the invention can be selected from polyamine reacted with 45EO per primary and secondary amino function, PEI's reacted with 43EO per primary and secondary amino function, PEI's reacted with 15EO + 5PO per primary and secondary amino function, PEI's reacted with 15PO + 30EO per primary and secondary amino function secondary amino function, PEI's reacted with 5PO + 39.5EO per primary and secondary amino function, PEI's reacted with 5PO + 15EO per primary and secondary amino function, PEI's reacted with 10PO + 35EO per primary and secondary amino function, PEI's reacted with 15PO + 30EO per primary and secondary amino function secondary amino function and PEI's reacted with 15PO + 5EO per primary and secondary amino function. A most preferred alkoxylated polyamine is PEI containing 10 to 20 nitrogen atoms reacted with 20 units of EO per primary or secondary amino function of the polyamine. A further preferred subject of the invention is the use of polyalkoxylated

Polyamines obtainable by reaction of polyamines with ethylene oxide and

optionally in addition propylene oxide. Be with ethylene oxide and propylene oxide

used polyalkyoxylated polyamines, the proportion of propylene oxide in the total amount of the alkylene oxide is preferably 2 mol% to 18 mol%, especially 8 mol% to 15 mol%.

The viscoelastic, solid-form surfactant composition according to the invention preferably additionally contains, based on its weight, polyalkoxylated polyamines in a total amount of from 0.5 to 12% by weight, in particular from 5.0 to 9.0% by weight.

In a further preferred embodiment, the viscoelastic, solid-form surfactant composition according to the invention, in particular as a laundry detergent, additionally contains at least one soil-release agent. Soil release agents are often referred to as "soil release" agents or because of their ability to render the treated surface, preferably textiles, soil repellent, "soil repellents." Because of their chemical similarity to polyester fibers, particularly effective soil release agents Fabrics made of other materials which can show the desired effect are copolyesters containing dicarboxylic acid units, alkylene glycol units and polyalkylene glycol units. Soil release polymers of the type mentioned, as well as their use in laundry detergents for textiles, have been known for a long time.

For example, polymers of ethylene terephthalate and polyethylene terephthalate in which the polyethylene glycol units have molecular weights of 750 to 5,000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate is 50:50 to 90:10, and their use in detergents in the German Patent DE 28 57 292 described. Polymers having a molecular weight of 15,000 to 50,000 of ethylene terephthalate and polyethylene oxide terephthalate, wherein the polyethylene glycol units have molecular weights of 1000 to 10,000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate is 2: 1 to 6: 1, can according to the German Offenlegungsschrift DE 33 24 258 are used in detergents. European patent EP 066 944 relates to textile treatment compositions containing a copolyester of ethylene glycol, polyethylene glycol, aromatic dicarboxylic acid and sulfonated aromatic dicarboxylic acid in certain molar ratios. European Patent EP 185,427 discloses methyl or ethyl end-capped polyesters having ethylene and / or propylene terephthalate and polyethylene oxide terephthalate units and detergents containing such soil release polymer. European Patent EP 241 984 relates to a polyester which, besides oxyethylene groups and terephthalic acid units, also contains substituted ethylene units and also glycerol units. From the European patent EP 241 985, polyesters are known, which in addition to oxyethylene groups and terephthalic acid units contain 1, 2-propylene, 1, 2-butylene and / or 3-methoxy-1, 2-propylene groups and glycerol units and with to C ₄ alkyl groups Endgruppenverschlossen are. European Patent EP 253 567 relates to soil release polymers having a molecular weight of 900 to 9000 from ethylene terephthalate and polyethylene oxide terephthalate, wherein the polyethylene glycol units have molecular weights of 300 to 3000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate 0, 6 to 0.95. ₄ alkyl or acyl groups end-capped polyesters with polypropylene terephthalate and polyoxyethylene terephthalate units are at least in part by Ci- known from European Patent Application EP 272 033rd European Patent EP 274 907 describes sulfoethyl end-capped terephthalate-containing soil release polyesters. In the European

Patent application EP 357,280 are prepared by sulfonation of unsaturated end groups soil release polyester with terephthalate, alkylene glycol and poly-C _2-4 glycol units.

In a preferred embodiment of the invention, the inventive

Surfactant composition at least one soil release-capable polyester, comprising the structural units E-1 to E-III or E-1 to E-IV,

- [(O-CHR ⁵ -CHR ⁶ ) c-0R ⁷ ] f (E-III)

- [polyfunctional unit] _g (E-IV) in which

a, b and c independently of one another each represent a number from 1 to 200,

d, e and f independently of one another each represent a number from 1 to 50,

g is a number from 0 to 5,

Ph is a 1,4-phenylene radical,

sPh is a 1, 3-phenylene radical substituted in position 5 by a group -SO3M,

M is Li, Na, K, Mg / 2, Ca / 2, Al / 3, ammonium, mono-, di-, tri- or tetraalkylammonium, wherein the alkyl radicals of the ammonium ions are C 1 -C 22 -alkyl- or C 2 -C 10 -hydroxyalkyl radicals or any mixtures thereof, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ independently of one another each represent hydrogen or a C 1 -C 18 -n- or iso-alkyl group,

R ^{7 is} a linear or branched C 1 -C 30 -alkyl group or a linear or branched C 2 -C 30 -alkenyl group, a cycloalkyl group having 5 to 9 carbon atoms, a C 6 -C 30 -aryl group or a C 6 -C 30 -arylalkyl group, and

Polyfunctional unit for a unit having 3 to 6 functional groups capable of esterification reaction.

Preference is given to polyesters in which R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently hydrogen or methyl, R ^{7 is} methyl, a, b and c are each independently a number from 1 to 200, in particular 1 to 20, particularly preferably 1 to 5, very preferably a and b = 1 and c can be a number from 2 to 10, d is a number between 1 and 25, in particular between 1 and 10, particularly preferably between 1 and 5, e is a number between 1 and 30, in particular between 2 and 15, particularly preferred between 3 and 10 and f a number between 0.05 and 15, in particular between 0.1 and 10 and particularly prefers between 0.25 and 3 means. Such polyesters can be obtained, for example, by polycondensation of terephthalic acid dialkyl ester, 5-sulfoisophthalic acid dialkyl ester,

Alkylene glycols, optionally polyalkylene glycols (at a, b and / or c> 1) and on one side

end-capped polyalkylene glycols (corresponding to unit E-III). It should be pointed out that for numbers a, b, c> 1 there is a polymeric skeleton and thus the coefficients as an average can assume any value in the given interval. This value reflects the number average molecular weight. As the unit (El) is an ester of terephthalic acid with one or more difunctional, aliphatic alcohols in question, are preferably used here ethylene glycol (R ¹ and R ^{2 are} each H) and / or 1, 2-propylene glycol (R ¹ = H and R ² = - CH3 or vice versa) and / or shorter-chain polyethylene glycols and / or poly [ethylene glycol-co-propylene glycol] having number-average molecular weights of 100 to 2000 g / mol. In the structures, for example, from 1 to 50 units (E1) may be contained per polymer chain. As the unit (E-II) is an ester of 5-sulfoisophthalic acid with one or more difunctional, aliphatic alcohols in question, preferably used are the aforementioned. In the structures, for example, 1 to 50 units (E-II) may be present. As nonionic polyalkylene glycol monoalkyl ethers closed on one side according unit (E-III) are preferably used poly [ethylene glycol-co-propylene glycol] monomethyl ether (having average molecular weights of 100 to 2000 g / mol and polyethylene glycol monomethyl ether of the general formula CH3-0- C ₂ H ₄ 0 ) _n -H with n = 1 to 99, in particular 1 to 20 and particularly preferably 2 to 10. Since the theoretical quantitative quantitative conversion to be achieved maximum average molecular weight of a polyester structure is specified by using such unilaterally closed ether, is considered as the preferred amount of the structural unit (E-Ill) the one to achieve the following

necessary average molecular weights is necessary. Except linear polyesters, which are from the Structural units (E1), (E-II) and (E-III) result, according to the invention is also the use of crosslinked or branched polyester structures. This is expressed by the presence of a crosslinking polyfunctional structural unit (E-IV) having at least three to a maximum of 6 functional groups capable of esterification reaction. As a functional

For example, groups can be acid, alcohol, ester, anhydride or

Be named epoxy groups. Different functionalities in one molecule are also possible. As examples may citric acid, malic acid, tartaric acid and

Gallic acid, more preferably 2,2-dihydroxymethylpropionic serve. Furthermore, polyhydric alcohols such as pentaerythrol, glycerol, sorbitol and / or trimethylolpropane can be used. These may also be polybasic aliphatic or aromatic carboxylic acids, such as benzene-1,2,3-tricarboxylic acid (hemimellitic acid), benzene-1,2,4-tricarboxylic acid (trimellitic acid), or benzene-1,3,5-tricarboxylic acid ( Trimesithsäure) act. The proportion by weight of crosslinking monomers, based on the total weight of the polyester, can be, for example, up to 10% by weight, in particular up to 5% by weight and more preferably up to 3% by weight. The polyesters containing the structural units (El), (E-II) and (E-III) and optionally (E-IV) generally have number average molecular weights in the range from 700 to 50,000 g / mol, the number average molecular weight being determined can be determined by size exclusion chromatography in aqueous solution using calibration using narrowly distributed polyacrylic acid Na salt standards. The number-average molecular weights are preferably in the range from 800 to 25,000 g / mol, in particular from 1,000 to 15,000 g / mol, particularly preferably from 1,200 to 12,000 g / mol. According to the invention are preferred as part of the particle of the second kind solid

Polyester, the softening points above 40 ° C, used; they preferably have a softening point between 50 and 200 ° C, more preferably between 80 ° C and 150 ° C, and most preferably between 100 ° C and 120 ° C. The synthesis of the polyesters can be carried out by known processes, for example by first heating the abovementioned components with the addition of a catalyst at atmospheric pressure and then the required

Building molecular weights in vacuum by distilling off superstoichiometric amounts of the glycols used. Suitable for the reaction are the known transesterification and condensation catalysts, such as, for example, titanium tetraisopropylate, dibutyltin oxide, alkali metal or alkaline earth metal alcoholates or antimony trioxide / calcium acetate. For further details, see EP 442 101.

The viscoelastic, solid-form surfactant composition according to the invention may additionally comprise at least one enzyme as washing or cleaning agent. In principle, all enzymes established in the state of the art for textile treatment can be used in this regard. Preferably, it is one or more enzymes which can develop a catalytic activity in a surfactant-containing liquor, in particular a protease, amylase, lipase, cellulase, hemicellulase, mannanase, pectin-splitting enzyme, tannase, xylanase, xanthanase, .beta.-glucosidase, Carrageenase, perhydrolase, oxidase, oxidoreductase and mixtures thereof. Preferred hydrolytic enzymes include, in particular, proteases, amylases, in particular α-amylases, cellulases, lipases, hemicellulases, in particular pectinases, mannanases, β-glucanases, and mixtures thereof. Proteases, amylases and / or lipases and mixtures thereof are particularly preferred, and proteases are particularly preferred. These enzymes are basically of natural origin; Starting from the natural molecules, improved variants are available for use in detergents or cleaning agents, which are preferably used accordingly.

Among the proteases, those of the subtilisin type are preferable. Examples of these are the subtilisins BPN 'and Carlsberg, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase, proteinase K and the subtilases, but not the subtilisins in the narrower sense Proteases TW3 and TW7. Subtilisin Carlsberg is available in a further developed form under the trade name Alcalase® from Novozymes A / S, Bagsvaerd, Denmark. The subtilisins 147 and 309 are sold under the trade names Esperase®, and Savinase® by the company Novozymes. From the protease from Bacillus lentus DSM 5483 derived under the name BLAP® protease variants derived. Further useful proteases are, for example, those under the trade names Durazym®, Relase®, Everlase®, Nafizym®, Natalase®, Kannase® and Ovozyme® from Novozymes, which are available under the trade names, Purafect®, Purafect® OxP, Purafect® Prime, Excellase® and Properase® from the company Genencor, which was sold under the

Trade name Protosol® from Advanced Biochemicals Ltd., Thane, India, sold under the trade name Wuxi® by Wuxi Snyder Bioproducts Ltd., China, under the trade names Proleather® and Protease P® by Amano Pharmaceuticals Ltd.,

Nagoya, Japan, and the enzyme available under the name Proteinase K-16 from Kao Corp., Tokyo, Japan. Particular preference is also given to using the proteases from Bacillus gibsonii and Bacillus pumilus.

Examples of amylases which can be used according to the invention are the a-amylases from Bacillus licheniformis, B. amyloliquefaciens or B. stearothermophilus and also their further developments improved for use in detergents or cleaners. The B. licheniformis enzyme is available from Novozymes under the name Termamyl® and from Genencor under the name Purasta DST. Further development products of this α-amylase are available from Novozymes under the trade names Duramyl® and TermamyKDultra, from Genencor under the name Purasta DOxAm, and from Daiwa Seiko Inc., Tokyo, Japan, as Keistase®. The B. amyloliquefaciens a-amylase is sold by Novozymes under the name BAN®, and variants derived from the B. stearothermophilus a-amylase under the names BSG® and Novamyl®, also from the company Company Novozymes. Furthermore, the a-amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948). Likewise, fusion products of all the molecules mentioned can be used. In addition, the further developments of the a-amylase from Aspergillus niger and A. oryzae available under the trade name Fungamyl® from the company Novozymes are suitable. Further advantageously usable commercial products are, for example, the amylase-LT®, as well as Stainzyme® or Stainzyme ultra® or Stainzyme plus®, the latter likewise of the

Company Novozymes. Also variants of these enzymes obtainable by point mutations can be used according to the invention.

Examples of lipases or cutinases which can be used according to the invention, which are contained in particular because of their triglyceride-cleaving activities, but also in order to generate in situ peracids from suitable precursors, are the lipases which are originally obtainable from Humicola lanuginosa (Thermomyces lanuginosus) or further developed, in particular those with the amino acid exchange D96L. They are sold for example by the company Novozymes under the trade names Lipolase®, Lipolase®Ultra, LipoPrime®, Lipozyme® and Lipex®.

Furthermore, for example, the cutinases can be used, which were originally isolated from Fusarium solani pisi and Humicola insolens. Lipases which are likewise useful are sold by Amano under the names Lipase CE®, Lipase P®, Lipase B® or Lipase CES®, Lipase AKG®, Bacillus sp. Lipase®, Lipase AP®, Lipase M-AP® and Lipase AML®. By Genencor, for example, the lipases or cutinases can be used, the initial enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii. Other important commercial products are the preparations M1 Lipase.RTM. And Lipomax.RTM. Originally sold by Gist-Brocades and the enzymes marketed by Meito Sangyo KK, Japan, under the name Lipase MY-30®, Lipase OF® and Lipase PL® to mention also the product Lumafast® from the company Genencor.

Depending on the purpose, cellulases may be present as pure enzymes, as enzyme preparations or in the form of mixtures in which the individual components advantageously supplement each other in terms of their various performance aspects, in particular in portions for textile washing. These performance aspects include in particular the contributions of the cellulase to the primary washing performance of the composition (cleaning performance), to the secondary washing performance of the composition (anti-redeposition effect or graying inhibition), to softening (tissue effect) or to the exercise of a "stone-washed" effect.A useful fungal, endoglucanase (EC ) -rich cellulase preparation, or their further developments is from the company

Novozymes under the trade name Celluzyme® offered. The products Endolase® and Carezyme®, also available from Novozymes, are based on the 50 kD EG or the 43 kD EG from H. insolens DSM 1800. Other usable commercial products this company is Cellusoft®, Renozyme® and Celluclean®. Also usable are, for example, the 20 kD-EG from Melanocarpus available from AB Enzymes, Finland, under the trade names Ecostone® and Biotouch®. Further commercial products of AB Enzymes are Econase® and Ecopulp®. Other suitable cellulases are from Bacillus sp. CBS 670.93 and CBS 669.93, those derived from Bacillus sp. CBS 670.93 from the company Genencor under the trade name Puradax® is available. Further commercial products of Genencor are "Genencor detergent cellulase L" and lndiAge®Neutra. Also variants of these enzymes obtainable by point mutations can be used according to the invention. Particularly preferred cellulases are Thielavia terrestris cellulase variants, cellulases from melanocarpus, in particular melanocarpus albomyces, cellulases of the EGIII type from Trichoderma reesei or variants obtainable therefrom.

Furthermore, in particular for the removal of certain located on the substrate

Problematic soils can be used other enzymes, which are summarized by the term hemicellulases. These include, for example, mannanases, xanthanlyases,

Xanthanases, xyloglucanases, xylanases, pullulanases, pectin-cleaving enzymes and β-glucanases. The β-glucanase obtained from Bacillus subtilis is available under the name Cereflo® from Novozymes. Hemicellulases which are particularly preferred according to the invention are mannanases, which are available, for example, under the trade name Mannaway® from the

Novozymes or Purabrite® are sold by Genencor.

For the purposes of the present invention, pectin-destroying enzymes are likewise counted as enzymes with the designations pectinase, pectate lyase, pectin esterase,

Pectin methethoxylase, pectin methoxylase, pectin methyl esterase, pectase, pectin methyl esterase, pectin esterase, pectin-pectyl hydrolase, pectin-polymerase, endopolygalacturonase, pectolase, pectin hydrolase, pectin-polygalacturonase, endo-polygalacturonase, poly-a-1, 4-galacturonide glycanohydrolase, endogalacturonase, endo-D-galacturonase, galacturan 1, 4-a-galacturonidase, exopolygalacturonase, poly (galacturonate) hydrolase, exo-D-galacturonase, exo-D-galacturonanase, exopoly-D-galacturonase, exo-poly-a-galacturonosidase,

Exopolygalacturonosidase or Exopolygalacturanosidase. Examples of enzymes suitable for this purpose are, for example, under the name Gamanase®, Pektinex AR®, X-Pect® or Pectaway® from Novozymes, under the name Rohapect UF®, Rohapect TPL®, Rohapect PTE100®, Rohapect MPE®, Rohapect MA plus HC, Rohapect DA12L®, Rohapect 10L®, Rohapect B1 L® from AB Enzymes, and available under the name Pyrolase® from Diversa Corp., San Diego, CA, USA.

Of all these enzymes, particular preference is given to those which have been stabilized per se with respect to oxidation in a comparatively stable manner or, for example, via point mutagenesis.

These include, in particular, the already mentioned commercial products Everlase® and Purafect®OxP as examples of such proteases and Duramyl® as an example of such a-amylase.

The viscoelastic, solid surfactant composition of the present invention preferably contains enzymes in total amounts of 1 x 10 ⁸ to 5 percent by weight based on active protein. Preferably, the enzymes are present in a total amount of from 0.001 to 2 wt.%, More preferably from 0.01 to 1.5 wt.%, Even more preferably from 0.05 to 1.25 wt.%, And most preferably from 0.01 to 0.5 wt .-% included.

Furthermore, as additional ingredients in the surfactant composition according to the invention as washing or cleaning agents builders, complexing agents, optical brighteners

(preferably in laundry detergents), pH adjuster, perfume, dye, dye transfer inhibitor or mixtures thereof.

The use of builders (builders) such as silicates, aluminum silicates (especially zeolites), salts of organic di- and polycarboxylic acids and mixtures of these substances, preferably water-soluble builders, may be advantageous.

In a preferred embodiment according to the invention, the use of phosphates (also polyphosphates) is largely or completely omitted. The inventive

Viscoelastic, solid surfactant composition in this embodiment preferably contains less than 5 wt%, more preferably less than 3 wt%, most preferably less than 1 wt%, of phosphate (s). Particularly preferred is the invention

Surfactant composition in this embodiment completely phosphate-free, i. the

Compositions 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 the viscoelastic, solid composition according to the invention is preferably from 15 to 80% by weight and in particular from 20 to 70% by weight for dishwashing detergents.

Suitable organic builders according to the invention are, for example, the polycarboxylic acids (polycarboxylates) which can be used in the form of their sodium salts, polycarboxylic acids 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 five

Carry acid functions throughout the molecule. Preferred polycarboxylic acids are thus dicarboxylic acids, tricarboxylic acids, tetracarboxylic acids and pentacarboxylic acids, in particular di-, tri- and tetracarboxylic acids. The polycarboxylic acids may carry further 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, sugar acids (preferably aldaric acids, for example galactaric acid and

Glucaric acid), aminocarboxylic acids, especially aminodicarboxylic acids, aminotricarboxylic acids, aminotetracarboxylic acids such as nitrilotriacetic acid (NTA), glutamine-N, N-diacetic acid (also referred to as N, N-bis (carboxymethyl) -L-glutamic acid or GLDA),

Methylglycinediacetic acid (MGDA) and its derivatives and mixtures thereof. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, GLDA, MGDA and mixtures thereof.

Also suitable as organic builders are polymeric polycarboxylates (organic polymers having a multiplicity of (in particular greater than 10) 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. In particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.

Particularly preferred surfactant compositions according to the invention contain as one of their essential builders one or more salts of citric acid, ie citrates. These are in the surfactant compositions according to the invention (especially for textile washing) preferably in a proportion of 0.3 to 10 wt .-%, in particular from 0.5 to 8 wt .-%, especially from 0.7 to 6.0 wt. -%, particularly preferably 0.8 to 5.0 wt .-%, in each case based on the total weight of the composition. One or more salts of

Citric acid are present in the surfactant compositions according to the invention (in particular for the cleaning of hard surfaces, in particular for dishwashing), preferably in a proportion of from 2 to 40% by weight, in particular from 5 to 30% by weight, especially from 7 to 28% by weight. %, particularly preferably 10 to 25 wt .-%, most preferably 15 to 20 wt .-%, each based on the total weight of the composition.

The viscoelastic, solid-form surfactant compositions according to the invention may contain in particular phosphonates as further builder. The phosphonate compound used is preferably a hydroxyalkane and / or aminoalkane phosphonate. Among the

Hydroxyalkane phosphonates is the 1-hydroxyethane-1,1-diphosphonate (HEDP) of particular importance. As Aminoalkanphosphonate are preferably

Ethylenediamine tetramethylene phosphonate (EDTMP), diethylene triamine pentamethylene phosphonate (DTPMP) and their higher homologs in question. Phosphonates are present in viscoelastic, solid-colored surfactant compositions according to the invention preferably in amounts of from 0.1 to 10% by weight, in particular in amounts of from 0.5 to 8% by weight, very particularly preferably from 2.5 to 7.5% by weight. %, in each case based on the total weight of the composition. Particularly preferred (especially for use in dishwashing detergents) is the combined use of citrate, (hydrogen) carbonate and phosphonate. These can be used in the above quantities. In particular, in this combination amounts of, in each case based on the total weight of the composition, 10 to 25 wt .-% citrate, 10 to 30 wt .-% carbonate (or bicarbonate), and 2.5 to 7.5 wt .-% Phosphonate used in the surfactant compositions of the invention.

Further particularly preferred inventive surfactant compositions, in particular detergents or cleaners, preferably dishwashing agents, more preferably automatic dishwashing detergents, are characterized in that in addition to citrate and (hydrogen) carbonate and optionally phosphonate they contain at least one further phosphorus-free builder.

In particular, it is selected from the aminocarboxylic acids, the further phosphorus-free builder preferably being selected from methylglycinediacetic acid (MGDA),

Glutamic acid diacetate (GLDA), aspartic acid diacetate (ASDA), hydroxyethyliminodiacetate (HEIDA), iminodisuccinate (IDS) and ethylenediamine disuccinate (EDDS), most preferably 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, especially 7 to 25% by weight. Particularly preferred is the use of MGDA or GLDA, in particular MGDA, as granules. Advantageous are those MGDA granules which contain as little water as possible and / or a lower hygroscopicity compared to the non-granulated powder

(Water absorption at 25 ° C, atmospheric pressure). The combination of at least three, in particular at least four, builders from the above-mentioned group has proven to be advantageous for the cleaning and rinsing performance of surfactant compositions according to the invention, in particular dishwashing agents, preferably automatic dishwasher detergents. In addition, other builders may be included.

As organic builders polymeric polycarboxylates are also suitable, these are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid,

for example, those having a molecular weight of 500 to 70,000 g / mol. Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of from 1000 to 20 000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molecular weights of from 1100 to 10 000 g / mol, and more preferably from 1200 to 5000 g / mol, may again be preferred from this group.

The viscoelastic, solid-form surfactant compositions according to the invention can furthermore comprise, as builder, crystalline layer-form silicates of the general formula NaMSixO _{2x +} iy H2O, in which M is sodium or hydrogen, x is a number from 1, 9 to 22, preferably from 1, 9 to 4, with particularly preferred values for x being 2, 3 or 4, and y being a number from 0 to 33, preferably from 0 to 20. It is also possible to use amorphous sodium silicates having a modulus Na 2 ≦ D: S1O 2 of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which are preferably Delayed and have secondary washing properties.

An optical brightener is preferably stilbenedisulfonic acids from the substance classes of distyrylbiphenyls, the stilbenes, the 4,4 ^{^{'diamino-2,2',}} coumarins, the dihydroquinolinones, the 1, 3-diaryl pyrazolines, naphthalimides of the benzoxazole systems, benzisoxazole systems, benzimidazole systems, heterocyclic substituted pyrene derivatives, and mixtures thereof.

Particularly preferred optical brighteners include disodium 4,4'-bis (2-morpholino-4-anilino-s-triazin-6-ylamino) stilbene disulfonate (available, for example, as Tinopal® DMS from BASF SE), disodium 2,2 '. bis (phenyl-styryl) disulfonate (available, for example, as Tinopal® CBS from BASF SE), 4,4'-bis [(4-anilino-6- [bis (2-hydroxyethyl) amino] -1, 3.5 -triazin-2-yl) -amino] stilbene-2,2'-disulphonic acid (available, for example, as Tinopal® UNPA from BASF SE), hexasodium 2,2'- [vinylenebis [(3-sulphonato-4,1-phenylene) imino [6- (diethylamino) -1, 3,5-triazine-4,2-diyl] imino]] bis (benzene-1,4-disulfonate) (for example obtainable as Tinopal® SFP from BASF SE), 2, 2 '- (2,5-thiophenediyl) bis [5-1, 1-dimethylethyl) benzoxazole (available, for example, as Tinopal® SFP from BASF SE) and / or 2,5-bis (benzoxazol-2-yl) thiophene.

It is preferred that the dye transfer inhibitor is a polymer or copolymer of cyclic amines such as vinylpyrrolidone and / or vinylimidazole. When

Color transfer inhibiting polymers include polyvinylpyrrolidone (PVP),

Polyvinylimidazole (PVI), copolymers of vinylpyrrolidone and vinylimidazole (PVP / PVI),

Polyvinylpyridine N-oxide, poly-N-carboxymethyl-4-vinylpyridium chloride, polyethylene glycol-modified copolymers of vinylpyrrolidone and vinylimidazole, and mixtures thereof.

Particular preference is given to using polyvinylpyrrolidone (PVP), polyvinylimidazole (PVI) or copolymers of vinylpyrrolidone and vinylimidazole (PVP / PVI) as color transfer inhibitor. The polyvinylpyrrolidones (PVP) used preferably have an average molecular weight of 2,500 to 400,000 and are commercially available from ISP Chemicals as PVP K 15, PVP K 30, PVP K 60 or PVP K 90 or from BASF as Sokalan® HP 50 or Sokalan® HP 53 available. The copolymers of vinylpyrrolidone and vinylimidazole (PVP / PVI) used preferably have a molecular weight in the range from 5,000 to 100,000. Commercially available is a PVP / PVI copolymer, for example, from BASF under the name Sokalan® HP 56. Another extremely preferred color transfer inhibitor are polyethylene glycol-modified copolymers of vinylpyrrolidone and vinylimidazole, which are available, for example, under the name Sokalan® HP 66 from BASF are. Within the scope of a preferred embodiment according to the invention, the viscoelastic, solid-form surfactant composition according to the invention contains incorporated solid particles (in the US Pat

Hereinafter also referred to as particles). As such dispersed solid particles are solid substances which do not dissolve in the liquefied phase of the surfactant composition according to the invention at temperatures of up to 5 ° C units above the sol-gel temperature of the solid-form surfactant composition according to the invention and are present as a separate phase. These particles are used in the preparation of the viscoelastic

Suspending surfactant compositions in the liquid phase above the sol-gel temperature and then cooling the liquid phase below the sol-gel temperature to obtain the viscoelastic surfactant composition according to the invention.

The solid particles are preferably selected from polymers, pearlescent pigments,

Microcapsules, speckles or mixtures thereof.

For the purposes of the present invention, microcapsules include any type of capsule known to those skilled in the art, but in particular core-shell capsules and matrix capsules. Matrix capsules are porous shaped bodies that have a structure similar to a sponge. Core-shell capsules are shaped bodies having a core and a shell. Suitable microcapsules are those capsules which have an average diameter Xso, 3 (volume average) of from 0.1 to 200 μm, preferably from 1 to 100 μm, more preferably from 5 to 80 μm, particularly preferably from 10 to 50 μm and in particular from 15 to 40 pm. The mean particle size diameter X 50.3 is determined by sieving or by means of a particle size analyzer Camsizer from Retsch.

The microcapsules of the invention preferably contain at least one active ingredient, preferably at least one perfume. These preferred microcapsules are perfume microcapsules.

In a preferred embodiment of the invention, the microcapsules have a semipermeable capsule wall (shell).

For the purposes of the present invention, a semipermeable capsule wall is a capsule wall which is semipermeable, ie it releases small quantities of the capsule core continuously over time, without the capsule having to be filled, for example. was damaged or opened by friction. Such capsules continuously continue to set small amounts of the capsule drug, e.g. Perfume, free.

In a further preferred embodiment of the invention, the microcapsules have an impermeable shell. An impermeable shell in the sense of the present invention is a capsule wall which is substantially impermeable, that is to say releases the capsular core only by damaging or opening the capsule. Such capsules contain in the capsule core significant amounts of at least one fragrance, so that when damaged or when opening the capsule a very intense fragrance is provided. The resulting scent intensities are usually so high that lower amounts of the microcapsules can be used to achieve the same scent intensity as conventional microcapsules.

In a preferred embodiment of the invention, the inventive

Surfactant composition both microcapsules with semipermeable shell, so too

Microcapsules with impermeable shell. Through the use of both capsule types, a significantly improved fragrance intensity can be provided over the entire laundry cycle.

In a further preferred embodiment of the invention, the composition according to the invention may also contain two or more different microcapsule types with semipermeable or impermeable shell.

As materials for the shell of the microcapsules are usually high molecular weight

Compounds such as proteinaceous compounds such as gelatin, albumin, casein and others, cellulose derivatives such as methylcellulose, ethylcellulose,

Cellulose acetate, cellulose nitrate, carboxymethylcellulose and other and especially synthetic polymers such as polyamides, polyethylene glycols, polyurethanes,

Epoxy resins and others. Preferably serves as a wall material, ie as a shell, melamine-formaldehyde polymer, melamine-urea polymer, melamine-urea-formaldehyde polymer, polyacrylate polymer or polyacrylate copolymer. Capsules according to the invention are

for example, but not limited to, US 2003/0125222 A1, DE 10 2008 051 799 A1 or WO 01/49817.

Preferred melamine-formaldehyde microcapsules are prepared in which melamine-formaldehyde precondensates and / or their C 1 -C ₄ -alkyl ethers in water in which the at least one odor modulator compound and optionally further ingredients, such as at least one

Perfume, condensed in the presence of a protective colloid. Suitable protective colloids are, for example, cellulose derivatives, such as hydroxyethylcellulose, carboxymethylcellulose and methylcellulose, polyvinylpyrrolidone, copolymers of N-vinylpyrrolidone, polyvinyl alcohols, partially hydrolyzed polyvinyl acetates, gelatin, gum arabic, xanthan gum, alginates, pectins, degraded starches, casein, polyacrylic acid, polymethacrylic acid, copolymers of acrylic acid and methacrylic acid, sulfonic acid-containing water-soluble polymers containing sulfoethyl acrylate, sulfoethyl methacrylate or sulfopropyl methacrylate, and polymers of N- (sulfoethyl) -maleimide, 2-acrylamido-2-alkylsulfonic acids, styrenesulfonic acids and formaldehyde and condensates of phenolsulfonic acids and formaldehyde. It is preferred to coat the microcapsules used according to the invention wholly or partly on their surface with at least one cationic polymer. Accordingly, at least one cationic polymer of polyquaternium-1, polyquaternium-2, polyquaternium-4, polyquaternium-5, polyquaternium-6, polyquaternium-7, polyquaternium-8, polyquaternium-9, polyquaternium-10 is suitable as cationic polymer for coating the microcapsules , Polyquaternium-1, Polyquaternium-12, Polyquaternium-13, Polyquaternium-14, Polyquaternium-15, Polyquaternium-16, Polyquaternium-17, Polyquaternium-18, Polyquaternium-19, Polyquaternium-20,

Polyquaternium-22, Polyquaternium-24, Polyquaternium-27, Polyquaternium-28, Polyquaternium-29, Polyquaternium-30, Polyquaternium-31, Polyquaternium-32, Polyquaternium-33,

Polyquaternium-34, Polyquaternium-35, Polyquaternium-36, Polyquaternium-37, Polyquaternium-39, Polyquaternium-43, Polyquaternium-44, Polyquaternium-45, Polyquaternium-46,

Polyquaternium-47, Polyquaternium-48, Polyquaternium-49, Polyquaternium-50, Polyquaternium-51, Polyquaternium-56, Polyquaternium-57, Polyquaternium-61, Polyquaternium-69,

Polyquaternium-86th Very particular preference is given to polyquaternium-7. The polyquaternium nomenclature of the cationic polymers used in the context of this application is taken from the declaration of cationic polymers according to the International Nomenclature of Cosmetic Ingredients (INCI Declaration) of cosmetic raw materials.

Preferably usable microcapsules have average diameters Xso, 3 in the range of 1 to 100 pm, preferably from 5 to 95 pm, in particular from 10 to 90 pm, for example from 10 to 80 pm.

The shell of the microcapsules surrounding the core or (filled) cavity preferably has an average thickness in the range from about 5 to 500 nm, preferably from about 50 nm to 200 nm, in particular from about 70 nm to about 180 nm.

Pearlescent pigments are pigments that have a pearlescent shine. Pearlescent pigments consist of thin leaflets that have a high refractive index and partially reflect the light and are partially transparent to the light. The nacreous gloss is produced by interference of the light striking the pigment (interference pigment). Pearlescent pigments are usually thin flakes of the above material, or contain the o.g. Material as thin multilayer films or as parallel arranged components in a suitable carrier material.

The pearlescent pigments which can be used according to the invention are either natural

Pearlescent pigments such as e.g. Fischsilber (guanine / hypoxanthine mixed crystals from fish scales) or mother of pearl (from ground mussel shells), monocrystalline flake-shaped

Pearlescent pigments, such as bismuth oxychloride, and mica-based pearlescent pigments as well as mica / metal oxide. The latter pearlescent pigments are mica, which have been provided with a metal oxide coating.

By using the pearlescent pigments in the suspension according to the invention, gloss and, if appropriate, additional color effects are achieved.

Mica-based and mica / metal oxide-based pearlescent pigments are preferred according to the invention. Mica belongs to the layer silicates. The most important representatives of these silicates are muscovite, phlogopite, paragonite, biotite, lepidolite and margarite. For the production of

Pearlescent pigments in conjunction with metal oxides, the mica, predominantly muscovite or phlogopite, coated with a metal oxide. Suitable metal oxides Cr ₂ Ü3 and Fe include T1O2, ₂ 03. By appropriate coating are interference pigments as well as color luster pigments according to the invention obtained as pearlescent pigments. In addition to a glittering optical effect, these pearlescent pigment types also have color effects. Furthermore, the pearlescent pigments which can be used according to the invention can furthermore contain a color pigment which does not derive from a metal oxide.

The grain size of the pearlescent pigments preferably used is preferably at a mean diameter Xso, 3 (volume average) between 1 .0 and 100 .mu.m, more preferably between 10.0 and 60.0 pm.

For the purposes of the invention, speckles are macroparticles, in particular macrocapsules, which have an average diameter Xso, 3 (volume average) of more than 300 μm, in particular from 300 to 1500 μm, preferably from 400 to 1000 μm.

Speckles are preferably matrix capsules. The matrix is preferably colored. Matrix formation occurs, for example, via gelation, polyanion-polycation interactions, or polyelectrolyte-metal ion interactions, and is well known in the art as well as the production of particles with these matrix-forming materials. An exemplary matrix-forming material is alginate. For the production of alginate-based speckles is an aqueous alginate solution, which if necessary, in addition to the entrapped drug or the

contains, dripped and then cured in a precipitation bath containing Ca ²⁺ ions or Al ³⁺ - ions. Alternatively, other, matrix-forming materials can be used instead of alginate.

The surfactant compositions according to the invention, in particular as dishwashing compositions, in a preferred embodiment contain as further constituent at least one zinc salt as glass corrosion inhibitor. The zinc salt may be an inorganic or to act as an organic zinc salt. The zinc salt to be used according to the invention preferably has a solubility in water above 100 mg / l, preferably above 500 mg / l, more preferably above 1 g / l and especially above 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 benzoate, 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, zinc acetate is used as the zinc salt. The zinc salt is preferably present in surfactant compositions according to the invention in an amount of from 0.01% by weight to 5% by weight, more preferably in an amount of from 0.05% by weight to 3% by weight, in particular in an amount of 0.1 wt .-% to 2 wt .-%, based on the total weight of the composition. Additionally or alternatively to the o.g. Salts (in particular the zinc salts) may polyethyleneimines, such as those available under the name Lupasol® (BASF), preferably used in an amount of 0 to 5 wt .-%, in particular 0.01 to 2 wt .-%, as glass corrosion inhibitors become.

The viscoelastic solid surfactant composition of the present invention necessarily contains at least one said organic compound of component (ii).

According to the invention, such surfactant compositions are preferably suitable in which the carbocyclic structural unit b) is selected from at least one optionally substituted aryl group, in particular an optionally substituted phenyl group. It is particularly preferred if a substituted aryl group, in particular a substituted phenyl group, is substituted by at least one of the following radicals: a hydroxy group, a (C 1 -C 6) -alkyl group, a (C 2 -C 6) -alkenyl group, a C 6) acyl group, a (C 2 -C 6) acyloxy group, a (C 1 -C 6) alkoxy group, an amino group, a (C 2 -C 6) acylamino group, a (C 1 -C 6) -alkylaminocarbonyl group, an aryl group, an aroyl group, an aroyloxy group, an aryloxy group, an aryl (C 1 -C ₄ ) alkyloxy group, an aryl (C 1 -C 3) alkyl group, a

Heteroaryl group, a Hetroaryl- (Ci-C3) -alkyl group, a (Ci-C ₄ ) -Hydroxyalkylgruppe, a (Ci-C ₄ ) -Aminoalkylgruppe, a carboxy (Ci-C3) -alkylgruppe.

The further cyclic structural unit c) is different from the carbocyclic structural unit b). The further cyclic structural unit c) binds covalently either directly or via a divalent, bridging structural unit (preferably via (C 1 -C ₄ ) -alkanediyl) to the carbocyclic structural unit b). The carbon atoms of the at least two carbonyl groups from the further cyclic structural unit c) are ring-forming. Such organic compounds of component (ii) have proved to be particularly suitable in which the further cyclic structural unit c) at least two endocyclic amide groups (-NH-C (= 0) -). In this case contains the Structural unit c) already at least two groups -NH- as groups a). The further cyclic structural unit c) is particularly preferably selected from at least one 2,5-diketopiperazine structural unit.

Preferred viscoelastic solid surfactant compositions of the invention contain, based on the total weight of the composition, organic compound of component (ii) in a total amount of at least 0.5% by weight, in particular from 0.5 to 3.0% by weight. In this case, it has again turned out to be particularly preferred if the surfactant compositions according to the invention (based in each case on the total weight of the composition) of organic compound of component (ii) in a total amount of at least 0.55 wt.%, In particular of at least 0.7 wt. -%, particularly preferably of at least 0.8 wt .-% contains. More preferably (in each case based on the total weight of the composition) organic compound of component (ii) in a total amount of 0.5 to 3.0 wt.%, In particular from 0.7 to 2.5 wt .-%, most preferably from 0.8 to 2.0% by weight, most preferably from 0.85 to 1.5% by weight.

The requirements and features of an organic compound of the invention

Component (ii) meet the organic compounds according to the following formula (I). Preferred surfactant compositions according to the invention therefore comprise as component (ii) at least one 2,5-diketopiperazine compound of the formula (I)

wherein

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

Hydroxy group, a (C 1 -C 6) -alkyl group, a (C 2 -C 6) -alkenyl group, a (C 2 -C 6) -acyl group, a (C 2 -C 6) -acyloxy group, a (C 1 -C 6) -alkoxy group, an amino group, a (C ₂ -C 6) -acylamino group, a (C 1 -C 6) -alkylaminocarbonyl group, an aryl group, an aroyl group, an aroyloxy group, an aryloxy group, an aryl- (C 1 -C ₄ ) -alkyloxy group, an aryl- (C 1 -C 3) alkyl group, a heteroaryl group, a Hetroaryl- (Ci-C3) alkyl group, a a (Ci-C ₄₎ hydroxyalkyl group, a _(C1-C4) aminoalkyl group, a carboxy (Ci-C3) alkyl group, wherein at least two of the radicals R ¹ to R ⁴ together with the remainder of the molecule can form a 5 or 6-membered ring, R ⁵ represents a hydrogen atom, a linear (C 1 to C 6) alkyl group, a branched (C 3 to Cio) alkyl group, a (C 3 to C 6) cycloalkyl group, a (C 2 to C 6) alkenyl group, a (C 2 to C 6 ) alkynyl group, a (Ci-C ₄₎ hydroxyalkyl group, a (C ₁ - C ₄₎ alkoxy (Ci-C ₄₎ alkyl group, a _(Ci-C4) acyloxy (Ci-C ₄₎ alkyl, aryloxy (C 1 -C ₄ ) alkyl, O- (aryl- (C 1 -C ₄ ) alkyl) oxy (C 1 -C ₄ ) alkyl, (C 1 -C ₄ ) alkylsulfanyl - (Ci-C ₄₎ alkyl group, an aryl group, an aryl (Ci-C3) - alkyl group, a heteroaryl group, a Hetroaryl- (Ci-C3) alkyl group, a (C ₁ -C ₄₎ - hydroxyalkyl group, a (C 1 -C ₄ ) -Aminoalkyl group, an N- (C 1 -C ₄ ) -alkylamino (C 1 -C ₄ ) -alkyl group, an N, N- (C 1 -C ₄ ) -dialkylamino- (C 1 -C ₄ ) alkyl group, an N- (C 2 -C 8) -acylamino (C 1 -C 4) -alkyl group, an N- (C 2 -C 8) -acyl-N- (C 1 -C 4) -alkylamino- (C 1 -C 4) -alkyl group , an N- (C ₂ -C 8) -royl-N- (C ₁ -C ₄ ) -alkylamino (C 1 -C ₄ ) -alkyl group, an N, N- (C ₂ -C 8) -diacylamino- (C ₁ -C ₄ ) -alkyl group, a e N- (aryl- (C 1 -C ₄ ) -alkyl) amino- (C 1 -C ₄ ) -alkyl group, an N, N-di (aryl- (C 1 -C ₄ ) -alkyl) amino- (C 1 -C ₄ ) alkyl group, a (C ₁ -C ₄₎ - carboxyalkyl group, a (Ci-C ₄₎ alkoxycarbonyl (Ci-C3) alkyl group, a (C ₁ -C ₄₎ - acyloxy (Ci-C3) alkyl group , a guanidino (Ci-C3) alkyl group, a

Aminocarbonyl- (C 1 -C 4) -alkyl group, an N- (C 1 -C ₄ ) -alkylaminocarbonyl- (C 1 -C ₄ ) -alkyl group, an N, N-di (C 1 -C ₄ ) -alkyl) aminocarbonyl- (C 1 -C ₄ ) -alkyl group; C ₄ ) alkyl group, an N- (C ₂ -C 8) -acylaminocarbonyl (C 1 -C ₄ ) -alkyl group, an N, N- (C ₂ -C 8) -diacylaminocarbonyl- (C 1 -C ₄ ) -alkyl group, an N- (C ₂ -C 8) -Acyl-N- (C 1 -C ₄ ) -alkylaminocarbonyl- (C 1 -C ₄ ) -alkyl group, an N- (aryl- (C 1 -C ₄ ) -alkyl) aminocarbonyl- (C 1 -C ₄ ) - alkyl group, an N- (aryl- (C 1 -C ₄ ) -alkyl) -N- (C 1 -C 6) -alkylaminocarbonyl (C 1 -C ₄ ) -alkyl group or an N, N-di (aryl- (C 1 -C ₄ ) alkyl ₄ ) -alkyl) aminocarbonyl (Ci-C ₄ ) alkyl group.

All radicals defined according to this application which contain an aromatic radical aryl or heteroaryl are unsubstituted or substituted. By a substitution, the skilled person understands the exchange of at least one directly to the aromatic ring system-binding hydrogen atom by at least one of a hydrogen atom other than the rest

Substituted hydrogen are preferably all defined under the definitions of R ⁵ and R ¹ according to formula (I) radicals other than a hydrogen atom, in particular a hydroxy group, an amino group, a (Ci-C6) alkyl group, a (C2 -C6) alkenyl group, a (C2-C6) acyl group, a (C2-C6) acyloxy group, a (Ci-C6) alkoxy group, an amino group, a (C2-C6) acylamino group, a (Ci-C6 ) -Alkylaminocarbonyl group, an aryl group, an aroyl group, an aroyloxy group, an aryloxy group, an aryl- (C 1 -C ₄ ) -alkyloxy group, an aryl- (C 1 -C 3) -alkyl group, a heteroaryl group, a heteroaryl- (C 1 -C 3) - alkyl group, a (Ci-C ₄ ) -hydroxyalkyl group, a (Ci-C ₄ ) -Aminoalkylgruppe.

Under an alkyl group (or an alkyl structure fragment of a more complex group) is according to the invention a group selected from linear alkyl group of branched alkyl group or Cyclic alkyl group (also: cycloalkyl group) understood. Preferred linear or branched (C 1 -C 6) -alkyl groups are selected from among methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, neopentyl, n-hexyl. Preferred branched (C3-Cio) -alkyl groups are selected from iso-propyl, sec-butyl, isobutyl, tert-butyl, neo-pentyl, iso-octyl, 2-ethylhexyl, 2-ethylheptyl. Preferred cyclic alkyl groups ((C3-C6) -cycloalkyl groups) are selected from cyclopentyl, cyclohexyl.

Preferred (C 2 -C 6) alkenyl groups are selected from vinyl, allyl, 2-butenyl.

Preferred (C 2 -C 6) alkynyl groups are selected from ethynyl, propargyl, but-2-ynyl, hex-3-ynyl. Preferred (C 2 -C 6) -acyl groups are selected from acetyl, propanoyl, butanoyl, pentanoyl, hexanoyl, in particular acetyl.

Preferred (C 2 -C 6) -acyloxy groups are selected from acetyloxy, propanoyloxy, butanoyloxy, pentanoyloxy and hexanoyloxy, especially acetyloxy.

According to the invention, an alkoxy group is understood as meaning an alkyl group which bonds via an oxygen atom and is selected from a linear alkyl group of branched alkyl group or cyclic alkyl group (also: cycloalkyl group). Preferred (C 1 -C 6) -alkoxy groups are

Methoxy, ethoxy, n-propoxy, iso -propoxy, n-butoxy, sec-butoxy, iso-butoxy, tert-butoxy.

Preferred (C 2 -C 6) -acylamino groups are acetylamino, propanoylamino, butanoylamino, pentanoylamino and hexanoylamino, in particular acetylamino.

Preferred (C ₂ -C 6) -alkylaminocarbonyl groups are ethylaminocarbonyl (ie CH 3 CH ₂ -NH-C (= O) -), propylaminocarbonyl, butanoylamino, pentanoylamino and hexanoylamino, especially acetylamino.

Preferred aryl groups are phenyl, naphthyl, anthracenyl, these being substituted or unsubstituted.

Aroyl groups are arene carbonyl groups in which a carbonyl group bonds directly to the aromatic ring system. Preferred aroyl groups are benzoyl, naphthoyl and anthracenoyl, which are substituted or unsubstituted.

Aroyloxy groups are aroyl groups that attach via an additional carbon atom-binding oxygen atom. Preferred aroyloxy groups are selected from benzoyloxy, naphthoyloxy and anthracenoyloxy, these being substituted or unsubstituted.

A preferred aryloxy group is the phenoxy group or the naphthoxy group, which are substituted or unsubstituted.

Preferred aryl- (C 1 -C 3) -alkyl groups are selected from benzyl, 2-phenylethyl, naphthylmethyl,

2-naphthylethyl, which are substituted or unsubstituted.

Preferred heteroaryl groups are pyridyl, pyrimidinyl, imidazolyl, indolyl, furyl, thiophenyl, 1, 3,5-triazolyl

Preferred heteroaryl (C 1 -C 3) -alkyl groups are selected from furfuryl, 2-indol-3-yl-ethyl, indole

3-ylmethyl, pyridylmethyl, which are substituted or unsubstituted. It has been found to be particularly preferred if the viscoelastic, solid-form surfactant compositions according to the invention comprise at least one 2,5-diketopiperazine compound of the formula (I) in which R ^{5 represents} a (Ci-C ₄ ) -hydrocarbyl group substituted by an aromatic radical in particular a radical of the following formulas (IV) or (VI) (vide infra).

Preferred viscoelastic, solid surfactant compositions of the invention contain, based on the total weight of the composition, 2,5-diketopiperazine compound of the formula (I) in a total amount of at least 0.5% by weight, in particular from 0.5 to 3.0% by weight. -%. It has turn out to be particularly preferred when the compositions of the invention (in each case based on the total weight of

Composition) 2,5-diketopiperazine compound according to formula (I) in a total amount of at least 0.55 wt.%, In particular of at least 0.7 wt .-%, particularly preferably of at least 0.8 wt .-%. More preferred (in each case based on the total weight of the composition) 2,5-diketopiperazine compound according to formula (I) in a total amount of 0.5 to 3.0 wt.%, In particular from 0.7 to 2.5 wt. %, most preferably from 0.8 to 2.0 wt%, most preferably from 0.85 to 1.5 wt%.

All of the abovementioned quantities for the 2,5-diketopiperazine compound preferably also relate to the selected DKP compounds of the formula (I), which are identified below as being preferred.

It is inventively preferred when R ³ and R ⁴ according to formula (I) represent a hydrogen atom. It is particularly preferred according to the invention if R ² , R ³ and R ⁴ according to formula (I) represent a hydrogen atom. Therefore, very particularly preferred compositions according to the invention comprise at least one 2,5-diketopiperazine compound of the formula (Ia)

wherein R ¹ and R ^{5 are} as defined under formula (I) (vide supra).

It has proved to be preferred if the radical R ¹ according to formula (I) and according to formula (I-a) binds in the para position of the phenyl ring. Therefore, within the meaning of the present invention those compositions according to the invention which contain at least one 2,5-diketopiperazine compound according to formula (Ib),

wherein R ¹ and R ^{5 are} as previously defined under formula (I) (vide supra). The numerals 3 and 6 positioned on the ring atoms in formula (lb) are illustrative only of positions 3 and 6 of the diketopiperazine ring, as generally used in the context of the invention for the

Naming of all 2,5-diketopiperazines invention can be used.

Particularly preferred compounds of the formula (I-b) have the following radicals:

Also preferred are:

3-benzyl-6-iso-propyl-2,5-diketo [3S, 6S] piperazine,

3-Benzyl-6- (4-aminobutyl) -2,5-diketo [3R, 6R] piperazine

3,6-di (benzyl) -2,5-diketo [3S, 6S] piperazine.

The following definitions of preferred radicals R ¹ to R ⁵ apply to compounds of the formula (I), but also to compounds of the formulas (Ia) and (Ib), with the proviso that for the formulas (Ia) and (Ib) the radicals R ² , R ³ and R ^{4 are} necessarily a hydrogen atom. It has proved to be advantageous if in the composition according to the invention at least one compound of the formula (I) is contained, in which, according to formula (I), the radicals R ¹ , R ² , R ³ and R ⁴ independently of one another represent a hydrogen atom, hydroxy, methyl, ethyl, isopropyl, n-propyl, n-butyl C 2 -C 6) acyloxy group, an aryloxy group, a tosyloxy group, a triflyloxy group, a benzyloxy group or a benzoyloxy group.

In addition, those compositions according to the invention which have been found to contain at least one compound according to formula (I) in which R ⁵ is a hydrogen atom, a methyl group, an isopropyl group, an isobutyl group, a tert-butyl group, a 2- (Methylsulfanyl) ethyl group, a hydroxymethyl group, a (C1-C3) alkoxymethyl group, a benzyloxymethyl group, an acetyloxymethyl group, a

Benzoyloxymethyl group, a tosyloxymethyl group, a 1-hydroxyethyl group, a 1- (C 1 -C 3) alkoxy) ethyl group, a 1- (acetyloxy) ethyl group, a 1- (benzoyloxy) ethyl group, a 1- (tosyloxy) ethyl group, a mercaptomethyl group , a (C 1 -C 3) -alkylsulfanylmethyl group, an acetylsulfanylmethyl group, a benzoylsulfanylmethyl group, a tosylsulfanylmethyl group, a group according to formula (II),

in which R 'is a hydrogen atom, a (C 1 to C ₄ ) -alkyl group, a (C ₂ to C ₄ ) -alkenyl group, an aryl group or an aryl- (C 1 to C ₄ ) -alkyl group,

a group according to formula (III),

a group according to formula (IV), in which n is 0 or 1, X is an oxygen atom or a group -NH- and R "is a hydrogen atom, a (Ci-C ₄ ) alkyl group, a (C2 to C ₄ ) alkenyl group, an aryl group or a Aryl- (C 1 to C ₄ ) -alkyl group,

a group according to formula (V),

in which n represents 1 or 2 and R "and R"'independently of one another represent a hydrogen atom, a (C 1 -C ₄ ) -alkyl group, a (C ₂ -C 6) -acyl group, a benzoyl group, an aryl- (C 1 to C ₄ ) - alkyl group, an aminoiminomethyl group or a tosyl group,

a group according to formula (VI),

in which n is 0 or 1 and R is a hydrogen atom, a hydroxy group, a (C 1 -C ₄ ) -alkyl group, a (C 1 -C ₄ ) -alkoxy group, an N- (C 1 -C ₄ ) -alkylamino group, an aryl group (Ci to C4) - alkyl group, an acetyloxy group, a benzoyloxy group, a triflyloxy group or a tosyloxy group.

It is preferable that R 'represented by formula (II) represents a hydrogen atom, a methyl group, an ethyl group, an iso-propyl group, an n-propyl group, an allyl group, a benzyl group or a phenyl group.

It is preferable that R 'represented by the formula (III) represents a hydrogen atom, a methyl group, an ethyl group, an iso-propyl group, a benzyl group, a benzoyloxy group or a phenyl group.

It is preferable that R 'represented by the formula (IV) represents a hydrogen atom, a methyl group, an ethyl group, an iso-propyl group, a benzyl group, a benzoyloxy group or a phenyl group.

It is preferred that R "and R" 'according to formula (V) are independently hydrogen, methyl, ethyl, n-propyl, iso-propyl, benzyl, benzoyl, acetyl, one

Aminoiminomethyl group or a tosyl group. It is preferable that R of the formula (VI) is a hydrogen atom, a hydroxy group, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, a tert-butyl group, a phenyl group, a methoxy group, an acetyloxy group, a

Tosyloxygruppe, a triflyloxy group, a benzyloxy group or a benzoyloxy group.

In this case, it is again preferred, when selecting the aforementioned preferred radicals R ¹ to R ⁵ , if, according to formula (I) and according to formulas (Ia) and (Ib), the radical R ¹ binds in the para position of the phenyl ring.

The 2,5-diketopiperazine compounds of the formula (I) have chiral centers at least at the carbon atoms of positions 3 and 6 of the 2,5-diketopiperazine ring. The numbering of ring positions 3 and 6 was exemplified in formula (l-b). The 2,5-diketopiperazine compound of the formula (I) of the inventive compositions is preferably based on the stereochemistry of the carbon atoms at 3- and 6-position of the 2,5-Diketopiperazinringes the configuration isomer 3S, 6S, 3R, 6S, 3S, 6R , 3R, 6R or mixtures thereof, more preferably 3S, 6S.

Very particularly preferred compositions according to the invention contain at least one

2,5-diketopiperazine compound of the formula (I) selected from 3-benzyl-6-carboxyethyl-2,5-diketopiperazine (also: 3- (5-benzyl-3,6-dioxopiperazin-2-yl) propanoic acid), 3 Benzyl-6-carboxymethyl-2,5-diketopiperazine, 3-benzyl-6- (p -hydroxybenzyl) -2,5-diketopiperazine, 3-benzyl-6-isopropyl-2,5-diketopiperazine, 3-benzyl 6- (4-aminobutyl) -2,5-diketopiperazine, 3,6-di (benzyl) -2,5-diketopiperazine, 3,6-di (4-hydroxybenzyl) -2,5-diketopiperazine, 3,6- Di (4- (benzyloxy) benzyl) -2,5-diketopiperazine, 3-benzyl-6- (4-imidazolyl) methyl-2,5-diketopiperazine, 3-benzyl-6-methyl-2,5-diketopiperazine, 3 -Benzyl-6- (2- (benzyloxycarbonyl) ethyl) -2,5-diketopiperazine (also: 3- (5-Benzyl-

3.6-dioxopiperazin-2-yl) propanoic acid benzyl ester) or mixtures thereof. In turn, compounds with the aforementioned configuration isomers are preferably suitable for selection.

Most preferably, the viscoelastic, solid-shaped ones of the invention contain

Surfactant compositions preferably at least one 2,5-diketopiperazine compound of the formula (I) selected from 3,6-bis (4-hydroxybenzyl) piperazine-2,5-dione, 3-benzyl-6-isopropylpiperazine-2,5-dione, 3,6-Bis (4- (benzyloxy) benzyl) piperazine-2,5-dione, 3-benzyl-piperazine-2,5-dione, 3-benzyl-6-carboxymethyl-piperazine-2,5-dione, or mixtures thereof. In turn, compounds with the aforementioned configuration isomers are preferably suitable for selection, the S, S configuration being particularly preferred in each case. Most preferred is (3S, 6S) -3,6-bis (4-hydroxybenzyl) piperazine-2,5-dione, (3R, 6R) -3,6-bis (4-hydroxybenzyl) piperazine-2,5-dione , (3S, 6R) -3,6-Bis (4-hydroxybenzyl) piperazine-2,5-dione, (3R, 6S) -3,6-bis (4-hydroxybenzyl) piperazine-2,5-dione or mixtures thereof in the surfactant compositions according to the invention as component (ii). (3S, 6S) -3,6-bis (4-hydroxybenzyl) -piperazine-2,5-dione is again most preferred.

The 2,5-diketopiperazine compounds present in the agents according to the invention are prepared by means of known synthesis methods (compare Suzuki et al., Chem. Pharm. Bull. 1981, 29 (1), 233-237).

The viscoelastic solid surfactant composition of the present invention contains water. It is preferred if in the surfactant composition water, based on the total weight of the composition, preferably in a total amount of between 0 and 70 wt .-%, more preferably between 4 and 70 wt .-%, more preferably between 10 and 70 wt .-%, more preferably between 0 and 60 wt .-%, more preferably between 4 and 60 wt .-%, more preferably between 10 and 60 wt .-%, more preferably between 0 to 40 wt .-%, more preferably between 4 and 40 wt .-%, more preferably between 10 and 40 wt .-%, particularly preferably between 0 to 25 wt .-%, more preferably between 4 and 25 wt .-%, more preferably between 10 and 25 wt .-%, is contained. The proportion of water in the surfactant composition is most preferably 20% by weight or less, again more preferably 15% by weight or less, again more preferably 12% by weight or less, especially 4 to 20% by weight. The percentages by weight are based on the total weight of the composition.

The solubility of the said surfactant composition, as well as its stability is improved, if preferably the surfactant composition additionally contains at least one organic

Solvents having at least one hydroxyl group, no amino group and one

Molecular weight of at most 500 g / mol.

Said organic solvent is again preferably selected from (C 2 -C 5) -alkanols having at least one hydroxyl group (particularly preferably selected from the group consisting of ethanol, ethylene glycol, 1,2-propanediol, glycerol, 1,3-propanediol, n-propanol, Isopropanol, 1,1,1-trimethylolpropane, 2-methyl-1,3-propanediol, 2-hydroxymethyl-1,3-propanediol, or mixtures thereof), triethylene glycol, butyl diglycol, polyethylene glycols having a weight-average molecular weight M _w of at most 500 g / mol, glycerol carbonate, propylene carbonate, 1-methoxy-2-propanol, 3-methoxy-3-methyl-1-butanol, butyl lactate, 2-isobutyl-2-methyl-4-hydroxymethyl-1,3-dioxolane, 2,2 - Dimethyl-4-hydroxymethyl-1, 3-dioxolane, dipropylene glycol, or mixtures thereof. It is again particularly preferred if said organic solvent in a total amount of 5 to 40 wt .-%, in particular from 10 to 35 wt .-%, is included.

The solution of the technical problem could be further optimized by the fact that in the

Surfactant composition is preferably additionally at least one polyalkylene oxide compound having a weight-average molecular weight M _w of at least 4000 g / mol, in particular of at least 6000 g / mol, more preferably of at least 8000 g / mol.

It has proved to be preferred when said polyalkylene oxide compound is selected from polyethylene oxide, ethylene oxide-propylene oxide copolymer and mixtures thereof.

Very particular preference is given to using as the polyalkylene oxide compound polyethylene oxide having a weight average molecular weight M _w of at least 4000 g / mol, in particular of at least 6000 g / mol, more preferably of at least 8000 g / mol.

In particular, the stability of said surfactant composition is further improved if the surfactant composition additionally comprises at least one polymeric polyol, in particular

Polyvinyl alcohol, is included. Polymeric polyols have more than 3 hydroxy groups according to the present invention. suitable polymeric polyols preferably have an average molecular weight of 4000 to 100000 g / mol.

The surfactant composition according to the invention preferably contains, based on the total weight thereof, a total amount of from 1 to 30% by weight, in particular from 2 to 20% by weight, of the polymeric polyol.

Polyvinyl alcohols are thermoplastics which are produced as a white to yellowish powder mostly by hydrolysis of polyvinyl acetate. Polyvinyl alcohol (PVOH) is resistant to almost all anhydrous organic solvents. Preference is given to polyvinyl alcohols having an average molar mass of 30,000 to 60,000 g / mol.

Preference is given to polyvinyl alcohols which are present as white-yellowish powders or granules

Polymerization degrees in the range of about 100 to 2500 (molecular weights of about 4000 to 100,000 g / mol) and degrees of hydrolysis of 87-99 mol%, which accordingly also contain a residual content of acetyl groups.

In the context of the present invention, it is preferred that the surfactant composition comprises a polyvinyl alcohol whose degree of hydrolysis is preferably 70 to 100 mol%, in particular 80 to 90 mol%, particularly preferably 81 to 89 mol% and especially 82 to 88 mol%. % is. In a preferred embodiment, the water-soluble packaging is at least 20 wt .-%, particularly preferably at least 40 wt .-%, most preferably to at least 60 wt .-% and in particular at least 80 wt .-% of a polyvinyl alcohol whose degree of hydrolysis 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol -%, is.

PVOH powders having the aforementioned properties which are suitable for use in the at least one second phase are sold, for example, under the name Mowiol® or Poval® by Kuraray. Particularly suitable are the Poval® qualities, in particular the grades 3-83, 3-88 and 3-98 and Mowiol® 4-88 from Kuraray.

The water solubility of polyvinyl alcohol can be improved by post-treatment with aldehydes

(Acetalization) or ketones (ketalization) are changed. As particularly preferred and particularly advantageous due to their pronounced cold water solubility, polyvinyl alcohols have been found to be acetalated or ketalized with the aldehyde or keto groups of saccharides or polysaccharides or mixtures thereof. To use extremely advantageous are the reaction products of polyvinyl alcohol and starch. Furthermore, the water solubility can be changed by complexing with Ni or Cu salts or by treatment with dichromates, boric acid, borax and thus set specifically to desired values.

Surprisingly, it has been found that PVOH and / or gelatin are particularly suitable for producing surfactant compositions which meet the requirements shown above.

Therefore, a surfactant composition according to the invention which comprises PVOH and at least one organic solvent as described above is particularly preferred.

To stabilize the viscoelastic solid composition of the present invention, it is preferable that the composition additionally contains at least one stabilizer selected from magnesium oxide, inorganic salt of Mg, Ca, Zn, Na or K (especially sulfate, carbonate or acetate, more preferably magnesium sulfate, zinc acetate or calcium acetate), acetamido monoethanolamine, hexamethylenetetramine, guanidine, polypropylene glycol ether, salt of amino acids or mixtures thereof.

It is preferred according to the invention when in the viscoelastic, solid-shaped

Surfactant composition to increase product safety at least one bittering agent is included.

Preferred bittering agents have a bitter value of at least 1,000, preferably at least 10,000, more preferably at least 200,000. The standardized method described in the European Pharmacopoeia (5th Edition, Grundwerk, Stuttgart 2005, Volume 1 General Part Monograph Groups, 2.8.15 Bitter Value, p. 278) is used to determine the bitterness value. As a comparison serves an aqueous solution of quinine hydrochloride whose bitterness value is set at 200,000. This means that 1 gram of quinine hydrochloride makes 200 liters of water bitter. The interindividual taste differences in the organoleptic test of bitterness are compensated by a correction factor in this method.

Very particularly preferred bittering agents are selected from denatonium benzoate, glycosides, isoprenoids, alkaloids, amino acids and mixtures thereof, more preferably

Denatonium benzoate.

Glycosides are organic compounds of the general structure R-O-Z, in which an alcohol (R-OH) is connected via a glycosidic bond with a sugar moiety (Z).

Suitable glycosides are, for example, flavonoids such as quercetin or naringin or

Iridoid qlvcosides such as aucubin and especially seccoidoid qlvcosides such as amarogentin,

Dihydrofoliamentin, Gentiopikrosid, Gentiopikrin, Swertiamarin, Sweroside, Gentioflavosid, Centaurosid, Methiafolin, Harpagoside and Centapikrin, Sailicin or Kondurangin.

Isoprenoids are compounds that formally derive from isoprene. Examples are in particular terpenes and terpenoids.

Suitable isoprenoids include, for example, sequiterpene lactones, such as absinthine, artabsine, cnicin, lactucin, lactucopyrin or salzolidideolide, monoterpene ketones (thujones), such as

for example, α-thujone or β-thujone, tetranortriterpenes (limonoids) such as desoxylimones, deoxylmonic acid, limonin, ichangin, isobaconic acid, obacunone, obacunonic acid, nomilin or nomilinic acid, terpenes such as marrubin, premarubin, carnosol, carnosic acid or quassin.

Alkaloids refer to naturally occurring, chemically heterogeneous, mostly alkaline, nitrogen-containing organic compounds of secondary metabolism which act on the animal or human organism.

Suitable alkaloids are, for example, quinine hydrochloride, quinine hydrogen sulfate,

Quinine dihydrochloride, quinine sulfate, columbine and caffeine.

Suitable amino acids include, for example, threonine, methionine, phenylalanine, tryptophan, arginine, histidine, valine and aspartic acid.

Particularly preferred bitter substances are quinine sulfate (bitter value = 10,000), naringin (bitter value = 10,000), sucrose octaacetate (bitter value = 100,000), quinine hydrochloride, denatonium benzoate (Bitter value> 100,000,000) and mixtures thereof, very particularly preferred

Denatonium benzoate (eg available as Bitrex ^®).

The viscoelastic, solid surfactant composition contains based on the

Total weight preferred bittering agent in a total amount of at most 1 part by weight of bittering agent to 250 parts by weight of viscoelastic, solid surfactant composition (1: 250), more preferably of at most 1: 500, most preferably of at most 1: 1000.

The viscoelastic solid surfactant composition can be prepared by first placing a liquid composition containing the organic compound of component (ii) at a temperature above the sol-gel transition temperature of the liquid composition and then forming the heated liquid composition into a mold , preferably in a cavity of a trough mold, and cooled in said form below the sol-gel transition temperature to form a viscoelastic, solid shaped body.

It is also possible to first bring a first liquid composition containing at least one said organic compound of component (ii) to a temperature above the sol-gel transition temperature of the first liquid composition and having said first liquid composition having a second liquid composition a temperature below the sol-gel transition temperature of the first composition containing water and at least one surfactant to give a liquid composition containing greater than 1% by weight of at least one said organic compound of component (ii), 0.1 to 70 Wt .-% of at least one surfactant and water, to mix and bring into a form.

The particular liquid composition is in the form of curing the liquid

Composition brought under the sol-gel transition temperature of the liquid composition. It is inventively preferred when the liquid composition for forming said shaped body to not less than 20 ° C, in particular not less than 25 ° C, more preferably not less than 30 ° C, cooled.

The sol-gel temperature can be determined by conventional methods. As part of the

Present invention, the organic compound of component (ii) was homogenized in water at 133 ° C in a closed vessel with pressure equalization in the heating Thermoshaker at 400 rpm to determine the sol-gel temperature until the organic compound of

Component (ii) has completely dissolved and it creates a transparent solution. This solution is cooled in the heating thermoshaker to 80 ° C with 0 rpm. To determine the sol-gel transition temperature, a temperature-dependent oscillating measurement (devices as above (vide supra)) at a deformation of 0.1%, a frequency of 1 Hz and cooling rate of 5 ° C / min is performed. Before the measurement is started, the temperature is given as 80 ° C and the Shut down the top plate to minimize the temperature difference between the bottom and top plates. After the sample in the heating thermoshaker has cooled to 80 ° C, the top plate is raised and 0.5 g of the sample is carefully applied to the bottom plate with a pipette as a sol. Then the upper plate is shut down and the measurement is started. The measurements are carried out at different temperatures.

A corresponding shaped article can also be produced by extrusion of the viscoelastic, solid-form surfactant composition, with optional subsequent rounding. This can produce a free-flowing product or pellets.

It is preferred according to the invention if the viscoelastic, solid-form surfactant composition of the first subject of the invention is present as a shaped article.

A molded body is a single body that stabilizes itself in its embossed form. This dimensionally stable body is formed from a molding compound (e.g., a composition) by deliberately placing this molding material in 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. All possible shapes are possible, such as sphere, cube, cuboid, round disc, tub, shell, prism, octahedron, tetrahedron, egg shape, dog, cat, mouse, horse, torso, bust, cushion, automobile, oval disc with imprinted trademark, and much more.

It is preferred according to the invention if the shaped body of the viscoelastic, solid-form surfactant composition of the first subject of the invention has a weight of at least 1 g, preferably of at least 5 g, particularly preferably of at least 10 g.

It is preferred according to the invention if the shaped body of the viscoelastic, solid-form surfactant composition of the first subject of the invention has a weight of at most 80 g, in particular of at most 70 g, more preferably of at most 50 g, very particularly preferably of at most 40 g, most preferably of at most 30 g, owns. In this context, the aforementioned minimum weights of the molding are particularly preferred.

Most preferably, the shaped body of the viscoelastic, solid-shaped

Surfactant composition of the first subject of the invention has a weight of from 10 to 80 g, in particular from 10 to 70 g, more preferably from 10 to 50 g, most preferably from 10 to 30 g, for example 15 g or 25 g. It is again preferred if said

Molded body contains surfactant in the total amounts marked as preferred (vide supra).

The shaped body of said viscoelastic solid composition may also comprise at least two different viscoelastic, solid surfactant compositions of the first Subject of the invention to form at least two phases, preferably of at least two different colored phases included. For example, from a first viscoelastic, solid-form surfactant compositions of the first subject of the invention, a mold body can be prepared as a first phase, in the well a second viscoelastic, solid-form surfactant composition of the first subject of the invention is introduced as the second phase. Likewise, the shaped body may be formed of various, viscoelastic, solid compositions arranged as stacked phases.

A corresponding molded body of the surfactant composition according to the invention may preferably be used as a container with at least one well, e.g. in the form of a tub or shell, be designed such that the volume of the walls is smaller than the total volume of all troughs. The walls of a molded body of this embodiment preferably have an average thickness of not more than 5 mm, in particular not more than 2 mm, more preferably not more than 1 mm. The total volume of the wells of this embodiment preferably has a volume of at least 5 ml, more preferably at least 10 ml, more preferably at least 15 ml.

A phase in the sense 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 features, for example, ingredients, external appearance, etc. Preferably, different phases can be visually distinguished. For the consumer, a first phase is clearly differentiated from a second phase. If the agent of the portion according to the invention has more than one first phase, then these can preferably likewise be differentiated from one another by the naked eye, because they differ, for example, from one another in color. The same applies if two or more second phases are present. Also in this case, a visual differentiation of the phases, for example due to a color or transparency difference is preferably possible. Phases in the sense of the present invention are thus self-contained areas that can be optically distinguished from the consumer by the naked eye. The individual phases may have different properties when used.

It is inventively preferred if, in order to increase product safety, at least one bittering agent has been incorporated homogeneously into the shaped body and / or the surface of the shaped body has been provided by coating with at least one bittering agent. It is preferred to incorporate the at least one bittering agent homogeneously into the shaped body as an ingredient of the viscoelastic, solid surfactant composition. Preferred bittering agents and amounts are the aforementioned (vide supra). In order to prevent sticking together of individual moldings which are located together in one packaging, it may be preferable to remove the moldings with a powdered solid. Preferred powdering agents are selected from talc, sodium sulfate, starch, pectin, amylopectin, dextrin, lactic acid, lactose or mixtures thereof.

The surfaces of the molded article may be printed for further aesthetic enrichment and / or for attachment of clues or manufacturer names. The use of inkjet printing is preferred.

All the aforementioned preferred embodiments of the invention

Surfactant compositions are also for providing a composition of the invention

Shaped body preferred.

A second object of the invention is a portion containing at least one viscoelastic solid surfactant composition of the first subject of the invention. In this case, it is preferred according to the invention if the portion contains the viscoelastic, solid-form surfactant composition according to the invention of the first subject of the invention as a shaped body. It is again preferred if the portion, based on its total weight, the molding to at least 5 wt .-%, in particular at least 15 wt .-%, in particular at least 50 wt .-%, in particular at least 80 wt .-% , in particular at least 90 wt .-%, particularly preferably at least 95 wt .-%, contains.

One serving is a standalone dosing unit that provides a quantity of fabric treatment agent for one application, preferably for use in a washing machine. The viscoelastic, solid surfactant composition of the present invention may be either the sole textile treatment agent of the portion, or may be formulated in portion with at least one additional composition other than the viscoelastic solid surfactant composition of the first subject of the invention, and in total form the textile treatment agent of the portion.

It is preferred according to the invention if the portion according to the invention comprises at least one shaped body of the viscoelastic, solid-form surfactant composition of the first

Invention article which has a weight of at least 1 g, preferably of at least 5 g, more preferably of at least 10 g possesses.

Invention article which has a weight of at most 80 g, in particular of at most 70 g, more preferably of at most 50 g, most preferably of has at most 40 g. In this context, the aforementioned minimum weights of the molding are particularly preferred.

The portion according to the invention very particularly preferably has a shaped body of the viscoelastic, solid-form surfactant composition of the first subject of the invention with a weight of from 1 to 80 g, in particular from 1 to 70 g, more preferably from 1 to 50 g, more preferably from 1 to 30 g, in particular from 10 to 80 g, especially from 10 to 70 g, more preferably from 10 to 50 g, most preferably from 10 to 30 g, for example 15 g or 25 g. In this case, it is again preferred if said shaped body contains surfactant in the total amounts characterized as being preferred (vide supra).

Very particularly preferred portions are those of the embodiments (P1) to (P4):

(P1): Portion containing, based on the weight of the portion, at least 80% by weight, preferably at least 90% by weight, of a shaped body of at least one viscoelastic, solid-form surfactant composition of the first subject of the invention, the shaped body having a weight of at least 1 g, preferably of at least 5 g, more preferably at least 10 g, most preferably from 10 to 30 g.

(P2): Portion containing, based on the weight of the portion, at least 80% by weight, preferably at least 90% by weight, of a shaped body of at least one viscoelastic, solid-form surfactant composition of the first subject of the invention, the shaped body being transparent and having a weight of at least 1 g, preferably of at least 5 g, more preferably at least 10 g, most preferably from 10 to 30 g.

(P3): Portion containing, based on the weight of the portion, at least 80% by weight, preferably at least 90% by weight, of a shaped article of at least one viscoelastic, solid-form surfactant composition, based on the total weight of the

surfactant

(I) 10 to 60 wt .-% of at least one anionic surfactant, wherein as anionic surfactant preferably at least one C9-i3-alkylbenzenesulfonate is contained, and

2 to 35 wt .-% of at least one nonionic surfactant, wherein as nonionic surfactant preferably at least one alkoxylated alcohol having 8 to 18 carbon atoms and an average of 4 to 12 moles of ethylene oxide (EO) per mole of alcohol is included, with the proviso that surfactant in a Total amount of from 10 to 70% by weight, in particular from 15 to 70% by weight,

and

(ii) at least one diketopiperazine compound of the formula (I)

wherein

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

Hydroxy, (Ci-C6) alkyl group, a (C ₂ -C 6) -alkenyl, _(C2-C6) - acyl group, a (C ₂ -C 6) acyloxy group, a (Ci-C6) alkoxy group, a

Amino group, a (C ₂ -C 6) -acylamino group, a (C ₁ -C 6) -alkylaminocarbonyl group, an aryl group, an aroyl group, an aroyloxy group, an aryloxy group, an aryl- (C ₁ -C 4) -alkyloxy group, an aryl- C3) alkyl group, a heteroaryl group, a hetroaryl (Ci-C3) alkyl group, a (Ci-C4) hydroxyalkyl group, a (C1-C4) -aminoalkyl group, a carboxy (Ci-C3) alkyl group, wherein at least two of the radicals R ¹ to R ⁴ together with the remainder of the molecule can form a 5 or 6-membered ring,

R ⁵ represents a hydrogen atom, a linear (C _{1 to} C 6) alkyl group, a branched (C ₃ to Cio) alkyl group, a (C _{3 to} C 6) cycloalkyl group, a (C _{2 to} C 6) alkenyl group, a (C ₂ -C 6) alkynyl group, a (C 1 -C 4) -hydroxyalkyl group, a (C 1 -C 4) -alkoxy (C 1 -C 4) -alkyl group, a (C 1 -C 4) -acyloxy- (C 1 -C 4) -alkyl group, a Aryloxy- (C 1 -C 4) -alkyl group, a 0- (aryl- (C 1 -C 4) -alkyl) oxy- (C 1 -C 4) -alkyl group, a (C 1 -C 4) -alkylsulfanyl- (C 1 -C 4) -alkyl group , an aryl group, an aryl- (C 1 -C 3) -alkyl group, a heteroaryl group, a heteroaryl- (C 1 -C 3) -alkyl group, a (C 1 -C 4) -hydroxyalkyl group, a (C 1 -C 4) -aminoalkyl group, an N- (C ₁ -C 4) -alkylamino (C ₁ -C 4) -alkyl group, an N, N- (C ₁ -C 4) -dialkylamino- (C ₁ -C 4) -alkyl group, an N- (C ₂ -Cs) -acylamino- C 1 -C 4) -alkyl group, an N- (C 2 -C 8) -acyl-N- (C 1 -C 4) -alkylamino- (C 1 -C 4) -alkyl group, an N- (C 2 -C 8) -royl-N- ( C 1 -C 4) -alkylamino (C 1 -C 4) -alkyl group, an N, N- (C 2 -C 8) -diacylamino- (C 1 -C 4) -alkyl group, an N- (aryl- (C 1 -C 4) -alkyl) amino- (Ci-C4 ) alkyl group, an N, N-di (aryl- (Ci-C4) -alkyl) amino (Ci-C4) -alkylgruppe, a (C1-C4) - carboxyalkyl group, a (Ci-C4) -alkoxycarbonyl- ( C 1 -C 3) alkyl group, a (C 1 -C 4) acyloxy (C 1 -C 3) alkyl group, a guanidino (C 1 -C 3) alkyl group, a

Aminocarbonyl- (C 1 -C 4) -alkyl group, an N- (C 1 -C 4) -alkylaminocarbonyl- (C 1 -C 4) -alkyl group, an N, N-di (C 1 -C 4) -alkyl) aminocarbonyl- (C 1 -C 4 ) alkyl group, an N- (C ₂ -C 8) -acylaminocarbonyl- (C ₁ -C 4) -alkyl group, an N, N- (C ₂ -C 8) -diacylaminocarbonyl- (C ₁ -C 4) -alkyl group, an N- ( C 2 -C 8) acyl-N- (C 1 -C 4) -alkylaminocarbonyl- (C 1 -C 4) -alkyl group, an N- (aryl- (C 1 -C 4) -alkyl) aminocarbonyl- (C 1 -C 4) -alkyl group, a N- (Aryl- (C 1 -C ₄ ) -alkyl) -N- (C 1 -C 6) -alkylaminocarbonyl (C 1 -C ₄ ) -alkyl group or an N, N-di (aryl- (C 1 -C ₄ ) -alkyl) aminocarbonyl (C 1 -C ₄ ) alkyl group,

and

(Iii) between 0 to 40 wt .-%, particularly preferably between 0 to 25 wt .-%, water, wherein the molding has a weight of at least 1 g, preferably of at least 5 g, more preferably at least 10 g, most preferably from 10 to 30 g.

(P4): Portion containing, based on the weight of the portion, at least 80% by weight, preferably at least 90% by weight, of a shaped body of at least one viscoelastic, solid-form surfactant composition, based on the total weight of the

surfactant

(I) 10 to 60 wt .-% of at least one anionic surfactant, wherein as anionic surfactant

preferably at least one C9 -i3-alkylbenzenesulfonate is contained, and

2 to 35 wt .-% of at least one nonionic surfactant, wherein as nonionic surfactant preferably at least one alkoxylated alcohol having 8 to 18 carbon atoms and an average of 4 to 12 moles of ethylene oxide (EO) per mole of alcohol is included, with the proviso that surfactant in a Total amount of 10 to 70 wt .-% is included, and

(ii) at least one diketopiperazine compound of the formula (I)

wherein

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

Hydroxy group, a (C 1 -C 6) -alkyl group, a (C 2 -C 6) -alkenyl group, a (C 2 -C 6) -acyl group, a (C 2 -C 6) -acyloxy group, a (C 1 -C 6) -alkoxy group, an amino group, a (C ₂ -C 6) -acylamino group, a (C 1 -C 6) -alkylaminocarbonyl group, an aryl group, an aroyl group, an aroyloxy group, an aryloxy group, an aryl- (C 1 -C ₄ ) -alkyloxy group, an aryl- (C 1 -C 3) alkyl group, heteroaryl group, heteroaryl (C 1 -C 3) alkyl group, (C 1 -C ₄ ) hydroxyalkyl group, (C 1 -C ₄ ) aminoalkyl group, carboxy (C 1 -C 3) alkyl group, wherein at least two the radicals R ¹ to R ⁴ together with the remainder of the molecule can form a 5 or 6-membered ring, R ⁵ represents a hydrogen atom, a linear (C 1 to C 6) alkyl group, a branched (C 3 to Cio) alkyl group, a (C 3 to C 6) cycloalkyl group, a (C 2 to C 6) alkenyl group, a (C 2 to C 6 ) Alkynyl group, a (C 1 -C ₄ ) -hydroxyalkyl group, a (C 1 -C ₄ ) -alkoxy (C 1 -C ₄ ) -alkyl group, a (C 1 -C ₄ ) -acyloxy- (C 1 -C ₄ ) - alkyl group, an aryloxy- (C 1 -C ₄ ) -alkyl group, a 0- (aryl- (C 1 -C ₄ ) -alkyl) oxy- (C 1 -C ₄ ) -alkyl group, a (C 1 -C ₄ ) -alkylsulfanyl- C 1 -C ₄ ) -alkyl group, an aryl group, an aryl- (C 1 -C 3) -alkyl group, a heteroaryl group, a heteroaryl- (C 1 -C 3) -alkyl group, a (C 1 -C ₄ ) -hydroxyalkyl group, a (C 1 -C ₄ ) -alkyl group C ₄ ) -aminoalkyl group, an N- (C 1 -C ₄ ) -alkylamino- (C 1 -C ₄ ) -alkyl group, an N, N- (C 1 -C ₄ ) -dialkylamino- (C 1 -C ₄ ) -alkyl group, an N - (C ₂ -C 8) -acylamino (C ₁ -C ₄ ) -alkyl group, an N- (C ₂ -C 8) -acyl-N- (C ₁ -C ₄ ) -alkylamino (C 1 -C ₄ ) -alkyl group, a N- (C ₂ -C 8) -royl-N- (C 1 -C ₄ ) -alkylamino (C 1 -C ₄ ) -alkyl group, an N, N- (C ₂ -C 8) -diacylamino- (C 1 -C ₄ ) - alkyl group, an N- (A ryl- (C 1 -C ₄ ) -alkyl) amino- (C 1 -C ₄ ) -alkyl group, an N, N-di (aryl- (C 1 -C ₄ ) -alkyl) amino- (C 1 -C ₄ ) -alkyl group , a (C 1 -C ₄ ) -carboxyalkyl group, a (C 1 -C ₄ ) -alkoxycarbonyl- (C 1 -C 3) -alkyl group, a (C 1 -C ₄ ) -acyloxy- (C 1 -C 3) -alkyl group, a guanidino ( C 1 -C 3) -alkyl group, an aminocarbonyl- (C 1 -C ₄ ) -alkyl group, an N- (C 1 -C ₄ ) -alkylaminocarbonyl- (C 1 -C ₄ ) -alkyl group, an N, N-di (C 1 -C ₄ ) -alkyl group C ₄ ) -alkyl) aminocarbonyl- (C ₁ -C ₄ ) -alkyl group, an N- (C ₂ -C 8) -acylaminocarbonyl- (C ₁ -C ₄ ) -alkyl group, an N, N- (C ₂ -C 8) -diacylaminocarbonyl - (Ci-C4) alkyl group, a N- (C2-C8) acyl-N- (Ci-C4) - alkylaminocarbonyl (Ci-C ₄₎ alkyl group, an N- (aryl (Ci-C ₄ ) -alkyl) aminocarbonyl- (C 1 -C 4) -alkyl group, an N- (aryl- (C 1 -C 4) -alkyl) -N- (C 1 -C 6) -alkylaminocarbonyl- (C 1 -C 4) -alkyl group or an N, N-di (aryl- (C 1 -C ₄ ) -alkyl) aminocarbonyl (C 1 -C ₄ ) -alkyl group. and

(iii) between 0 to 40% by weight, particularly preferably between 0 to 25% by weight, of water, the shaped body being transparent and having a weight of at least 1 g, preferably of at least 5 g, particularly preferably at least 10 g, most preferably from 10 to 30 g.

All the aforementioned preferred embodiments of the invention

Surfactant composition and the inventive molding are also for the

Provision of a portion of the invention preferred.

When using the portion of the direct skin contact of the user with the

viscoelastic, solid, to prevent surfactant composition, the shaped body is preferably coated with water-soluble material. Such a coating has also proved to be favorable with regard to the storage stability of the shaped bodies according to the invention used in the portions. Within the scope of a preferred embodiment, said shaped body of the portion is coated on the surface with at least one water-soluble material, preferably with at least one water-soluble polymer. The coating can be effected for example by spraying a solution or by immersion in a melt, wherein in the latter method, the melting temperature is preferably below the sol-gel temperature. It may again be preferred to spray the shaped bodies coated with at least one water-soluble material with at least one pulverulent solid. Preferred means for Abpuderung are the aforementioned (vide supra).

According to another embodiment as a pouch, a portion according to the invention may comprise at least one chamber with walls of water-soluble material into which at least one shaped body of a viscoelastic, solid-form surfactant composition of the first subject of the invention is introduced. Summed up over all chambers of the portion, the compositions made up in total yield the portion of the portion to be dosed (here a textile treatment agent). Corresponding portions of this embodiment are well known to those skilled in the art as pouch products.

A chamber is a space bounded by walls (e.g., by a foil), which may exist even without the material to be dosed (possibly changing its shape). A layer of a surface coating thus does not explicitly fall under the definition of a wall. The water-soluble material in a pouch forms the walls of the chamber and thereby envelops the compositions of the fabric treatment agent.

Soluble in water is a material, when at 20 ° C 0.1 g of the material with stirring

(Stirring speed magnetic stirrer 300 rpm, stirring bar: 6.8 cm long, diameter 10 mm, beaker 1000mL low form from Schott, Mainz) within 600 seconds in 800 mL of water dissolves so that with the naked eye no single solid particles of the Materials are more visible.

The water-solubility of the film-forming material used for the production of pouches can be determined by means of a square film of said material (film: 22 x 22 mm with a thickness of 20 mm) fixed in a square frame (inside edge length: 20 mm) 76 pm) according to the following measurement protocol. Said framed film is immersed in 800 mL of distilled water heated to 20 ° C in a 1 liter beaker with a circular bottom surface (Schott, Mainz, 1000 mL beaker, low mold) so that the surface of the clamped film is at right angles to the Bottom surface of the beaker is arranged, the upper edge of the frame is 1 cm below the water surface and the

Lower edge of the frame is aligned parallel to the bottom surface of the beaker such that the lower edge of the frame along the radius of the bottom surface of the beaker and the center of the lower edge of the frame is located above the center of the radius of the beaker bottom. The material should dissolve with stirring (stirring speed magnetic stirrer 300 rpm, stirring bar: 6.8 cm long, diameter 10 mm) within 600 seconds in such a way that with the naked eye, no single solid-shaped film particles are more visible.

The water-soluble material generally used for coating the shaped body preferably contains at least one water-soluble polymer. It is particularly preferable that the water-soluble material contains polyvinyl alcohol or a polyvinyl alcohol copolymer.

Suitable water-soluble material and water-soluble films as the water-soluble material are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer whose molecular weight is in the range of 10,000 to 1,000,000 gmol ^-1 , preferably 20,000 to 500,000 gmol ¹ , more preferably 30,000 to 100,000 gmol ¹ and especially from 40,000 to 80,000 gmol ^-1 .

The production of polyvinyl alcohol is usually carried out by hydrolysis of polyvinyl acetate, since the direct synthesis route is not possible. The same applies to polyvinyl alcohol copolymers which are prepared from correspondingly polyvinyl acetate copolymers. Preferably, when the water-soluble material comprises at least one polyvinyl alcohol whose degree of hydrolysis is 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and

especially 82 to 88 mol%.

In addition, polymers selected from the group comprising acrylic acid-containing polymers, polyacrylamides, oxazoline polymers, polystyrenesulfonates, polyurethanes, polyesters, polyether polylactic acid, and / or mixtures of the above polymers may be added to the water-soluble material.

Preferred polyvinyl alcohol copolymers include, in addition to vinyl alcohol, dicarboxylic acids as further monomers. Suitable dicarboxylic acids are itaconic acid, malonic acid, succinic acid and

Mixtures thereof, with itaconic acid being preferred.

Likewise preferred polyvinyl alcohol copolymers include, in addition to vinyl alcohol, an ethylenically unsaturated carboxylic acid, its salt or its esters. Such polyvinyl alcohol copolymers particularly preferably contain, in addition to vinyl alcohol, acrylic acid, methacrylic acid, acrylates, methacrylates or mixtures thereof.

The water-soluble material of the film material used to provide the pouch walls has a preferred thickness in a range from 65 to 180 μm, in particular from 70 to 150 μm, more preferably from 75 to 120 μm. In the said water-soluble material of the coating of the shaped body of the portion or the walls of the pouch of the portion is preferably incorporated to increase the product safety a bittering agent. Corresponding embodiments of the water-soluble material with bittering agent are described in the publications EP-B1-2 885 220 and EP-B1-2 885 221. A preferred bittering agent is selected from the aforementioned bittering agents (vide supra), in particular denatonium benzoate.

Portions of the present invention in the form of a pouch can be made by either vertical fill seal (VFFS) or thermoforming techniques. Particularly preferably, walls of at least one chamber are produced by sealing at least one film of water-soluble material, in particular by sealing in the context of a form-fill-seal method. The thermoforming process generally includes forming a first layer of water-soluble film material to form at least one protrusion for receiving at least one composition therein, filling the composition into the respective protrusion, covering the composition-filled protrusions with a second layer of water-soluble one Film material and sealing the first and second layers together at least around the protrusions.

Another object of the invention is a method for substrate treatment comprising the method steps

(a) providing a surfactant-containing liquor by mixing 0.5 L to 40.0 L of water with a viscoelastic, solid surfactant composition of the first subject of the invention, and

(b) bringing into contact at least one textile with the surfactant-containing liquor prepared according to (a).

The following points represent particular embodiments of the invention:

1. Viscoelastic, solid-form surfactant composition containing based on the

total weight

(i) a total amount of from 0.1 to 70% by weight of at least one surfactant

and

(ii) at least one organic compound having a molecular weight of <1000 g / mol, a solubility in water of less than 0.1 g / L (20 ° C, pH 7) and a structure containing

a) at least two groups selected from -OH, -NH-, or mixtures thereof, and

b) at least one carbocyclic structural unit having at least two endocyclic double bonds, in particular at least one carbocyclic, aromatic structural unit,

and

c) at least one further cyclic structural unit containing at least two

Has carbonyl groups

and

(iii) water. Composition according to item 1, characterized in that the

Tenside composition has a storage modulus between 10 ³ Pa and 10 ⁸ Pa, preferably between 10 ⁴ Pa and 10 ⁸ Pa and a loss modulus (at 20 ° C, a deformation of 0.1% and a frequency of 1 Hz) and the memory module in the frequency range between 10 ³ Hz and 10 ² is at least twice greater than the loss modulus, preferably at least five times greater than the loss modulus, more preferably at least ten times greater than the loss modulus. Composition according to item 1 or 2, characterized in that it contains at least one anionic surfactant. Composition according to item 3, characterized in that at least one anionic surfactant selected from the group consisting of Cs -is-alkylbenzenesulfonates,

Olefinsulfonates, C 12-18 alkanesulfonates, ester sulfonates, alkyl sulfates, alkenyl sulfates, fatty alcohol ether sulfates and mixtures thereof. Composition according to point 1 to 4, characterized in that as surfactant at least one compound of formula (T-1) is contained,

+

Y

(T-1),

in the

R ^' and R ^"are independently H or alkyl and together contain 9 to 19, preferably 9 to 15 and especially 9 to 13 C atoms, and Y ^{+ is} a monovalent cation or the nth part of an N-valent cation (especially Na ⁺⁾ mean. a composition according to any one of items 1 to 5, characterized in that they contain at least one nonionic surfactant. Composition according to one of the items 1 to 6, characterized in that it contains as surfactant at least one nonionic surfactant of the formula (T-2)

R ² -O- (X0) _m -H, (T-2) in the

R ^{2 is} a linear or branched Cs-C-is-alkyl radical, an aryl radical or alkylaryl radical,

XO independently of one another for an ethylene oxide (EO) or propylene oxide (PO)

Grouping,

m stands for integers from 1 to 50. Composition according to one of the items 1 to 7, characterized in that it has a total surfactant content of 10 to 60 wt .-%, in particular from 15 to 65 wt .-%, preferably from 20 to 60 wt .-%, based on their total weight , Composition according to one of the items 1 to 8, characterized in that the further cyclic structural unit c) is selected from at least one 2,5-diketopiperazine structural unit. Composition according to one of the items 1 to 9, characterized in that the carbocyclic structural unit b) is selected from at least one phenyl group. Composition according to one of the items 1 to 10, characterized in that the component (ii) is selected from at least one diketopiperazine compound of the formula (I)

wherein

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

Hydroxy group, a (C 1 -C 6) alkyl group, a (C 2 -C 6) alkenyl group, a (C 2 -C 6) acyl group, a (C 2 -C 6) acyloxy group, a (C 1 -C 6) alkoxy group, a

Amino group, a (C 2 -C 6) -acylamino group, a (C 1 -C 6) -alkylaminocarbonyl group, an aryl group, an aroyl group, an aroyloxy group, an aryloxy group, a Aryl- (C 1 -C 4) -alkyloxy group, an aryl- (C 1 -C 3) -alkyl group, a heteroaryl group, a heteroaryl- (C 1 -C 3) -alkyl group, a (C 1 -C 4) -hydroxyalkyl group, a (C 1 -C 4) Aminoalkyl group, a carboxy (C 1 -C 3) -alkyl group, where at least two of the radicals R ¹ to R ⁴ together with the remainder of the molecule can form a 5 or 6-membered ring,

Aminocarbonyl- (C 1 -C 4) -alkyl group, an N- (C 1 -C 4) -alkylaminocarbonyl- (C 1 -C 4) -alkyl group, an N, N-di (C 1 -C 4) -alkyl) aminocarbonyl- (C 1 -C 4 ) alkyl group, an N- (C ₂ -C 8) -acylaminocarbonyl- (C ₁ -C 4) -alkyl group, an N, N- (C ₂ -C 8) -diacylaminocarbonyl- (C ₁ -C 4) -alkyl group, an N- ( C 2 -C 8) acyl-N- (C 1 -C 4) -alkylaminocarbonyl- (C 1 -C 4) -alkyl group, an N- (aryl- (C 1 -C 4) -alkyl) aminocarbonyl- (C 1 -C 4) -alkyl group, a N- (aryl- (C 1 -C 4) -alkyl) -N- (C 1 -C 6) -alkylaminocarbonyl (C 1 -C 4) -alkyl group or an N, N-di (aryl- (C 1 -C 4) -alkyl) aminocarbonyl - alkyl (Ci-C4). A composition according to item 1 1, characterized in that according to formula (I) R ¹ binds in the para position of the phenyl ring and preferably R ² to R ^{4 are} hydrogen. Composition according to one of the items 1 1 or 12, characterized in that according to formula (I) the radicals R ¹ , R ² , R ³ and R ^{4 are} independently of one another

Hydrogen atom, hydroxy group, methyl group, ethyl group, iso-propyl group, n-propyl group, n-butyl group, iso-butyl group, sec-butyl group, tert-butyl group, phenyl group, benzyl group, etc.

Methoxy group, a (C ₂ -C 6) acyloxy group, an aryloxy group, a tosyloxy group, a triflyloxy group, a benzyloxy group or a benzoyloxy group. Composition according to one of the items 1 1 to 13, characterized in that according to formula (I) R ⁵ represents a hydrogen atom, a methyl group, an isopropyl group, an isobutyl group, a tert-butyl group, a 2- (methylsulfanyl) ethyl Group, one

Hydroxymethyl group, a (C 1 -C 3) -alkoxymethyl group, a benzyloxymethyl group, an acetyloxymethyl group, a benzoyloxymethyl group, a tosyloxymethyl group, a 1-hydroxyethyl group, a 1- (C 1 -C 3) -alkoxy) ethyl group, a 1- (acetyloxy) ethyl group, a 1- (benzoyloxy) ethyl group, a 1- (tosyloxy) ethyl group, a mercaptomethyl group, a (C 1 -C 3) alkylsulfanylmethyl group, an acetylsulfanylmethyl group, a

Benzoylsulfanylmethyl group, a tosylsulfanylmethyl group,

a group according to formula (II),

a group according to formula (III),

a group according to formula (IV),

in which n is 0 or 1, X is an oxygen atom or a group -NH- and R "is a hydrogen atom, a (Ci-C ₄ ) alkyl group, a (C2 to C ₄ ) alkenyl group, an aryl group or a Aryl- (C 1 to C ₄ ) -alkyl group,

a group according to formula (V), in which n represents 1 or 2 and R "and R"'independently of one another represent a hydrogen atom, a (C 1 -C ₄ ) -alkyl group, a (C ₂ -C 6) -acyl group, a benzoyl group, an aryl- (C 1 to C ₄ ) alkyl group, an aminoiminomethyl group or a tosyl group,

a group according to formula (VI),

in which n is 0 or 1 and R is a hydrogen atom, a hydroxy group, a (C 1 -C ₄ ) -alkyl group, a (C 1 -C ₄ ) -alkoxy group, an N- (C 1 -C ₄ ) -alkylamino group, an aryl group (C 1 to C ₄ ) alkyl group, an acetyloxy group, a benzoyloxy group, a triflyloxy group or a tosyloxy group. Composition according to item 14, characterized in that R 'according to formula (II) represents a hydrogen atom, a methyl group, an ethyl group, an iso-propyl group, an n-propyl group, an allyl group, a benzyl group or a phenyl group. Composition according to one of the items 14 or 15, characterized in that

R 'according to formula (III) represents a hydrogen atom, a methyl group, an ethyl group, an iso-propyl group, a benzyl group, a benzoyloxy group or a phenyl group. Composition according to one of the items 14 to 16, characterized in that

R 'according to formula (IV) represents a hydrogen atom, a methyl group, an ethyl group, an iso-propyl group, a benzyl group, a benzoyloxy group or a phenyl group. Composition according to one of the items 14 to 17, characterized in that R "and R" 'according to formula (V) independently represent a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, a

Benzyl group, a benzoyl group, acetyl group, an aminoiminomethyl group or a tosyl group. Composition according to one of the items 14 to 18, characterized in that R according to formula (VI) is a hydrogen atom, a hydroxy group, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, a tert-butyl group, a

Phenyl group, a methoxy group, an acetyloxy group, a tosyloxy group, a triflyloxy group, a benzyloxy group or a benzoyloxy group. Composition according to one of the items 14 to 19, characterized in that the 2,5-diketopiperazine compound of the formula (I) relates to the stereochemistry of the

Carbon atoms at the 3- and 6-positions of the 2,5-diketopiperazine ring

Configuration isomers 3S, 6S, 3R, 6S, 3S, 6R, 3R, 6R or mixtures thereof (preferably 3S, 6S). Composition according to one of the items 1 to 20, characterized in that the organic compound of component (ii) is selected from 3-benzyl-6-carboxyethyl-2,5-diketopiperazine, 3-benzyl-6-carboxymethyl-2,5- diketopiperazine, 3-benzyl-6- (4-hydroxybenzyl) -2,5-diketopiperazine, 3-benzyl-6-iso-propyl-2,5-diketopiperazine, 3-benzyl-6- (4-aminobutyl) -2, 5-diketopiperazine, 3,6-di (benzyl) -2,5-diketopiperazine, 3,6-di (4-hydroxybenzyl) -2,5-diketopiperazine, 3,6-di (4- (benzyloxy) benzyl) - 2,5-diketopiperazine, 3-benzyl-6- (4-imidazolyl) methyl-2,5-diketopiperazine, 3-benzyl-6-methyl-2,5-diketopiperazine, 3-benzyl-6- (2- (benzyloxycarbonyl ) ethyl) -2,5-diketopiperazine or mixtures thereof. Composition according to one of the items 1 to 21, characterized in that, based on the total weight of the composition, the component (ii) in an amount of at least 0.5 wt .-%, in particular from 0.5 to 3.0 wt .-% , is included. Composition according to one of the preceding points, characterized in that water in a total amount between 0 and 70 wt .-%, more preferably between 0 and 60 wt .-%, more preferably between 0 to 40 wt .-%, more preferably between 0 to 25 Gew .-%, is included. Composition according to one of the preceding points, characterized in that it additionally contains at least one organic solvent having at least one hydroxyl group, no amino group and having a molecular weight of at most 500 g / mol (preferably selected from (C2-Cs) -alkanols having at least one hydroxyl group

(Particularly preferably ethanol, ethylene glycol, 1, 2-propanediol, glycerol, 1, 3-propanediol, n-propanol, isopropanol, 1, 1, 1-trimethylolpropane, 2-methyl-1, 3-propanediol, 2-hydroxymethyl-1 , 3-propanediol), triethylene glycol, butyl diglycol, polyethylene glycols with a

weight average molecular weight M _w of at most 500 g / mol, glycerol carbonate,

Propylene carbonate, 1-methoxy-2-propanol, 3-methoxy-3-methyl-1-butanol, butyl lactate, 2-isobutyl-2-methyl-4-hydroxymethyl-1,3-dioxolane, 2,2-dimethyl-4- hydroxymethyl-1,3-dioxolane, dipropylene glycol, or mixtures thereof). Composition according to item 23, characterized in that said organic solvent is contained in a total amount of from 5 to 40% by weight, in particular from 10 to 35% by weight. Composition according to one of the preceding points, characterized in that in addition at least one polyalkylene oxide compound having a weight average molecular weight M _w of at least 4000 g / mol is contained. Composition according to item 25, characterized in that

Polyalkylene oxide compound is selected from polyethylene oxide, ethylene oxide-propylene oxide copolymer and mixtures thereof. Composition according to one of the preceding points, characterized in that additionally at least one polymeric polyol, in particular polyvinyl alcohol, is contained. Composition according to one of the preceding points, characterized in that the storage modulus is in a range from 10 ⁵ Pa to 10 ⁷ Pa. Composition according to one of the preceding points, characterized in that additionally at least one stabilizer is selected, selected from magnesium sulfate, zinc acetate, calcium acetate, magnesium oxide, inorganic salt (in particular sulfate, acetate or carbonate) of Mg, Ca, Zn, Na or K, acetamido monoethanolamine .

Hexamethylenetetramine, guanidine, polypropylene glycol ether, salt of amino acids or mixtures thereof. Composition according to one of the preceding points, characterized in that it is in the form of a shaped body, in particular having a weight of at least 1 g, preferably of at least 5 g, more preferably of 10 to 30 g. Composition according to one of the preceding points, characterized in that the composition is transparent. Portion containing at least one surfactant composition according to one of the items 1 to 31. Portion according to item 32, characterized in that it additionally comprises at least one further composition. Portion according to one of the items 32 or 33, characterized in that it is designed as a shaped body of at least one surfactant composition of points 1 to 23, wherein the shaped body preferably has a weight of at least 1 g, more preferably of at least 5 g, most preferably of 10 up to 30 g. Portion according to item 32 or 33, characterized in that it comprises at least one chamber with wall of water-soluble material, wherein the portion contains at least one viscoelastic, solid shaped article according to item 22. Method for substrate treatment comprising the method steps

(A) providing an aqueous liquor by mixing 0.5 L to 40.0 L of water with 0.5 to 100 g of a composition according to any one of items 1 to 31, and

(b) bringing into contact at least one textile with the aqueous liquor prepared according to (a). Process for the preparation of a solid surfactant composition according to one of the items 1 to 31, characterized in that first a liquid composition containing at least one organic compound having a molecular weight of <1000 g / mol, a solubility in water of less than 0, 1 g / L (20 ° C, pH 7) and a structure containing

a) at least two groups selected from -OH, -NH-, or mixtures thereof, and

b) at least one carbocyclic structural unit having at least two

and

in the presence of water and 0, 1 to 70 wt .-% of surfactant and optionally optional additives to a temperature above the sol-gel transition temperature of the liquid

The composition is then brought, and then the heated liquid composition in a mold, preferably in a cavity of a trough mold, given and cooled in said mold below the sol-gel transition temperature to form a viscoelastic, solid shaped body. Examples

1.0 Synthesis of 2,5-Diketopiperazine Derivatives 1.1 General Synthetic Instructions

Materials:

Unless otherwise indicated, all reactions were carried out at room temperature and

Laboratory conditions performed. All chemicals used in the synthesis were purchased from commercial suppliers and used as received. Dry dichloromethane (CH 2 Cl 2) was obtained using an inert PS-MD-6 solvent purification system.

Thin-layer chromatographic studies were performed on fluorescently-labeled Silica Gel 60 plates (Macherey-Nagel, ALUGRAM Xtra SIL G / UV254) and visualized by UV light (254 nm / 366 nm). If necessary, additional ninhydrin was used. Column chromatography was performed with silica gel (0.040-0.063 mm).

NMR spectra were measured on a Bruker Avance 360WB spectrometer. The

chemical shifts of the ¹ H NMR spectra are reported as d (parts per million) relative to the signal from C / 6-DMSO (at 2.50 ppm (quin)). Chemical shifts for ¹³ C NMR spectra are reported as d (parts per million) relative to the cfe-DMSO signal at 39.5 ppm (sept.). The following abbreviations were used to describe the signals: br. = broad, s = singlet, d = doublet, dd = doublet of doublets t = triplet, m = multiplet. Clutch constants J are given in Hertz.

High resolution (HR) ESI mass spectra were measured on a Bruker impact II. All signals were given as a quotient from mass to charge m / z.

IR spectra were measured on a Nicolet Thermo iS10 scientific spectrometer with diamond ATR unit. The absorption bands were reported in cnr ¹ with the following relative intensity data: s (strong, 0-33% T); m (medium, 34 - 66% T), w (weak, 67 - 100% T), and br (broad).

Melting points of solids and compounds that solidified after chromatography were determined on a Buchi M-5600 melting point measuring device and were not corrected. The measurements were taken at a heating rate of 5 ° C / min and the melting points in ° C. Synthesis Method:

The synthesis was carried out analogously to Suzuki et al., Chem. Pharm. Bull. 1981, 29 (1), 233-237.

The / V-Boc protected amino acid (1.0 eq) and the C-ester protected amino acid (1.0 eq) were dissolved in anhydrous CH 2 Cl 2 (0.4 M) and cooled down to 0 ° C. HBTU (1.0 eq) and NEt3 (2.0 eq) were added successively and stirred until all starting materials had reacted. Meanwhile, the reaction mixture was slowly warmed to 25 ° C. The mixture was washed with saturated NaHCCb solution (2x) and the combined aqueous phases were extracted with CH 2 Cl 2 (3c). The combined organic phases were dried over anhydrous Na ₂ SO ₄ and the solvent removed under reduced pressure. Purification by F / as /? - column chromatography (S1O2) provided the dipeptide as a colorless solid.

The dipeptide (1 .0 eq) was dissolved in CH 2 Cl 2 (0.4 M) and cooled down to 0 ° C. TFA (5.0 eq) was added in one portion and stirred until the starting material had reacted. Meanwhile, the reaction mixture was slowly warmed to 25 ° C. All fleeting

Components were removed under reduced pressure and the residue coevaporated to remove residual TFA with toluene (5c). The TFA salt was isolated as a colorless solid.

The TFA salt (1.0 eq) was dissolved in 2-butanol (0.1 M) and AcOH (3.0 eq) and NEt3 (2.0 eq) were added. The mixture was stirred at 80 ° C until complete conversion of the starting material and finally cooled to 25 ° C. The precipitate was filtered off, washed with THF (3c) and dried in a fine vacuum. Finally, the cyclized dipeptide was obtained as a colorless solid.

If the cyclized dipeptide still carried protecting groups, these were removed by hydrogenation. For this purpose, the protected cyclic dipeptide was mixed in MeOH (0.1 M) and palladium on activated carbon (5 mol%) was added. The suspension was saturated with hydrogen and stirred until complete conversion at 25 ° C. After filtration and removal of the solvent under reduced pressure, the deprotected cyclic dipeptide was isolated as a colorless solid.

1.2 Characterization: a) (3S, 6S) -3-Benzyl-6-methylpiperazine-2,5-dione (DKP 1): Mp .: 267 - 269 ° C decomposition. ¹ H NMR (360 MHz, DMSO-de): d = 8.13 (s, 1H), 8.03 (s, 1H), 7.33-7.18 (m, 3H), 7.18-7.10 (m, 2H), 4.17 (s, 1 H), 3.67 - 3.56 (m, 1 H), 3.12 (dd, J = 13.4, 3.7 Hz,

1 H), 2.85 (dd, J = 13.4, 4.9 Hz, 1 H), 0.45 (d, J = 7.0 Hz, 3H) ppm. ¹³ C { ¹ H} NRM (91 MHz, DMSOde): d = 167.7, 165.8, 136.1, 130.4 (2x), 128.1 (2x), 126.7, 55.4, 49.7, 38.3, 19.7 ppm. IR (ATR, neat): v = 3184 (w), 3033 (w), 2979 (w), 2889 (w), 1663 (s), 1484 (m), 1466 (s), 1455 (s), 1371 (w), 1338 (s), 1242 (w), 121 1 (w), 1 191 (w), 1 160 (w), 1 104 (m), 1054 (m), 969 (w), 923 ( w), 856 (s),

777 (m), 752 (m), 696 (s) cm ¹ . HR-MS (ESI): calculated for Ci ₂ Hi ₄ N ₂ O ₂ Na [M + Na] ⁺ : m / z =

241.09475, found: 241.09485 (Dev .: 0.10 mmu; 0.43 ppm). b) (3S, 6S) -3-Benzyl-6-sopropylpiperazine-2,5-dione (DKP 2):

Mp: 262-264 ° C decomposition. ¹ H NMR (360 MHz, DMSO-de): d = 8.13 (s, 1H), 7.92 (s, 1H), 7.28-7.12 (m, 5H), 4.21 (s, 1H), 3.53 ( s, 1 H), 3.15 (dd, J = 13.4, 4.0 Hz, 1 H), 2.86 (dd, J = 13.5, 4.7 Hz,

1 H), 1.77 - 1.63 (m, 1H), 0.64 (d, J = 7.0 Hz, 3H), 0.24 (d, J = 6.6 Hz, 3H) ppm. ¹³ C { ¹ H} NRM (91 MHz, DMSO-de): d = 166.6, 166.5, 136.3, 130.4 (2x), 128.0 (2x), 126.5, 59.2, 55.0, 37.8, 31.0,

18.3, 16.1 ppm. IR (ATR, neat): v = 3186 (w), 3047 (w), 2966 (w), 2886 (w), 1661 (s), 1452 (s),

1374 (w), 1344 (m), 1252 (w), 1215 (w), 1 175 (w), 1 107 (w), 1060 (w), 1014 (w), 923 (w), 851 (m ), 832 (m), 800 (m), 760 (m), 698 (s) cm ¹ . HR-MS (ESI): calculated for C i ₄ Hi ₈ N ₂ O ₂ Na [M + Na] ⁺ : m / z = 269.12605, found: 269.12624 (Ex: 0.19 mmu, 0.72 ppm). c) (3S, 6S) -3,6-Dibenzylpiperazine-2,5-dione (DKP 3):

Mp .: 298-300 ° C decomposition. ¹ H-NMR (360 MHz, DMSO-de): d = 7.93 (s, 2H), 7.33-7.16 (m, 6H), 7.04 (d, J = 7.4 Hz, 4H), 4.02 - 3.93 (m, 2H ), 2.58 (dd, J = 13.7, 4.9 Hz, 2H), 2.23 (dd, J = 13.7, 6.2 Hz, 2H) ppm. ¹³ C { ¹ H} NRM (91 MHz, DMSO-de): d = 166.2 (2x), 136.6 (2x), 129.9 (4x), 128.2 (4x), 126.5 (2x), 55.4 (2x), 39.4 (2x) ppm. IR (ATR, neat): v = 3197 (w), 3054 (w), 2927 (w), 1660 (s), 1497 (w), 1460 (w), 1338 (m), 1268 (w), 1212 (w), 1 194 (w), 1091 (w), 1033 (w), 1015 (w), 922 (w), 872 (w), 853 (w), 803 (m), 755 (s), 699 (s), 659 (m) cm ¹ . HR-MS (ESI): calculated for

Ci8HisN ₂ 0 ₂ Na [M + Na] ⁺ : m / z = 317.12605, found: 317.12621 (Ex: 0.16 mmu, 0.50 ppm). d) (3S, 6S) -3-Benzyl-6- (4-hydroxybenzyl) piperazine-2,5-dione (DKP 4):

Mp .: 297-299 ° C decomposition. ¹ H-NMR (360 MHz, DMSO-de): d = 9.23 (s, 1H), 7.88 (s, 2H), 7.32-7.15 (m, 3H), 7.03 (d, J = 7.2 Hz, 2H) , 6.83 (d, J = 8.1 Hz, 2H), 6.67 (d, J = 8.3 Hz, 2H), 3.97 - 3.91 (m, 2H), 3.91 - 3.86 (m, 2H), 2.57 (dd, J = 13.6 , 4.8 Hz, 1H), 2.54 - 2.51 (m, 1H), 2.23 - 2.12 (m, 2H) ppm. ¹³ C { ¹ H} NRM (91 MHz, DMSO-de): d = 166.3, 166.2, 156.1, 136.7, 130.9 (2x), 129.8 (2x), 128.2 (2x), 126.5, 126.5, 1 15.1 (2x ), 55.7, 55.4, 38.6 ppm. IR (ATR, neat): v = 3535 (w), 3204 (br), 3029 (w), 1653 (s), 1615 (m), 1589 (m), 1516 (s), 1496 (w), 1464 (s), 1331 (m), 1274 (m), 1248 (m), 1224 (m), 1200 (m), 1173 (s), 1101 (m), 1078 (m), 1013 (w), 878 (w), 805 (s), 750 (s), 696 (s), 660 (s) cm ^-1 . HR-MS (ESI): calculated for CisHis ^ OsNa [M + Na] ⁺ : m / z = 333.12096, found: 333.12102 (Ex: 0.06 mmu, 0.16 ppm). e) (3S, 6S) -3- (4-aminobutyl) -6-benzylpiperazine-2,5-dione (DKP 5):

Mp: 199-201 ° C decomposition. ¹ H NMR (360 MHz, DMSO-de): d = 8.14 (s, 1H), 8.05 (s, 1H), 7.31-7.17 (m, 3H), 7.17-7.10 (m, 2H), 4.23-4.14 (m, 1H), 3.60-3.50 (m, 1H), 3.15 (dd, J = 13.4, 3.7 Hz, 1H), 2.83 (dd, J = 13.4, 4.9 Hz, 1H), 2.74 (br. s, 2H ), 2.32 (t, J = 7.0 Hz, 2H), 1.13-0.96 (m, 3H), 0.81-0.56 (m, 3H) ppm. ¹³ C { ¹ H} NRM (91 MHz, DMSO-de): d = 167.0, 166.1, 136.1, 130.4 (2x), 128.0 (2x), 126.7, 55.3, 53.9, 41.4, 38.1, 33.2, 33.0, 20.9 ppm. IR (ATR, neat): v = 3184 (w), 3030 (w), 2926 (m), 2894 (m), 2359 (w), 1660 (s), 1453 (s), 1339 (m), 1246 (w), 1213 (w), 1192 (w), 1101 (m), 1033 (w), 1009 (w), 919 (m), 840 (m), 754 (s), 696 (s) cm ¹ , HR-MS (ESI): calculated for C15H22N3O2 [M + H] ⁺ : m / z = 276.17065, found: 276.17088 (Ex: 0.23 mmu, 0.81 ppm). f) (3S, 6S) -3 - ((1 / - / - imidazol-4-yl) methyl) -6-benzylpiperazine-2,5-dione (DKP 6):

Mp .: 244-246 ° C decomposition. ¹ H-NMR (360 MHz, DMSO-de): "5 = 11.81 (s, 1H), 8.11 (s, 1H), 7.79 (s, 1H), 7.52 (s, 1H), 7.35 - 7.18 (m , 3H), 7.15 (d, J = 7.3 Hz, 2H), 6.59 (s, 1H), 4.18 - 4.09 (m,

1H), 3.83 (d, J = 8.4 Hz, 1H), 2.90-2.76 (m, 2H), 2.55 (dd, J = 14.8, 3.8 Hz, 1H), 1.56 (dd, J =

14.5, 9.0 Hz, 1H) ppm. ¹³ C { ¹ H} NRM (91 MHz, DMSO-de): d = 166.7, 166.1, 136.3, 135.0, 130.2,

128.2, 126.7, 55.3, 54.4, 38.6, 31.3 ppm (two signals unresolved). IR (ATR, neat): v = 3185 (w), 3055 (w), 2973 (w), 2881 (w), 2360 (w), 1672 (s), 1496 (w), 1454 (m), 1339 (m), 1272 (w),

1240 (w), 1179 (w), 1135 (w), 1093 (m), 1012 (w), 982 (w), 930 (w), 822 (m), 758 (m), 699 (s), 660 (m) cm ¹ . HR-MS (ESI): calculated for C15H17N4O2 [M + H] ⁺ : m / z = 285.13460, found: 285.13493 (Dev .: 0.33 mmu, 1.15 ppm). g) Benzyl 3 - ((2S, 5S) -5-benzyl-3,6-dioxopiperazin-2-yl) -propanoate (DKP 7):

Mp .: 218-220 ° C. ¹ H-NMR (360 MHz, DMSO-de): δ = 8.25 (s, 1H), 8.10 (s, 1H), 7.46-7.30 (m, 5H), 7.24-7.09 (m, 4H), 7.03 (t , J = 7.2 Hz, 1H), 5.02 (s, 2H), 4.23 - 4.17 (m, 1H), 3.74 - 3.65 (m, 1H), 3.15 (dd, J = 13.4, 3.6 Hz, 1H), 2.82 ( dd, J = 13.4, 4.9Hz, 1H), 1.79-1.61 (m, 2H), 1.33-1.20 (m, 1H), 1.14-1.00 (m, 1H) ppm. ¹³ C { ¹ H} NMR (91 MHz, DMSO-d ₆ ): δ = 172.0, 166.4, 166.2,

136.3, 135.9, 130.4 (2x), 128.5 (2x), 128.1, 128.0 (2x), 128.0 (2x), 126.8, 65.3, 55.3, 52.8, 37.9, 28.4, 28.3 ppm. IR (ATR, neat): v = 3190 (w), 3060 (w), 2969 (w), 2902 (w), 1732 (m), 1672 (s), 1456 (m), 1436 (m), 1394 (w), 1338 (m), 1260 (m), 1215 (w), 1152 (s), 1102 (m), 1012 (w), 956 (m), 864 (m), 844 (m), 819 (m), 753 (s), 700 (s), 656 (m) cm ¹ . HR-MS (ESI): calculated for C _2i H ₂₂ N ₂ O ₄ Na [M + Na] ⁺ : m / z = 389.14718, found: 389.14730 (Ex: 0.12 mmu, 0.32 ppm). h) 3 - ((2S, 5S) -5-benzyl-3,6-dioxopiperazin-2-yl) propanoic acid (also called: (3S, 6S) -3-benzyl-6-carboxyethylpiperazine-2,5-dione) (DKP 8):

Mp .: 241-243 ° C decomposition. ¹ H-NMR (360 MHz, DMSO-de): «5 = 1 1.91 (br s, 1 H), 8.20 (d, J = 2.1 Hz, 1 H), 8.09 (d, J = 2.3 Hz, 1 H), 7.31 - 7.20 (m, 2H), 7.22 - 7.1 1 (m, 3H), 4.22 - 4.15 (m, 1H), 3.72 - 3.64 (m, 1H), 3.14 (dd, J = 13.4, 3.8 Hz, 1 H), 2.84 (dd, J = 13.4, 4.9 Hz, 1 H), 1 .75 - 1.57 (m, 2H), 1.33 - 1 .17 (m, 1 H), 1.1 1 - 0.99 ( m, 1 H) ppm. ¹³ C { ¹ H} NMR (91 MHz, DMSO-d ₆ ): δ = 173.9, 166.6, 166.3, 136.0, 130.3 (2x), 128.0 (2x), 126.8, 55.3, 53.0, 38.0, 28.6, 28.5 ppm , IR (ATR, neat): v = 3150 (br), 3030 (w), 2981 (w), 2886 (w), 2361 (w), 1736 (s), 1664 (s), 1470 (m), 1454 (m), 1409 (m), 1335 (m), 1321 (m), 131 1 (m), 1272 (m), 1 175 (s), 1098 (m), 904 (m), 855 (s) , 820 (s), 777 (m), 750 (m), 699 (s), 682 (m) cm ¹ . HR-MS (ESI): calculated for Ci ₄ Hi ₆ N ₂ O ₄ Na [M + Na] ⁺ : m / z = 299.10023, found: 299.10028 (Ex: 0.05 mmu, 0.17 ppm). i) (3S, 6S) -3,6-bis (4- (benzyloxy) benzyl) piperazine-2,5-dione (DKP 9):

Mp: 269-271 ° C. ¹ H-NMR (360 MHz, DMSO-de): d = 7.89 (s, 2H), 7.41-2.25 (m, 10H), 7.01-6.88 (m, 8H), 5.05 (s, 4H), 3.92 (s , 2H), 2.59 - 2.50 (m, 2H), 2.21 (dd, J = 13.7, 6.2 Hz, 2H) ppm. ¹³ C { ¹ H} NRM (91 MHz, DMSO-de): d = 166.3 (2x), 157.2 (2x), 137.2 (2x), 130.9 (4x), 128.7 (2x), 128.4 (4x), 127.7 (2x), 127.5 (4x), 1 14.6 (4x), 69.1 (2x), 55.6 (2x), 38.5 (2x) ppm. IR (ATR, neat): v = 3179 (w), 3030 (w), 2881 (w), 2852 (w), 1660 (s), 161 1 (m), 1508 (s), 1463 (s), 1453 (s), 1376 (w), 1340 (m), 1310 (m), 1297 (m), 1237 (s), 1225 (s), 1 174 (s), 1 1 10 (m), 1042 ( m), 1016 (m), 922 (m), 833 (s), 808 (s), 773 (s), 755 (m), 732 (s), 721 (s), 694 (s), 653 ( m) cm ¹ . HR-MS (ESI):

Calcd for C3 H3oN ₂ ₂ 0 ₄ Na [M + Na] ^+: m / z = 529.20978, found: 529.20998 (Dev .: 0:20 mmu; 00:37 ppm). j) (3S, 6S) -3,6-Bis (4-hydroxybenzyl) piperazine-2,5-dione (DKP 10):

Mp .: 259-261 ° C decomposition. ¹ H-NMR (360 MHz, DMSO-de): d = 9.23 (s, 2H), 7.80 (s, 2H), 6.84 (d, J = 8.0 Hz, 4H), 6.68 (d, J = 7.9 Hz, 4H), 3.85 (s, 2H), 2.56 - 2.50 (m, 2H), 2.09 (dd, J = 13.7, 6.6 Hz, 2H) ppm. ¹³ C { ¹ H} NRM (91 MHz, DMSO-d ₆ ): δ = 166.3 (2x), 156.1 (2x), 130.8 (4x), 126.6 (2x), 1 15.1 (4x), 55.8 (2x) , 38.9 (2x) ppm. IR (ATR, neat): v = 3516 (w), 3145 (w), 1665 (s), 1614 (m), 1598 (m), 1515 (s), 1456 (s), 1378 (w), 1337 (m), 1308 (w), 1272 (m), 1237 (s), 1 173 (m), 1 104 (m), 1085 (w), 1013 (w), 950 (w), 925 (w) , 884 (w), 825 (s), 796 (s), 776 (s), 717 (m) cm ¹ . HR-MS (ESI): calculated for C-isH-islHc Na [M + Na] ⁺ : m / z = 349.1 1588, found: 349.1 1579 (Dev .: -0.09 mmu; -0.26 ppm). 3.0 Preparation of viscoelastic, solid surfactant compositions

The following viscoelastic, solid surfactant composition according to Table 2.1 (vide infra) was prepared. For this purpose, a selection of 2,5-diketopiperazine compounds according to Table 2 (vide infra) in the amount indicated there was mixed together with the remaining ingredients of a formulation from R1 to R3 as follows.

Overall, therefore, five compositions E1 to E5 according to the invention (compare Table 2.2 in conjunction with Table 2.1) were prepared.

Table 2.1: Viscoelastic, solid surfactant composition

Table 2.2: 2,5-diketopiperazine compound (DKP) used in F1 with amount used in wt .-%

Active substance by weight of the selected composition from Table 2.1

3.0 Provision of viscoelastic, solid laundry detergents

To provide the moldings, the clear, liquid detergents F1 to F6 were prepared according to Table 3.1.

Table 3.1: Liquid detergent

To prepare a shaped body from one of the liquid detergents of Table 3.1, first a premix was used as a solution of 1.0 g of (3S, 6S) -3,6-di (4-hydroxybenzyl) -2,5-diketopiperazine (DKP 10) and 92 g of the selected liquid detergent of Table 3.1 prepared under heating. 15 g of the still hot and clear premix were incorporated into 85 g of the room temperature liquid detergent of Table 3.1 with vigorous stirring. 19 g of the resulting solution was quickly added to a cube-well mold. The temperature of the solution was gradually lowered to room temperature in the well. After solidification, the molded body was removed from the trough.

4.0 Provision of viscoelastic, solid dishwashing detergents

To provide the moldings, the liquid dishwashing detergents G1 and G2 were prepared according to Table 4.1.

Table 4.1: Liquid dishwashing detergent G1 & G2 for the machine

4.1 Production of a molded article from G1:

To prepare a molded article from G1, a premix was first prepared from the liquid dishwashing detergent G1 of Table 4.1 as a solution of 1.0 g of (3S, 6S) -3,6-di (4-hydroxybenzyl) -2,5-diketopiperazine (DKP 10) and 92 g G1 of Table 4.1 prepared under heating. 15 g of the still hot and clear premix was in 85 g of the room temperature

Dishwashing agent G1 of Table 4.1 incorporated with vigorous stirring. 19 g of the resulting solution was quickly added to a cube-well mold. The temperature of the solution was gradually lowered to room temperature in the well. After solidification, the molded body was removed from the trough.

4.1 Preparation of a 2-phase molded body of G2:

To produce a single shaped body from the two phases of composition G2, a first premix was first prepared from a liquid dishwashing detergent G2 (phase 1) of table 4.1 as a solution of 1.0 g (3S, 6S) -3,6-di (4 -hydroxybenzyl) -2,5-diketopiperazine (DKP 10) and 92 g of G2 (phase 1) of Table 4.1 prepared under heating. In a separate vessel, a second premix of composition G2 (phase 2) of Table 4.1 was prepared analogously.

15 g of the still hot and clear premix 1 were incorporated into 85 g of the dishwashing liquid G2 (phase 1) of Table 4.1, with vigorous stirring. 9.5 g of the resulting solution was quickly added to a cube-well mold, which was then half-filled. The temperature of the solution was gradually lowered to room temperature in the well.

After solidification, the molded body of phase 1 was left in the trough. 15 g of the still hot and clear premix 2 were dissolved in 85 g of room temperature

Dishwashing agent G2 (phase 2) of Table 4.1 incorporated with vigorous stirring. 9.5 g of the resulting solution was rapidly added to the cube-well mold on the already cured G2 shaped body (Phase 1). The temperature of the solution was gradually lowered to room temperature in the well.

The resulting G2 shaped body was removed from the trough after phase 2 hardening. A stable one-piece molded article with two phases (red and blue) was obtained.

Claims

claims

1. Viscoelastic, solid-form surfactant composition containing based on the

total weight

(i) a total amount of from 0.1 to 70% by weight of at least one surfactant

and

a) at least two groups selected from -OH, -NH-, or mixtures thereof, and

b) at least one carbocyclic structural unit having at least two

and

c) at least one further cyclic structural unit containing at least two

Has carbonyl groups

and

(iii) water.

2. Composition according to claim 1, characterized in that the

Tenside composition has a storage modulus between 10 ³ Pa and 10 ⁸ Pa, preferably between 10 ⁴ Pa and 10 ⁸ Pa and a loss modulus (at 20 ° C, a deformation of 0.1% and a frequency of 1 Hz) and the memory module in the frequency range between 10 ³ Hz and 10 ² Hz is at least two times greater than the loss modulus, preferably at least five times greater than the loss modulus, more preferably at least ten times greater than the loss modulus.

3. Composition according to claim 1 or 2, characterized in that it comprises at least one anionic surfactant, preferably at least one anionic surfactant selected from the group consisting of Cs -is-alkylbenzenesulfonates, Olefinsulfonaten, Ci2-i8-alkanesulfonates, ester sulfonates, alkyl sulfates, alkenyl sulfates , Fatty alcohol ether sulfates and mixtures thereof.

4. Composition according to claim 1 to 3, characterized in that as surfactant

at least one compound of the formula (T-1) is contained,

(T-1),

in the

5. Composition according to one of claims 1 to 4, characterized in that they contain at least one nonionic surfactant.

6. A composition according to any one of claims 1 to 5, characterized in that it contains as surfactant at least one nonionic surfactant of the formula (T-2)

R ² -O- (X0) m H, (T-2) in the

R ^{2 is} a linear or branched C ¹ -C 6 -alkyl radical, an aryl radical or an alkylaryl radical, X is, independently of one another, an ethylene oxide (EO) or propylene oxide (PO) radical

Grouping,

m stands for integers from 1 to 50.

7. Composition according to one of claims 1 to 6, characterized in that the further cyclic structural unit c) is selected from at least one 2,5-diketopiperazine structural unit.

8. Composition according to one of claims 1 to 7, characterized in that component (ii) is selected from at least one diketopiperazine compound of the formula (I)

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

Hydroxy, (Ci-C6) alkyl group, a (C ₂ -C 6) -alkenyl, _(C2-C6) - acyl group, a (C ₂ -C 6) acyloxy group, a (Ci-C6) alkoxy group, an amino group, a (C ₂ -C 6) -acylamino group, a (C ₁ -C 6) -alkylaminocarbonyl group, an aryl group, an aroyl group, an aroyloxy group, an aryloxy group, an aryl- (C ₁ -C 4) -alkyloxy group, an aryl- (Ci C3) alkyl group, a heteroaryl group, a Hetroaryl- (Ci-C3) alkyl group, a (Ci-C4) hydroxyalkyl group, a (C1-C4) aminoalkyl group, a carboxy (Ci-C3) alkyl group, wherein at least two of the radicals R ¹ to R ⁴ together with the remainder of the molecule can form a 5 or 6-membered ring,

Aminocarbonyl- (C 1 -C 4) -alkyl group, an N- (C 1 -C 4) -alkylaminocarbonyl- (C 1 -C 4) -alkyl group, an N, N-di (C 1 -C 4) -alkyl) aminocarbonyl- (C 1 -C 4 ) alkyl group, an N- (C ₂ -C 8) -acylaminocarbonyl- (C ₁ -C 4) -alkyl group, an N, N- (C ₂ -C 8) -diacylaminocarbonyl- (C ₁ -C 4) -alkyl group, an N- ( C 2 -C 8) acyl-N- (C 1 -C 4) -alkylaminocarbonyl- (C 1 -C 4) -alkyl group, an N- (aryl- (C 1 -C 4) -alkyl) aminocarbonyl- (C 1 -C 4) -alkyl group, a N- (aryl- (C 1 -C 4) -alkyl) -N- (C 1 -C 6) -alkylaminocarbonyl (C 1 -C 4) -alkyl group or an N, N-di (aryl- (C 1 -C 4) -alkyl) aminocarbonyl - alkyl (Ci-C4).

9. The composition according to claim 8, characterized in that according to formula (I) R ¹ binds in the para position of the phenyl ring and preferably R ² to R ^{4 are} hydrogen.

1 0. A composition according to any one of claims 8 or 9, characterized in that

according to formula (I) R ⁵ represents a hydrogen atom, a methyl group, an isopropyl group, an iso-butyl group, a tert-butyl group, a 2- (methylsulfanyl) ethyl group, a hydroxymethyl group, a (Ci-C3) alkoxymethyl group, a benzyloxymethyl group, an acetyloxymethyl group, a benzoyloxymethyl group, a tosyloxymethyl group, a 1-hydroxyethyl group, a 1 - ((C 1 -C 3) alkoxy) ethyl group, a 1- (acetyloxy) ethyl group, a 1- (benzoyloxy) ethyl group, a 1- (tosyloxy) ethyl group, a mercaptomethyl group, a (C 1 -C 3) alkylsulfanylmethyl group, a Acetylsulfanylmethyl group, a

Benzoylsulfanylmethyl group, a tosylsulfanylmethyl group,

a group according to formula (II),

a group according to formula (III),

a group according to formula (IV),

a group according to formula (V),

in which n is 1 or 2 and R "and R"'are each independently a hydrogen atom, a (Ci-C ₄ ) alkyl group, a (C2 - C6) acyl group, a benzoyl group, an aryl (Ci to C ₄ ) alkyl group, an aminoiminomethyl group or a tosyl group, a group according to formula (VI),

in which n is 0 or 1 and R is a hydrogen atom, a hydroxy group, a (C ₁ -C ₄₎ - alkyl, (Ci-C ₄₎ alkoxy, N- (Ci-C ₄₎ alkylamino group, a Aryl (Ci to C ₄ ) -alkylgruppe, an Acetyloxygruppe, a Benzoyloxygruppe, a Triflyloxygruppe or a Tosyloxygruppe means.

1 1. Composition according to one of claims 1 to 10, characterized in that

based on the total weight of the composition, the organic compound of component (ii) in an amount of at least 0.5 wt .-%, in particular from 0.5 to 3.0 wt .-%, is included.

12. Composition according to one of the items 1 to 1 1, characterized in that the

organic compound of component (ii) is selected from 3-benzyl-6-carboxyethyl-2,5-diketopiperazine, 3-benzyl-6-carboxymethyl-2,5-diketopiperazine, 3-benzyl-6- (4-hydroxybenzyl) - 2,5-diketopiperazine, 3-benzyl-6-iso-propyl-2,5-diketopiperazine, 3-benzyl-6- (4-aminobutyl) -2,5-diketopiperazine, 3,6-di (benzyl) -2 , 5-diketopiperazine, 3,6-di (4-hydroxybenzyl) -2,5-diketopiperazine, 3,6-di (4- (benzyloxy) benzyl) -2,5-diketopiperazine, 3-benzyl-6- (4 - imidazolyl) methyl 2,5-diketopiperazine, 3-benzyl-6-methyl-2,5-diketopiperazine, 3-benzyl-6- (2- (benzyloxycarbonyl) ethyl) -2,5-diketopiperazine or mixtures thereof.

13. Composition according to one of the preceding claims, characterized in that water in a total amount between 0 and 70 wt .-%, more preferably between 0 and 60 wt .-%, more preferably between 0 to 40 wt .-%, more preferably between 0 to 25 wt .-%, is included.

14. A process for substrate treatment comprising the process steps

(A) providing an aqueous liquor by mixing 0.5 L to 40.0 L of water with 0.5 to 100 g of a composition according to any one of claims 1 to 13, and

(b) bringing into contact at least one textile with the aqueous liquor prepared according to (a).

15. A process for the preparation of a solid surfactant composition according to any one of claims 1 to 13, characterized in that initially a liquid Composition containing at least one organic compound with a

Molecular weight of <1000 g / mol, a solubility in water of less than 0.1 g / L (20 ° C, pH 7) and a structure containing

a) at least two groups selected from -OH, -NH-, or mixtures thereof, and

b) at least one carbocyclic structural unit having at least two

and

The composition is then brought, and then the heated liquid composition in a mold, preferably in a cavity of a trough mold, given and cooled in said mold below the sol-gel transition temperature to form a viscoelastic, solid shaped body.