DE102018201831A1 - Detergent composition with yield value - Google Patents

Abstract

A liquid surfactant composition with yield value, in particular detergent, containing, based on the total weight thereof, (i) at least one 2,5-diketopiperazine compound of the formula (I) wherein R, R, R, R are as defined in claim 1 and (ii) a total amount of 0.1 to 70 wt .-% of at least one surfactant and (iii) water, are storage stable even when incorporating solid particles. The surfactant compositions are eminently suitable as liquid detergent compositions.

Description

The present invention is in the technical field of liquid surfactant compositions and relates to the generation of yield value in said liquid surfactant compositions. Furthermore, the present invention relates to a process for the preparation of the said liquid limit liquid surfactant compositions and to a process for textile treatment with said liquid surfactant composition.

For incorporation into liquid surfactant compositions, in particular detergents or cleaners, either those ingredients are suitable which dissolve in the liquid phase of the composition or can be suspended in an undissolved, homogeneous manner. In the case of insoluble ingredients, a stable, homogeneous suspension is necessary for the function and aesthetics of the detergent. Sedimented solid particles can agglomerate and, when used, lead to local overconcentration of the ingredient and thus uneven dosage per wash load. Visible clumps, greasy precipitates, or solid ingredient deposits on an e.g. transparent wall of the storage vessel also mean an aesthetic flaw.

Solid particles which are incorporated into a transparent or translucent, liquid phase and (possibly colored) in nude human eye in suspension as individualized particles are often referred to as speckles. Such particles have for this purpose a corresponding particle size and offer the consumer an aesthetic appeal. Microcapsules are also solid ingredients and include any type of capsule known to those skilled in the art, but especially 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. However, all of these solid particles, especially the speckles, tend to sediment in liquid surfactant compositions.

The sedimentation of particles from the suspension is usually avoided by the use of surfactant compositions having a flow limit. A yield point can be generated by the selection of special surfactant combinations usually in the presence of an electrolyte salt by establishing a lamellar phase. The use of selected polymeric thickeners is also conceivable for generating a yield stress.

In particular, surfactant compositions having a high surfactant concentration are difficult to endow with a yield value in the range of 0.01 to 5 Pa. By using lyotropic liquid-crystalline mesophases, a high yield point usually results in an excessively high yield point. The flow behavior is inhomogeneous in such a case (so-called "lumpy" flow). Furthermore, too high a flow limit causes the suspended particles to adhere to the wall of the storage vessel of the surfactant composition. If polymeric thickeners are used to form the yield point, this can sometimes be achieved with a high surfactant concentration using a very high amount of the polymeric thickener, and often it is not possible at all. Large amounts of thickener impair the cleaning performance of surfactant compositions, which can additionally lead to graying of the textile, in particular during textile treatment.

The publication WO 2002/40627 relates to aqueous liquid detergents which contain a textiles substantive low solubility agent, a crystalline hydroxy group-containing stabilizer and a non-surfactant, dissolved ingredient. The premix used to prepare the liquid detergent contains water, surfactant and 0.1 to 5% by weight of said thickener in crystalline form as a solid.

The publication WO 2005/012475 also relates to liquid limit liquid detergents prepared by the use of an already structured premix containing a hydroxy group-containing thickener in crystalline form.

The publication WO 2015/200062 relates to a premix for the preparation of liquid detergents with yield point, which is already structured by a crystalline hydroxyl-containing thickener and additionally contains an alkyl sulfate surfactant.

Hanabusa et al. report the use of low molecular weight 2,5-diketopiperazine compounds as a gelator for organic liquids, e.g. Crude or edible oil (J. Chem. Soc. Chem. Commun., 1994, 1401-1402).

Nachtsheim et al. succeeded in the use of accessible from proteinogenic amino acids 2,5-diketopiperazines as hydrogels for medical purposes (Chem. Commun., 2013, 49, 7818-7820).

The present invention has for its object to provide liquid surfactant compositions, in particular detergents or cleaners with excellent detergency or cleaning power, which have a yield point and in which solid particles (especially speckles) can be homogeneously suspended, so that they are stable in storage conditions Remain suspension.

For this purpose, any liquid surfactant compositions should be structured without yield point by adding a thickener. The thickening effect should thus be almost independent of the surfactants contained or of the formation of liquid-crystalline phases.

In addition, it was an object to provide a manufacturing method for said liquid surfactant compositions in which - especially in a continuous production process - a thickener is easily metered.

It has surprisingly been found that it is possible to prepare liquid surfactant compositions having a yield point by using special 2,5-diketopiperazine compounds. When these surfactant compositions are used as a continuous phase of a suspension, the solid phase is suspended therein homogeneously and stably. In addition, thermodynamically multiphase surfactant formulations can be prevented from macroscopic separation. By adding the said DKP compound (DKP = diketopiperazine (also: piperazine dione)), a formulation which is similar to an emulsion of several immiscible liquid phases can be converted into a storage-stable, macroscopically single-phase and homogeneous product.

worin

R¹, R², R³ und R⁴

stehen unabhängig voneinander für ein Wasserstoffatom, eine Hydroxygruppe, eine (C₁-C₆)-Alkylgruppe, eine (C₂-C₆)-Alkenylgruppe, eine (C₂-C₆)-Acylgruppe, eine (C₂-C₆)-Acyloxygruppe, eine (C₁-C₆)-Alkoxygruppe, eine Aminogruppe, eine (C₂-C₆)-Acylaminogruppe, eine (C₁-C₆)-Alkylaminocarbonylgruppe, eine Arylgruppe, eine Aroylgruppe, eine Aroyloxygruppe, eine Aryloxygruppe, eine Aryl-(C₁-C₄)-alkyloxygruppe, eine Aryl-(C₁-C₃)-alkylgruppe, eine Heteroarylgruppe, eine Hetroaryl-(C₁-C₃)-alkylgruppe, eine eine (C₁-C₄)-Hydroxyalkylgruppe, eine (C₁-C₄)-Aminoalkylgruppe, eine Carboxy-(C₁-C₃)-alkylgruppe, wobei mindestens zwei der Reste R¹ bis R⁴ gemeinsam mit dem Restmolekül einen 5 oder 6-gliedrigen Ring bilden können,

R⁵

steht für ein Wasserstoffatom, eine lineare (C₁ bis C₆)-Alkylgruppe, eine verzweigte (C₃ bis C₁₀)-Alkylgruppe, eine (C₃ bis C₆)-Cycloalkylgruppe, eine (C₂-C₆)-Alkenylgruppe, eine (C₂-C₆)-Alkinylgruppe, eine (C₁-C₄)-Hydroxyalkylgruppe, eine (C₁-C₄)-Alkoxy-(C₁-C₄)-alkylgruppe, eine (C₁-C₄)-Acyloxy-(C₁-C₄)-alkylgruppe, eine Aryloxy-(C₁-C₄)-alkylgruppe, eine O-(Aryl-(C₁-C₄)-alkyl)oxy-(C₁-C₄)-alkylgruppe, eine (C₁-C₄)-Alkylsulfanyl-(C₁-C₄)-alkylgruppe, eine Arylgruppe, eine Aryl-(C₁-C₃)-alkylgruppe, eine Heteroarylgruppe, eine Hetroaryl-(C₁-C₃)-alkylgruppe, eine (C₁-C₄)-Hydroxyalkylgruppe, eine (C₁-C₄)-Aminoalkylgruppe, eine N-(C₁-C₄)-Alkylamino-(C₁-C₄)-alkylgruppe, eine N,N-(C₁-C₄)-Dialkylamino-(C₁-C₄)-alkylgruppe, eine N-(C₂-C₈)-Acylamino-(C₁-C₄)-alkylgruppe, eine N-(C₂-C₈)-Acyl-N-(C₁-C₄)-alkylamino-(C₁-C₄)-alkylgruppe, eine N-(C₂-C₈)-Aroyl-N-(C₁-C₄)-alkylamino-(C₁-C₄)-alkylgruppe, eine N,N-(C₂-C₈)-Diacylamino-(C₁-C₄)-alkylgruppe, eine N-(Aryl-(C₁-C₄)-alkyl)amino-(C₁-C₄)-alkylgruppe, eine N,N-Di(aryl-(C₁-C₄)-alkyl)amino-(C₁-C₄)-alkylgruppe, eine (C₁-C₄)-Carboxyalkylgruppe, eine (C₁-C₄)-Alkoxycarbonyl-(C₁-C₃)-alkylgruppe, eine (C₁-C₄)-Acyloxy-(C₁-C₃)-alkylgruppe, eine Guanidino-(C₁-C₃)-alkylgruppe, eine Aminocarbonyl-(C₁-C₄)-alkylgruppe, eine N-(C₁-C₄)-Alkylaminocarbonyl-(C₁-C₄)-alkylgruppe, eine N,N-Di((C₁-C₄)-Alkyl)aminocarbonyl-(C₁-C₄)-alkylgruppe, eine N-(C₂-C₈)-Acylaminocarbonyl-(C₁-C₄)-alkylgruppe, eine N,N-(C₂-C₈)-Diacylaminocarbonyl-(C₁-C₄)-alkylgruppe, eine N-(C₂-C₈)-Acyl-N-(C₁-C₄)-alkylaminocarbonyl-(C₁-C₄)-alkylgruppe, eine N-(Aryl-(C₁-C₄)-alkyl)aminocarbonyl-(C₁-C₄)-alkylgruppe eine N-(Aryl-(C₁-C₄)-alkyl)-N-(C₁-C₆)-alkylaminocarbonyl-(C₁-C₄)-alkylgruppe oder eine N,N-Di(aryl-(C₁-C₄)-alkyl)aminocarbonyl-(C₁-C₄)-alkylgruppe,

und
(ii) eine Gesamtmenge von 0,1 bis 70 Gew.-% mindestens eines Tensids
und
(iii) Wasser.A first subject of the invention is therefore a liquid surfactant composition with yield point, in particular detergent, based on their total weight
(i) at least one 2,5-diketopiperazine compound of the formula (I)

wherein

R ¹ , R ² , R ³ and R ⁴

independently of one another 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, a 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, an an (C ₁ - C ₄ ) -hydroxyalkyl group, a (C ₁ -C ₄ ) -aminoalkyl group, a carboxy (C ₁ -C ₃ ) -alkyl group, wherein at least two of the radicals R ¹ to R ⁴ together with the remainder of the molecule 5 or 6-membered Can form a ring,

R ⁵

represents a hydrogen atom, a linear (C ₁ to C ₆ ) alkyl group, a branched (C ₃ to C ₁₀ ) 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, an aryloxy (C ₁ -C ₄ ) -alkyl group, an O- (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 hetroaryl ( 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 -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, an 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, (C ₁ -C ₄ ) carboxyalkyl group, (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) 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 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 ) -alk yl) 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
(ii) a total amount of from 0.1 to 70% by weight of at least one surfactant
and
(iii) water.

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 replacement of at least one directly to the aromatic ring system-binding hydrogen atom by at least one other than a hydrogen atom. As a non-hydrogen atom, all are preferably defined under the definitions of R ⁵ and R ¹ according to formula (I) Understood radicals other than a hydrogen atom, in particular a hydroxy group, an amino 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 (C ₁ -C ₃ ) alkyl group , a (C ₁ -C ₄ ) -hydroxyalkyl group, a (C ₁ -C ₄ ) -aminoalkyl group ,

An alkyl group (or an alkyl structure fragment of a more complex group) is understood according to the invention to mean a group selected from linear alkyl group of branched alkyl group or cyclic alkyl group (also: cycloalkyl group). 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, neo Pentyl, n-hexyl. Preferred branched (C ₃ -C ₁₀ ) -alkyl groups are selected from iso-propyl, sec-butyl, isobutyl, tert-butyl, neo-pentyl, iso-octyl, 2-ethylhexyl, 2-ethylheptyl. Preferred cyclic alkyl groups ((C ₃ -C ₆ ) -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, in particular 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, isopropoxy, n-butoxy, sec-butoxy, iso-butoxy, tert-butoxy. Preferred (C ₂ -C ₆ ) -acylamino groups are acetylamino, propanoylamino, butanoylamino, pentanoylamino and hexanoylamino, especially acetylamino.
Preferred (C ₂ -C ₆ ) -alkylaminocarbonyl groups are ethylaminocarbonyl (ie CH ₃ CH ₂ -NH-C (= O) -), propylaminocarbonyl, butanoylamino, pentanoylamino and hexanoylamino, in particular 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, these being 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, indol-3-yl-methyl, pyridylmethyl, these being substituted or unsubstituted.

Preferred liquid compositions of the invention contain, based on the total weight of the composition, 2,5-diketopiperazine compound according to formula (I) in a total amount of at least 0.01% by weight, in particular from 0.01 to 2.0% by weight. , It has again turned out to be particularly preferred if the compositions according to the invention (in each case based on the total weight of the composition) 2,5-diketopiperazine compound according to formula (I) in a total amount of at least 0.05 wt.%, In particular of at least 0.1 wt .-%, particularly preferably of at least 0.3 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 0.05 to 1.8 wt .-%, in particular from 0.1 to 1.5 wt. %, most preferably from 0.3 to 1.0% by weight, most preferably from 0.5 to 1.0% by weight.

All of the abovementioned amounts are preferably also based on the selected DKP compounds of the formula (I) which are identified below as being preferred.

worin R¹ und R⁵ wie unter Formel (I) (vide supra) definiert sind.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 contain at least one 2,5-diketopiperazine compound according to formula (Ia)

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

worin R¹ und R⁵ wie zuvor unter Formel (I) (vide supra) definiert sind. Die an den Ringatomen in Formel (I-b) positionierten Ziffern 3 und 6 markieren zur Veranschaulichung lediglich die Positionen 3 und 6 des Diketopiperazinringes, wie sie generell im Rahmen der Erfindung für die Namensgebung aller erfindungsgemäßen 2,5-Diketopiperazine genutzt werden.It has proved to be preferred if the radical R ¹ according to formula (I) and according to formula (Ia) binds in the para position of the phenyl ring. Therefore, for the purposes of the present invention, those compositions according to the invention which contain at least one 2,5-diketopiperazine compound according to formula (Ib) are preferred,

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 (Ib) for illustration only mark the positions 3 and 6 of the Diketopiperazine ring, as they are generally used in the context of the invention for the naming of all inventive 2,5-diketopiperazines.

Particularly preferred compounds of the formula (Ib) have the following radicals: R ¹ R ⁵ Hydrogen atom 2-carboxyethyl Hydrogen atom p-hydroxybenzyl hydroxy p-hydroxybenzyl Hydrogen atom 2- (benzyloxycarbonyl) ethyl Hydrogen atom 4-imidazolylmethyl Hydrogen atom methyl benzyloxy p- (benzyloxy) benzyl

• 3-Benzyl-6-iso-propyl-2,5-diketo-[3S, 6S]-piperazin,
• 3-Benzyl-6-(4-aminobutyl)-2,5-diketo-[3R, 6R]-piperazin
• 3,6-Di(benzyl)-2,5-diketo-[3S, 6S]-piperazin.

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, aryloxy, tosyloxy, triflyloxy, benzyloxy or benzoyloxy.

in der R' ein Wasserstoffatom, eine (C₁ bis C₄)-Alkylgruppe, eine (C₂ bis C₄)-Alkenylgruppe, eine Arylgruppe oder eine Aryl-(C₁ bis C₄)-alkylgruppe bedeutet,
eine Gruppe gemäß Formel (III),

in der R' ein Wasserstoffatom, eine (C₁ bis C₄)-Alkylgruppe, eine (C₂ bis C₄)-Alkenylgruppe, eine Arylgruppe oder eine Aryl-(C₁ bis C₄)-alkylgruppe bedeutet,
eine Gruppe gemäß Formel (IV),

in der n für 0 oder 1 steht, X für ein Sauerstoffatom oder eine Gruppe -NH- steht und R" ein Wasserstoffatom, eine (C₁-C₄)-Alkylgruppe, eine (C₂ bis C₄)-Alkenylgruppe, eine Arylgruppe oder eine Aryl-(C₁ bis C₄)-alkylgruppe bedeutet,
eine Gruppe gemäß Formel (V),

in der n für 1 oder 2 steht und R" und R'" unabhängig voneinander für ein Wasserstoffatom, eine (C₁-C₄)-Alkylgruppe, eine (C₂ - C₆)-Acylgruppe, eine Benzoylgruppe, eine Aryl-(C₁ bis C₄)-alkylgruppe, eine Aminoiminomethylgruppe oder eine Tosylgruppe stehen,
eine Gruppe gemäß Formel (VI),

in der n für 0 oder 1 steht und R ein Wasserstoffatom, eine Hydroxygruppe, eine (C₁-C₄)-Alkylgruppe, eine (C₁-C₄)-Alkoxygruppe, eine Aryl-(C₁ bis C₄)-alkylgruppe, eine Acetyloxygruppe, eine Benzoyloxygruppe, eine Triflyloxygruppe oder eine Tosyloxygruppe bedeutet.In addition, such compositions according to the invention have been found to be particularly suitable, which 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, hydroxymethyl group, (C ₁ -C ₃ ) alkoxymethyl group, benzyloxymethyl group, acetyloxymethyl group, benzoyloxymethyl group, tosyloxymethyl group, 1-hydroxyethyl group, 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),

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 (IV),

wherein n is 0 or 1, X is an oxygen atom or a group -NH-, and R "is a hydrogen atom, a (C ₁ -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 (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 -C ₄ ) -alkyl group C ₁ to C ₄ ) alkyl group, an aminoiminomethyl group or a tosyl group,
a group according to formula (VI),

wherein n is 0 or 1 and R is hydrogen, hydroxy, (C ₁ -C ₄ ) alkyl, (C ₁ -C ₄ ) alkoxy, aryl (C ₁ to C ₄ ) alkyl , 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, aminoiminomethyl or a tosyl group.

It is preferred that R of the formula (VI) is hydrogen, hydroxy, methyl, ethyl, n-propyl, iso-propyl, tert-butyl, phenyl, methoxy, acetyloxy, tosyloxy, a triflyloxy group, a benzyloxy group or a benzoyloxy group.

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 (I-b). The 2,5-diketopiperazine compound of the formula (I) of the compositions according to the invention is preferably based on the stereochemistry of the carbon atoms at the 3- and 6-position of the 2,5-diketopiperazine ring the configurational isomer 3S, 6S, 3R, 6S, 3S, 6R , 3R, 6R or mixtures thereof, more preferably 3S, 6S.

Very particularly preferred compositions according to the invention comprise 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-dioxopiperazine -2-yl) propanoic acid), 3-benzyl-6-carboxymethyl-2,5-diketopiperazine, 3-benzyl-6- (p -hydroxybenzyl) -2,5-diketopiperazine, 3-benzyl-6-iso-propyl 2,5-diketopiperazine, 3-benzyl-6- (4-aminobutyl) -2,5-diketopiperazine, 3,6-di (benzyl) -2,5-diketopiperazine, 3,6-di (p-hydroxybenzyl) - 2,5-diketopiperazine, 3,6-di (p- (benzyloxy) benzyl) -2,5-diketopiperazine, 3-benzyl-6- (4-imidazolyl) methyl-2,5-diketopiperazine, 3-benzyl-6 -methyl-2,5-diketopiperazine, 3-benzyl-6- (2- (benzyloxycarbonyl) ethyl) -2,5-diketopiperazine (also: benzyl 3- (5-benzyl-3,6-dioxopiperazin-2-yl) propanoate) ) or mixtures thereof. In turn, compounds with the aforementioned configuration isomers are preferably suitable for selection.

Most preferably, the compositions of the invention preferably contain at least one 2,5-diketopiperazine compound of formula (I) selected from 3-benzyl-6-methylpiperazine-2,5-dione, 3- (4-aminobutyl) -6-benzylpiperazine-2 , 5-dione, 3- (1H-imidazol-4-yl) methyl) -6-benzyl-piperazine-2,5-dione, benzyl 3- (5-benzyl-3,6-dioxopiperazin-2-yl) -propanoate 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.

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

• 10 bis 70 Gew.-% oder 12 bis 70 Gew.-% oder 15 bis 70 Gew.-% oder 20 bis 70 Gew.-% oder 5 bis 65 Gew.-% oder 10 bis 65 Gew.-% oder 12 bis 65 Gew.-% oder 15 bis 65 Gew.-% oder 20 bis 65 Gew.-% oder 5 bis 60 Gew.-% oder 10 bis 60 Gew.-% oder 12 bis 60 Gew.-% oder 15 bis 60 Gew.-% oder 20 bis 60 Gew.-% oder 5 bis 55 Gew.-% oder 10 bis 55 Gew.-% oder 12 bis 55 Gew.-% oder 15 bis 55 Gew.-% oder 20 bis 55 Gew.-%.

The surfactant composition according to the invention contains a total amount of from 0.1 to 70% by weight of at least one surfactant. It is preferred according to the invention if the total weight of the surfactant composition is from 5 to 70% by weight, preferably from 10 to 65% by weight, more preferably from 12 to 60% by weight, very particularly preferably from 15 to 60 Wt .-%, most preferably from 20 to 55 wt .-%, of at least one surfactant. The following total amount of total surfactants of the inventive surfactant composition are also particularly preferred:

• 10 to 70% by weight or 12 to 70% by weight or 15 to 70% by weight or 20 to 70% by weight or 5 to 65% by weight or 10 to 65% by weight or 12 to 65% by weight or 15 to 65% by weight or 20 to 65% by weight or 5 to 60% by weight or 10 to 60% by weight or 12 to 60% by weight or 15 to 60% by weight % or 20 to 60 wt.% or 5 to 55 wt.% or 10 to 55 wt.% or 12 to 55 wt.% or 15 to 55 wt.% or 20 to 55 wt. %.

The surfactant composition of the invention preferably contains at least one anionic surfactant. It is preferred that the anionic surfactant is selected from the group consisting of C _8-18 alkylbenzenesulfonates, C _8-18 olefin sulfonates, C _12-18 alkanesulfonates, C _8-18 ester sulfonates, C _8-18 alkyl sulfates, C _8-18 alkenyl sulfates, fatty alcohol ether sulfates and mixtures thereof. Most preferably, the anionic surfactant is selected from at least one C _8-18 alkyl benzene sulfonate.

It has been found that these sulfonate and sulfate surfactants are particularly suitable for the preparation of stable liquid washing detergents with yield point.

worin

R¹

für einen linearen oder verzweigten, substituierten oder unsubstituierten Rest, ausgewählt aus C_8-18-Alkyl-, Aryl- oder C_8-18-Alkylarylresten und die Gruppierung -A- für eine chemische Bindung oder einen Rest -(OZ)_n-O- steht, worin OZ für eine Ethylenoxid- (EO) oder Propylenoxid- (PO) Gruppierung und n für eine ganze Zahl von 1 bis 50, vorzugsweise von 1 bis 20 und insbesondere von 2 bis 10, ganz besonders bevorzugt 2, 3, 4, 5, 6, 7 oder 8,

Y⁺

für ein einwertiges Kation oder den n-ten Teil eines n-wertigen Kations, steht.

It is preferred according to the invention if the surfactant composition contains at least one anionic surfactant of the formula (T1)

wherein

R ¹

for a linear or branched, substituted or unsubstituted radical selected from C _8-18 alkyl, aryl or C _8-18 alkylaryl radicals and the grouping -A- for a chemical bond or a radical - (OZ) _n -O in which OZ is an ethylene oxide (EO) or propylene oxide (PO) grouping and n is an integer from 1 to 50, preferably from 1 to 20 and in particular from 2 to 10, very particularly preferably 2, 3, 4 , 5, 6, 7 or 8,

Y ⁺

is a monovalent cation or the nth part of an n-valent cation.

• wobei OZ für eine Ethylenoxid- (EO) oder Propylenoxid- (PO) Gruppierung und n für eine ganze Zahl von 1 bis 50, vorzugsweise von 1 bis 20 und insbesondere von 2 bis 10, ganz besonders bevorzugt 2, 3, 4, 5, 6, 7 oder 8, steht,

und R¹ gemäß Formel (T1) für einen linearen oder verzweigten, substituierten oder unsubstituierten Alkylrest steht. Es ergeben sich daraus Alkylethersulfate mit der Formel (T1-1) R'-(OZ)_n-O-SO₃- Y⁺ (T1-1). It has been found to be suitable according to the invention if said surfactant composition contains at least one such surfactant of the above formula (I), wherein A of the formula (T1) for the structural unit - (OZ) _n -O-,

• where OZ is an ethylene oxide (EO) or propylene oxide (PO) grouping and n is an integer from 1 to 50, preferably from 1 to 20 and in particular from 2 to 10, very particularly preferably 2, 3, 4, 5, 6, 7 or 8, stands,

and R ¹ according to formula (T1) is a linear or branched, substituted or unsubstituted alkyl radical. This results in alkyl ether sulfates of the formula (T1-1) R '- (OZ) _n -O-SO ₃ - Y ⁺ (T1-1).

In this formula (T1-1), R ^{1 is} a linear or branched, substituted or unsubstituted alkyl radical, preferably a linear, unsubstituted alkyl radical, more preferably a fatty alcohol radical. Preferred radicals R ¹ are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl radicals and mixtures thereof, where the representatives with an even number of carbon atoms Atoms are preferred. Particularly preferred radicals R ¹ are derived from C ₁₂ -C ₁₈ -fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or C ₁₀ -C ₁₈ -oxo alcohols. Y ⁺ is defined as before in formula (T1).

OZ is according to formula (T1-1) an ethylene oxide (EO) or propylene oxide (PO) grouping, preferably an ethylene oxide grouping. The index n is according to formula (1-1) an integer from 1 to 50, preferably from 1 to 20 and in particular from 2 to 10. Most preferably, n stands for the numbers 2, 3, 4, 5, 6, 7 or 8. Y ⁺ is according to formula (T1-1) a monovalent cation or the nth part of an n-valent cation, preference being given to the alkali metal ions and including Na ⁺ or K ⁺ , with Na ^{+ being} extremely preferred. Other cations Y ⁺ may be selected from NH ₄ ⁺ , ½Zn ²⁺ , ½Mg ²⁺ , ½Ca ²⁺ , ½Mn ²⁺ , and mixtures thereof.

mit k = 11 bis 19, n = 2, 3, 4, 5, 6, 7 oder 8. Ganz besonders bevorzugte Vertreter sind Na-C_12-14 Fettalkoholethersulfate mit 2 EO (k = 11-13, n = 2 in Formel A-1). Der angegebenen Ethoxylierungsgrad stellt einen statistischen Mittelwert dar, der für ein spezielles Produkt eine ganze oder eine gebrochene Zahl sein kann. Die angegebenen Alkoxylierungsgrade stellen statistische Mittelwerte dar, die für ein spezielles Produkt eine ganze oder eine gebrochene Zahl sein können. Bevorzugte Alkoxylate/Ethoxylate weisen eine eingeengte Homologenverteilung auf (narrow range ethoxylates, NRE).Detergents or cleaning agents may contain as compound of the formula (I) or as the compound of the formula (T1-1) at least one alkyl ether sulfate selected from fatty alcohol ether sulfates of the formula (T1-2)

with k = 11 to 19, n = 2, 3, 4, 5, 6, 7 or 8. Very particularly preferred representatives are Na-C _12-14 fatty alcohol _ether sulfates with 2 EO (k = 11-13, n = 2 in formula A-1). The stated degree of ethoxylation represents a statistical average that may be an integer or a fractional number for a particular product. The indicated degrees of alkoxylation represent statistical averages, which may be an integer or a fractional number for a particular product. Preferred alkoxylates / ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).

in der
R' und R" unabhängig H oder Alkyl sind und zusammen 9 bis 19, vorzugsweise 9 bis 15 und insbesondere 9 bis 13 C-Atome enthalten, und Y⁺ ein einwertiges Kation oder den n-ten Teil eines n-wertigen Kations (insbesondere Na⁺) bedeuten (ausgehend von Formel (T1): -A- = chemische Bindung, R¹ = lineares oder verzweigtes Alkylaryl, Y⁺ = Na⁺). Ein ganz besonders bevorzugter Vertreter lässt sich durch die Formel (T1-3a) beschreiben:

It is particularly preferred according to the invention if the surfactant compositions according to the invention comprise as anionic surfactant of the formula (T1) at least one compound of the formula (T1-3)

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 ⁺ ) (starting from formula (T1): -A- = chemical bond, R ¹ = linear or branched alkylaryl, Y ⁺ = Na ⁺ ). A particularly preferred representative can be described by the formula (T1-3a):

• - mindestens einem Fettalkoholethersulfat der Formel (T1-1) R¹-(OZ)_n-O-SO₃ ^- Y*⁺ (T1-1). worin R¹ steht für einen linearen oder verzweigten (C₈-C₁₈)-Alkylrest, OZ steht für eine Ethylenoxid- (EO) oder eine Propylenoxid- (PO) Gruppierung, n steht für eine ganze Zahl von 1 bis 50, vorzugsweise von 1 bis 20 und insbesondere von 2 bis 10, und Y*⁺ steht für ein einwertiges Kation oder den n-ten Teil eines n-wertigen Kations,

und

• - mindestens einem linearen oder verzweigten Alkylbenzolsulfonat der Formel A-4
  
  in der R' und R" zusammen 9 bis 19, vorzugsweise 11 bis 15 und insbesondere 11 bis 13 C-Atome enthalten und Y⁺ für ein einwertiges Kation oder den n-ten Teil eines n-wertigen Kations (insbesondere für Na⁺) steht,

enthalten.The detergents or cleaners according to the invention preferably contain as surfactant of the formula (T1) a combination of

• at least one fatty alcohol ether sulfate of the formula (T1-1) R ¹ - (OZ) _n -O-SO ₃ ^- Y ⁺ (T1-1). wherein R ¹ is a linear or branched (C ₈ -C ₁₈ ) alkyl radical, OZ is an ethylene oxide (EO) or a propylene oxide (PO) grouping, n is an integer from 1 to 50, preferably from 1 to 20 and in particular from 2 to 10, and Y * ⁺ stands for a monovalent cation or the n-th part of an n-valent cation,

and

• at least one linear or branched alkylbenzenesulfonate of the formula A-4
  
  in which R 'and R "together contain 9 to 19, preferably 11 to 15 and in particular 11 to 13 C atoms and Y ^{+ stands} for a monovalent cation or the n-th part of an n-valent cation (especially for Na ⁺ ) .

contain.

The liquid washing or cleaning agent may also contain soaps as anionic surfactant. 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.

When the surfactant composition of the present invention contains anionic surfactant, it is again preferable that, based on the total weight of the composition, anionic surfactant is contained in a total amount of 6 to 70% by weight, more preferably 10 to 50% by weight, more preferably 15 to 40% by weight .-%, is included.

The surfactant composition according to the invention may contain as surfactant preferably at least one nonionic surfactant. In a particularly preferred embodiment, the surfactant composition according to the invention additionally contains at least one nonionic surfactant in addition to at least one anionic surfactant. Suitable additional nonionic surfactants include alkoxylated fatty acid alkyl esters, alkoxylated fatty acid amides, hydroxylated alkyl glycol ethers, polyhydroxy fatty acid amides, alkylphenol polyglycol ethers, amine oxides, alkyl (poly) glucosides, and mixtures thereof.

R²

für einen linearen oder verzweigten C₈-C₁₈-Alkylrest, einen Arylrest oder Alkylarylrest,

XO

unabhängig voneinander für eine Ethylenoxid- (EO) oder Propylenoxid- (PO) Gruppierung,

m

für ganze Zahlen von 1 bis 50 stehen.

The agent according to the invention particularly preferably contains as nonionic surfactant at least one compound of the formula (T2) R ^{2 is} -O- (XO) _m -H, (T2) in the

R ²

a linear or branched C ₈ -C ₁₈ -alkyl radical, an aryl radical or alkylaryl radical,

XO

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

m

stand for integers from 1 to 50.

Particularly preferred radicals R ^{2 of} the formula (T2) are derived from C ₁₂ -C ₁₈ -fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or C ₈ -C ₁₈ -oxo alcohols.

XO is preferably an ethylene oxide group according to formula (T2).

The index m is according to formula (T2) preferably for a number from 1 to 20 and in particular from 2 to 10. Very particularly preferably m stands for the numbers 2, 3, 4, 5, 6, 7 or 8.

The nonionic surfactant used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 4 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical may be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten. In particular, however, alcohol ethoxylates with linear radicals of alcohols of native origin having 12 to 18 carbon atoms, for example coconut, palm, tallow or oleyl alcohol, and on average 4 to 8 EO per mole of alcohol are preferred. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 4 EO or 7 EO, C _9-11 alcohols with 7 EO, C _13-15 alcohols with 5 EO, 7 EO or 8 EO, C _12-18 Alcohols with 5 EO or 7 EO and mixtures of these. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to or instead of these preferred nonionic surfactants, fatty alcohols containing more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO. Nonionic surfactants containing EO and PO groups together in the molecule can also be used according to the invention. Also suitable are also a mixture of a (more) branched ethoxylated fatty alcohol and an unbranched ethoxylated fatty alcohol, such as a mixture of a C _16-18 fatty alcohol with 7 EO and 2-propylheptanol with 7 EO. Most preferably, the surfactant composition according to the invention contains a C _12-18 fatty alcohol with 7 EO or a C _13-15 oxo alcohol with 7 EO as nonionic surfactant.

As amine oxide, in principle all amine oxides established for this purpose in the prior art are compounds which have the formula R ¹ R ² R ³ NO, where each of R ¹ , R ² and R ^{3 is} independently of the others an optionally substituted C ₁ -C ₃₀ hydrocarbon chain is used. Particularly preferably used amine oxides are those in which R ^{1 is} C ₁₂ -C ₁₈ alkyl and R ² and R ^{3 are} each independently C ₁ -C ₄ alkyl, in particular C ₁₂ -C ₁₈ alkyl dimethyl amine oxides. Exemplary representatives of suitable amine oxides are N-cocoalkyl-N, N-dimethylamine oxide, N-tallowalkyl-N, N-dihydroxyethylamine oxide, myristyl / cetyldimethylamine oxide or lauryldimethylamine oxide.

It is inventively preferred if the surfactant compositions of the invention based on the total weight of nonionic surfactant in a total amount between 0 and 35 wt .-% and preferably from 5 to 30 wt .-%, most preferably from 7 to 28 wt .-%, respectively based on the total mean.

The surfactant composition according to the invention contains water as a further obligatory constituent. Particularly preferred liquid detergents contain - based on their weight - water in a total amount of 5 to 90 wt .-%, preferably 10 to 85 wt .-%, particularly preferably 25 to 75 wt .-% and in particular 35 to 65 wt. %. Alternatively, the detergents may be low-water detergents, the total amount of water in a preferred embodiment being between 0 and 25% by weight, in particular between 1 and 20% by weight and particularly preferably between 2 and 18% by weight. , in each case based on the total liquid surfactant composition.

It is very particularly preferred according to the invention that the yield strength of the surfactant compositions according to the invention is in the range from 0.01 to 60 Pa, preferably from 0.1 to 30 Pa, more preferably from 1 to 15 Pa (rotational rheometer from TA Instruments, type AR G2, 20 ° C).

In addition, nonaqueous solvents may additionally be added to the surfactant composition according to the invention. Preferred surfactant compositions in this context are characterized in that they additionally contain 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 (C ₂ -C ₈ ) -alkanols having at least one Hydroxy 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 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 preferable that the surfactant composition of the present invention contains said organic solvent (especially its preferred agent) in a total amount of 0 to 20% by weight, especially 0.5 to 20% by weight.

It is further preferred if the surfactant composition contains a (C ₂ -C ₆ ) -alcohol having at least one hydroxyl group (in particular ethanol and / or glycerol) in amounts of between 0.5 and 5% by weight, based on the total composition.

In the context of a preferred embodiment according to the invention, the surfactant composition according to the invention additionally contains suspended solid particles (also referred to below as particles). Solid particles suspended as such are solid substances which do not dissolve in the liquid phase of the surfactant composition according to the invention at 20 ° C. and are present as a separate phase.

The 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 X _50.3 (volume average) of 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 microns have. 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).

A semipermeable capsule wall in the context of the present invention is a capsule wall which is semipermeable, ie continuously releases small amounts of the capsule core over time, without the capsule having been damaged or opened by friction, for example. Capsules of this type continuously release small amounts of the active ingredient contained in the capsule, eg perfume, over a relatively long period of time.

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 significant amounts of the at least one perfume in the capsule core, so that a very intense fragrance is provided when damaged or when the capsule is opened. 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 surfactant composition according to the invention contains both microcapsules with a semipermeable shell, and thus also microcapsules with an 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.

Suitable materials for the shell of the microcapsules are usually high molecular weight compounds such as protein compounds such as gelatin, albumin, casein and others, cellulose derivatives such as methylcellulose, ethylcellulose, cellulose acetate, cellulose nitrate, carboxymethylcellulose and others and especially also synthetic polymers such as polyamides, polyethylene glycols, polyurethanes, epoxy resins and others. Preferably serves as a wall material, ie as shell, melamine-formaldehyde polymer, melamine-urea polymer, melamine-urea-formaldehyde polymer, polyacrylate polymer or polyacrylate copolymer. Capsules according to the invention are used, for example, but not exclusively US 2003/0125222 A1 . DE 10 2008 051 799 A1 or WO 01/49817 described.

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 other ingredients, such as at least one fragrance, in Presence of a protective colloid condensed. 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-11, 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, Polyquaterni um-86th Very particular preference is given to polyquaternium-7. The polyquaternium nomenclature of 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.

Preference for use microcapsules have average diameter X _50.3 in the range of 1 to 100 .mu.m, preferably from 5 to 95 .mu.m, in particular from 10 to 90 .mu.m, for example from 10 to 80 microns.

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, e.g. Fish silver (guanine / hypoxanthine mixed crystals from fish scales) or mother-of-pearl (from ground mussel shells), monocrystalline platelet-shaped pearlescent pigments, e.g. Bismuth oxychloride and perglaze pigments based on mica and 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. To produce the pearlescent pigments in conjunction with metal oxides, the mica, predominantly muscovite or phlogopite, is coated with a metal oxide. Suitable metal oxides include TiO ₂ , Cr ₂ O ₃ and Fe ₂ O ₃ . By appropriate coating, interference pigments and color luster pigments are obtained as pearlescent pigments according to the invention. 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 particle size of the pearlescent pigments preferably used is preferably at an average diameter X _50.3 (volume average) between 1.0 and 100 μm, more preferably between 10.0 and 60.0 μm.

For the purposes of the invention, speckles are macroparticles, in particular macrocapsules, which have an average diameter X _50.3 (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 producing alginate-based speckles an aqueous alginate solution, which optionally additionally contains the entrapped active ingredient or active ingredients to be entrapped, and then dripped in a Ca ²⁺ or Al ³⁺ ions is cured containing precipitation bath. Alternatively, other, matrix-forming materials can be used instead of alginate.

The surfactant compositions according to the invention may additionally contain further ingredients which further improve the performance and / or aesthetic properties of the composition depending on the intended use. In the context of the present invention, the compositions according to the invention, in particular if they are suitable as textile treatment agents (for example as detergents or softeners), builders, bleaches, bleach activators, bleach catalysts, esterquats, silicone oils, emulsifiers, thickeners, electrolytes, pH adjusters, fluorescers, dyes , Hydrotropes, foam inhibitors, anti redeposition agents, solvents, enzymes, optical brighteners, grayness inhibitors, anti-shrinkage agents, anti-crease agents, color transfer inhibitors, color protectants, wetting improvers, antimicrobial agents, germicides, fungicides, antioxidants, corrosion inhibitors, Preservatives, antistatic agents, ironing aids, repellents and impregnating agents, polymers, swelling and anti-slip agents and UV absorbers.

A surfactant composition suitable as a textile treatment or cleaning agent preferably contains at least one water-soluble, organic and / or water-soluble, inorganic builder. The water-soluble organic builder substances include polycarboxylic acids, in particular citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid and sugar acids, monomeric and polymeric aminopolycarboxylic acids, in particular methylglycinediacetic acid, nitrilotriacetic acid and ethylenediaminetetraacetic acid and polyaspartic acid, polyphosphonic acids, in particular aminotris (methylenephosphonic acid), ethylenediamine tetrakis (Methylenephosphonic) and 1-hydroxyethane-1,1-diphosphonic acid, polymeric hydroxy compounds such as dextrin and polymeric (poly) carboxylic acids, polymeric acrylic acids, methacrylic acids, maleic acids and copolymers of these, which may also contain copolymerized small amounts of polymerizable substances without carboxylic acid functionality. Suitable, although less preferred, compounds of this class are copolymers of acrylic or methacrylic acid with vinyl ethers, such as vinylmethyl ethers, vinyl esters, ethylene, propylene and styrene, in which the acid content is at least 50% by weight. The organic builder substances can be used, in particular for the preparation of liquid textile treatment or cleaning agents, in the form of aqueous solutions, preferably in the form of 30 to 50 percent by weight aqueous solutions. All of the acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali metal salts.

Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof.

Organic builders may, if desired, be included in amounts of up to 40% by weight, more preferably up to 25% by weight, and preferably from 1% to 8% by weight. Quantities close to the stated upper limit are preferably used in paste-form or liquid, in particular hydrous, compositions according to the invention. Aftertreatment agents, such as e.g. Softener, may optionally also be free of organic builder.

A composition suitable for use according to the invention as a textile treatment or cleaning agent preferably contains at least one enzyme. Suitable enzymes include those from the class of proteases, cutinases, amylases, pullulanases, hemicellulases, cellulases, lipases, oxidases and peroxidases and mixtures thereof. Particularly suitable are from fungi or bacteria, such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus, Humicola lanuginosa, Humicola insolens, Pseudomonas pseudoalcaligenes or Pseudomonas cepacia derived enzymatic agents. The optionally used enzymes may be adsorbed to carriers and / or embedded in encapsulants to protect against premature inactivation. They are, if desired, in the compositions preferably in amounts not exceeding 5 wt .-%, in particular from 0.2 wt .-% to 2 wt .-%, contained.

An optical brightener is preferably selected from the substance classes of distyrylbiphenyls, stilbenes, 4,4'-diamino-2,2'-stilbenedisulfonic acids, coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, naphthalimides, 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) (obtainable, for example, 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.

In addition, the compositions according to the invention which are suitable as textile treatment or cleaning compositions may also contain components which have a positive influence on the oil and grease washability from textiles, so-called soil release active ingredients. This effect becomes particularly clear when a textile is soiled, which has been previously washed several times with an agent containing this oil and fat dissolving component. Examples of preferred oil and fat dissolving components include nonionic cellulose ethers such as methylcellulose and methylhydroxypropylcellulose with a proportion of methoxyl Groups of 15 to 30 wt .-% and of hydroxypropoxyl groups from 1 to 15 wt .-%, each based on the nonionic cellulose ether, and known from the prior art polymers of phthalic acid and / or terephthalic acid or of their Derivatives with monomeric and / or polymeric diols, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionic modified derivatives thereof.

The textile treatment or cleaning agents may also color transfer inhibitors, preferably in amounts of 0.1 wt .-% to 2 wt .-%, in particular 0.1 wt .-% to 1 wt .-%, containing, in a preferred embodiment of the invention polymers of vinylpyrrolidone , Vinylimidazole, vinylpyridine N-oxide or copolymers thereof.

Graying inhibitors have the task of keeping suspended from the textile fiber dirt suspended in the fleet. Water-soluble colloids of mostly organic nature are suitable for this purpose, for example starch, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or of cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Also, water-soluble polyamides containing acidic groups are suitable for this purpose. Furthermore, other than the above-mentioned starch derivatives can be used, for example aldehyde starches. Preference is given to using cellulose ethers, such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose and mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof, for example in amounts of from 0.1 to 5% by weight, based on the compositions.

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

In particular, low-moisture, liquid compositions according to the invention may be present in pre-portioned form, the composition according to the invention being filled into a water-soluble casing and thus being able to form part of a water-soluble packaging. When the composition of the invention is packaged in a water-soluble casing, it is preferred that the content of water is between 5 and 20% by weight based on the total agent, and that anionic surfactants, if present, are in the form of their ammonium salts.

In a second aspect of the invention, the present invention relates to the use of at least one said DKP compound of the formula (I) (vide supra) for the preparation of liquid, aqueous surfactant compositions, in particular detergents or cleaning agents, having a yield point.

In a third aspect of the invention, the present invention relates to the use of a said surfactant composition as a continuous phase to provide a suspension.

1. (a) Bereitstellen einer wässrigen Flotte durch Mischen von 0,5 Liter bis 40,0 Liter Wasser mit 0,5 bis 100 g einer Tensidzusammensetzung des ersten Erfindungsgegenstandes, und
2. (b) In Kontakt bringen eines Substrats, insbesondere eines Textils oder Geschirr, mit der gemäß (a) hergestellten wässrigen Flotte.

In still another subject of the invention, the invention is directed to a process for substrate treatment comprising the process steps

1. (A) providing an aqueous liquor by mixing from 0.5 liter to 40.0 liters of water with 0.5 to 100 g of a surfactant composition of the first subject of the invention, and
2. (B) bringing into contact a substrate, in particular a textile or dishes, with the aqueous liquor prepared according to (a).

Preferred methods are those in which the substrate is a fabric.

It is preferred if in step (b) the substrate is in contact with the aqueous liquor prepared according to (a) for 10 to 240 minutes, in particular 20 to 180 minutes.

Further, it is preferable that the substrate is rinsed and dried after step (b).

It is particularly preferred to carry out the process in an automatic washing machine. In this case, prior to step (a), the substrate is placed in the drum of the washing machine. The surfactant composition of the first subject of the invention is filled in the dispensing compartment of the washing machine or placed in a container, which is then placed together with the substrate in the drum of the washing machine.

It is inventively preferred if 10 to 110 g, in particular 15 to 100 g of the surfactant composition of the first subject of the invention with 5 to 25 l of water, in particular with 10 to 20 l of water are mixed for the preparation of said solution.

In the described methods, in various embodiments of the invention, temperatures of 60 ° C or less, for example 50 ° C or less, are employed. These temperature data refer to the temperatures used in step (b).

worin R¹ bis R⁵ wie im ersten Erfindungsgegenstand beschrieben definiert sind,
in Gegenwart von Wasser und 0,1 bis 70 Gew.-% Tensid sowie gegebenenfalls optionalen Zusatzstoffen bei einer Temperatur über der Sol-Gel-Übergangstemperatur der flüssigen Zusammensetzung homogenisiert wird, und anschließend die erwärmte flüssige Zusammensetzung unter die Sol-Gel-Übergangstemperatur abgekühlt wird.A further subject of the invention relates to a process for the preparation of a liquid surfactant composition with yield point, characterized in that first a liquid composition containing at least one 2,5-diketopiperazine compound of the formula (I),

wherein R ¹ to R ^{5 are defined} as described in the first subject of the invention,
in the presence of water and 0.1 to 70 wt .-% of surfactant and optionally optional additives at a temperature above the sol-gel transition temperature of the liquid composition is homogenized, and then the heated liquid composition is cooled below the sol-gel transition temperature ,

The surfactant composition can also be first preheated to said temperature without the DKP compound of the formula (I) and cooled after addition of the DKP compound of the formula (I). In the context of this embodiment, it is preferred if, for the production of said liquid surfactant composition, a liquid premix containing water and based on the weight of said liquid surfactant composition 0.1 to 70 wt .-% of surfactant and optionally optional additives to a temperature of 10 to 150 ° C is brought and at least one 2,5-diketopiperazine compound of the formula (I) is added.

It is further preferred if, for the preparation of the liquid surfactant composition according to the invention, a liquid first premix containing at least one liquid and optionally surfactant and optionally optional additives is brought to a temperature of 50 to 150 ° C and at least one 2,5-diketopiperazine compound of Formula (I) is added and dissolved with stirring and then this still tempered liquid first premix in a at a temperature of 10 to 35 ° C located second premix containing water and surfactant, is mixed.

In the preparation of surfactant compositions according to the invention, anionic surfactants can initially be presented in their acid form in an aqueous medium, and then the pH is increased by addition of alkalizing agents (preferably alkanolamines, such as monoethanolamine) to release neutralization heat and the anionic surfactants are converted into the salt form , The resulting heat of neutralization is preferred for increasing the temperature for the heating of the system used via the sol-gel transition temperature. Preferred processes are thus characterized by the fact that the heat released when the pH is increased is used to increase the temperature.

The sol-gel transition temperature can be determined in advance by known methods. For example, this can be done via a rheological measurement with oscillating deformation constant frequency as a function of temperature. In such a measurement, when the sol-gel transition temperature is exceeded, a collapse of the modulus of the sample is observed. Likewise, the sol-gel transition can often be visually recognized by the naked eye.

1. 1. Flüssige Tensidzusammensetzung mit Fließgrenze, insbesondere Waschmittel, enthaltend bezogen auf deren Gesamtgewicht
   1. (i) mindestens eine 2,5-Diketopiperazin-Verbindung der Formel (I)
      
      worin

      R¹, R², R³ und R⁴

      stehen unabhängig voneinander für ein Wasserstoffatom, eine Hydroxygruppe, eine (C₁-C₆)-Alkylgruppe, eine (C₂-C₆)-Alkenylgruppe, eine (C₂-C₆)-Acylgruppe, eine (C₂-C₆)-Acyloxygruppe, eine (C₁-C₆)-Alkoxygruppe, eine Aminogruppe, eine (C₂-C₆)-Acylaminogruppe, eine (C₁-C₆)-Alkylaminocarbonylgruppe, eine Arylgruppe, eine Aroylgruppe, eine Aroyloxygruppe, eine Aryloxygruppe, eine Aryl-(C₁-C₄)-alkyloxygruppe, eine Aryl-(C₁-C₃)-alkylgruppe, eine Heteroarylgruppe, eine Hetroaryl-(C₁-C₃)-alkylgruppe, eine (C₁-C₄)-Hydroxyalkylgruppe, eine (C₁-C₄)-Aminoalkylgruppe, eine Carboxy-(C₁-C₃)-alkylgruppe, wobei mindestens zwei der Reste R¹ bis R⁴ gemeinsam mit dem Restmolekül einen 5 oder 6-gliedrigen Ring bilden können,

      R⁵

      steht für ein Wasserstoffatom, eine lineare (C₁ bis C₆)-Alkylgruppe, eine verzweigte (C₃ bis C₁₀)-Alkylgruppe, eine (C₃ bis C₆)-Cycloalkylgruppe, eine (C₂-C₆)-Alkenylgruppe, eine (C₂-C₆)-Alkinylgruppe, eine (C₁-C₄)-Hydroxyalkylgruppe, eine (C₁-C₄)-Alkoxy-(C₁-C₄)-alkylgruppe, eine (C₁-C₄)-Acyloxy-(C₁-C₄)-alkylgruppe, eine Aryloxy-(C₁-C₄)-alkylgruppe, eine O-(Aryl-(C₁-C₄)-alkyl)oxy-(C₁-C₄)-alkylgruppe, eine (C₁-C₄)-Alkylsulfanyl-(C₁-C₄)-alkylgruppe, eine Arylgruppe, eine Aryl-(C₁-C₃)-alkylgruppe, eine Heteroarylgruppe, eine Hetroaryl-(C₁-C₃)-alkylgruppe, eine (C₁-C₄)-Hydroxyalkylgruppe, eine (C₁-C₄)-Aminoalkylgruppe, eine N-(C₁-C₄)-Alkylamino-(C₁-C₄)-alkylgruppe, eine N,N-(C₁-C₄)-Dialkylamino-(C₁-C₄)-alkylgruppe, eine N-(C₂-C₈)-Acylamino-(C₁-C₄)-alkylgruppe, eine N-(C₂-C₈)-Acyl-N-(C₁-C₄)-alkylamino-(C₁-C₄)-alkylgruppe, eine N-(C₂-C₈)-Aroyl-N-(C₁-C₄)-alkylamino-(C₁-C₄)-alkylgruppe, eine N,N-(C₂-C₈)-Diacylamino-(C₁-C₄)-alkylgruppe, eine N-(Aryl-(C₁-C₄)-alkyl)amino-(C₁-C₄)-alkylgruppe, eine N,N-Di(aryl-(C₁-C₄)-alkyl)amino-(C₁-C₄)-alkylgruppe, eine (C₁-C₄)-Carboxyalkylgruppe, eine (C₁-C₄)-Alkoxycarbonyl-(C₁-C₃)-alkylgruppe, eine (C₁-C₄)-Acyloxy-(C₁-C₃)-alkylgruppe, eine Guanidino-(C₁-C₃)-alkylgruppe, eine Aminocarbonyl-(C₁-C₄)-alkylgruppe, eine N-(C₁-C₄)-Alkylaminocarbonyl-(C₁-C₄)-alkylgruppe, eine N,N-Di((C₁-C₄)-Alkyl)aminocarbonyl-(C₁-C₄)-alkylgruppe, eine N-(C₂-C₈)-Acylaminocarbonyl-(C₁-C₄)-alkylgruppe, eine N,N-(C₂-C₈)-Diacylaminocarbonyl-(C₁-C₄)-alkylgruppe, eine N-(C₂-C₈)-Acyl-N-(C₁-C₄)-alkylaminocarbonyl-(C₁-C₄)-alkylgruppe, eine N-(Aryl-(C₁-C₄)-alkyl)aminocarbonyl-(C₁-C₄)-alkylgruppe eine N-(Aryl-(C₁-C₄)-alkyl)-N-(C₁-C₆)-alkylaminocarbonyl-(C₁-C₄)-alkylgruppe oder eine N,N-Di(aryl-(C₁-C₄)-alkyl)aminocarbonyl-(C₁-C₄)-alkylgruppe,

      und
   2. (ii) eine Gesamtmenge von 0,1 bis 70 Gew.-% mindestens eines Tensids und
   3. (iii) Wasser.
2. 2. Zusammensetzung nach Punkt 1, dadurch gekennzeichnet, dass bezogen auf das Gesamtgewicht der Zusammensetzung 2,5-Diketopiperazin-Verbindung gemäß Formel (I) in einer Gesamtmenge von 0,01 bis 2,0 Gew.-%, insbesondere von 0,05 bis 1,8 Gew.-%, insbesondere von 0,1 bis 1,5 Gew.-%, ganz besonders bevorzugt von 0,3 bis 1,0 Gew.-%, am bevorzugtesten von 0,5 bis 1,0 Gew.-% enthalten ist.
3. 3. Zusammensetzung nach Punkt 1 oder 2, dadurch gekennzeichnet, dass gemäß Formel (I) R¹ in para-Position des Phenylringes bindet und bevorzugt R² bis R⁴ für Wasserstoff stehen.
4. 4. Zusammensetzung nach einem der vorangehenden Punkte, dadurch gekennzeichnet, dass gemäß Formel (I) die Reste R¹, R², R³ und R⁴ unabhängig voneinander stehen für ein Wasserstoffatom, eine Hydroxygruppe, eine Methylgruppe, eine Ethylgruppe, eine iso-Propylgruppe, eine n-Propylgruppe, eine n-Butylgruppe, eine iso-Butylgruppe, eine sec-Butylgruppe, eine tert-Butylgruppe, eine Phenylgruppe, eine Benzylgruppe, eine Methoxygruppe, eine (C₂-C₆)-Acyloxygruppe, eine Aryloxygruppe, eine Tosyloxygruppe, eine Triflyloxygruppe, eine Benzyloxygruppe oder eine Benzoyloxygruppe.
5. 5. Zusammensetzung einem der vorangehenden Punkte, dadurch gekennzeichnet, dass gemäß Formel (I) R⁵ steht für ein Wasserstoffatom, eine Methylgruppe, eine Isopropylgruppe, eine iso-Butylgruppe, eine tert-Butylgruppe, eine 2-(Methylsulfanyl)ethyl-Gruppe, eine Hydroxymethylgruppe, eine (C₁-C₃)-Alkoxymethylgruppe, eine Benzyloxymethylgruppe, eine Acetyloxymethylgruppe, eine Benzoyloxymethylgruppe, eine Tosyloxymethylgruppe, eine 1-Hydroxyethylgruppe, eine 1-((C₁-C₃)-Alkoxy)ethylgruppe, eine 1-(Acetyloxy)ethylgruppe, eine 1-(Benzoyloxy)ethylgruppe, eine 1-(Tosyloxy)ethylgruppe, eine Mercaptomethylgruppe, eine (C₁-C₃)-Alkylsulfanylmethylgruppe, eine Acetylsulfanylmethylgruppe, eine Benzoylsulfanylmethylgruppe, eine Tosylsulfanylmethylgruppe, eine Gruppe gemäß Formel (II),
   
   in der R' ein Wasserstoffatom, eine (C₁ bis C₄)-Alkylgruppe, eine (C₂ bis C₄)-Alkenylgruppe, eine Arylgruppe oder eine Aryl-(C₁ bis C₄)-alkylgruppe bedeutet, eine Gruppe gemäß Formel (III),
   
   in der R' ein Wasserstoffatom, eine (C₁ bis C₄)-Alkylgruppe, eine (C₂ bis C₄)-Alkenylgruppe, eine Arylgruppe oder eine Aryl-(C₁ bis C₄)-alkylgruppe bedeutet, eine Gruppe gemäß Formel (IV),
   
   in der n für 0 oder 1 steht, X für ein Sauerstoffatom oder eine Gruppe -NH- steht und R" ein Wasserstoffatom, eine (C₁-C₄)-Alkylgruppe, eine (C₂ bis C₄)-Alkenylgruppe, eine Arylgruppe oder eine Aryl-(C₁ bis C₄)-alkylgruppe bedeutet, eine Gruppe gemäß Formel (V),
   
   in der n für 1 oder 2 steht und R" und R'" unabhängig voneinander für ein Wasserstoffatom, eine (C₁-C₄)-Alkylgruppe, eine (C₂ - C₆)-Acylgruppe, eine Benzoylgruppe, eine Aryl-(C₁ bis C₄)-alkylgruppe, eine Aminoiminomethylgruppe oder eine Tosylgruppe stehen, eine Gruppe gemäß Formel (VI),
   
   in der n für 0 oder 1 steht und R ein Wasserstoffatom, eine Hydroxygruppe, eine (C₁-C₄)-Alkylgruppe, eine (C₁-C₄)-Alkoxygruppe, eine Aryl-(C₁ bis C₄)-alkylgruppe, eine Acetyloxygruppe, eine Benzoyloxygruppe, eine Triflyloxygruppe oder eine Tosyloxygruppe bedeutet.
6. 6. Zusammensetzung nach Punkt 5, dadurch gekennzeichnet, dass R' gemäß Formel (II) für ein Wasserstoffatom, eine Methylgruppe, eine Ethylgruppe, eine iso-Propylgruppe, eine n-Propylgruppe, eine Allylgruppe, eine Benzylgruppe oder eine Phenylgruppe steht.
7. 7. Zusammensetzung nach einem der Punkte 5 oder 6, dadurch gekennzeichnet, dass R' gemäß Formel (III) für ein Wasserstoffatom, eine Methylgruppe, eine Ethylgruppe, eine iso-Propylgruppe, eine Benzylgruppe, eine Benzoyloxygruppe oder eine Phenylgruppe steht.
8. 8. Zusammensetzung nach einem der Punkte 5 bis 7, dadurch gekennzeichnet, dass R' gemäß Formel (IV) für ein Wasserstoffatom, eine Methylgruppe, eine Ethylgruppe, eine iso-Propylgruppe, eine Benzylgruppe, eine Benzoyloxygruppe oder eine Phenylgruppe steht.
9. 9. Zusammensetzung nach einem der Punkte 5 bis 8, dadurch gekennzeichnet, dass R" und R'" gemäß Formel (V) unabhängig voneinander stehen für ein Wasserstoffatom, eine Methylgruppe, eine Ethylgruppe, eine n-Propylgruppe, eine iso-Propylgruppe, eine Benzylgruppe, eine Benzoylgruppe, Acetylgruppe, eine Aminoiminomethylgruppe oder eine Tosylgruppe.
10. 10. Zusammensetzung nach einem der Punkte 5 bis 9, dadurch gekennzeichnet, dass R gemäß Formel (VI) ein Wasserstoffatom, eine Hydroxygruppe, eine Methylgruppe, eine Ethylgruppe, eine n-Propylgruppe, eine iso-Propylgruppe, eine tert-Butylgruppe, eine Phenylgruppe, eine Methoxygruppe, eine Acetyloxygruppe, eine Tosyloxygruppe, eine Triflyloxygruppe, eine Benzyloxygruppe oder eine Benzoyloxygruppe bedeutet.
11. 11. Zusammensetzung nach einem der vorangehenden Punkte, dadurch gekennzeichnet, dass die 2,5-Diketopiperazin-Verbindung der Formel (I) bezogen auf die Stereochemie der Kohlenstoffatome an 3- und 6-Position des 2,5-Diketopiperazinringes das Konfigurationsisomere 3S,6S , 3R,6S , 3S,6R , 3R,6R oder Mischungen daraus (bevorzugt 3S, 6S) ist.
12. 12. Zusammensetzung nach einem der Punkte 1 bis 11, dadurch gekennzeichnet, dass die 2,5-Diketopiperazin-Verbindung der Formel (I) ausgewählt wird aus 3-Benzyl-6-carboxyethyl-2,5-diketopiperazin, 3-Benzyl-6-carboxymethyl-2,5-diketopiperazin, 3-Benzyl-6-(p-hydroxybenzyl)-2,5-diketopiperazin, 3-Benzyl-6-iso-propyl-2,5-diketopiperazin, 3-Benzyl-6-(4-aminobutyl)-2,5-diketopiperazin, 3,6-Di(benzyl)-2,5-diketopiperazin, 3,6-Di(p-hydroxybenzyl)-2,5-diketopiperazin, 3,6-Di(p-(Benzyloxy)benzyl)-2,5-diketopiperazin, 3-Benzyl-6-(4-imidazolyl)methyl-2,5-diketopiperazin, 3-Benzyl-6-methyl-2,5-diketopiperazin, 3-Benzyl-6-(2-(benzyloxycarbonyl)ethyl)-2,5-diketopiperazin oder Mischungen daraus.
13. 13. Zusammensetzung nach einem der vorangehenden Punkte, dadurch gekennzeichnet, dass sie mindestens ein anionisches Tensid enthält.
14. 14. Zusammensetzung nach einem der vorangehenden Punkte, dadurch gekennzeichnet, dass mindestens ein anionisches Tensid, ausgewählt aus der Gruppe bestehend aus C_8-18-Alkylbenzolsulfonaten, C_8-18-Olefinsulfonaten, C_12-18-Alkansulfonaten, C_8-18-Estersulfonaten, C_8-18-Alkylsulfaten, C_8-18-Alkenylsulfaten, Fettalkoholethersulfaten und Mischungen daraus, enthalten ist.
15. 15. Zusammensetzung nach einem der vorangehenden Punkte, dadurch gekennzeichnet, dass als Tensid mindestens eine Verbindung der Formel (T1-3) enthalten ist,
    
    in der R' und R" unabhängig H oder Alkyl sind und zusammen 9 bis 19, vorzugsweise 9 bis 15 und insbesondere 9 bis 13 C-Atome enthalten, und Y⁺ ein einwertiges Kation oder den n-ten Teil eines n-wertigen Kations (insbesondere Na⁺) bedeuten.
16. 16. Zusammensetzung nach einem der vorangehenden Punkte, dadurch gekennzeichnet, dass sie mindestens ein nichtionisches Tensid enthalten.
17. 17. Zusammensetzung nach einem der vorangehenden Punkte, dadurch gekennzeichnet, dass mindestens ein nichtionisches Tensid der Formel (T2) enthalten ist R²-O-(XO)m-H, (T2) in der

    R²

    für einen linearen oder verzweigten C₈-C₁₈-Alkylrest, einen Arylrest oder Alkylarylrest,

    XO

    unabhängig voneinander für eine Ethylenoxid- (EO) oder Propylenoxid- (PO) Gruppierung,

    m

    für ganze Zahlen von 1 bis 50 stehen.

18. 18. Zusammensetzung nach einem der vorangehenden Punkte, dadurch gekennzeichnet, dass Tensid in einer Gesamtmenge von 5 bis 70 Gew.-%, bevorzugt von 10 bis 65 Gew.-%, besonders bevorzugt von 12 bis 60 Gew.-%, ganz besonders bevorzugt von 15 bis 60 Gew.-%, am bevorzugtesten von 20 bis 55 Gew.-%, enthalten ist.
19. 19. Zusammensetzung nach einem der vorangehenden Ansprüche, dadurch gekennzeichnet, dass Wasser in einer Gesamtmenge von 5 bis 90 Gew.-%, bevorzugt 10 bis 85 Gew.-%, besonders bevorzugt 25 bis 75 Gew.-% und insbesondere 35 bis 65 Gew.-%, enthalten ist.
20. 20. Zusammensetzung nach einem der vorangehenden Punkte, dadurch gekennzeichnet, dass Wasser in einer Gesamtmenge zwischen 1 und 20 Gew.-%, bevorzugt zwischen 2 und 18 Gew.-%, enthalten ist.
21. 21. Zusammensetzung nach einem der vorangehenden Punkte, dadurch gekennzeichnet, dass sie zusätzlich mindestens ein organisches Lösemittel mit mindestens einer Hydroxygruppe, ohne Aminogruppe und mit einem Molekulargewicht von höchstens 500 g/mol enthält (bevorzugt ausgewählt aus (C₂-C₈)-Alkanolen mit mindestens einer Hydroxygruppe (besonders bevorzugt Ethanol, Ethylenglycol,1,2-Propandiol, Glycerin, 1,3-Propandiol, n-Propanol, Isopropanol, 1,1,1-Trimethylolpropan, 2-Methyl-1,3-propandiol, 2-Hydroxymethyl-1,3-propandiol), Triethylenglycol, Butyldiglycol, Polyethylenglycolen mit einer gewichtsmittleren Molmasse M_w von höchstens 500 g/mol, Glycerincarbonat, Propylencarbonat, 1-Methoxy-2-propanol, 3-Methoxy-3-methyl-1-butanol, Butyllactat, 2-Isobutyl-2-methyl-4-hydroxymethyl-1,3-dioxolan, 2,2-Dimethyl-4-hydroxymethyl-1,3-dioxolan, Dipropylenglycol, oder Mischungen daraus).
22. 22. Zusammensetzung nach Punkt 21, dadurch gekennzeichnet, dass besagtes organisches Lösemittel in einer Gesamtmenge von 0 bis 20 Gew.-%, insbesondere von 0,5 bis 20 Gew.-%, enthalten ist.
23. 23. Zusammensetzung nach einem der vorangehenden Punkte, dadurch gekennzeichnet, dass sie eine Fließgrenze im Bereich von 0,01 bis 60 Pa, bevorzugt von 0,1 bis 30 Pa, besonders bevorzugt von 1 bis 15 Pa, liegt (Rotationsrheometer der Firma TA-Instruments, Typ AR G2, 20°C).
24. 24. Zusammensetzung nach einem der vorangehenden Punkte, dadurch gekennzeichnet, dass sie zusätzlich suspendierte Feststoffpartikel enthält
25. 25. Verfahren zur Substratbehandlung umfassend die Verfahrensschritte
    1. (a) Bereitstellen einer wässrigen Flotte durch Mischen von 0,5 L bis 40,0 L Wasser mit 0,5 bis 100 g einer Zusammensetzung gemäß einem der Punkte 1 bis 24, und
    2. (b) In Kontakt bringen eines Substrats, insbesondere eines Textils oder Geschirr, mit der gemäß (a) hergestellten wässrigen Flotte.
26. 26. Verfahren zu Herstellung einer flüssigen Tensidzusammensetzung mit Fließgrenze, dadurch gekennzeichnet, dass zunächst eine flüssige Zusammensetzung, enthaltend mindestens eine 2,5-Diketopiperazin-Verbindung der Formel (I),
    
    worin R¹ bis R⁵ wie in einem der Punkte 1, 3 bis 10 definiert sind, in Gegenwart von Wasser und 0,1 bis 70 Gew.-% Tensid sowie gegebenenfalls optionalen Zusatzstoffen bei einer Temperatur über der Sol-Gel-Übergangstemperatur der flüssigen Zusammensetzung homogenisiert wird, und anschließend die erwärmte flüssige Zusammensetzung unter die Sol-Gel-Übergangstemperatur abgekühlt wird.
27. 27. Verfahren nach Punkt 26, dadurch gekennzeichnet, dass zur Herstellung der besagten flüssigen Zusammensetzung eine flüssige Vormischung, enthaltend Wasser und 0,1 bis 70 Gew.-% Tensid und gegebenenfalls optionalen Zusatzstoffen auf eine Temperatur von 10 bis 150°C gebracht wird und mindestens eine 2,5-Diketopiperazin-Verbindung der Formel (I) zugesetzt wird.
28. 28. Verfahren nach Punkt 26 oder 27, dadurch gekennzeichnet, dass zur Temperaturerhöhung die bei der Erhöhung des pH-Wertes freigesetzte Wärme genutzt wird.
29. 29. Verbindung der Formel (I-b)
    
    worin R¹ und R⁵ definiert sind:

R¹ R⁵ Wasserstoffatom 2-Carboxyethyl Wasserstoffatom p-Hydroxybenzyl Hydroxygruppe p-Hydroxybenzyl Wasserstoffatom 2-(Benzyloxycarbonyl)ethyl Wasserstoffatom 4-Imidazolylmethyl Wasserstoffatom Methyl Benzyloxy p-(Benzyloxy)-benzyl

• 30. 3-Benzyl-6-iso-propyl-2,5-diketo-[3S, 6S]-piperazin
• 31. 3-Benzyl-6-(4-aminobutyl)-2,5-diketo-[3R,6R]-piperazin
• 32. 3,6-Di(benzyl)-2,5-diketo-[3S,6S]-piperazin

Particularly preferred embodiments of the invention are characterized by the following points:

1. 1. Liquid surfactant composition with yield point, in particular detergent, containing based on their total weight
   1. (i) at least one 2,5-diketopiperazine compound of the formula (I)
      
      wherein

      R ¹ , R ² , R ³ and R ⁴

      independently of one another 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, a Aryloxy group, an aryl (C ₁ -C ₄ ) alkyloxy group, an aryl (C ₁ -C ₃ ) alkyl group, a heteroaryl group, a hetroaryl (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 form a 5 or 6-membered ring can form

      R ⁵

      represents a hydrogen atom, a linear (C ₁ to C ₆ ) alkyl group, a branched (C ₃ to C ₁₀ ) 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, an aryloxy (C ₁ -C ₄ ) -alkyl group, an O- (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 hetroaryl ( 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 -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, an 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 (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) 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, 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
   2. (ii) a total amount of 0.1 to 70% by weight of at least one surfactant and
   3. (iii) water.
2. 2. Composition according to item 1, characterized in that based on the total weight of the composition of 2,5-diketopiperazine compound according to formula (I) in a total amount of 0.01 to 2.0 wt .-%, in particular of 0.05 to 1.8% by weight, in particular from 0.1 to 1.5% by weight, very particularly preferably from 0.3 to 1.0% by weight, most preferably from 0.5 to 1.0% by weight .-% is included.
3. 3. Composition according to item 1 or 2, 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.
4. 4. Composition according to one of the preceding points, characterized in that according to formula (I) the radicals R ¹ , R ² , R ³ and R ^{4 are} independently of one another a hydrogen atom, a hydroxy group, a methyl group, an ethyl group, an iso Propyl, n-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, phenyl, benzyl, methoxy, (C ₂ -C ₆ ) acyloxy, aryloxy, a tosyloxy group, a triflyloxy group, a benzyloxy group or a benzoyloxy group.
5. 5. Composition according to one of the preceding points, 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, a 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 of the 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 of the formula (III)
   
   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 of the formula (IV),
   
   wherein n is 0 or 1, X is an oxygen atom or a group -NH-, and R "is a hydrogen atom, a (C ₁ -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 (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 -C ₄ ) -alkyl group C ₁ to C ₄ ) alkyl group, an aminoiminomethyl group or a tosyl group, a group according to formula (VI),
   
   wherein n is 0 or 1 and R is hydrogen, hydroxy, (C ₁ -C ₄ ) alkyl, (C ₁ -C ₄ ) alkoxy, aryl (C ₁ to C ₄ ) alkyl , an acetyloxy group, a benzoyloxy group, a triflyloxy group or a tosyloxy group.
6. 6. The composition according to item 5, 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.
7. 7. Composition according to one of the items 5 or 6, 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.
8. 8. The composition according to any one of items 5 to 7, 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 Benzoyloxygruppe or a phenyl group.
9. 9. A composition according to any one of items 5 to 8, characterized in that R "and R '" according to formula (V) independently of one another 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.
10. 10. The composition according to any one of items 5 to 9, 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 represents a methoxy group, an acetyloxy group, a tosyloxy group, a triflyloxy group, a benzyloxy group or a benzoyloxy group.
11. 11. Composition according to one of the preceding points, characterized in that the 2,5-diketopiperazine compound of formula (I) based on the stereochemistry of the carbon atoms at 3- and 6-position of the 2,5-Diketopiperazinringes the configurational isomer 3S, 6S , 3R, 6S, 3S, 6R, 3R, 6R or mixtures thereof (preferably 3S, 6S).
12. 12. The composition according to any one of items 1 to 11, characterized in that the 2,5-diketopiperazine compound of the formula (I) is selected from 3-benzyl-6-carboxyethyl-2,5-diketopiperazine, 3-benzyl-6 carboxymethyl-2,5-diketopiperazine, 3-benzyl-6- (p -hydroxybenzyl) -2,5-diketopiperazine, 3-benzyl-6-isopropyl-2,5-diketopiperazine, 3-benzyl-6-one 4-aminobutyl) -2,5-diketopiperazine, 3,6-di (benzyl) -2,5-diketopiperazine, 3,6-di (p-hydroxybenzyl) -2,5-diketopiperazine, 3,6-di (p - (benzyloxy) benzyl) -2,5-diketopiperazine, 3-benzyl-6- (4-imidazolyl) methyl-2,5-diketopiperazine, 3-benzyl-6-methyl-2,5-diketopiperazine, 3-benzyl 6- (2- (benzyloxycarbonyl) ethyl) -2,5-diketopiperazine or mixtures thereof.
13. 13. Composition according to one of the preceding points, characterized in that it contains at least one anionic surfactant.
14. 14. The composition according to one of the preceding points, characterized in that at least one anionic surfactant selected from the group consisting of C _8-18 -alkylbenzenesulfonates, C _8-18 -Olefinsulfonaten, C _12-18 -alkanesulfonates, C _8-18 - Ester sulfonates, C _8-18 alkyl sulfates, C _8-18 alkenyl sulfates, fatty alcohol ether sulfates and mixtures thereof.
15. 15. Composition according to one of the preceding points, characterized in that the surfactant is at least one compound of the formula (T1-3),
    
    in which R 'and R "are independently H or alkyl and together contain 9 to 19, preferably 9 to 15 and in particular 9 to 13 C atoms, and Y ⁺ a monovalent cation or the n-th part of an n-valent cation ( especially Na ⁺ ).
16. 16. Composition according to one of the preceding points, characterized in that they contain at least one nonionic surfactant.
17. 17. Composition according to one of the preceding points, characterized in that at least one nonionic surfactant of the formula (T2) is contained R ² -O- (XO) m H, (T2) in the

    R ²

    a linear or branched C ₈ -C ₁₈ -alkyl radical, an aryl radical or alkylaryl radical,

    XO

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

    m

    stand for integers from 1 to 50.

18. 18. Composition according to one of the preceding points, characterized in that surfactant in a total amount of 5 to 70 wt .-%, preferably from 10 to 65 wt .-%, particularly preferably from 12 to 60 wt .-%, most preferably from 15 to 60% by weight, most preferably from 20 to 55% by weight.
19. 19. The composition according to any one of the preceding claims, characterized in that water in a total amount of 5 to 90 wt .-%, preferably 10 to 85 wt .-%, particularly preferably 25 to 75 wt .-% and in particular 35 to 65 wt .-%, is included.
20. 20. The composition according to any one of the preceding points, characterized in that water in a total amount between 1 and 20 wt .-%, preferably between 2 and 18 wt .-%, is included.
21. 21. The composition according to any 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 (C ₂ -C ₈ ) -alkanols with at least one hydroxy 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 having a weight-average molecular weight M _w of at most 500 g / mol, glycerol carbonate, propylene carbonate, 1-methoxy-2-ol 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).
22. 22. The composition according to item 21, characterized in that said organic solvent in a total amount of 0 to 20 wt .-%, in particular from 0.5 to 20 wt .-%, is included.
23. 23. Composition according to one of the preceding points, characterized in that it has a yield point in the range from 0.01 to 60 Pa, preferably from 0.1 to 30 Pa, particularly preferably from 1 to 15 Pa (rotational rheometer of the TA-Company). Instruments, type AR G2, 20 ° C).
24. 24. Composition according to one of the preceding points, characterized in that it additionally contains suspended solid particles
25. 25. A process for substrate treatment comprising the process steps
    1. (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 24, and
    2. (B) bringing into contact a substrate, in particular a textile or dishes, with the aqueous liquor prepared according to (a).
26. 26. A process for the preparation of a liquid surfactant composition having a yield point, which comprises first of all a liquid composition comprising at least one 2,5-diketopiperazine compound of the formula (I)
    
    wherein R ¹ to R ^{5 are} as defined in any one of items 1, 3 to 10, in the presence of water and 0.1 to 70 wt .-% of surfactant and optionally optional additives at a temperature above the sol-gel transition temperature of the liquid Homogenizing the composition and then cooling the heated liquid composition below the sol-gel transition temperature.
27. 27. The method according to item 26, characterized in that for the preparation of said liquid composition, a liquid premix containing water and 0.1 to 70 wt .-% of surfactant and optionally optional additives is brought to a temperature of 10 to 150 ° C and at least one 2,5-diketopiperazine compound of the formula (I) is added.
28. 28. The method according to item 26 or 27, characterized in that the temperature increase, the heat released in the increase of the pH is used.
29. 29. Compound of formula (Ib)
    
    wherein R ¹ and R ^{5 are} defined:

R ¹ R ⁵ Hydrogen atom 2-carboxyethyl Hydrogen atom p-hydroxybenzyl hydroxy p-hydroxybenzyl Hydrogen atom 2- (benzyloxycarbonyl) ethyl Hydrogen atom 4-imidazolylmethyl Hydrogen atom methyl benzyloxy p- (benzyloxy) benzyl

• 30. 3-Benzyl-6-iso-propyl-2,5-diketo [3S, 6S] -piperazine
• 31. 3-Benzyl-6- (4-aminobutyl) -2,5-diketo [3R, 6R] -piperazine
• 32. 3,6-Di (benzyl) -2,5-diketo [3S, 6S] piperazine

Examples

Synthesis of 2,5-diketopiperazine compounds

General Synthesis Instructions

Materials:

Unless otherwise indicated, all reactions were performed at room temperature and laboratory conditions. 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 δ (parts per million) relative to the signal of d ₆ -DMSO (at 2.50 ppm (quin)). Chemical shifts for ¹³ C NMR spectra are reported as δ (parts per million) relative to the d ₆ -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 cm ^-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 Suzuki et al., Chem. Pharm. Bull. 1981, 29 (1), 233-237 ,

The N-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 NEt ₃ (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 NaHCO ₃ solution (2x) and the combined aqueous phases were extracted with CH ₂ Cl ₂ (3x). The combined organic phases were dried over anhydrous Na ₂ SO ₄ and the solvent removed under reduced pressure. Purification by flash column chromatography (SiO ₂ ) 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 volatiles were removed under reduced pressure and the residue was coevaporated with toluene to remove residual TFA (5x). 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 NEt ₃ (2.0 eq) 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 (3 ×) 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.

Characterization:

1. a) (3S, 6S) -3-Benzyl-6-methylpiperazine-2,5-dione (DKP 1):
   • Mp .: 267 - 269 ° C decomposition. ¹ H-NMR (360 MHz, DMSO-d ₆ ): δ = 8.13 (s, 1H), 8.03 (s, 1H), 7.33-7.18 (m, 3H), 7.18 - 7.10 (m, 2H), 4.17 ( s, 1H), 3.67 - 3.56 (m, 1H), 3.12 (dd, J = 13.4, 3.7 Hz, 1H), 2.85 (dd, J = 13.4, 4.9 Hz, 1H), 0.45 (d, J = 7.0 Hz , 3H) ppm. ¹³ C { ¹ H} NMR (91 MHz, DMSO-d ₆ ): δ = 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): ṽ = 3184 (w), 3033 (w), 2979 (w), 2889 (w), 1663 (s), 1484 (m), 1466 (s), 1455 (s), 1371 (w), 1338 (s), 1242 (w), 1211 (w), 1191 (w), 1160 (w), 1104 (m), 1054 (m), 969 (w), 923 (w), 856 (s), 777 (m), 752 (m), 696 (s) cm ^-1 . HR-MS (ESI): calculated for C ₁₂ H ₁₄ N ₂ O ₂ Na [M + Na] ⁺ : m / z = 241.09475, found: 241.09485 (Ex: 0.10 mmu; 0.43 ppm).
2. b) (3S, 6S) -3-Benzyl-6-isopropylpiperazine-2,5-dione (DKP 2):
   • Mp: 262-264 ° C decomposition. ¹ H-NMR (360 MHz, DMSO-d ₆ ): δ = 8.13 (s, 1H), 7.92 (s, 1H), 7.28 - 7.12 (m, 5H), 4.21 (s, 1H), 3.53 (s, 1H), 3.15 (dd, J = 13.4, 4.0 Hz, 1H), 2.86 (dd, J = 13.5, 4.7 Hz, 1H), 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} NMR (91 MHz, DMSO-d ₆ ): δ = 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): ṽ = 3186 (w), 3047 (w), 2966 (w), 2886 (w), 1661 (s), 1452 (s), 1374 (w), 1344 (m), 1252 (w), 1215 (w), 1175 (w), 1107 (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 ₁₄ H ₁₈ N ₂ O ₂ Na [M + Na] ^+: m / z = 269.12605, found: 269.12624 (Dev .: 0:19 mmu; 0.72 ppm).
3. c) (3S, 6S) -3,6-Dibenzylpiperazine-2,5-dione (DKP 3):
   • Mp .: 298-300 ° C decomposition. ¹ H-NMR (360 MHz, DMSO-d ₆ ): δ = 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-d ₆ ): δ = 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): ṽ = 3197 (w), 3054 (w), 2927 (w), 1660 (s), 1497 (w), 1460 (w), 1338 (m), 1268 (w), 1212 (w), 1194 (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 C ₁₈ H ₁₈ N ₂ O ₂ Na [M + Na] ^+: m / z = 317.12605, found: 317.12621 (Dev .: 0:16 mmu; 00:50 ppm).
4. 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-d ₆ ): δ = 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-d ₆ ): δ = 166.3, 166.2, 156.1, 136.7, 130.9 (2x), 129.8 (2x), 128.2 (2x), 126.5, 126.5, 115.1 (2x), 55.7, 55.4, 38.6 ppm. IR (ATR, neat): ṽ = 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 C ₁₈ H ₁₈ N ₂ O ₃ Na [M + Na] ^+: m / z = 333.12096, found: 333.12102 (Dev .: 0:06 mmu; 00:16 ppm).
5. e) (3S, 6S) -3- (4-aminobutyl) -6-benzylpiperazine-2,5-dione (DKP 5):
   • Mp: 199 - 201 ° C decomposition. ¹ H-NMR (360 MHz, DMSO-d ₆ ): δ = 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 (brs 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} NMR (91 MHz, DMSO-d ₆ ): δ = 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): ṽ = 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 C ₁₅ H ₂₂ N ₃ O ₂ [M + H] ^+: m / z = 276.17065, found: 276.17088 (Dev .: 0:23 mmu; 0.81 ppm).
6. f) (3S, 6S) -3 - ((1H-imidazol-4-yl) methyl) -6-benzylpiperazine-2,5-dione (DKP 6):
   • Mp .: 244-246 ° C decomposition. ¹ H-NMR (360 MHz, DMSO-d ₆ ): δ = 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-d ₆ ): δ = 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): ṽ = 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 C ₁₅ H ₁₇ N ₄ O ₂ [M + H] ^+: m / z = 285.13460, found: 285.13493 (Dev .: 0:33 mmu; 15.1 ppm).
7. 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-d ₆ ): 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} NRM (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): ṽ = 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 ₂₁ H ₂₂ N ₂ O ₄ Na [M + Na] ^+: m / z = 389.14718, found: 389.14730 (Dev .: 0:12 mmu; 00:32 ppm).
8. 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-d ₆ ): δ = 11.91 (br.s, 1H), 8.20 (d, J = 2.1 Hz, 1H), 8.09 (d, J = 2.3 Hz, 1H), 7.31 - 7.20 (m, 2H), 7.22 - 7.11 (m, 3H), 4.22 - 4.15 (m, 1H), 3.72 - 3.64 (m, 1H), 3.14 (dd, J = 13.4, 3.8 Hz, 1H), 2.84 (dd, J = 13.4, 4.9Hz, 1H), 1.75 - 1.57 (m, 2H), 1.33 - 1.17 (m, 1H), 1.11 - 0.99 (m, 1H) 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): ṽ = 3150 (br), 3030 (w), 2981 (w), 2886 (w), 2361 (w), 1736 (s), 1664 (s), 1470 (m), 1454 (m), 1409 (m), 1335 (m), 1321 (m), 1311 (m), 1272 (m), 1175 (s), 1098 (m), 904 (m), 855 (s), 820 (s), 777 (m), 750 (m), 699 (s), 682 (m) cm ^-1 . HR-MS (ESI): calculated for C ₁₄ H ₁₆ N ₂ O ₄ Na [M + Na] ^+: m / z = 299.10023, found: 299.10028 (Dev .: 0:05 mmu; 00:17 ppm).
9. 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-d ₆ ): δ = 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-d ₆ ): δ = 166.3 (2x), 157.2 (2x), 137.2 (2x), 130.9 (4x), 128.7 (2x), 128.4 (4x), 127.7 (2x), 127.5 (4x), 114.6 (4x), 69.1 (2x), 55.6 (2x), 38.5 (2x) ppm. IR (ATR, neat): ṽ = 3179 (w), 3030 (w), 2881 (w), 2852 (w), 1660 (s), 1611 (m), 1508 (s), 1463 (s), 1453 (s), 1376 (w), 1340 (m), 1310 (m), 1297 (m), 1237 (s), 1225 (s), 1174 (s), 1110 (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): calculated for C ₃₂ H ₃₀ N ₂ O ₄ Na [M + Na] ⁺ : m / z = 529.20978, found: 529.20998 (Ex: 0.20 mmu, 0.37 ppm).
10. 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-d ₆ ): δ = 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), 115.1 (4x), 55.8 (2x), 38.9 (2x) ppm. IR (ATR, neat): ṽ = 3516 (w), 3145 (w), 1665 (s), 1614 (m), 1598 (m), 1515 (s), 1456 (s), 1378 (w), 1337 (m), 1308 (w), 1272 (m), 1237 (s), 1173 (m), 1104 (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 ₁₈ H ₁₈ N ₂ O ₄ Na [M + Na] ^+: m / z = 349.11588, found: 349.11579 (-0.09 mmu .: Dev; -0.26 ppm).

Preparation of Liquid Surfactant Surfactant Compositions

The following framework surfactant composition having yield value was prepared according to Table 1 (vide infra). For this purpose, a range of 2,5-diketopiperazine compounds according to Table 2 (vide infra) in the amount indicated therein was mixed together with the remaining ingredients of F1 as follows.

Overall, four compositions E1 to E4 according to the invention (compare Table 2 in conjunction with Table 1) were thus prepared. TABLE 1 Surfactant composition Chemical name F1% by weight of active substance C _10-13 -alkylbenzenesulfonic acid 7.20 C _12-18 fatty alcohol ether sulfate with 2 moles of ethylene oxide 3.90 C _13-15 alkyl ethers with 7 moles of ethylene oxide 6.90 at the 2-position branched C _13-15 alkyl alcohol ethoxylated with 8 moles of ethylene oxide - Phosphonate (sodium DTPMP) 0.65 Citric acid monohydrate 3.20 NaOH (50% by weight solution in water) 6.20 C _12-18 coconut fatty acid 2.90 1,2-propanediol 5.60 ethanol 2.10 a 2,5-diketopiperazine compound according to Table 2 see. Table 2 Enzymes (protease, amylase, cellulase, lipase, mannanase) 0.40 boric acid 0.60 perfume oil 1.20 Further additives (preservative, defoamer, optical brightener, dye) 9.30 water ad 100 Table 2: used in F1 2,5-diketopiperazine compound (DKP) with amount in wt .-% of active substance based on the weight of the composition F1 of Table 1 resulting composition according to the invention Chemical name DKP to F1 [% by weight] E1 (DKP 1) 0.8 E2 (DKP 5) 1.0 E3 (DKP 6) 2.0 E4 (DKP 7) 1.0

All compositions E1 to E4 had yield value. It could be incorporated stably into all compositions E1 to E4 Speckles.

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• WO 2002/40627 [0006]
• WO 2005/012475 [0007]
• WO 2015/200062 [0008]
• US 2003/0125222 Al [0071]
• DE 102008051799 A1 [0071]
• WO 0149817 [0071]

Cited non-patent literature

• Suzuki et al., Chem. Pharm. Bull. 1981, 29 (1), 233-237 [0036, 0116]

Claims (15)

Liquid surfactant composition with yield value, in particular detergent, containing, based on the total weight thereof, (i) at least one 2,5-diketopiperazine compound of the formula (I)

wherein R ¹ , R ² , R ³ and R ⁴ are each independently hydrogen, hydroxy, (C ₁ -C ₆ ) alkyl, (C ₂ -C ₆ ) alkenyl, (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 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, wherein at least two of the radicals R ¹ to R ^{4 can} form a 5 or 6-membered ring together with the remainder of the molecule, R ⁵ stands for a hydrogen atom, a linear (C ₁ to C ₆ ) -alkyl group, a branched (C ₃ to C ₁₀ ) -alkyl group, a (C ₃ to C ₆ ) -cycloalkyl group, a (C ₂ -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, an aryloxy (C ₁ -C ₄ ) -alkyl group, an O- (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 hetroaryl (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 -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, an 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 ) - alkylgrup pe, 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) 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 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 (ii) a total of from 0.1 to 70% by weight of at least one surfactant and (iii) water. Composition after Claim 1 , characterized in that based on the total weight of the composition 2,5-diketopiperazine compound of the formula (I) in a total amount of 0.01 to 2.0 wt .-%, in particular from 0.05 to 1.8 wt. %, in particular from 0.1 to 1.5% by weight, very particularly preferably from 0.3 to 1.0% by weight, most preferably from 0.5 to 1.0% by weight. Composition after Claim 1 or 2 , 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 preceding claims, characterized in that according to formula (I) the radicals R ¹ , R ² , R ³ and R ^{4 are} independently of one another a hydrogen atom, a hydroxy group, a methyl group, an ethyl group, an iso-propyl group, n-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, phenyl, benzyl, methoxy, (C ₂ -C ₆ ) acyloxy, aryloxy, tosyloxy , a triflyloxy group, a benzyloxy group or a benzoyloxy group. Composition according to one of the preceding claims, 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 (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),

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 of the formula (III)

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 of the formula (IV),

wherein n is 0 or 1, X is an oxygen atom or a group -NH-, and R "is a hydrogen atom, a (C ₁ -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 (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 -C ₄ ) -alkyl group C ₁ to C ₄ ) alkyl group, an aminoiminomethyl group or a tosyl group, a group according to formula (VI),

wherein n is 0 or 1 and R is hydrogen, hydroxy, (C ₁ -C ₄ ) alkyl, (C ₁ -C ₄ ) alkoxy, aryl (C ₁ to C ₄ ) alkyl , an acetyloxy group, a benzoyloxy group, a triflyloxy group or a tosyloxy group. Composition according to one of Claims 1 to 5 characterized in that the 2,5-diketopiperazine compound of formula (I) is selected from 3-benzyl-6-carboxyethyl-2,5-diketopiperazine, 3-benzyl-6-carboxymethyl-2,5-diketopiperazine, 3 -Benzyl-6- (p -hydroxybenzyl) -2,5-diketopiperazine, 3-Benzyl-6-iso-propyl-2,5-diketopiperazine, 3-Benzyl-6- (4-aminobutyl) -2,5-diketopiperazine , 3,6-di (benzyl) -2,5-diketopiperazine, 3,6-di (p -hydroxybenzyl) -2,5-diketopiperazine, 3,6-di (p- (benzyloxy) benzyl) -2,5 diketopiperazine, 3-benzyl-6- (4-imidazolyl) methyl-2,5-diketopiperazine, 3-benzyl-6-methyl-2,5-diketopiperazine, 3-benzyl-6- (2- (benzyloxycarbonyl) -ethyl) 2,5-diketopiperazine or mixtures thereof. Composition according to any one of the preceding claims, characterized in that it comprises at least one anionic surfactant. Composition according to one of the preceding claims, characterized in that at least one nonionic surfactant of the formula (T2) is contained R ^{2 is} -O- (XO) _m -H, (T2) in which R ^{2 is} a linear or branched C ₈ -C ₁₈ -alkyl radical, an aryl radical or alkylaryl radical, XO independently of one another are an ethylene oxide (EO) or propylene oxide (PO) grouping, m is an integer from 1 to 50. Composition according to one of the preceding claims, characterized in that surfactant in a total amount of 5 to 70 wt .-%, preferably from 10 to 65 wt .-%, particularly preferably from 12 to 60 wt .-%, most preferably from 15 to 60% by weight, most preferably from 20 to 55% by weight. Composition according to one of the preceding claims, characterized in that water in a total amount of 5 to 90 wt .-%, preferably 10 to 85 wt .-%, particularly preferably 25 to 75 wt .-% and in particular 35 to 65 parts by weight. %, is included. Composition according to any one of the preceding claims, characterized in that water is present in a total amount of between 1 and 20% by weight and more preferably between 2 and 18% by weight. Compound of the formula (Ib)

wherein R ¹ and R ^{5 are} defined: R ¹ R ⁵ Hydrogen atom 2-carboxyethyl Hydrogen atom p-hydroxybenzyl hydroxy p-hydroxybenzyl Hydrogen atom 2- (benzyloxycarbonyl) ethyl Hydrogen atom 4-imidazolylmethyl Hydrogen atom methyl benzyloxy p- (benzyloxy) benzyl 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