EP3638759A1

EP3638759A1 - Viscoelastic, solid surfactant composition

Info

Publication number: EP3638759A1
Application number: EP18732295.3A
Authority: EP
Inventors: Peter Schmiedel; Filiz Yapici; Anna KLEMMER; Matthias Sunder; Oliver Kurth
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 2017-06-16
Filing date: 2018-06-12
Publication date: 2020-04-22
Also published as: WO2018229039A1; KR102510193B1; US20200115655A1; KR20200019703A; US11396641B2; DE102017210143A1

Abstract

The invention relates to a viscoelastic, solid surfactant composition, containing, in relation to the total weight thereof, (i) a total amount of 0.1 to 70 wt% of at least one surfactant, (ii) a total amount of more than 1 wt % of at least one benzylidene alditol compound of formula (I), wherein *- represents a covalent single bond between an oxygen atom of the alditol backbone and the provided moiety, n represents 0 or 1, preferably 1, m represents 0 or 1, preferably 1, R¹, R² and R³ represent, independently of each other, a hydrogen atom, a halogen atom, a C₁-C₄-alkyl group, a cyano group, a nitro group, an amino group, a carboxyl group, a hydroxy group, a group –C(=O)-NH-NH₂, a group –NH-C(=O)-(C₂-C₄-alkyl), a C₁-C₄-alkoxy group, a C₁-C₄-alkoxy-C₂-C₄-alkyl group, two of the moieties form a 5- or 6-membered ring together with the residual molecule, R⁴, R⁵ and R⁶ represent, independently of each other, a hydrogen atom, a halogen atom, a C₁-C₄-alkyl group, a cyano group, a nitro group, an amino group, a carboxyl group, a hydroxy group, a group –C(=O)-NH-NH₂, a group -NH-C(=O)-(C₂-C₄-alkyl), a C₁-C₄-alkoxy group, a C₁-C₄-alkoxy-C₂-C₄-alkyl group, two of the moieties form a 5- or 6-membered ring together with the residual molecule, and (iii) water, is a readily soluble, aesthetically pleasing and storage-stable form of a solid composition for providing surfactant-containing liquors.

Description

"Viscoelastic, solid surfactant composition"

The present invention relates to the technical field of festförm igen

Surfactant compositions for providing surfactant-containing liquors for substrate treatment, in particular for cleaning hard surfaces such as e.g. Dishes, or for cleaning textiles.

Detergents or cleaners are usually in solid form (for example as a powder or tablets) or in liquid form (or as a flowing gel). In particular, liquid detergents or cleaners are becoming increasingly popular with consumers.

Solid detergents or cleaning agents have the advantage that, in contrast to liquid washing or cleaning agents, they do not require any preservatives and the constituents contained in them (such as, for example, bleaching agents or enzymes) can be incorporated more stably. Liquid supply forms are increasingly gaining acceptance on the market, in particular due to their rapid solubility and the associated rapid availability of the active ingredients contained. This offers the consumer the possibility, for example, to use time-reduced rinse programs for dishwashing applications and still obtain a good cleaning performance. To guarantee this also for pre-portioned compositions, the portions must have a total of good solubility in the solvent of the liquor, usually in water, and dissolve as far as possible without residue.

Consumers have become accustomed to conveniently dosing pre-portioned automatic detergents or dishwashing detergents, such as dishwashing or detergent pouches, and use these products in the form of tablets (solid detergents or cleaners) or in the form of pouches (also: pillows or pouches), which are commonly used are filled with at least one liquid washing or cleaning agent. However, in addition to the aforementioned advantages, the use of liquids has the disadvantage, for example, that leaks in the sachet of the portion cause the liquid detergent or cleaning agent to run out.

Disposable portions in water-soluble bags enjoy the consumer not only because of increasing popularity, because the consumer with the chemical composition is no longer in contact, but not least because of the attractive appearance of the bag. The appearance of the dosage form is becoming increasingly important. In addition to a good cleaning performance and a sufficient storage stability, a good appearance is one of the reasons for choosing a product. From the point of view of the consumer, it is also desirable to combine the advantages of the forms of solid and liquid preparations and an improved dosage form, especially for liquid or liquid detergents, which is better than the prior art

To provide cleaning agents. For this purpose, a one-time portioning of the components contained must be possible and at the same time a visually appealing appearance for the consumer can be achieved.

Viscoelastic, solid surfactant compositions having a storage modulus of 40,000 to 800,000 Pa are known from the document WO 02/086074 A1. The viscoelastic surfactant compositions disclosed therein are liquid crystalline surfactant phases. The preparation of the viscoelastic surfactant compositions of the prior art is of

Phase behavior of the respective surfactants contained depending, which limits the freedom from formulation with regard to the selection of surfactants and their amounts used.

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

Surprisingly, it has been found that by formulation of a composition containing at least one surfactant and at least one Benzylidenalditol compound in a specific amount, this goal can be achieved.

An object of the invention is therefore, as a first embodiment, a viscoelastic, solid surfactant composition containing, based on its total weight

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

and

(ii) a total amount of more than 1% by weight of at least one benzylidenalditol compound of the formula (I)

wherein ^* - for a single covalent bond between an oxygen atom of the alditol

Skeleton and the rest provided,

n is 0 or 1, preferably 1,

m is 0 or 1, preferably 1,

R, R ² and R ³ independently represent a hydrogen atom, a halogen atom, a

C 1 -C 4 -alkyl group, a cyano group, a nitro group, an amino group, a carboxyl group, a hydroxy group, a group -C (= O) -NH-NH 2, a group -NH-C (= O) - (C 2 -C 4) Alkyl), a C 1 -C 4 -alkoxy group, a C 1 -C 4 -alkoxy-C 2 -C 4 -alkyl group, two of the radicals together with the remainder of the molecule form a 5- or 6-membered ring,

R ⁴ , R ⁵ and R ⁶ independently represent a hydrogen atom, a halogen atom, a C ¹ -C ⁴ -alkyl group, a cyano group, a nitro group, a

Amino group, a carboxyl group, a hydroxy group, a group - C (= O) -NH-NH ₂ , a group -NH-C (= O) - (C ₂ -C 4 -alkyl), a C ₁ -C 4 alkoxy group, a Ci-C4-alkoxy-C2-C4-alkyl group, two of the radicals together with the remainder of the molecule form a 5- or 6-membered ring, and

(iii) water.

Particularly preferred as a second embodiment of the first subject of the invention is a viscoelastic, solid surfactant composition containing, based on their total weight

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

and

(I)

wherein ^* - for a single covalent bond between an oxygen atom of the alditol

Skeleton and the rest provided,

n is 0 or 1, preferably 1,

m is 0 or 1, preferably 1,

R, R ² and R ³ independently represent a hydrogen atom, a halogen atom, a

(iii) water,

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

To further optimize the stability properties of the said composition, it is preferred if the storage modulus is at least five times greater than the loss modulus, more preferably at least ten times greater than the loss modulus (in each case at 20 ° C., a deformation of 0.1%). and a frequency of 1 Hz).

All definitions and preferred embodiments below, unless otherwise defined, apply equally to the first embodiment and the second embodiment.

The viscoelastic, solid surfactant composition incorporates all the advantages of a liquid composition, provides an aesthetic product form with a good dissolution profile and excellent performance profile on the substrate. WO 2010/108002 discloses structured liquid surfactant compositions containing not more than 1% by weight of a benzylidene alditol - contain compound as structurant. Viscoelastic, solid surfactant compositions containing benzylidenalditol compounds are not described therein. The viscoelastic solid surfactant composition of the present invention is storage and dimensionally stable. The said viscoelastic, solid surfactant composition exhibits no syneresis even after prolonged storage.

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

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

Theological characterization is in the context of this invention with a

Rotational rheometer, for example TA-Instruments, type AR G2, Malvern "Kinexus", performed using a cone-plate measuring system with 40 mm diameter and 2 ° opening angle at a temperature of 20 ° C. These are

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

Instruments or measurement geometries of comparable specifications.

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

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

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

To determine the frequency dependence of the modules, a frequency ramp, e.g. between 0.01 Hz and 10 Hz at a constant deformation amplitude. The

Deformation amplitude must be chosen so that it is in the linear range, ie below the above-mentioned critical deformation. In the case of the invention

Compositions, a deformation amplitude of 0, 1% has proven to be suitable. The modules G 'and G "are plotted against the frequency in a log-log plot.

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

A chemical compound is an organic compound when the molecule of the chemical compound contains at least one covalent bond between carbon and hydrogen. This definition applies inter alia to "organic bleach activators" as a chemical compound mutatis mutandis.

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

In the context of this application for polymeric ingredients specified mean

Molar masses are always, unless explicitly indicated otherwise

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

A surfactant-containing liquor in the context of the invention is a liquid preparation obtainable by use of a surfactant-containing dilution with at least one solvent (preferably water) for the treatment of a substrate. For example, hard surfaces (such as dishes) or fabrics or textiles (such as clothing) may be used as the substrate.

The portions according to the invention are preferably used to provide a surfactant-containing liquor in the context of automatic cleaning processes, as described, for example, in US Pat. from one

Dishwasher or a washing machine for textiles are executed.

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

If, in the context of the application, numerical ranges are defined from one number to another number, then the limit values are included in the range. If, in the context of the application, numerical ranges are defined between a number and another number, the limits do not include the range.

The compositions of the invention preferably have a flow limit. The yield stress refers to the smallest stress (force per area) above which a plastic substance behaves rheologically like a liquid. It is given in Pascal (Pa).

The flow limit of the compositions was measured using a rotary rheometer from TA-Instruments, type AR G2. This is a so-called

Schubspannungskontrolliert.es rheometer. For measuring a yield point with a

shear stress controlled rheometer various methods are described in the literature, which are known in the art.

For the determination of the yield points in the context of the present invention, the following was carried out at 20 ° C:

The samples were loaded in the rheometer in a "stepped-flow procedure" with a gradually increasing shear stress σ with time

Shear stress in the course of 10 minutes at 10 points per shear decadence from the smallest possible value (e.g., 2 mPa) to e.g. 10 Pa can be increased. The time interval is chosen such that the measurement is carried out "quasi-statically", ie that the deformation of the sample can be brought into equilibrium for every given shear stress value.As a function of this shear stress, the equilibrium deformation γ of the sample is measured If the investigated sample has a yield point, two distinct areas can be distinguished in this plot: Below a certain shear stress, one finds a purely elastic one

Deformation according to Hooke's law. The slope of the curve γ (σ) (log-log plot) in this area is one. Above this shear stress, the flow range begins and the slope of the curve is suddenly higher. The shear stress at which the bending of the curve takes place, ie the transition from the elastic to a plastic deformation, marks the yield point. A convenient determination of the break point is possible by applying tangents to the two curve parts. Samples without yield point do not show a characteristic kink in the function γ (σ).

The solid, viscoelastic composition according to the invention preferably has a yield point in the range from 8 to 350 Pa, more preferably from 10 to 320 Pa (conical plate measuring system with 40 mm diameter and 2 ° opening angle at a temperature of 20 ° C). The viscoelastic, solid surfactant composition according to the invention contains, based on the total weight thereof, a total amount of from 0.1 to 70% by weight of surfactant. Suitable surfactants according to the invention are preferably anionic surfactants, nonionic surfactants, zwitterionic surfactants, amphoteric surfactants or cationic surfactants.

Preferred surfactant compositions contain, based on their total weight, a total amount of 0, 1 to 5.0 wt .-% of at least one surfactant. Such

Surfactant compositions are suitable for use according to the invention, in particular in a dishwashing machine. It is again particularly preferred if the

Surfactant contains at least one nonionic surfactant.

Preferred surfactant compositions contain, based on their total weight, a total amount of from 5 to 70% by weight, particularly preferably from 20 to 65% by weight, very particularly preferably from 25 to 60% by weight, of at least one surfactant. Such surfactant compositions are suitable for the use according to the invention, but in particular for use in a washing machine for textile washing. In this case, it is again particularly preferred if the surfactant composition contains at least one anionic surfactant and optionally additionally at least one nonionic surfactant.

A preferred viscoelastic, solid surfactant composition according to the invention is characterized in that it contains at least one anionic surfactant. Surfactant compositions according to the invention containing anionic surfactant may be mentioned

Fields of application are used, but are preferably for the washing of textiles, particularly preferably for use in a washing machine for textile laundry.

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 8 to 70% by weight, especially 25 to 60% by weight, more preferably 30 to 40% by weight .-%, is included.

The anionic surfactant used may preferably be sulfonates and / or sulfates.

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

Olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as obtained for example from Ci2-i8 monoolefins with terminal or internal double bond by sulfonating with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation, into consideration. Also suitable are C 12 -is alkanesulfonates and the esters of α-sulfo fatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids. Particularly preferred surfactant compositions according to the invention comprise as anionic surfactant at least one compound of the formula (T1)

in the

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

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

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

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

Also, fatty alcohol ether sulfates, such as the sulfuric acid monoesters of straight-chain or branched C7-2i alcohols ethoxylated with from 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C9-11 alcohols having on average 3.5 moles of ethylene oxide (EO) or C12- Fatty alcohols with 1 to 4 EO are suitable.

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

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

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

In a most preferred embodiment, the surfactant composition comprises a monoethanolamine-neutralized alkylbenzenesulfonic acid, especially C9-13-alkylbenzenesulfonic acid, and / or a monoethanolamine-neutralized fatty acid.

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

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

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

Surfactant compositions as nonionic surfactant at least one fatty alcohol alkoxylate having the following formula (T2), wherein R ^'is a linear or branched Cs-ds-alkyl radical, an aryl radical or alkylaryl radical, XO is independently an ethylene oxide (EO) or propylene oxide (PO) grouping and m is an integer from 1 to 50. In the above formula, R ^'is a linear or branched, substituted or unsubstituted alkyl radical. In a preferred

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

XO of formula (T2) is an ethylene oxide (EO) or propylene oxide (PO) moiety, preferably an ethylene oxide moiety.

The index m of the formula (T2) is an integer from 1 to 50, preferably 2 to 20 and preferably 2 to 10. In particular, m is 3, 4, 5, 6 or 7. The inventive

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

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

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

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

With particular preference, the surfactant compositions according to the invention contain nonionic surfactants from the group of the alkoxylated alcohols. The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as they are usually present in Oxoalkoholresten. In particular, however, preferred are alcohol ethoxylates having linear radicals of alcohols of native origin having 12 to 18 carbon atoms, for example coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 moles of EO per mole of alcohol. The preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO or 4 EO, Csn alcohol with 7 EO, cis-is alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C12-14 alcohol with 3 EO and Ci ₂ -8-alcohol with 5 EO.

Preferred alcohol ethoxylates have a narrow homolog distribution (narrow rank ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used, in particular as automatic dishwashing detergents. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

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

Carbon atoms (Ci6-2o-alcohol), preferably a cis-alcohol and at least 12 moles, preferably at least 15 moles and in particular at least 20 moles of ethylene oxide. Of these, the so-called "narrow ranks ethoxylates" are particularly preferred.

Preferably used surfactants come from the groups of alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols and mixtures of these surfactants with structurally complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene ((PO / EO / PO) surfactants). Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control. Particularly preferred nonionic surfactants, in particular for machine dishwashing detergents, have been found in the context of the present invention to be the low-foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units. Among these, in turn, surfactants with EO-AO-EO-AO blocks are preferred, wherein in each case one to ten EO or AO groups are bonded to each other before a block of the other groups follows. Here are nonionic surfactants of the general formula (T-4)

Ri-O- (CH ₂ -CH ₂ -O) - (CH ₂ -CH-O) - (CH ₂ -CH ₂ -O) - (CH ₂ -CH-O) -H

R2 R3

(T-4)

in which R is a straight-chain or branched, saturated or mono- or polyunsaturated C 6-24-alkyl or alkenyl radical; each group R ² or R ^{3 is} independently selected from -Chta, -CH 2 CH 3, -CH 2 CH 2 -CH 3, -CH (CH 3) 2 and the indices w, x, y, z independently of one another are integers from 1 to 6.

Preferred nonionic surfactants of the above formula can be prepared by known methods from the corresponding alcohols R -OH and ethylene or alkylene oxide. The radical R in the above formula may vary depending on the origin of the alcohol. When native sources are used, the radical R has an even number of carbon atoms and is usually unbranched, the linear radicals being selected from alcohols of native origin having 12 to 18 carbon atoms, for example coconut, palm, tallow or oleyl alcohol , are preferred. Examples of alcohols which are accessible from synthetic sources are the Guerbet alcohols or methyl-branched or linear and methyl-branched radicals in the 2-position, such as are usually present in oxo alcohol radicals. Irrespective of the type of alcohol used to prepare the nonionic surfactants contained in the surfactant composition, nonionic surfactants in which R in the above formula is an alkyl group of 6 to 24, preferably 8 to 20, more preferably 9 to 15 and especially 9 to 11 are preferred Carbon atoms.

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

Further preferred nonionic surfactants, in particular for automatic dishwashing detergents, are nonionic surfactants of the general formula (T-5) R 0 (AlkO) x M (OAlk) _y OR ² (T-5) where R and R ² independently of one another represent a branched or unbranched, saturated or unsaturated, optionally hydroxylated alkyl radical having 4 to 22 carbon atoms; Alk is a branched or unbranched alkyl radical having 2 to 4 carbon atoms; x and y independently represent values between 1 and 70; and M is an alkyl radical from the group CH _2, CHR ^3, CR ³ R ^4, CH 2 CHR ³ and CHR ³ CHR ^4, wherein R ³ and R ⁴ independently represent a branched or unbranched, saturated or unsaturated alkyl radical having 1 to 18 Carbon atoms.

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

R is -CH (OH) CH ₂ -O (CH ₂ CH ₂ O) x CH ₂ CHR (OCH ₂ CH ₂ ) y -CH ₂ CH (OH) -R ² (T-6) wherein R, R and R ² independently represent an alkyl or alkenyl radical containing 6 to 22 carbon atoms; x and y independently represent values between 1 and 40.

Particular preference is given here to compounds of the general formula (T-7)

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

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

R is -CH (OH) CH ₂ 0- (AO) w- (AO) x- (A "0) _y - (A" O) z ² (T-8) in the

R is a straight-chain or branched, saturated or mono- or polyunsaturated C 6-24-alkyl or alkenyl radical;

R ^{2 is} hydrogen or a linear or branched hydrocarbon radical having 2 to 26 carbon atoms; - A, Α ', A "and A'" independently represent a radical from the group -CH ₂ CH ₂ , - CH ₂ CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ), -CH ₂ -CH ₂ -CH ₂ -CH ₂ , -CH ₂ -CH (CH ₃ ) -CH ₂ -, -CH ₂ -CH (CH ₂ -CH ₃ ),

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

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

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

By using these nonionic surfactants having one or more free hydroxyl groups on one or both terminal alkyl radicals, the stability of the enzymes optionally additionally present in the surfactant compositions according to the invention can be markedly improved.

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

in addition to a radical R, which is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 2 to 30 carbon atoms, preferably having 4 to 22 carbon atoms, furthermore a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R ² Have from 1 to 30 carbon atoms, where n stands for values between 1 and 90, preferably for values between 10 and 80 and in particular for values between 20 and 60. Especially preferred are surfactants of the above formula in which R is C7 to C13, n is an integer from 16 to 28 and R ^{2 is} Cs to C12.

Particularly preferred, in particular for automatic dishwashing detergents, are surfactants of the formula R 0 [CH ₂ CH (CH ₃ ) O] x [CH ₂ CH ₂ O] yCH ₂ CH (OH) R ² , in which R is a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms or mixtures thereof, R ^{2 is} a linear or branched one

Hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x for values between 0.5 and 1, 5 and y is a value of at least 15 stands. The group of these nonionic surfactants includes, for example, the C2-26 fatty alcohol (PO) i- (EO) is-4o-2-hydroxyalkyl ethers, in particular also the coco fatty alcohol (PO) i (EO) 22-2-hydroxydecyl ethers ,

Particularly preferred are, in particular for automatic dishwashing detergents, those end-capped poly (oxyalkylated) nonionic surfactants of the formula R 0 [CH ₂ CH ₂ O] x [CH ₂ CH (R ³ ) O] _y CH ₂ CH (OH) R ² ,

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

Further preferred nonionic surfactants, in particular for machine dishwashing detergents, are the end-capped poly (oxyalkylated) nonionic surfactants of the formula R 0 [CH ₂ CH (R ³ ) O] x [CH ₂ ] k CH (OH) [CH ₂ ] jOR ² ,

in which R and R ^{2 are} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{3 is} H or a methyl, ethyl, n-propyl, iso-propyl, n Butyl, 2-butyl or 2-methyl-2-butyl radical, x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5. If the value x> 2, each R ³ in the above formula

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

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

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

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

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

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

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

Carbon atoms;

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

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

The group of these nonionic surfactants include, for example, the C4-22 fatty alcohol (EO) io-so-2-hydroxyalkyl ethers, in particular also the C8-12 fatty alcohol (EO) 22-2-hydroxydecyl ethers and the C4-22 fatty alcohol (EO) 4o 8o-2-hydroxyalkyl ethers.

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

Lauryl dimethyl.

Suitable nonionic surfactants are, for example, alkyl glycosides of the general formula RO (G) x in which R is a primary straight-chain or methyl-branched, in particular 2-methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose. The degree of oligomerization x, the distribution of monoglycosides and Indicating oligoglycosides, is any number between 1 and 10; preferably x is 1, 2 to 1, 4.

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

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

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

Other usable nonionic surfactants may be, for example

polyol

alkoxylated triglycerides,

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

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

hydroxy mixed,

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

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

Fatty acid N-alkyl glucamides.

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

Portions which are particularly preferred according to the invention each contain one in each case in the liquid composition, based on the total weight of the liquid composition

Total amount of

From 30 to 40% by weight of at least one anionic surfactant and

18 to 28% by weight of at least one nonionic surfactant.

Very particularly preferred compositions according to the invention comprise at least one surfactant combination as described below for the compositions (A) to (D):

(A) viscoelastic, solid surfactant composition, containing as surfactant in each case based on the total weight of the composition at least in each case a total amount of - 25 to 60 wt .-% of at least one anionic surfactant, wherein as anionic surfactant at least one C9-i3-alkylbenzenesulfonate is contained, and

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

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

From 25 to 60% by weight of at least one anionic surfactant, the anionic surfactant containing at least 25 to 60% by weight of at least one C9-i3-alkylbenzenesulfonate, and

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

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

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

From 30 to 40% by weight of at least one anionic surfactant, the anionic surfactant containing at least one C9-i3-alkylbenzenesulfonate, and

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

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

From 30 to 40% by weight of at least one anionic surfactant, the anionic surfactant containing at least 30 to 40% by weight of at least one C9-i3-alkylbenzenesulfonate, and

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

It is preferred according to the invention if the composition according to the invention contains, in addition to the anionic and nonionic surfactant, at least one polyalkoxylated polyamine.

The polyalkoxylated polyamine in the context of the present invention and its individual aspects is a polymer having an N-atom-containing backbone which carries polyalkoxy groups on the N atoms. The polyamine has at the ends (terminus and / or side chains) primary amino functions and internally preferably both secondary and tertiary amino functions; if necessary, it can also only be secondary inside Have amino functions, so that not a branched, but a linear polyamine results. The ratio of primary to secondary amino groups in the polyamine is preferably in the range of 1: 0.5 to 1: 1, 5, in particular in the range of 1: 0.7 to 1: 1. The ratio of primary to tertiary amino groups in the polyamine is preferably in the range of 1: 0.2 to 1: 1, in particular in the range of 1: 0.5 to 1: 0.8. Preferably, the polyamine has an average molecular weight in the range of 500 g / mol to 50,000 g / mol, in particular from 550 g / mol to 5000 g / mol. The N atoms in the polyamine are separated from one another by alkylene groups, preferably by alkylene groups having 2 to 12 C atoms, in particular 2 to 6 C atoms, wherein not all alkylene groups must have the same C atom number. Particularly preferred are ethylene groups, 1, 2-propylene groups, 1, 3-propylene groups, and their

Mixtures. Polyamines bearing ethylene groups as said alkylene group are also referred to as polyethyleneimine or PEI. PEI is an inventively particularly preferred polymer with N-atom-containing backbone.

The primary amino functions in the polyamine can carry 1 or 2 polyalkoxy groups and the secondary amino functions 1 polyalkoxy group, although not every amino function must be alkoxy group-substituted. The average number of alkoxy groups per primary and secondary amino function in the polyalkoxylated polyamine is preferably from 1 to 100, in particular from 5 to 50. The alkoxy groups in the polyalkoxylated polyamine are preferably polypropoxy groups which are bonded directly to N atoms, and / or Polyethoxy groups which are attached to any existing propoxy and N atoms which do not carry propoxy groups.

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

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

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

If desired, the terminal OH function polyalkoxy substituents in the polyalkoxylated polyamine may be partially or completely etherified with an O-C10, in particular C1-C3-alkyl group.

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

A further preferred subject of the invention is the use of polyalkoxylated

Polyamines obtainable by reaction of polyamines with ethylene oxide and

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

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

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

In a further preferred embodiment, the inventive

Surfactant composition additionally at least one soil-release agent. Soil repellents are often referred to as "soil release" agents or because of their ability to render the treated surface, preferably textiles, "dirt repellent" as "soil repellents". Because of their chemical similarity to polyester fibers particularly effective soil release agents, but can also show the desired effect on fabrics made of other materials, are copolyesters containing dicarboxylic acid units, alkylene glycol units and polyalkylene glycol units. Dirt-releasing polyesters of the type mentioned as well as their use in laundry detergents for textiles have been known for a long time.

For example, polymers of ethylene terephthalate and polyethylene terephthalate in which the polyethylene glycol units have molecular weights of 750 to 5,000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate is 50:50 to 90:10, and their use in detergents in the German Patent DE 28 57 292 described. Polymers having a molecular weight of 15,000 to 50,000 of ethylene terephthalate and polyethylene oxide terephthalate, wherein the polyethylene glycol units have molecular weights of 1000 to 10,000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate is 2: 1 to 6: 1, can according to the German Offenlegungsschrift DE 33 24 258 are used in detergents. European patent EP 066 944 relates to textile treatment compositions containing a copolyester of ethylene glycol, polyethylene glycol, aromatic dicarboxylic acid and sulfonated aromatic dicarboxylic acid in certain molar ratios. From the European patent EP 185 427 are methyl or ethyl group-endcapped polyesters having ethylene and / or propylene terephthalate and polyethylene oxide terephthalate units and detergents containing such soil release polymer. European Patent EP 241 984 relates to a polyester which, besides oxyethylene groups and terephthalic acid units, also contains substituted ethylene units and also glycerol units. From the European patent EP 241 985, polyesters are known, which in addition to oxyethylene groups and terephthalic acid units contain 1, 2-propylene, 1, 2-butylene and / or 3-methoxy-1, 2-propylene groups and glycerol units and with O- to C4-alkyl groups are end-capped. European Patent EP 253 567 relates to soil release polymers having a molecular weight of 900 to 9000 of ethylene terephthalate and polyethylene oxide terephthalate, wherein the polyethylene glycol units have molecular weights of 300 to 3000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate 0.6 to 0.95. From the European patent application EP 272 033 polyesters with poly-propylene terephthalate and polyoxyethylene terephthalate units are known at least partially by Ο-4-alkyl or acyl radicals end-capped. European Patent EP 274 907 describes sulfoethyl end-capped terephthalate-containing soil release polyesters. In the European

Patent application EP 357,280 are prepared by sulfonation of unsaturated end groups soil release polyester with terephthalate, alkylene glycol and poly-C2-4-glycol units.

In a preferred embodiment of the invention, the inventive

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

O II II

- [(O-CHR-CHR ² ) _a -O-C-Ph-C-] d (El) OO

II II

- [(O-CHR ³ -CH R ⁴ ) _b -O-C-sPh-C-] e (El I)

- [(O-CHR ⁵ -CHR ⁶ ) c-OR ⁷ ] _f (E-III) - [polyfunctional unit-] _g (E-IV) in which

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

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

g is a number from 0 to 5,

Ph is a 1,4-phenylene radical,

sPh is a 1, 3-phenylene radical substituted in position 5 by a group -SO3M, M is Li, Na, K, Mg / 2, Ca / 2, Al / 3, ammonium, mono-, di-, tri- or tetraalkylammonium, wherein the alkyl radicals of the ammonium ions are C 1 -C 22 -alkyl- or C 2 -C 10 -hydroxyalkyl radicals or any mixtures thereof,

R ¹ , R ³ , R ⁴ , R ⁵ and R ⁶ independently of one another each represent hydrogen or a C 1 -C 18 -n- or iso-alkyl group,

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

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

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

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

end-capped polyalkylene glycols (corresponding to unit E-III). It should be pointed out that for numbers a, b, c> 1 there is a polymeric skeleton and thus the coefficients as an average can assume any value in the given interval. This value reflects the number average molecular weight. As the unit (El) is an ester of terephthalic acid with one or more difunctional, aliphatic alcohols in question, are preferably used here ethylene glycol (R and R ^{2 are} each H) and / or 1, 2-propylene glycol (R = H and R ² = - CH3 or vice versa) and / or shorter-chain polyethylene glycols and / or poly [ethylene glycol-co-propylene glycol] having number-average molecular weights of 100 to 2000 g / mol. In the structures, for example, from 1 to 50 units (E1) may be contained per polymer chain. As the unit (E-II) is an ester of 5-sulfoisophthalic acid with one or more difunctional, aliphatic alcohols in question, preferably used are the aforementioned. In the structures, for example, 1 to 50 units (E-II) may be present. Poly (ethylene glycol-co-propylene glycol) monomethyl ethers with average molecular weights of from 100 to 2000 g / mol and polyethylene glycol monomethyl ethers of the general formula CH.sub.3-0- (C.sub.2H.sub.40) _n -H are preferably used as nonionically unilaterally sealed polyalkylene glycol monoalkyl ethers according to unit (E-III) with n = 1 to 99, in particular 1 to 20 and particularly preferably 2 to 10. Since the use of such unilaterally closed ethers gives the theoretical maximum molecular weight of a polyester structure to be achieved in the case of quantitative conversion, the preferred Use amount of the structural unit (E-III) that is necessary to achieve the mean molecular weights described below. Apart from linear polyesters which result from the structural units (E1), (E-II) and (E-III), the use of crosslinked or branched polyester structures is also according to the invention. This is expressed by the presence of a crosslinking polyfunctional structural unit (E-IV) having at least three to a maximum of 6 functional groups capable of esterification reaction. As a functional

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

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

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

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

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

The surfactant composition of the invention may additionally contain at least one enzyme. In principle, all enzymes established in the state of the art for textile treatment can be used in this regard. Preferably, it is one or more enzymes which can develop a catalytic activity in a surfactant-containing liquor, in particular a protease, amylase, lipase, cellulase, hemicellulase, mannanase, pectin-splitting enzyme, tannase, Xylanase, xanthanase, β-glucosidase, carrageenase, perhydrolase, oxidase, oxidoreductase and mixtures thereof. Preferred hydrolytic enzymes include, in particular, proteases, amylases, in particular α-amylases, cellulases, lipases, hemicellulases, in particular pectinases, mannanases, β-glucanases, and mixtures thereof. Proteases, amylases and / or lipases and mixtures thereof are particularly preferred, and proteases are particularly preferred. These enzymes are basically of natural origin;

Starting from the natural molecules are available for use in washing or

Detergents improved variants available, which are preferably used accordingly.

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

Trade name Protosol® from Advanced Biochemicals Ltd. Thane, India, sold under the trade name Wuxi® by Wuxi Snyder Bioproducts Ltd. , China, under the trade names Proleather® and Protease P® from Amano Pharmaceuticals Ltd., Nagoya, Japan, and the enzyme available under the name Proteinase K-16 from Kao Corp., Tokyo, Japan. Particular preference is also given to using the proteases from Bacillus gibsonii and Bacillus pumilus.

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

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

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

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

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

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

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

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

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

Novozymes or Purabrite® are sold by Genencor. For the purposes of the present invention, pectin-destroying enzymes are likewise counted as enzymes with the designations pectinase, pectate lyase, pectin esterase,

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

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

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

These include, in particular, the already mentioned commercial products Everlase® and Purafect® OxP as examples of such proteases and Duramyl® as an example of such an α-amylase. The surfactant composition of the invention preferably contains enzymes in total amounts of

1 x 10 ⁸ to 5 percent by weight based on active protein. Preferably, the enzymes are present in a total amount of from 0.001 to 2 wt.%, More preferably from 0.01 to 1.5 wt.%, Even more preferably from 0.05 to 1.25 wt.%, And most preferably from 0.01 to 0.5 wt .-% in this portion.

In addition, builders, complexing agents, optical brighteners (preferably in portions for textile washing), pH adjusters, perfume, dye, can be used as additional ingredients.

Color transfer inhibitor (dye transfer inhibitor) or mixtures thereof in the

be contained according to the invention surfactant composition.

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

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

Surfactant composition in this embodiment preferably contains less than 5% by weight, more preferably less than 3% by weight, especially less than 1% by weight of phosphate (s). The surfactant composition according to the invention is particularly preferred in this

Embodiment completely phosphate-free, i. the compositions contain less than 0.1% by weight of phosphate (s).

The builders include in particular carbonates, citrates, phosphonates, organic

Builders and silicates. The proportion by weight of the total builders in the total weight of the composition according to the invention is preferably from 15 to 80% by weight and in particular from 20 to 70% by weight.

Suitable organic builders according to the invention are, for example, the polycarboxylic acids (polycarboxylates) which can be used in the form of their sodium salts, polycarboxylic acids meaning those carboxylic acids which have more than one, in particular two to eight

Acid functions, preferably two to six, in particular two, three, four or five

Carry acid functions throughout the molecule. Preferred polycarboxylic acids are thus dicarboxylic acids, tricarboxylic acids, tetracarboxylic acids and pentacarboxylic acids, in particular di-, tri- and tetracarboxylic acids. The polycarboxylic acids may carry further functional groups, such as hydroxyl or amino groups. For example, these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids (preferably aldaric acids, for example galactaric acid and Glucaric acid), aminocarboxylic acids, especially aminodicarboxylic acids, aminotricarboxylic acids, aminotetracarboxylic acids such as nitrilotriacetic acid (NTA), glutamine-N, N-diacetic acid (also referred to as N, N-bis (carboxymethyl) -L-glutamic acid or GLDA),

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

Also suitable as organic builders are polymeric polycarboxylates (organic polymers having a multiplicity of (in particular greater than 10) carboxylate functions in the

Macromolecule), polyaspartates, polyacetals and dextrins.

In addition to their builder effect, the free acids typically also have the property of an acidifying component. In particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.

Particularly preferred surfactant compositions according to the invention, in particular

Dishwashing detergent, preferably automatic dishwashing detergent, contained as one of its

essential builders one or more salts of citric acid, ie citrates. These are preferably in a proportion of 2 to 40 wt .-%, in particular from 5 to 30 wt .-%, particularly from 7 to 28 wt .-%, particularly preferably 10 to 25 wt .-%, most preferably 15 to 20 wt .-%, each based on the total weight of the composition.

Also particularly preferred is the use of carbonate (s) and / or bicarbonate (s), preferably alkali metal carbonate (s), more preferably sodium carbonate (soda), in amounts of 2 to 50 wt .-%, preferably from 4 to 40 wt. -% and in particular from 10 to 30 wt .-%, most preferably 10 to 24 wt .-%, each based on the weight of the composition.

Dishwashing agents, preferably automatic dishwasher detergents, are characterized in that they contain at least two builders from the group of silicates, phosphonates, carbonates,

Amino carboxylic acids and citrates, wherein the weight fraction of these builders, based on the total weight of the surfactant composition according to the invention, preferably 5 to 70 wt .-%, preferably 15 to 60% by weight and in particular 20 to 50 wt .-%. The combination of two or more builders from the above-mentioned group has proved to be advantageous for the cleaning and rinsing performance of detergents or cleaners according to the invention, in particular dishwashing detergents, preferably automatic dishwashing detergents. In addition to the builders mentioned here, one or more other builders may additionally be present.

Preferred surfactant compositions according to the invention, in particular dishwashing agents, preferably automatic dishwasher detergents, are characterized by a builder combination of citrate and Carbonate and / or hydrogen carbonate. In a very particularly preferred embodiment according to the invention, a mixture of carbonate and citrate is used, the amount of carbonate preferably being from 5 to 40% by weight, in particular from 10 to 35% by weight, very particularly preferably from 15 to 30% by weight. and the amount of citrate is preferably from 5 to 35 wt .-%, in particular 10 to 25 wt .-%, most preferably 15 to 20 wt .-%, each based on the total amount of the cleaning agent, wherein the total amount of these two Builders preferably 20 to 65 wt .-%, in particular 25 to 60 wt .-%, preferably 30 to 50 wt .-%, is. In addition, one or more further builders may additionally be included.

The surfactant compositions according to the invention, in particular dishwashing detergents, preferably automatic dishwashing detergents, may in particular contain phosphonates as further builder. As the phosphonate compound is preferably a hydroxyalkane and / or

Aminoalkanephosphonat used. Among the hydroxyalkane phosphonates, the 1-hydroxyethane-1, 1-diphosphonate (HEDP) is of particular importance. Preferred aminoalkanephosphonates are ethylenediamine tetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. Phosphonates are preferably present in surfactant compositions according to the invention in amounts of from 0.1 to 10% by weight, in particular in amounts of from 0.5 to 8% by weight, very particularly preferably from 2.5 to 7.5

Wt .-%, each based on the total weight of the composition.

Particularly preferred is the combined use of citrate, (hydrogen) carbonate and phosphonate. These can be used in the above quantities. In particular, in this combination amounts of, in each case based on the total weight of the composition, 10 to 25 wt .-% citrate, 10 to 30 wt .-% carbonate (or bicarbonate), and 2.5 to 7.5 wt .-% Phosphonate used.

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

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

Glutamic acid diacetate (GLDA), aspartic acid diacetate (ASDA), hydroxyethyliminodiacetate (HEIDA), iminodisuccinate (IDS) and ethylenediamine disuccinate (EDDS), most preferably MGDA or GLDA. A particularly preferred combination is, for example, citrate,

(Hydrogen) carbonate and MGDA and optionally phosphonate.

The percentage by weight of the further phosphorus-free builder, in particular of the MGDA and / or GLDA, is preferably 0 to 40% by weight, in particular 5 to 30% by weight, especially 7 to 25 Wt .-%. Particularly preferred is the use of MGDA or GLDA, in particular MGDA, as granules. Advantageous are those MGDA granules which contain as little water as possible and / or a lower hygroscopicity compared to the non-granulated powder

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

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

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

The content of the surfactant composition according to the invention, in particular dishwashing detergent, preferably automatic dishwashing detergent, of (homo) polymeric polycarboxylates is preferably from 0.5 to 20% by weight, preferably from 2 to 15% by weight and in particular from 4 to 10% by weight.

The surfactant compositions of the present invention, bevozugt as detergents or cleaning compositions, especially dishwashing detergent, preferably automatic dishwashing detergent can be used as builder also crystalline layered silicates of general formula NaMSix02x + i ^■ y H2O wherein M is sodium or hydrogen, x is a number from 1, 9 to 22, preferably from 1, 9 to 4, with particularly preferred values for x being 2, 3 or 4, and y being a number from 0 to 33, preferably from 0 to 20. It is also possible to use amorphous sodium silicates having a modulus Na 2 O: SiO 2 of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which are preferably delayed in dissolution and secondary wash properties.

In certain surfactant compositions according to the invention, in particular detergents or cleaners, preferably dishwasher detergents, more preferably mechanical

Dishwashing, the content of silicates, based on the total weight of

Composition, limited to amounts below 10 wt .-%, preferably below 5 wt .-% and in particular below 2 wt .-% limited.

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

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

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

Color transfer inhibiting polymers include polyvinylpyrrolidone (PVP),

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

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

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

The surfactant compositions according to the invention, in particular dishwashing agents, in a preferred embodiment contain as further constituent at least one zinc salt

Glass corrosion inhibitor. The zinc salt may be an inorganic or organic zinc salt. The zinc salt to be used according to the invention preferably has a solubility in water above 100 mg / l, preferably above 500 mg / l, more preferably above 1 g / l and especially above 5 g / l (all solubilities at 20 ° C water temperature). The inorganic zinc salt is preferably selected from the group consisting of

Zinc bromide, zinc chloride, zinc iodide, zinc nitrate and zinc sulfate. The organic zinc salt is preferably selected from the group consisting of zinc salts monomeric or polymeric organic acids, in particular from the group consisting of zinc acetate, zinc acetylacetonate, zinc benzoate, zinc formate, zinc lactate, zinc gluconate, zinc ricinoleate, zinc abietate, zinc valerate and zinc p-toluenesulfonate. In a particularly preferred embodiment according to the invention, zinc acetate is used as the zinc salt. The zinc salt is preferably present in surfactant compositions according to the invention in an amount of from 0.01% by weight to 5% by weight, more preferably in an amount of from 0.05% by weight to 3% by weight, in particular in an amount of 0.1 wt .-% to 2 wt .-%, based on the total weight of the composition. Additionally or alternatively to the abovementioned salts (in particular the zinc salts), polyethyleneimines, such as are obtainable, for example, under the name Lupasol® (BASF), may preferably be present in an amount of from 0 to 5% by weight, in particular from 0.01 to 2% by weight. %, are used as glass corrosion inhibitors.

The viscoelastic, solid surfactant composition necessarily contains, based on the total amount of the second composition, a total amount of more than 1% by weight of said benzylidene alditol. Because of the stereochemistry of the alditols, it should be mentioned that both benzylidene alditols according to the invention are suitable in the L configuration or in the D configuration or a mixture of both. Due to the natural availability, the benzylidenalditol compounds according to the invention are preferably used in the D configuration. It has been found to be preferred when the alditol skeleton of the in the

Benzylidenalditol compound according to formula (I) of D-glucitol, D-mannitol, D-arabinitol, D-ribitol, D-xylitol, L-glucitol, L-mannitol, L-arabinitol, L-ribitol or L-xylitol derives.

Particular preference is given to those surfactant compositions which are characterized in that R, R ² , R ³ , R ⁴ , R ⁵ and R ⁶ according to Benzylidenalditol compound of formula (I) independently of one another hydrogen, methyl, ethyl, chlorine, fluorine or Methoxy, preferably a hydrogen atom, mean. n according to benzylidenalditol compound of the formula (I) is preferably 1.m according to the benzylidenalditol compound. Formula (I) is preferably 1.

With very particular preference the surfactant composition according to the invention contains

Benzylidenalditol compound of the formula (I) at least one compound of the formula (1-1)

wherein R, R ² , R ³ , R ⁴ , R ⁵ and R ^{6 are} as defined in claim 1. Most preferably, according to formula (1-1), R 1, R ² , R ³ , R ⁴ , R ⁵ and R ^{6 are} independently

Hydrogen atom, methyl, ethyl, chlorine, fluorine or methoxy, preferably for a

Hydrogen atom.

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

The benzylidenalditol compound of the formula (I) contained in the surfactant composition is preferably contained in a total amount of more than 1.5% by weight, more preferably more than 2.0% by weight, based on the total weight of the second composition. More preferably, the benzylidene-alditol compound of the formula (I) contained in the second surfactant composition is in a total amount of more than 1.6% by weight or more than 1.7% by weight or more, based on the total weight of the composition 1, 8 wt .-%, or more than 1, 9 wt .-%, or more than 2.0 wt .-%, or more than 2.1 wt.%, Or more than 2.2 wt .-% , or more than 2.3 wt%, or more than 2.4 wt%, or more than 2.5 wt%.

The benzylidenalditol compound of the formula (1-1) contained in the surfactant composition is preferably contained in a total amount of more than 1.5% by weight, more preferably more than 2.0% by weight, based on the total weight of the composition , More preferably, the benzylidene-alditol compound of the formula (1-1) contained in the Tendis composition is in a total amount of more than 1.65% by weight or more than 1.7% by weight or more, based on the total weight of the composition as 1, 8 wt .-%, or more than 1, 9 wt .-%, or more than 2.0 wt .-%, or more than 2, 1 wt.%, or more than 2.2 parts by weight. %, or more than 2.3 wt .-%, or more than 2.4 wt .-%, or more than 2.5 wt .-%, included.

In addition to the quantity lower limit (or its preferred

Mengenuntergrenzen) of said Benzylidenalditol compound, it is favorable, in the Benzylidenalditol compound of the formula (I), based on the total weight of the composition, preferably in a total amount of at most 15% by weight, in particular of at most 10% by weight.

In addition to the quantity lower limit (or its preferred

Lower limit amounts) of said benzylidene-alditol compound, it is preferable that the benzylidene-alditol compound of the formula (1-1) contained in the surfactant composition is preferably in a total amount of at most 15% by weight, especially at most 10% by weight, based on the total weight of the composition. -%, use.

The surfactant composition of the present invention contains water. It is preferred if in the surfactant composition water based on the total weight of

Composition is preferably contained in a total amount between 0 to 40 wt .-%, more preferably between 0 to 25 wt .-%. The proportion of water in the

The surfactant composition is most preferably 20% by weight or less, again more preferably 15% by weight or less, again more preferably 12% by weight or less, more preferably between 1 and 4% by weight. The percentages by weight are based on the total weight of the composition.

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

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

Molecular weight of at most 500 g / mol.

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

It is again particularly preferred if said organic solvent in a total amount of 5 to 95 wt .-%, in particular from 20 to 90 wt .-%, is included.

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

Surfactant composition is preferably additionally at least one polyalkylene oxide compound having a weight-average molecular weight M _w of at least 4000 g / mol, in particular of at least 6000 g / mol, more preferably of at least 8000 g / mol. It has proved to be preferred when said polyalkylene oxide compound is selected from polyethylene oxide, ethylene oxide-propylene oxide copolymer and mixtures thereof.

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

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

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

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

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

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

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

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

PVOH powders having the aforementioned properties which are suitable for use in the at least one second phase are sold, for example, under the name Mowiol® or Poval® by Kuraray. Particularly suitable are the Poval® qualities, in particular the grades 3-83, 3-88 and 3-98 and Mowiol® 4-88 from Kuraray. The water solubility of polyvinyl alcohol can be improved by post-treatment with aldehydes

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

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

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

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

Preferred inorganic zinc salts include the zinc salts (vide supra) which can be used as a glass corrosion inhibitor.

The viscoelastic, solid surfactant composition can be prepared by first comprising a liquid composition containing, based on the total weight thereof

Total amount of more than 1 wt .-% of at least one Benzylidenalditol compound of formula (I), in the presence of water and 0, 1 to 70 wt .-% surfactant and optionally optional additives

wherein ^* -, n, m, R, R ² , R ³ , R ⁴ , R ⁵ and R ^{6 are} as defined in claim 1,

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

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

A second object of the invention is a portion containing at least one viscoelastic solid surfactant composition of the first subject of the invention.

A preferred portion is characterized in that it additionally comprises at least one further composition.

A preferred portion is present as a film of the surfactant composition of the invention.

A particularly preferred portion comprises at least one chamber with wall of water-soluble material, wherein the portion comprises an agent based on the

Total weight of the composition contains a total amount of 0, 1 to 70 wt .-% of at least one surfactant, said means containing at least one viscoelastic, solid shaped body of a viscoelastic, solid composition of the first subject of the invention. Again preferably a suitable portion comprises at least one chamber with wall of water-soluble material, wherein the portion comprises an agent, based on the

Total weight of the composition contains a total amount of 0, 1 to 70 wt .-% of at least one surfactant, said means comprises at least two phases, characterized in that a) a first phase is a granular mixture of a solid composition, and

b) a second phase is present as a viscoelastic, solid shaped body of a viscoelastic, solid composition of the first subject of the invention.

In the aforementioned embodiment as a portion, there is an agent which comprises at least two compositions each forming a phase. Said compositions are contained in the compartment in a chamber formed of water-soluble material. In this case, each composition of the composition can be packaged in a separate chamber, or there are at least two compositions in one and the same chamber. Portions are preferred which are characterized in that the first phase and the second phase are contained together in the same chamber.

Furthermore, such portions are preferred according to the invention, in which the granular mixture of the first phase is in direct contact with the shaped body of the second phase.

One serving is an independent dosing unit with at least one chamber. Over all

Chambers summed up give the total in it ready-made compositions the good to be dosed good portion (here a remedy). A chamber is a space delimited by walls (for example by a foil), which also without the material to be dosed (possibly under

Change of its form) can exist. A layer of a surface coating thus does not explicitly fall under the definition of a wall.

The water-soluble material forms walls of the chamber and thereby envelops the

Compositions of the agent.

The wall is according to the invention of a water-soluble material. The water solubility of the material can be determined by means of a quadratic frame (edge length on the inside: 20 mm) fixed square film of said material (film: 22 x 22 mm with a thickness of 76 μιη) according to the following measurement protocol. Said framed film is placed in 800 mL of distilled water heated to 20 ° C in a 1 liter round glass beaker

Soil surface (Schott, Mainz, beaker 1000 mL, low mold) immersed so that the surface of the clamped film is arranged at right angles to the bottom surface of the beaker, the upper edge of the frame is 1 cm below the water surface and the lower edge of the frame parallel to the bottom surface of the beaker is oriented such that the lower edge of the frame along the radius of the bottom surface of the beaker and the center of the lower edge of the frame is located above the center of the radius of the beaker bottom. The material should dissolve with stirring (stirring speed magnetic stirrer 300 rpm, stirring bar: 6.8 cm long, diameter 10 mm) within 600 seconds such that with the bare Eye no single festiform foil particles are more visible. The walls are preferably made of a water-soluble film. This film may according to the invention preferably have a thickness of at most 150 μιη (more preferably of at most 120 μιη). Preferred walls are therefore made of a water-soluble film and have a thickness of at most 150 μιη (more preferably of at most 120 μιη, most preferably of at most 90 μιη) on.

Such water-soluble portions may be obtained either by methods of vertical

Formfüllversiegelns (VFFS) or thermoforming process are produced. Particularly preferably, walls of at least one chamber are produced by sealing at least one film of water-soluble material, in particular by sealing in the context of a form-fill-seal method.

The thermoforming process generally includes forming a first layer of water-soluble film material to form at least one protrusion for receiving at least one composition therein, filling the composition into the respective protrusion, covering the composition-filled protrusions with a second layer of water-soluble one Film material and sealing the first and second layers together at least around the protrusions.

The water-soluble material preferably contains at least one water-soluble polymer. In addition, the water-soluble material preferably contains a water-soluble film material selected from polymers or polymer blends. The wrapper may be formed of one or two or more layers of the water-soluble film material. The water-soluble film material of the first layer and the further layers, if present, may be the same or different.

It is preferable that the water-soluble material is polyvinyl alcohol or a

Contains polyvinyl alcohol copolymer.

Suitable water-soluble films as the water-soluble material are preferably based whose molecular weight CMO each in the range of 10,000 to 1,000,000 on a polyvinyl alcohol or a polyvinyl alcohol copolymer, preferably from 20,000 to 500,000 gmol \ particularly preferably gmol 30,000 to 100,000 gmor and in particular from 40,000 to 80,000 ^" lies.

The production of polyvinyl alcohol is usually carried out by hydrolysis of polyvinyl acetate, since the direct synthesis route is not possible. The same applies to polyvinyl alcohol copolymers which are prepared from correspondingly polyvinyl acetate copolymers. It is preferred if at least one layer of the water-soluble material comprises a polyvinyl alcohol whose degree of hydrolysis makes up 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%. The film material suitable as water-soluble material may additionally be added polymers selected from the group comprising acrylic acid-containing polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters, polyether polylactic acid, and / or mixtures of the above polymers.

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

Mixtures thereof, with itaconic acid being preferred.

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

As a water-soluble material of the walls used sheet material has a preferred thickness in a range of 65 to 180 μιη, in particular from 70 to 150 μιη, more preferably 75 to 120 μιη, on.

In the said water-soluble material of the walls of the portion is preferably incorporated to increase the product safety a bittering agent. Corresponding embodiments of the water-soluble material with bittering agent are described in the publications EP-B1-2 885 220 and EP-B1-2 885 221. A preferred bittering agent is denatonium benzoate.

Suitable water-soluble films for use as the water-soluble material of the wall of the water-soluble portion according to the invention are films sold under the name Monosol M8630 by MonoSol LLC. Other suitable films include films named Solublon® PT, Solublon® KA, Solublon® KC or Solublon® KL from Aicello Chemical Europe GmbH or the films VF-HP from Kuraray, or HiSelon SH2312 from Nippon Gohsei.

A phase in the sense of the present invention is a spatial area in which physical parameters and the chemical composition are homogeneous. A phase is different from another phase in terms of different characteristics, such as ingredients,

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

A granular mixture is formed from a variety of loose, solid particles which in turn comprise so-called grains. A grain is a term for the particulate constituents of powders (grains are the loose, solid particles), dusts (grains are the solute solids), granules (loose, solid particles are agglomerates of several grains) and other granular mixtures. A preferred embodiment of the granular mixture of the composition of the first phase is the powder or granules. The said solid particles of the granular mixture in turn preferably have a particle diameter Xso, 3 (volume average) of 10 to 1500 μιη, more preferably from 200 μιη to 1200 μιη, more preferably from 600 μιη to 1 100 μιη, on. These particle sizes can be determined by sieving or by means of a particle size analyzer Camsizer from Retsch.

The granular mixture of the solid composition of the present invention which is used as the first phase is preferably in free-flowing form (particularly preferably as a free-flowing powder or free-flowing granules). The means of the portion according to the invention thus comprises at least a first phase of a free-flowing, granular mixture of a festformigen

Composition, as well as at least one previously defined second phase.

The flowability of a granular mixture affects its ability to trickle freely under its own weight from a Rieseltest funnel with a spout of 16.5 mm diameter. The quality of the flowability is determined, in which the flow time of 1000 ml of granular mixture from a standardized, initially closed at its outlet trickle funnel with a spout of 16.5 mm diameter by measuring the time for the complete outflow of the powder after opening the spout measured and with the discharge speed (in

Seconds) of a standard test sand whose exit velocity is defined as 100%. The defined sand mixture for calibrating the Rieselapparatur is dry sea sand.

Particularly suitable are those granular mixtures which have a flowability in% to the standard test substance stated above of greater than 40%, preferably greater than 55%, in particular greater than 60%, particularly preferably between 63% and 80%, for example between 65% and 75%. exhibit.

Lower values for the flowability are rather not suitable, since from a process engineering point of view an exact dosage of the granular mixture is necessary. In particular, the values greater than 60% have proven to be advantageous, since due to the good meterability of the granular mixture only small fluctuations in the metered amount or the composition result. The more accurate dosage leads to a constant product performance, economic losses due to overdose are thus avoided. Furthermore, it is advantageous that the granular mixtures are easy to dose, so you can achieve a faster flow of dosing. Furthermore, it is better avoided by such a good flowability that granular mixture reaches the part of the water-soluble casing, which is intended for the production of the sealed seam and should therefore remain as free as possible of granular mixture.

The agent, as well as its components like the viscoelastic, solid-shaped

Surfactant composition and the granular mixture, in addition to the mandatory ingredients may contain other optional ingredients. The said

Total amounts, if necessary, are selected from predetermined weight ranges such that, together with the amounts of optional ingredients for the said composition, based on their total weight, they yield 100% by weight.

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

Another object of the present invention is a process for the preparation of portions, in particular detergent portions containing an agent having at least a first and at least one different second phase, comprising: a) providing a mold having at least one mold cavity; optionally containing a web for dividing the bottom of the mold cavity b) feeding a water-soluble film onto the mold cavity; c) forming an open chamber in the mold cavity by deforming the water-soluble film; d) filling the open chamber or parts thereof with at least a second phase as described above or the tempered, liquid composition necessary for the preparation of the second phase, as described above; e) optionally filling the open chamber or parts thereof with at least one further second phase as described above, which second phase may optionally be different from the second phase according to d); f) optionally solidifying the second phase (s); g) then filling the open chamber with at least a first phase different from the at least one second phase as described above; h) providing a second water-soluble film as a lid; i) bringing the open chamber and lid over one another to seal the portion at a sealing area; j) sealing the lid with the open chamber.

The mold comprises at least one trough (mold cavity). For example, the mold may be provided as a single mold or as part of an array of treadmill shapes, as known in the treadmill and drum process. The mold comprises an area on which the film can be placed, e.g. a seal region typically defined around the opening of a mold cavity. The mold cavity can have different geometries, if there are edges, it is advantageous that they are rounded. Rounded edges and / or dome-shaped troughs serve to draw the film somewhat more homogeneously as the film is drawn into the trough, thereby keeping the film thickness uniform, and to avoid breaking or breaking points, which in turn results in a more stable one Portion pack leads.

Optionally, but according to a particular embodiment, the mold preferably contains at least one mold cavity which has a web for subdividing the bottom of the mold cavity. As a result, bulges or pockets form in the formed chamber, which visually create a positive appearance. In particular, if only the areas of these bulges are completely or partially, preferably almost completely filled with the / the second phase (s), this area is once again clearly separated from the granular mixture of the first phase and visually creates a particularly good appearance.

The water-soluble film can be fed from a roll and fed to the mold cavity. The foil is positioned and held on the mold. The holding can take place through suction holes on the molding surface, which is not part of the mold cavity. The film can also be held by mechanical means on the mold, such as brackets. For example, the foil may be held in place by a punch which presses on the sealing area. In the continuous production processes, e.g. Drum method and

In the method according to the invention, it is preferred that the speed of the film is adapted to the speed of the treadmill formed from the molds, so that the film is not unnecessarily thinned by adhering to a running mold.

After the film is held in place, relative to the mold cavity, is in the

Form trough a chamber formed by the film at least partially, to the Mold cavity is adjusted. The adaptation is produced by elastic and / or plastic deformation. Preferably, the film deformation has a greater plastic than elastic portion. The deformation of the water-soluble film is produced for example by deep drawing or by means of suitable stamp. A preferred variant is thermoforming, by

Actuation of negative pressure (Formierdruck) in the mold cavity, this includes the mold cavity preferably small openings, preferably in the bottom region, which are connected by appropriate lines air pressure moderately connected to a vacuum pump.

After forming the open chamber, these or parts thereof are filled in step d) with the at least one second phase of the product or its tempered, liquid composition intended for solidification. As soon as the at least one second phase has solidified, if necessary after an additional period of time which is necessary for solidification, further product constituents (further second phases according to optional step e) or at least a first phase according to step g)) can then be introduced into the chamber become. In this case, the at least one first phase according to step g) is preferably free-flowing.

It is preferred in the aforementioned Herste II method that the chamber containing the second phase, (in step d) is not completely filled with the / the second phase (s). In this case, the chamber can preferably only partially, preferably only in the lower region or only in the region or just above the range formed by the optional web according to a)

Bulges or pockets of the chamber are filled with the second phase (s).

If the chamber or parts thereof is filled with at least two second phases, it is preferred according to a particular embodiment that these second phases are substantially the same or differ only slightly, for example by a different dye. They preferably have a very similar, in particular the same, composition with regard to the active ingredients used (apart from excipients such as, for example, dyes). In this case, in particular migration phenomena between the second phases, and thus the expression of a non-advantageous optics during storage by, for example, inflated or shrunken phases, are avoided.

When filled with product, preferably the deformed foil is kept in the trough during filling. For example, under negative pressure, the negative pressure is broken only after the seal. The negative pressure after forming the chamber in the

Relative to the Formierdruck, a lower strength (higher pressure) may have, which only fulfills the holding function.

The chamber is filled by the introduction of at least a first and at least a second phase, in particular by those as described above as being according to the invention. It is important that the seal area remains free of product. For example, if the chamber is at least partially elastically deformed, this elastic deformation after filling and prior to sealing should not degrade such that the product flows over and out of the open chamber and thus contaminates the seal area.

According to a particular embodiment, the lid is positioned on the open chamber so that in the next step the lid can be applied to the sealing area. The position of the lid is generally determined relative to the position of the chamber. If the chamber is moving with a moving mold in a treadmill, the lid must move equally so that the relative position to the chamber remains the same.

The lid is then applied to the open chamber, which is closed in this way. The contact between lid and foil in the sealing area thus closes the chamber.

A preferred embodiment of the seal is a material fusion between the film and the lid, for example by dissolving the film before applying the lid, or by melting film and / or lid in the sealing area. Alternatively, the

Sealing by gluing, or welding.

The positioning, applying, and sealing can take place either in separate steps or simultaneously.

The mold may also comprise at least one second mold cavity, such that

Process steps a) to d) at least two open chambers are generated. The at least two chambers are formed in the same plane. It is preferred that the lid in step h) is positioned over the at least two open chambers and the lid is applied in step i) to at least both chambers for sealing the portion of a sealing area. Since the at least two chambers are connected to the same lid, the chamber remain in a certain position relative to each other, in contrast to the prior art where adjacent chambers are connected by the web formed by the thin films of the packages.

It is particularly preferred that the lid is provided as part of a tape by feeding / transferring a tape comprising at least one lid. The singulation of the lid may take place prior to positioning, after positioning but before application, during application, or after application to the chamber.

When singulated before positioning, the lid is preferably punched out.

Lid and foil can also be separated simultaneously with the sealing. The device that produces the seal by melting consists of at least two parts, which is one The form itself and the other part is a counter-stamp which presses from the lid side on the form. It is preferred that in the sealing step, the pressure exerted during sealing by the mold and further part must be less at the sealing area than the pressure exerted in the separating area. It surrounds the

Separation area the sealing area.

In the case of separation after sealing, the lid and foil are alternatively preferably separated from the band in the same step, and thus the portion packs are separated.

As an alternative, likewise preferred process for the preparation of portions according to the invention, the following is furthermore particularly suitable. This method comprises the steps of: a) providing a mold having at least one mold cavity; optionally including a web for dividing the bottom of the mold cavity; b) supplying a water-soluble film to the mold cavity; c) forming an open chamber in the mold cavity by deforming the water-soluble film; d) filling the open chamber with at least one granular mixture of the first phase; e) providing a second mold with at least one second mold cavity; optionally containing a web for dividing the bottom of the mold cavity f) feeding a second water-soluble film onto the second mold cavity; g) forming a second open chamber in the second mold cavity by deforming the water-soluble film; h) filling the second open chamber or parts thereof with at least one second phase as described above, i) optionally filling the second open chamber or parts thereof from step h) with at least one further second phase as described above ( or the tempered liquid composition necessary for the preparation of the second phase, as described above), this at least one further second phase optionally being different from the second phase according to h); j) optionally solidifying the second phase (s); k) bringing the two open chambers together to seal the sachet to a sealing area, the filled areas facing each other;

I) sealing the open chambers with each other.

Unless otherwise stated, this procedure also applies to the procedure described for the first method.

In this second method, two different chambers are formed, with one chamber containing at least a first phase and the other chamber at least a second phase.

Preferably, in step k), the chamber containing the at least one granular mixture of a first phase, in particular a granular, free-flowing mixture of a first phase, is arranged so that the mixture does not fall out.

In this case, the chamber is then preferably containing the at least one second phase

disposed above / above the chamber containing the at least one first phase. In this case, the filled chamber areas to each other. It is important here that the liquid composition used to prepare the second phase is already solidified or gelatinous or no longer flowable in step k) so that it does not run out of the chamber. After sealing, this results in a multiphase Einkammerpouch, which has a particularly good appearance.

For both aforementioned production methods, the following preferably applies:

For the at least one first phase that applies to the inventive cleaning agents described above. It is preferred that the at least one first phase is free-flowing. In particular, the flowability of the at least one first phase preferably has a value of greater than 55%, in particular greater than 60%, particularly preferably between 63% and 80%, for example between 65% and 75%, with respect to the standard test sand.

For the at least one second phase to be used in the method according to the invention, the one mentioned above, to which reference is explicitly made, also applies.

Depending on the method II, the second phase (s) can be clearly above or below the sealing seam plane (the first-mentioned method) or approximately at the level of the sealing seam

(latter method) are.

A preferred portion is designed as a shaped body. The portion may particularly preferably be in the form of a shaped body, in particular a tablet. Furthermore, a molded body as Kompaktat a granular mixture with at least one trough as Serve basic moldings, wherein in at least one trough of the base molding a molded body is introduced from a viscoelastic, festformigen composition of the first subject of the invention. Such a portion is characterized in that said shaped body comprises a base body formed of at least one said further composition, said base body containing at least one trough into which the surfactant composition of the first subject of the invention is incorporated.

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

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

(B) bringing into contact a substrate, in particular a textile or crockery, with the prepared according to (a) surfactant-containing liquor.

The following points represent particular embodiments of the invention:

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

total weight

(i) a total amount of 0, 1 to 70 wt .-% of at least one surfactant

and

(ii) a total amount of more than 1% by weight of at least one benzylidenalditol

Compound of the formula (I)

(I) represents a single covalent bond between an oxygen atom of the alditol skeleton and the intended radical, 0 or 1, preferably 1,

is 0 or 1, preferably 1, R, R ² and R ³ independently represent a hydrogen atom, a halogen atom, a C 1 -C 4 -alkyl group, a cyano group, a nitro group, a

Amino group, a carboxyl group, a hydroxy group, a group - C (= O) -NH-NH ₂ , a group -NH-C (= O) - (C ₂ -C 4 -alkyl), a C ₁ -C 4 alkoxy group, a Ci-C4-alkoxy-C2-C4-alkyl group, two of the radicals together with the remainder of the molecule form a 5- or 6-membered ring,

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

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

Olefinsulfonaten, Ci2-is-alkanesulfonates, ester sulfonates, alkyl sulfates, alkenyl sulfates, fatty alcohol ether sulfates and mixtures thereof, is included. Composition according to point 1 to 4, characterized in that as surfactant at least one compound of formula (T1) is contained,

in the R ^' and R ^"are independently H or alkyl and together contain 9 to 19, preferably 9 to 15 and especially 9 to 13 C atoms, and Y ^{+ is} a monovalent cation or the nth part of an N-valent cation (especially Na ⁺⁾ mean. a composition according to any one of items 1 to 5, characterized in that they contain at least one nonionic surfactant. the composition according to any one of items 1 to 6, characterized in that it comprises as surfactant at least one nonionic surfactant of the formula (T2)

R ² -O- (XO) _m -H, (T2) in the

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

Grouping,

m stands for integers from 1 to 50. Composition according to one of the items 1 to 7, characterized in that, based on its total weight, it has a total surfactant content of from 0.5 to 40% by weight, preferably from 1.0 to 35% by weight, particularly preferably from 2 to 30% by weight %, most preferably from 2 to 20% by weight. Composition according to one of the items 1 to 8, characterized in that the alditol skeleton according to formula (I) of D-glucitol, D-mannitol, D-arabinitol, D-ribitol, D-xylitol, L-glucitol, L- Mannitol, L-arabinitol, L-ribitol or L-xylitol. Composition according to one of the items 1 to 9, characterized in that R, R ² , R ³ , R ⁴ , R ⁵ and R ⁶ independently represent a hydrogen atom, methyl, ethyl, chlorine, fluorine or methoxy, preferably a hydrogen atom. Composition according to one of the items 1 to 10, characterized in that it contains as Benzylidenalditol compound of formula (I) at least one compound of formula (1-1)

wherein R, R ² , R ³ , R ⁴ , R ⁵ and R ^{6 are} as defined in item 1. Composition according to one of the items 1 to 1 1, characterized in that the Benzylidenalditol compound of formula (I) is selected from 1, 3: 2,4-di-O-benzylidene-D-sorbitol; 1, 3: 2,4-di-O- (p-methylbenzylidene) -D-sorbitol; 1, 3: 2,4-di-O- (p-chlorobenzylidene) -d-sorbitol; 1, 3: 2,4-di-O- (2,4-dimethylbenzylidene) -D-sorbitol; 1, 3: 2,4-di-O- (p-ethylbenzylidene) -D-sorbitol; 1, 3: 2,4-di-O- (3,4-dimethylbenzylidene) -D-sorbitol or mixtures thereof. Composition according to one of the items 1 to 12, characterized in that the Benzylidenalditol compound of formula (I) in a total amount of more than 1, 5 wt .-%, in particular more than 2.0 wt .-%, is included , Composition according to one of the items 1 to 13, characterized in that water is contained in a total amount between 0 and 25 wt .-%. Composition according to one of the preceding points, characterized in that it additionally contains at least one organic solvent having at least one hydroxyl group, no amino group and having a molecular weight of at most 500 g / mol (preferably selected from (C2-Cs) -alkanols having at least one hydroxyl group

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

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

Propylene carbonate, 1-methoxy-2-propanol, 3-methoxy-3-methyl-1-butanol, butyl lactate, 2-isobutyl-2-methyl-4-hydroxymethyl-1,3-dioxolane, 2,2-dimethyl-4- hydroxymethyl-1,3-dioxolane, dipropylene glycol, or mixtures thereof). Composition according to item 15, characterized in that said organic solvent is present in a total amount of from 5 to 95% by weight, in particular from 20 to 90% by weight. Composition according to one of the preceding points, characterized in that in addition at least one polyalkylene oxide compound having a weight-average molecular weight Mw of at least 4000 g / mol is contained. Composition according to item 17, characterized in that

Polyalkylene oxide compound is selected from polyethylene oxide, ethylene oxide-propylene oxide copolymer and mixtures thereof. Composition according to one of the preceding points, characterized in that additionally at least one polymeric polyol, in particular polyvinyl alcohol, is contained. Composition according to one of the preceding points, characterized in that the storage modulus is in a range from 10 ⁵ Pa to 10 ⁷ Pa. Composition according to one of the preceding points, characterized in that it has a yield point in the range from 8 to 350 Pa, preferably from 10 to 320 Pa, measured with a cone-plate measuring system of 40 mm diameter and 2 ° opening angle at a temperature of 20 ° C. Composition according to one of the preceding points, characterized in that additionally at least one stabilizer is selected, selected from magnesium sulfate, zinc acetate, calcium acetate, magnesium oxide, inorganic salt (in particular sulfate, acetate or carbonate) of Mg, Ca, Zn, Na or K, acetamido monoethanolamine .

Hexamethylenetetramine, guanidine, polypropylene glycol ether, salt of amino acids or mixtures thereof. Portion containing at least one surfactant composition according to one of the items 1 to 22. Portion according to item 23, characterized in that it additionally comprises at least one further composition. Portion according to one of the items 23 or 24, characterized in that it is designed as a shaped body of at least one surfactant composition of points 1 to 22. Portion according to items 24 and 25, characterized in that said shaped body comprises a base body formed from at least one said further composition, said base body containing at least one trough into which the viscoelastic, solid surfactant composition according to any one of items 1 to 22 is incorporated. Portion according to item 23 or 24, characterized in that it comprises at least one chamber with wall of water-soluble material, the portion comprising an agent, based on the total weight of the agent, a total amount of 0, 1 to 70 wt .-% of at least one Surfactant, said agent containing at least one viscoelastic, solid shaped body of a viscoelastic, solid surfactant composition according to any one of items 1 to 22. Method for substrate treatment comprising the method steps

(A) providing an aqueous liquor by mixing 0.5 L to 40.0 L of water with 0.5 to 100 g of a composition according to any one of items 1 to 22, and

(B) bringing into contact a substrate, in particular a textile or dishes, with the aqueous liquor prepared according to (a). Process for the preparation of a solid-form surfactant composition according to one of the items 1 to 22, characterized in that first a liquid composition containing, based on its total weight, a total amount of more than 1% by weight of at least one benzylidenalditol compound of the formula (I),

(I) wherein * -, n, m, R, R ² , R ³ , R ⁴ , R ⁵ and R ^{6 are} as defined in point 1,

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

Composition, and then the heated liquid composition in a mold, preferably in a cavity of a trough mold, given and in said form below the sol-gel transition temperature to form a viscoelastic, solid-shaped

Molded body is cooled. Examples

Example 1: low-water moldings for the dishwasher

Formed bodies F1-F9 according to Tables 1 and 2 were produced. While stirring, a mixture of the appropriate ingredients was prepared and the mixture heated to 128 ° C until all ingredients were dissolved. 10 mL of this solution was placed in a trough mold. The temperature of the solution was gradually lowered to room temperature in the wells. After solidification, the moldings were removed from the trough. All molded bodies F1 to F9 have a storage modulus in the order of 10 ⁶ Pa, which is at least ten times larger than the loss modulus.

Table 1: Compositions of the moldings F1 to F7

F1 F2 F3 F4 F5 F6 F7

1,2-Propanediol 77.03 76.03 74.53 79.61 72.61 76, 1 1 70, 1 1

PEG 12000 - - - - 5.00 - -

Marlox FK 64 ¹ - - - 5.00 5.00 5.00 5.00

Plurafac LF 220 ² 10,58 10,58 10,58 5,00 5,00 5,00 5,00

Water 9,39 9,39 9,39 9,39 9,39 9,39 9,39

Zinc acetate - 1.00 2.50 - - 1.50 2.50

1.3: 2.4 to 0-dibenzylidene

3.00 3.00 3.00 1.00 3.00 3.00 3.00 D-sorbitol

Cio-12 fatty alcohol, ethoxylated and propoxylated (6 PO & 4 EO) (Sasol)

with ethylene oxide and higher alkylene oxide alkoxylated linear and branched fatty alcohols

(BASF)

Table 2: Compositions of the moldings F8 to F9

F8 F9

1,2-propanediol 72, 61, 76, 61

PEG 4000 - 1, 00

PEG 12000 5.00 -

Marlox FK 64 5.00 5.00

Plurafac LF 220 5,00 5,00

Water 9,39 9,39

Zinc acetate - -

Citric acid - -

1.3: 2,4-0-

3.00 3.00

dibenzylidene

Mowiol 4-88 ⁴ - -

Copolymer with AMPS

polyvinyl alcohol It has been found that even in the absence of a surfactant liquid crystalline phase by using Benzylidenalditol (here Dibenztylidensorbitol) in a special amount a stable viscoelastic, solid-like composition can be created.

The moldings according to the invention were found in water when used in the

Dishwasher on a good dissolution speed.

Example 2: water-containing moldings for the washing machine

Table 3: Liquid detergent for textiles

To prepare a shaped article from one of the liquid detergents of Table 3, a premix was first prepared as a solution of 8 g of 1, 3: 2,4-di-O-benzylidene-D-sorbitol and 92 g of the selected liquid detergent of Table 3 under heating. 15 g of the still hot and clear premix was in 85 g of the room temperature Liquid detergent of Table 3 incorporated with vigorous stirring. 19 g of the resulting solution was quickly added to a cube-well mold. The temperature of the solution was gradually lowered to room temperature in the well. After solidification, the molded body was removed from the trough. The molded articles prepared in this way each had a storage modulus of the order of 10 ⁶ Pa, which was at least ten times larger than the loss modulus.

The moldings according to the invention had a good dissolution rate in water when used in the washing machine.

Claims

Patent claims

1. Viscoelastic, solid surfactant composition containing, based on their total weight

(i) a total amount of 0, 1 to 70 wt .-% of at least one surfactant

and

(ii) a total amount of more than 1% by weight of at least one benzylidenalditol

Compound of the formula (I)

wherein

^* - for a single covalent bond between an oxygen atom of the

Alditol skeleton and the rest provided,

n is 0 or 1, preferably 1,

m is 0 or 1, preferably 1,

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

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

(iii) water.

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

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

3. Composition according to claim 1 or 2, characterized in that it contains at least one anionic surfactant.

4. The composition according to claim 3, characterized in that at least one

anionic surfactant selected from the group consisting of Cs -is-alkylbenzenesulfonates, Olefinsulfonaten, Ci2-is-alkanesulfonates, ester sulfonates, alkyl sulfates, alkenyl sulfates, fatty alcohol ether sulfates and mixtures thereof.

5. Composition according to one of claims 1 to 4, characterized in that as surfactant at least one compound of formula (T1) is contained,

in the

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

7. Composition according to one of claims 1 to 6, characterized in that the alditol skeleton according to formula (I) of D-glucitol, D-mannitol, D-arabinitol, D-ribitol, D-xylitol, L-glucitol, L-mannitol, L-arabinitol, L-ribitol or L-xylitol.

8. A composition according to any one of claims 1 to 7, characterized in that R, R ² , R ³ , R ⁴ , R ⁵ and R ^{6 are} independently a hydrogen atom, methyl, ethyl, chlorine, fluorine or methoxy, preferably a hydrogen atom, mean.

9. A composition according to any one of claims 1 to 8, characterized in that it comprises as Benzylidenalditol compound of formula (I) at least one compound of formula (1-1)

10. The composition according to any one of claims 1 to 9, characterized in that the Benzylidenalditol compound of formula (I) is selected from 1, 3: 2,4-di-O-benzylidene-D-sorbitol; 1, 3: 2,4-di-O- (p-methylbenzylidene) -D-sorbitol; 1, 3: 2,4-di-O- (p-chlorobenzylidene) -d-sorbitol; 1, 3: 2,4-di-O- (2,4-dimethylbenzylidene) -D-sorbitol; 1, 3: 2,4-di-O- (p-ethylbenzylidene) -D-sorbitol; 1, 3: 2,4-di-O- (3,4-dimethylbenzylidene) -D-sorbitol or mixtures thereof.

1 1. A composition according to any one of claims 1 to 10, characterized in that the Benzylidenalditol compound of formula (I) in a total amount of more than 1, 5 wt .-%, in particular of more than 2.0 wt .-% , is included.

12. The composition according to any one of claims 1 to 1 1, characterized in that

Water is contained in a total amount between 0 and 25 wt .-%.

13. Composition according to one of the preceding claims, characterized in that it additionally contains at least one organic solvent with at least one

Hydroxyl group, without amino group and having a molecular weight of at most 500 g / mol (preferably selected from (C2-Cs) alkanols with at least one

Hydroxyl group (particularly preferably ethanol, ethylene glycol, 1,2-propanediol, glycerol, 1,3-propanediol, n-propanol, isopropanol, 1,1,1-trimethylolpropane, 2-methyl-1,3-propanediol, 2-hydroxymethyl 1, 3-propanediol), triethylene glycol, butyl diglycol, polyethylene glycols 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).

14. The composition according to any one of the preceding claims, characterized in that in addition at least one polyalkylene oxide compound having a weight-average molecular weight M _w of at least 4000 g / mol is included.

15. A process for substrate treatment comprising the process steps

(A) providing an aqueous liquor by mixing 0.5 L to 40.0 L of water with 0.5 to 100 g of a composition according to any one of claims 1 to 14, and

(B) bringing into contact a substrate, in particular a textile or dishes, with the aqueous liquor prepared according to (a).