DE102023212179A1 - Concentrated detergent preparation with improved properties - Google Patents

Abstract

Detergent preparation containing, based on its total weight,
a) 1 to 8 wt.% of polyalkoxylated amine having a weight-average molecular weight M _w in the range from 600 g/mol to 10,000 g/mol, which is obtainable by reacting ammonia or primary alkyl or hydroxyalkylamines having a molecular weight below 200 g/mol with alkylene oxides;
b) 0.5 to 8 wt.% of ethoxylated polyethyleneimine having ethylene oxide segments bonded to the nitrogen atoms of the polyethyleneimine;
c) 0.5 to 7 wt.% of alkoxylated polyethyleneimine having alkylene oxide segments bonded to the nitrogen atoms of the polyethyleneimine, wherein the alkylene oxide segments comprise ethylene oxide segments and C ₃ -C ₆ alkylene oxide segments; and washing processes using these detergent preparations.

Description

The present invention relates to a polymer-based, highly concentrated detergent preparation. Furthermore, the application relates to detergent portion units comprising this detergent preparation and to a method for washing textiles using the detergent preparation or the detergent portion unit.

The packaging and distribution of detergents and cleaning agents are constantly evolving. For some time now, a key focus has been on convenient dosing of detergents and cleaning agents by the consumer and simplifying the steps required to carry out a washing or cleaning process. Pre-portioned detergents or cleaning agents, such as foil pouches with one or more compartments for solid or liquid detergents or cleaning agents, offer a technical solution.

A relevant trend for the production of these film bags is the miniaturization of these bags. In addition to increased consumer acceptance due to easier handling, this development is primarily driven by sustainability aspects, for example, with regard to transport volumes and costs and the amount of packaging used.

The concentration of modern detergents, especially modern liquid detergents, generally influences their optical and rheological properties, impacts their storage stability, and can affect their cleaning performance, especially if the high concentration of active ingredients leads to incompatibilities. Substance classes that have gained increasing importance in the course of the concentration of detergent formulations are enzymes and washing and cleaning-active polymers.

In the international application WO 2016/191238 A1 Textile detergents containing ethoxylated polyethyleneimine and alkyl ether sulfate are described.

The international application 2022/063487 describes textile detergents based on a combination of polyalkoxylated amines and alkyleneimines.

The application was based on the objective of providing visually appealing, concentrated, flowable detergent preparations that could be produced and portioned simply and efficiently, exhibited good storage stability, and were characterized, in particular, by good cleaning results. In particular, the detergent preparation should be packaged in water-soluble sachets and be based predominantly on ingredients that can be produced at least partially from renewable raw materials.

1. a) 1 bis 8 Gew.-% polyalkoxyliertes Amin mit einem gewichtsmittleren Molekulargewicht M_w im Bereich von 600 g/mol bis 10000 g/mol, das erhältlich ist durch Umsetzung von Ammoniak oder primären Alkyl- oder Hydroxyalkylaminen, die ein Molekulargewicht unter 200 g/mol aufweisen, mit Alkylenoxiden;
2. b) 0,5 bis 8 Gew.-% ethoxyliertes Polyethylenimin mit Ethylenoxid-Segmenten, die an die Stickstoffatome des Polyethylenimins gebunden sind;
3. c) 0,5 bis 7 Gew.-% alkoxyliertes Polyethylenimin mit Alkylenoxid-Segmenten, die an die Stickstoffatome des Polyethylenimins gebunden sind, wobei die Alkylenoxid-Segmente Ethylenoxid-Segmenten und C₃-C₆-Alkylenoxid-Segmente umfassen.

A first subject matter of the application is a detergent preparation containing, based on its total weight,

1. a) 1 to 8 wt.% of polyalkoxylated amine having a weight-average molecular weight M _w in the range from 600 g/mol to 10,000 g/mol, which is obtainable by reacting ammonia or primary alkyl or hydroxyalkylamines having a molecular weight below 200 g/mol with alkylene oxides;
2. b) 0.5 to 8 wt.% of ethoxylated polyethyleneimine having ethylene oxide segments bonded to the nitrogen atoms of the polyethyleneimine;
3. c) 0.5 to 7 wt.% of alkoxylated polyethyleneimine having alkylene oxide segments bonded to the nitrogen atoms of the polyethyleneimine, wherein the alkylene oxide segments comprise ethylene oxide segments and C ₃ -C ₆ alkylene oxide segments.

The detergent preparation is preferably free-flowing under standard conditions (20°C, 1013 mbar). Preferred detergent preparations have a viscosity (21°C, Brookfield Viscometer Type DV-II. Pro, spindle no. 2, 20 rpm) above 400 mPas, preferably above 1000 mPas.

The core of the detergent formulation is the combination of three detergent polymers. Surprisingly, this combination has been shown to improve the detergent formulation's cleaning performance.

A first optional component of the detergent preparation is the polyalkoxylated amine a). The weight fraction of this amine in the total weight of the detergent preparation is 1 to 8 wt. %, preferably 2 to 7 wt. %, and in particular 3 to 6 wt. %.

Preferred polyalkoxylated amines have a weight-average molecular weight M _w in the range from 1300 g/mol to 6000 g/mol, in particular from 1400 g/mol to 4500 g/mol. (The average molecular weights given here and later for other polymers are weight-average molecular weights M _w , which can basically be determined by gel permeation chromatography with the aid of an RI detector, the measurement being advantageously carried out against an external standard.) They can be prepared in a known manner from ammonia, a monoalkylamine, a monoalkyl-monoalkanolamine or a monoalkyl-dialkanolamine or a mono-, di- or trialkanolamine, for example triethanolamine, methyl-, ethyl-, propyl- and isopropyl-diethanolamine, methyl-, ethyl-, propyl- and isopropyl-diisopropanolamine, tripropanolamine, triisopropanolamine, N,N-di-(2-hydroxyethyl)cyclohexylamine, N,N-di-(2-hydroxypropyl)cyclohexylamine, n-butylamine, n-hexylamine, n-octylamine, Isopropylamine, sec-butylamine, tert-butylamine, cyclohexylamine, 2-ethylhexylamine, 2-phenylethylamine and mixtures thereof, which is reacted with an alkylene oxide, in particular selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide and mixtures thereof, in particular with a mixture containing propylene oxide and preferably ethylene oxide, particularly preferably with propylene oxide. The polyalkoxylated amines obtainable in this way can be block or random structures. Particular preference is given, inter alia, to a polyalkoxylated amine obtainable by propoxylation of triethanolamine, preferably with a length of the three side arms of 15 propylene oxide units each. Likewise preferred is a polyalkoxylated amine obtainable by propoxylation of triisopropanolamine, preferably with a length of the three side arms of 15 propylene oxide units each. Also suitable are polyalkoxylated monoalkylamines having a linear, branched, or cyclic alkyl group, wherein the alkoxylation is carried out with an alkylene oxide selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, and mixtures thereof, preferably with a mixture containing propylene oxide, particularly preferably with propylene oxide. Also preferred is a polyalkoxylated amine obtainable by propoxylation of tert-butylamine, preferably with a length of the two side arms of 12 propylene oxide units each.

in der R für eine lineare, gegebenenfalls verzweigte oder gegebenenfalls cyclische Alkylgruppe mit 1 bis 12 C-Atomen oder einer Gruppe -(CH₂CHR'O)_n''-(CH₂CHR''O)_m''-H steht,
R' und R'' unabhängig voneinander für H, CH₃ oder CH₂CH₃ stehen,
n, n' und n'' unabhängig voneinander für Zahlen von 0 bis 30, vorzugsweise von 0 bis 10 und insbesondere 0 bis 5 stehen, und
m, m' und m'' unabhängig voneinander für Zahlen von 0 bis 30, vorzugsweise von 5 bis 20 und insbesondere von 12 bis 16 stehen,
mit der Maßgabe, dass die Summe n + n' + n'' + m + m' + m'' mindestens 14 ist, vorzugsweise im Bereich von 18 bis 100 und insbesondere im Bereich von 20 bis 70 liegt. Bevorzugt ist in den Verbindungen der Formel I mindestens einer der Reste R' und R'' eine CH₃-Gruppe.Preferred polyalkoxylated amines satisfy the general formula (I),

in which R represents a linear, optionally branched or optionally cyclic alkyl group having 1 to 12 C atoms or a group -(CH ₂ CHR'O) _n'' -(CH ₂ CHR''O) _m'' -H,
R' and R'' independently represent H, CH ₃ or CH ₂ CH ₃ ,
n, n' and n'' independently of one another represent numbers from 0 to 30, preferably from 0 to 10 and in particular 0 to 5, and
m, m' and m'' independently of one another represent numbers from 0 to 30, preferably from 5 to 20 and in particular from 12 to 16,
with the proviso that the sum n + n' + n'' + m + m' + m'' is at least 14, preferably in the range from 18 to 100 and in particular in the range from 20 to 70. Preferably, in the compounds of formula I, at least one of the radicals R' and R'' is a CH ₃ group.

Polyalkoxylated amines that are particularly preferred due to their cleaning performance are those obtainable by reacting triethanolamine with alkylene oxides, preferably by reacting triethanolamine with ethylene oxide and propylene oxide. Polyalkoxylated amines that are obtainable by reacting triethanolamine with ethylene oxide and subsequent reaction with propylene oxide are very particularly preferred.

As a further optional component, the detergent preparation contains, in addition to the polyalkylene imine a), an ethoxylated polyalkyleneimine b) with ethylene oxide segments bonded to the nitrogen atoms of the polyethyleneimine. Detergent preparations particularly preferred due to their cleaning performance contain, based on their total weight, 0.7 to 6 wt.%, preferably 1 to 4 wt.%, of ethoxylated polyethyleneimine b).

The ethoxylated polyalkyleneimine b) is a polymer with a polyalkyleneimine backbone bearing polyalkoxy groups on the nitrogen atoms. The ethoxylated polyethyleneimine b) preferably has a polyethyleneimine backbone with a weight-average molecular weight in the range from 100 g/mol to 2000 g/mol, in particular from 400 g/mol to 800 g/mol. The weight-average molecular weight of the ethoxylated polyethyleneimine b) is preferably from 5000 g/mol to 20,000 g/mol, in particular from 8000 g/mol to 14,000 g/mol.

The polyalkyleneimine has primary amino functions at the ends and preferably both secondary and tertiary amino functions in the interior; if appropriate, it can also have only secondary amino functions in the interior, resulting in a linear rather than a branched-chain polyalkyleneimine. The ratio of primary to secondary amino groups in the polyalkyleneimine is preferably in the range from 1:0.5 to 1:1.5, in particular in the range from 1:0.7 to 1:1. The ratio of primary to tertiary amino groups in the polyalkyleneimine is preferably in the range from 1:0.2 to 1:1, in particular in the range from 1:0.5 to 1:0.8. The N atoms in the polyalkyleneimine are separated from one another by alkylene groups having 2 to 12 C atoms, in particular 2 to 6 C atoms, although not all alkylene groups need to have the same number of C atoms. Particularly preferred are ethylene groups, 1,2-propylene groups, 1,3-propylene groups, and mixtures thereof. The primary amino functions in the polyalkyleneimine can carry one or two polyalkoxy groups, and the secondary amino functions can carry one polyalkoxy group, although not every amino function needs to be substituted by an alkoxy group. The average number of alkoxy groups per primary and secondary amino function in the ethoxylated polyalkyleneimine is preferably 5 to 100, especially 10 to 50. The ethoxylated polyalkyleneimines are obtainable by reacting the polyalkyleneimines with ethylene oxide.

The third essential component of the detergent preparation is the alkoxylated polyethyleneimines c). The alkoxylated polyethyleneimines c) are different from the ethoxylated polyethyleneimines b).

The weight fraction of the alkoxylated polyethyleneimine in the total weight of the detergent preparation is preferably 0.7 to 5 wt.% and in particular 1 to 3 wt.% alkoxylated polyethyleneimine c). These weight fractions have proven particularly advantageous with regard to the desired cleaning performance.

The ethoxylated polyalkyleneimine c) is a polymer with a polyalkyleneimine backbone bearing polyalkoxy groups on the nitrogen atoms. The alkoxylated polyethyleneimine c) preferably has a polyethyleneimine backbone with a weight-average molecular weight in the range from 100 g/mol to 2000 g/mol, in particular from 400 g/mol to 800 g/mol. The weight-average molecular weight of the alkoxylated polyethyleneimine c) is preferably from 1000 g/mol to 1,000,000 g/mol, particularly preferably from 5000 to 500,000 g/mol, and in particular from 10,000 g/mol to 50,000 g/mol.

The polyalkyleneimine has primary amino functions at the ends and preferably both secondary and tertiary amino functions in the interior; if appropriate, it can also have only secondary amino functions in the interior, resulting in a linear rather than a branched-chain polyalkyleneimine. The ratio of primary to secondary amino groups in the polyalkyleneimine is preferably in the range from 1:0.5 to 1:1.5, in particular in the range from 1:0.7 to 1:1. The ratio of primary to tertiary amino groups in the polyalkyleneimine is preferably in the range from 1:0.2 to 1:1, in particular in the range from 1:0.5 to 1:0.8. The N atoms in the polyalkyleneimine are separated from one another by alkylene groups having 2 to 12 C atoms, in particular 2 to 6 C atoms, although not all alkylene groups need to have the same number of C atoms. Particularly preferred are ethylene groups, 1,2-propylene groups, 1,3-propylene groups, and mixtures thereof. The primary amino functions in the polyalkyleneimine can carry one or two polyalkoxy groups, and the secondary amino functions can carry one polyalkoxy group, although not every amino function needs to be substituted by an alkoxy group. The average number of alkoxy groups per primary and secondary amino function in the alkoxylated polyalkyleneimine is preferably 5 to 100, in particular 10 to 50.

The alkylene oxide segments of the alkoxylated polyethyleneimine c) preferably comprise ethylene oxide segments and C ₃ -alkylene oxide segments. Very particular preference is given to alkoxylated polyethyleneimines c) in which the alkylene oxide segments consist of ethylene oxide segments and C ₃ -alkylene oxide segments. These preferred alkoxylated polyalkyleneimines c) are obtainable, for example, by reacting the polyalkyleneimines with ethylene oxide and propylene oxide. Very particular preference is given to alkoxylated polyalkyleneimines c) which are obtainable by reacting polyalkyleneimines with ethylene oxide and subsequent reaction with propylene oxide.

For the cleaning performance of the detergent composition, it has proven advantageous if the ethoxylated polyethyleneimine b) and the alkoxylated polyethyleneimine c) are present in a weight ratio of 3:2 to 2:3, preferably 4:3 to 3:4.

For the same reason, detergent preparations are preferred in which the weight ratio of polyalkoxylated amine a) to the alkoxylated polyethyleneimines b) and c) is from 2:1 to 1:2, preferably from 3:2 to 2:3.

Preferred detergent preparations contain, based on their total weight, 35 to 60 wt.%, preferably 40 to 55 wt.% surfactant.

The group of surfactants includes nonionic, anionic, cationic, and amphoteric surfactants. The compositions according to the invention can comprise one or more of the aforementioned surfactants. Particularly preferred compositions contain surfactants from the group of anionic and nonionic surfactants.

The anionic surfactant is preferably selected from the group comprising C ₉ -C ₁₃ alkylbenzenesulfonates, olefinsulfonates, C ₁₂ -C ₁₈ alkanesulfonates, estersulfonates, alk(en)yl sulfates, fatty alcohol ether sulfates, and mixtures thereof. Compositions comprising C ₉ -C ₁₃ alkylbenzenesulfonates and fatty alcohol ether sulfates as anionic surfactant have particularly good dispersing properties. Suitable sulfonate-type surfactants are preferably C ₉ -C ₁₃ alkylbenzenesulfonates, olefinsulfonates, i.e. mixtures of alkene and hydroxyalkanesulfonates, and disulfonates, such as those obtained, for example, from C ₁₂ -C ₁₈ monoolefins with a terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Also suitable are C ₁₂ -C ₁₈ alkanesulfonates and the esters of α-sulfofatty acids (estersulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.

Preferred detergent preparations contain, based on their total weight, 18 to 40% by weight, preferably 24 to 36% by weight, of anionic surfactant.

in der
R' und R'' unabhängig H oder Alkyl sind und zusammen 8 bis 18, vorzugsweise 9 bis 15 und insbesondere 9 bis 13 C-Atome enthalten und Y⁺ ein einwertiges Kation oder den n-ten Teil eines n-wertigen Kations (insbesondere Monoethanolamin) bedeuten.It is particularly preferred if the composition contains at least one anionic surfactant of formula (II),

in the
R' and R'' are independently H or alkyl and together contain 8 to 18, preferably 9 to 15 and in particular 9 to 13 C atoms and Y ⁺ represents a monovalent cation or the nth part of an n-valent cation (in particular monoethanolamine).

The group of alkyl ether sulfates includes fatty alcohol ether sulfates, for example the sulfuric acid monoesters of straight-chain or branched C ₇ -C ₂₁ alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C 9-11 alcohols with an average of 3.5 mol of ethylene oxide (EO) or C 12-18 fatty alcohols with 1 to 4 EO. Alkyl ether sulfates with the formula (III) are preferred. R ¹ -O-(AO)n-SO ₃ ^- X ⁺ (III)

In this formula (II), R ¹ represents a linear or branched, substituted or unsubstituted alkyl radical, preferably a linear, unsubstituted alkyl radical, particularly preferably a fatty alcohol radical. Preferred radicals R ¹ of the formula (III) are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl radicals and mixtures thereof, with preference being given to those having an even number of carbon atoms. Particularly preferred radicals R ¹ of the formula (III) are derived from fatty alcohols having 12 to 18 carbon atoms, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl, or stearyl alcohol, or from oxo alcohols having 10 to 20 carbon atoms.

AO in formula (III) is an integer from 1 to 50, preferably from 1 to 20 and in particular from 2 to 10. n is very particularly preferably 2, 3, 4, 5, 6, 7 or 8. X is a monovalent cation or the nth part of an n-valent cation, preference being given to the alkali metal ions and among them Na ⁺ or K ⁺ , with Na ⁺ being extremely preferred. Further cations X+ can be selected from NH4 ⁺ , % Zn ²⁺ , ½ Mg ²⁺ , ½ Ca ²⁺ , ½ Mn ²⁺ , and mixtures thereof as well as primary and secondary amines, in particular monoethanolamine.

mit k = 11 bis 19, n = 2, 3, 4, 5, 6, 7 oder 8. Ganz besonders bevorzugte Vertreter sind Na Fettalkoholethersulfate mit 12 bis 18 C-Atomen und 2 EO (k = 11 bis 13, n = 2 in Formel III). Der angegebene Ethoxylierungsgrad stellt einen statistischen Mittelwert dar, der für ein spezielles Produkt eine ganze oder eine gebrochene Zahl sein kann. Die angegebenen Alkoxylierungsgrade stellen statistische Mittelwerte dar, die für ein spezielles Produkt eine ganze oder eine gebrochene Zahl sein können. Bevorzugte Alkoxylate/Ethoxylate weisen eine eingeengte Homologenverteilung auf (narrow range ethoxylates, NRE).Particularly preferred compositions contain an alkyl ether sulfate selected from fatty alcohol ether sulfates of the formula (IV)

with k = 11 to 19, n = 2, 3, 4, 5, 6, 7 or 8. Very particularly preferred representatives are Na fatty alcohol ether sulfates with 12 to 18 C atoms and 2 EO (k = 11 to 13, n = 2 in formula III). The stated degree of ethoxylation represents a statistical mean, which can be a whole or fractional number for a specific product. The stated degrees of alkoxylation represent statistical mean, which can be a whole or fractional number for a specific product. Preferred alkoxylates/ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).

Although alkyl ether sulfates can generally be used in detergent preparations, the addition of an anionic surfactant from the group of C ₈ - _{C 18} alkylbenzenesulfonates has proven superior in terms of cleaning performance. In a particularly preferred embodiment, the detergent preparation contains, based on its total weight, less than 10 wt. %, preferably less than 5 wt. %, particularly preferably less than 2 wt. %, and in particular no anionic surfactant from the group of alkyl ether sulfates.

In summary, preferred detergent preparations contain, based on their total weight, 15 to 35 wt.%, preferably 18 to 32 wt.% of anionic surfactant from the group of C _8-18 alkylbenzenesulfonates.

The use of anionic surfactants from the group of alkanolamine C _8-18 alkylbenzenesulfonates has proven to be particularly advantageous for the storage stability of the detergent preparation.

In preferred detergent preparations, the anionic surfactant is selected from the group of alkanolamine C _8-18 alkylbenzenesulfonates with alkanolamine from the group monoethanolamine, monoisopropanolamine, diisopropanolamine, preferably from the group monoethanolamine.

In very particularly preferred detergent preparations, the weight fraction of anionic surfactants from the group of alkanolamine-C _8-18 alkylbenzenesulfonates, preferably from the group of alkanolamine-C _8-18 alkylbenzenesulfonates with alkanolamine from the group monoethanolamine, monoisopropanolamine, diisopropanolamine, in particular from the group monoethanolamine, is 15 to 35 wt.%, preferably 18 to 32 wt.%.

The use of fatty acids has proven advantageous for storage stability. Preferred detergent preparations therefore contain, based on their total weight, 4 to 12% by weight, preferably 6 to 10% by weight, of fatty acid. Particularly preferred fatty acids are selected from the group of C _12-18 fatty acids, preferably from the group of caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, and mixtures thereof. For the purposes of this application, the fatty acids are classified as anionic surfactants.

The detergent preparations contain a nonionic surfactant as a further preferred optional component. Its weight fraction of the total weight of the detergent preparation is preferably 12 to 30 wt.%, preferably 15 to 28 wt.%, and in particular 18 to 26 wt.%.

In particular, the use of non-ionic surfactants from the group of alkyl ethoxylates is preferred, with preferred alkyl ethoxylates being from the group of ethoxylated primary C _8-18 alcohols, preferably the ethoxylated primary C _8-18 alcohols with a degree of alkoxylation ≥ 4, particularly preferably the C _12-14 alcohols with 4 EO or 7 EO, the C _9-11 alcohols with 7 EO, the C _13-15 alcohols with 5 EO, 7 EO or 8 EO, the C _13-15 oxo alcohols with 7 EO, C _12-18 alcohols with 5 EO or 7 EO, in particular C _12-18 fatty alcohols with 7 EO or C _13-15 oxo alcohols with 7 EO.

In summary, preferred detergent preparations contain, based on their total weight, 12 to 30 wt.%, preferably 15 to 28 wt.% and in particular 18 to 26 nonionic surfactant from the group of ethoxylated primary C _8-18 alcohols, preferably ethoxylated primary C _8-18 alcohols with a degree of alkoxylation ≥ 4, particularly preferably C _12-14 alcohols with 4 EO or 7 EO, C _9-11 alcohols with 7 EO, C _13-15 alcohols with 5 EO, 7 EO or 8 EO, C _13-15 oxo alcohols with 7 EO, C _12-18 alcohols with 5 EO or 7 EO, in particular C _12-18 fatty alcohols with 7 EO or C _13-15 -oxo alcohols with 7 EO.

With regard to the rheological properties of the detergent preparation, its processability and cleaning effect, it has proven advantageous to use non-ionic surfactant and anionic surfactant in a weight ratio of 3:1 to 1:3, preferably 2:1 to 1:2 and in particular 3:2 to 2:3.

Preferred detergent preparations contain, based on their total weight, 5 to 20% by weight, preferably 7 to 18% by weight, of water.

In addition to water, at least one organic solvent is preferably used as an additional solvent. The use of aqueous-organic solvent systems has proven particularly advantageous for manufacturability and storage and is therefore preferred.

In a preferred embodiment, the detergent preparation contains, based on its total weight, 5 to 30 wt.%, preferably 10 to 20 wt.% of organic solvent.

Preferred organic solvents are selected from the group ethanol, n-propanol, i-propanol, butanols, glycol, propanediol, butanediol, methylpropanediol, glycerol, diglycol, propyl diglycol, butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, methoxytriglycol, ethoxytriglycol, butoxytriglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol t-butyl ether, di-n-octyl ether and mixtures thereof, preferably from the group propanediol, glycerin, monoethanolamine and their mixtures.

The detergent preparation contains a phosphonate as a preferred optional ingredient.

The weight proportion of the phosphonate in the total weight of the detergent preparation is preferably 0.1 to 3 wt.% and in particular 0.2 to 1 wt.%.

As the phosphonate compound, a phosphonate is preferably selected from the group of hydroxyalkane and/or aminoalkane phosphonates, preferably from the group of aminoalkane phosphonates and in particular from the group of ethylenediaminetetramethylenephosphonate (EDTMP) and diethylenetriaminepentamethylenephosphonate (DTPMP).

To further increase the cleaning performance, preferred detergent preparations contain, based on their total weight, 0.5 to 7 wt.%, preferably 1.0 to 6 wt.% enzyme preparations.

In addition to the actual enzyme protein, an enzyme preparation comprises other components such as enzyme stabilizers, carrier materials, or fillers. The enzyme protein usually constitutes only a fraction of the total weight of the enzyme preparation. Preferably used enzyme preparations contain between 0.1 and 40 wt.%, preferably between 0.2 and 30 wt.%, more preferably between 0.4 and 20 wt.%, and most preferably between 0.8 and 10 wt.% of the enzyme protein. In such compositions, an enzyme stabilizer can be present in an amount of 0.05 to 35 wt.%, preferably 0.05 to 10 wt.%, based on the total weight of the enzyme composition.

The protein concentration can be determined using known methods, for example the BCA method (bicinchoninic acid; 2,2'-biquinolyl-4,4'-dicarboxylic acid) or the biuret method. The determination of the active protein concentration is carried out by titration of the active sites under Use of a suitable irreversible inhibitor (for proteases, for example, phenylmethylsulfonyl fluoride (PMSF)) and determination of the residual activity.

It is preferred if the detergent preparation contains at least one enzyme preparation, preferably at least three enzyme preparations of enzymes from the group lipase, mannanase, amylase, protease, cellulase, hexosaminidase, preparations of a pectinolytic enzyme and endoglucanase.

Detergent preparations preferred with regard to their cleaning performance contain, based on their total weight, 0.1 to 0.4 wt.% and in particular 0.2 to 0.3 wt.% of hexosaminidase preparation, particularly preferably b-hexosaminidase preparation.

The term “hexosaminidase” refers to a polypeptide with hexosaminidase activity (hexosaminidases) and includes enzymes that catalyze the hydrolysis of N-acetyl-D-hexosamine or N-acetyl-glucosamine polymers.

Polypeptides with hexosaminidase activity include dispersins such as Dispersin B (DspB), which are β-N-acetylglucosamine dispersins belonging to the glycoside hydrolase 20 family. Dispersins are produced by the periodontal pathogen Aggregatibacter actinomycetemcomitans, a Gram-negative oral bacterium. Dispersin B is a β-hexosaminidase that specifically hydrolyzes β-1,6-glycosidic bonds of acetylglucosamine polymers. The use of hexosaminidases from the β-hexosaminidase group is preferred.

According to the invention, it is preferred if the detergent preparation contains at least one lipase preparation. Lipases preferred according to the invention are selected from at least one enzyme from the group consisting of triacylglycerol lipase (E.C. 3.1.1.3), lipoprotein lipase (E.C. 3.1.1.34), and monoglyceride lipase (E.C. 3.1.1.23).

Preferred lipase preparations according to the invention are the commercial products marketed by Amano Pharmaceuticals under the names Lipase M-AP10®, Lipase LE®, and Lipase F® (also Lipase JV®). Lipase F®, for example, is naturally present in Rhizopus oryzae. Lipase M-AP10®, for example, is naturally present in Mucor javanicus.

A highly preferred lipase is commercially available under the trade name Lipex® from Novozymes (Denmark) and can be advantageously used in the detergent preparations according to the invention. Lipase Lipex® 100 L is particularly preferred.

Preferred detergent preparations are characterized in that they contain, based on their total weight, 0.01 to 1 wt.%, in particular 0.05 to 0.3 wt.%, of lipase preparation.

The detergent preparations preferably contain at least one amylase, in particular an α-amylase. α-Amylases (EC 3.2.1.1) act as enzymes that hydrolyze internal α-1,4-glycosidic bonds of starch and starch-like polymers. Examples include the α-amylases from Bacillus licheniformis, B. amyloliquefaciens, and B. stearothermophilus, as well as their improved versions for use in detergents or cleaning agents. The enzyme from B. licheniformis is available from Novozymes under the trade name ^Termamyl® and from Genencor under the trade name ^Purastar® ST. Further developments of these α-amylases are available from Novozymes under the trade names ^Duramyl® and ^Termamyl® ultra, from Genencor under the name ^Purastar® OxAm and from Daiwa Seiko Inc., Tokyo, Japan, as ^Keistase® . The α-amylase from B. amyloliquefaciens is marketed by Novozymes under the name ^BAN® , and derived variants of the α-amylase from B. stearothermophilus are marketed under the names ^BSG® and ^Novamyl® , also by Novozymes. Examples of α-amylases from other organisms are the further developments of the α-amylase from Aspergillus niger and A. oryzae, available from Novozymes under the trade names Fungamyl® ^.

The proportion by weight of the amylase preparation, in particular the α-amylase preparation, in the total weight of the detergent preparation is preferably 0.1 to 2 wt.%, in particular 0.2 to 1 wt.%.

According to the invention, it is preferred if the detergent preparation contains at least one protease as an enzyme. A protease is an enzyme that cleaves peptide bonds by hydrolysis. Each According to the invention, enzymes from class EC 3.4 fall under this (comprising each of the thirteen subclasses falling under it). "Protease activity" is present according to the invention if the enzyme has proteolytic activity (EC 3.4). Various types of protease activity are known: The three main types are: trypsin-like, in which cleavage of the amide substrate occurs after the amino acids Arg or Lys at P1; chymotrypsin-like, in which cleavage occurs after one of the hydrophobic amino acids at P1; and elastase-like, in which cleavage of the amide substrate occurs after Ala at P1.

Surprisingly, it was found that a protease of the alkaline protease type from Bacillus lentus DSM 5483 or a sufficiently similar protease (in terms of sequence identity) that exhibits several of these modifications in combination is particularly suitable for use in the detergent preparations according to the invention and is advantageously stabilized therein. Advantages of using this protease thus arise in particular with regard to washing performance and/or stability.

Most preferably, the detergent preparation according to the invention contains protease of the alkaline protease type from Bacillus lentus DSM 5483 or a sufficiently similar protease (based on sequence identity) which has several of these changes in combination,

The weight proportion of the protease preparation in the total weight of the detergent preparation is preferably 0.2 to 4 wt% and in particular 0.4 to 3 wt%.

Preferred detergent preparations further contain, as an optional ingredient, based on their total weight, 0.05 to 2 wt.%, preferably 0.1 to 0.4 wt.% of a preparation of a pectinolytic enzyme.

For the purposes of the present invention, the pectinolytic enzymes include enzymes with the names pectinase, pectate lyase, pectin esterase, pectin demethoxylase, pectin methoxylase, pectin methylesterase, pectase, pectin methylesterase, pectin esterase, pectin pectyl hydrolase, pectin depolymerase, 20 endopolygalacturonase, pectolase, pectin hydrolase, pectin polygalacturonase, endo-polygalacturonase, poly-α-1,4-galacturonide glycanohydrolase, endogalacturonase, endo-D-galacturonase, galacturan 1,4-α-galacturonidase, exopolygalacturonase, poly(galacturonate) hydrolase, exo-D-galacturonase, Exo-D-galacturonanase, exopoly-D-galacturonase, exo-poly-α-galacturonosidase, exopolygalacturonosidase, or exopolygalacturanosidase. The use of pectate lyases is particularly preferred.

Within the EC classification of enzymes, the numerical classification system for enzymes, the pectinolytic enzymes belong in particular to the enzyme classes (Enzyme Commission number) EC 3.1.1.11, EC 3.2.1.15, EC 3.2.1.67 and EC 3.2.1.82 and therefore belong to the third of the six main enzyme classes, the 10 hydrolases (EC 3.0), of which the glycosylases (EC 3.2.-.-) and, in turn, the glycosidases (EC 3.2.1.-), i.e. enzymes that hydrolyze O- and/or S-glycosyl compounds. Pectinolytic enzymes are therefore particularly effective against residues on dishes containing pectic acid and/or other galacturonans and catalyze their hydrolysis.

Pectate lyases within the meaning of the invention are enzymes which catalyze the non-hydrolytic cleavage of pectate by an endo-mechanism.

Examples of suitable pectinolytic enzymes are the enzymes and enzyme preparations available under the trade names Gamanase®, Pektinex AR®, X-Pect® or Pectaway® from Novozymes, under the trade names Rohapect UF®, Rohapect TPL®, Rohapect PTE100®, Rohapect MPE®, 30 Rohapect MA plus HC, Rohapect DA12L®, Rohapect 10L®, Rohapect B1L® from AB Enzymes and under the trade name Pyrolase® from Diversa Corp., San Diego, CA, USA.

As a preferred component, the detergent preparation contains 0.01 to 1% by weight, preferably 0.02 to 0.3% by weight of a mannanase preparation.

A mannanase catalyzes the hydrolysis of 1,4-beta-D-mannosidic bonds in mannans, galactomannans, glucomannans, and galactoglucomannans. These mannanases are classified according to enzyme nomenclature as E.C. 3.2.1.78.

The detergent preparations contain a cellulase preparation as a further preferred ingredient. Synonymous terms can be used for cellulases, in particular endoglucanase, endo-1,4-beta-glucanase, carboxymethylcellulase, endo-1,4-beta-D-glucanase, beta-1,4-glucanase, beta-1,4-endoglucan hydrolase, celludextrinase, or avicelase. The decisive factor for whether an enzyme is a cellulase within the meaning of the invention is its ability to hydrolyze 1,4-β-D-glucosidic bonds in cellulose.

Cellulases (endoglucanases, EG) suitable according to the invention include, for example, fungal, endoglucanase (EG)-rich compositions which are offered by the company Novozymes under the trade name Celluzyme®. The products Endolase® and Carezyme®, also available from Novozymes, are based on the 50 kD EG and the 43 kD EG from Humicola insolens DSM 1800, respectively. Other commercial products from this company that can be used are Cellusoft®, Renozyme® and Celluclean®. Also suitable are cellulases available from AB Enzymes, Finland, under the trade names Ecostone® and Biotouch®, which are based at least in part on the 20 kD EG from Melanocarpus. Other cellulases from AB Enzymes are Econase® and Ecopulp®. Other suitable cellulases are those from Bacillus sp. CBS 670.93 and CBS 669.93, with the one from Bacillus sp. CBS 670.93 available from Danisco/Genencor under the trade name Puradax®. Other commercial products from Danisco/Genencor that can be used are "Genencor detergent cellulase L" and IndiAge®Neutra.

The weight proportion of the cellulase preparation in the total weight of the detergent preparation is preferably 0.01 to 1 wt.%, preferably 0.05 to 0.3 wt.%.

As a further optional component, a preferred detergent preparation comprises 0.2 to 4% by weight, preferably 0.5 to 3% by weight, of fragrance preparation.

In addition to the actual fragrances, the fragrance preparation includes, for example, solvents, solid carrier materials or stabilizers.

A fragrance is a chemical substance that stimulates the sense of smell. To stimulate the sense of smell, the chemical substance should be at least partially dispersible in the air, i.e., the fragrance should be at least slightly volatile at 25°C. If the fragrance is very volatile, the odor intensity quickly fades. However, with lower volatility, the odor impression is more lasting, i.e., it does not disappear as quickly. In one embodiment, the fragrance therefore has a melting point in the range of -100°C to 100°C, preferably -80°C to 80°C, even more preferably -20°C to 50°C, in particular -30°C to 20°C. In a further embodiment, the fragrance has a boiling point in the range from 25°C to 400°C, preferably from 50°C to 380°C, more preferably from 75°C to 350°C, in particular from 100°C to 330°C.

Overall, a chemical substance should not exceed a certain molecular mass to function as a fragrance, since at too high a molecular mass, the required volatility can no longer be guaranteed. In one embodiment, the fragrance has a molecular mass of 40 to 700 g/mol, more preferably 60 to 400 g/mol.

The smell of a fragrance is perceived as pleasant by most people and often corresponds to the smell of flowers, fruits, spices, bark, resin, leaves, grasses, mosses, and roots. Fragrances can also be used to mask unpleasant odors or to impart a desired scent to a non-odorous substance. Individual odorous compounds, such as synthetic products such as esters, ethers, aldehydes, ketones, alcohols, and hydrocarbons, can be used as fragrances.

Preferably, mixtures of different fragrances are used, which together create an appealing scent. Such a mixture of fragrances can also be referred to as a perfume or perfume oil. Such perfume oils can also contain natural fragrance mixtures, such as those obtainable from plant sources.

To prolong the fragrance effect, it has proven advantageous to encapsulate the fragrance. In one embodiment, at least part of the fragrance is used in encapsulated form (fragrance capsules), particularly in microcapsules. However, the entire fragrance can also be used in encapsulated form. The microcapsules can be water-soluble and/or water-insoluble.

• - Duftstoffkapseln ausgewählt sind aus der Gruppe der Melamin-Harnstoff-Formaldehyd-haltigen Duftstoffkapseln, Melamin-Formaldehyd-haltigen Duftstoffkapseln, Harnstoff-Formaldehyd-haltigen Duftstoff-kapseln;
• - Biopolymer-haltige Duftstoffkapseln, insbesondere aus der Gruppe der Protein-haltigen Duftstoffkapseln und Polysaccharid-haltigen Duftstoffkapseln, insbesondere den Gelatinehaltigen Duftstoffkapseln, Chitosan-haltigen Duftstoffkapseln, Stärke-haltigen Duftstoffkapsel und Alginat-haltigen Duftstoffkapseln.

Fragrance capsules are typically characterized by a fragrance-containing core and a layer or shell surrounding this core. The capsules familiar to those skilled in the art can be used as fragrance capsules. The preferred group of fragrance capsules can be divided into two groups:

• - fragrance capsules are selected from the group of fragrance capsules containing melamine-urea-formaldehyde, fragrance capsules containing melamine-formaldehyde, fragrance capsules containing urea-formaldehyde;
• - Biopolymer-containing fragrance capsules, in particular from the group of protein-containing fragrance capsules and polysaccharide-containing fragrance capsules, in particular gelatin-containing fragrance capsules, chitosan-containing fragrance capsules, starch-containing fragrance capsules and alginate-containing fragrance capsules.

1. ¹⁾ polyalkoxyliertes Amin mit einem gewichtsmittleren Molekulargewicht M_w im Bereich von 600 g/mol bis 10000 g/mol, das erhältlich ist durch Umsetzung von Ammoniak oder primären Alkyl- oder Hydroxyalkylaminen, die ein Molekulargewicht unter 200 g/mol aufweisen, mit Alkylenoxiden
2. ²⁾ ethoxyliertes Polyethylenimin mit Ethylenoxid-Segmenten, die an die Stickstoffatome des Polyethylenimins gebunden sind
3. ³⁾ alkoxyliertes Polyethylenimin mit Alkylenoxid-Segmenten, die an die Stickstoffatome des Polyethylenimins gebunden sind, wobei die Alkylenoxid-Segmente Ethylenoxid-Segmenten und C₃-C₆-Alkylenoxid-Segmente umfassen
4. ⁴⁾ anionisches Tensid aus der Gruppe der C_8-18-Alkylbenzolsulfonate vorzugsweise aus der Gruppe der Alkanolamin-C_8-18-Alkylbenzolsulfonate mit Alkanolamin aus der Gruppe Monoethanolamin, Monoisopropanolamin, Diisopropanolamin, insbesondere aus der Gruppe Monoethanolamin
5. ⁵⁾ nichtionisches Tensid aus der Gruppe der ethoxylierten primären C_8-18-Alkohole
6. ⁶⁾ polyalkoxyliertes Amin mit einem gewichtsmittleren Molekulargewicht M_w im Bereich von 600 g/mol bis 10000 g/mol, das erhältlich ist durch von Triethanolamin mit Ethylenoxid und Propylenoxid
7. ⁷⁾ alkoxyliertes Polyethylenimin mit Alkylenoxid-Segmenten, die an die Stickstoffatome des Polyethylenimins gebunden sind, wobei die Alkylenoxid-Segmente Ethylenoxid-Segmenten und C₃-Alkylenoxid-Segmente umfasst

The composition of some preferred detergent preparations can be found in the following tables (data in wt. % based on the total weight of the preparation unless otherwise stated). The detergent preparations are flowable under standard conditions (20°C, 1013 mbar) and are packaged in the form of detergent portion units in which the detergent preparation is completely enclosed by a water-soluble film. formula 1 Formula 2 Formula 3 Formula 4 polyalkoxylated amine ¹⁾ 1 to 8 2 to 7 2 to 7 3 to 6 ethoxylated polyethyleneimine ²⁾ 0.5 to 8 0.5 to 8 0.7 to 6 1 to 4 alkoxylated polyethyleneimine ³⁾ 0.5 to 7 0.5 to 7 0.7 to 5 1 to 3 Surfactant 35 to 60 35 to 60 40 to 55 40 to 55 Misc to 100 to 100 to 100 to 100 Formula 6 Formula 7 Formula 8 Formula 9 polyalkoxylated amine ¹⁾ 1 to 8 2 to 7 2 to 7 3 to 6 ethoxylated polyethyleneimine ²⁾ 0.5 to 8 0.5 to 8 0.7 to 6 1 to 4 alkoxylated polyethyleneimine ³⁾ 0.5 to 7 0.5 to 7 0.7 to 5 1 to 3 anionic surfactant 18 to 40 18 to 40 18 to 40 24 to 36 non-ionic surfactant 12 to 30 12 to 30 12 to 30 18 to 26 Misc to 100 to 100 to 100 to 100 Formula 11 Formula 12 Formula 13 Formula 14 polyalkoxylated amine ¹⁾ 1 to 8 2 to 7 2 to 7 3 to 6 ethoxylated polyethyleneimine ²⁾ 0.5 to 8 0.5 to 8 0.7 to 6 1 to 4 alkoxylated polyethyleneimine ³⁾ 0.5 to 7 0.5 to 7 0.7 to 5 1 to 3 anionic surfactant ⁴⁾ 18 to 40 18 to 40 18 to 40 24 to 36 fatty acid 4 to 12 4 to 12 4 to 12 6 to 10 non-ionic surfactant ⁵⁾ 12 to 30 12 to 30 12 to 30 18 to 26 Misc to 100 to 100 to 100 to 100 Formula 16 Formula 17 Formula 18 Formula 19 polyalkoxylated amine ¹⁾ 1 to 8 2 to 7 2 to 7 3 to 6 ethoxylated polyethyleneimine ²⁾ 0.5 to 8 0.5 to 8 0.7 to 6 1 to 4 alkoxylated polyethyleneimine ³⁾ 0.5 to 7 0.5 to 7 0.7 to 5 1 to 3 anionic surfactant 18 to 40 18 to 40 18 to 40 24 to 36 non-ionic surfactant 12 to 30 12 to 30 12 to 30 18 to 26 organic solvent 5 to 30 10 to 20 10 to 20 10 to 20 Water 5 to 20 5 to 20 7 to 18 7 to 18 Misc to 100 to 100 to 100 to 100 Formula 21 Formula 22 Formula 23 Formula 24 polyalkoxylated amine ¹⁾ 1 to 8 2 to 7 2 to 7 3 to 6 ethoxylated polyethyleneimine ²⁾ 0.5 to 8 0.5 to 8 0.7 to 6 1 to 4 alkoxylated polyethyleneimine ³⁾ 0.5 to 7 0.5 to 7 0.7 to 5 1 to 3 anionic surfactant 18 to 40 18 to 40 18 to 40 24 to 36 non-ionic surfactant 12 to 30 12 to 30 12 to 30 18 to 26 Enzyme preparation 0.5 to 7 0.5 to 7 1 to 6 1 to 6 Misc to 100 to 100 to 100 to 100 Formula 26 Formula 27 Formula 28 Formula 29 polyalkoxylated amine ¹⁾ 1 to 8 2 to 7 2 to 7 3 to 6 ethoxylated polyethyleneimine ²⁾ 0.5 to 8 0.5 to 8 0.7 to 6 1 to 4 alkoxylated polyethyleneimine ³⁾ 0.5 to 7 0.5 to 7 0.7 to 5 1 to 3 anionic surfactant ⁴⁾ 18 to 40 18 to 40 18 to 40 24 to 36 fatty acid 4 to 12 4 to 12 4 to 12 6 to 10 non-ionic surfactant ⁵⁾ 12 to 30 12 to 30 12 to 30 18 to 26 Enzyme preparation 0.5 to 7 0.5 to 7 1 to 6 1 to 6 organic solvent 5 to 30 10 to 20 10 to 20 10 to 20 Water 5 to 20 5 to 20 7 to 18 7 to 18 Misc to 100 to 100 to 100 to 100 Formula 31 Formula 32 Formula 33 Formula 34 polyalkoxylated amine ⁶⁾ 1 to 8 2 to 7 2 to 7 3 to 6 ethoxylated polyethyleneimine ²⁾ 0.5 to 8 0.5 to 8 0.7 to 6 1 to 4 alkoxylated polyethyleneimine ³⁾ 0.5 to 7 0.5 to 7 0.7 to 5 1 to 3 Surfactant 35 to 60 35 to 60 40 to 55 40 to 55 Misc to 100 to 100 to 100 to 100 Formula 36 Formula 37 Formula 38 Formula 39 polyalkoxylated amine ⁶⁾ 1 to 8 2 to 7 2 to 7 3 to 6 ethoxylated polyethyleneimine ²⁾ 0.5 to 8 0.5 to 8 0.7 to 6 1 to 4 alkoxylated polyethyleneimine ³⁾ 0.5 to 7 0.5 to 7 0.7 to 5 1 to 3 anionic surfactant 18 to 40 18 to 40 18 to 40 24 to 36 non-ionic surfactant 12 to 30 12 to 30 12 to 30 18 to 26 Misc to 100 to 100 to 100 to 100 Formula 41 Formula 42 Formula 43 Formula 44 polyalkoxylated amine ⁶⁾ 1 to 8 2 to 7 2 to 7 3 to 6 ethoxylated polyethyleneimine ²⁾ 0.5 to 8 0.5 to 8 0.7 to 6 1 to 4 alkoxylated polyethyleneimine ³⁾ 0.5 to 7 0.5 to 7 0.7 to 5 1 to 3 anionic surfactant ⁴⁾ 18 to 40 18 to 40 18 to 40 24 to 36 fatty acid 4 to 12 4 to 12 4 to 12 6 to 10 non-ionic surfactant ⁵⁾ 12 to 30 12 to 30 12 to 30 18 to 26 Misc to 100 to 100 to 100 to 100 Formula 46 Formula 47 Formula 48 Formula 49 polyalkoxylated amine ⁶⁾ 1 to 8 2 to 7 2 to 7 3 to 6 ethoxylated polyethyleneimine ²⁾ 0.5 to 8 0.5 to 8 0.7 to 6 1 to 4 alkoxylated polyethyleneimine ³⁾ 0.5 to 7 0.5 to 7 0.7 to 5 1 to 3 anionic surfactant 18 to 40 18 to 40 18 to 40 24 to 36 non-ionic surfactant 12 to 30 12 to 30 12 to 30 18 to 26 organic solvent 5 to 30 10 to 20 10 to 20 10 to 20 Water 5 to 20 5 to 20 7 to 18 7 to 18 Misc to 100 to 100 to 100 to 100 Formula 51 Formula 52 Formula 53 Formula 54 polyalkoxylated amine ⁶⁾ 1 to 8 2 to 7 2 to 7 3 to 6 ethoxylated polyethyleneimine ²⁾ 0.5 to 8 0.5 to 8 0.7 to 6 1 to 4 alkoxylated polyethyleneimine ³⁾ 0.5 to 7 0.5 to 7 0.7 to 5 1 to 3 anionic surfactant 18 to 40 18 to 40 18 to 40 24 to 36 non-ionic surfactant 12 to 30 12 to 30 12 to 30 18 to 26 Enzyme preparation 0.5 to 7 0.5 to 7 1 to 6 1 to 6 Misc to 100 to 100 to 100 to 100 Formula 56 Formula 56 Formula 57 Formula 58 polyalkoxylated amine ⁶⁾ 1 to 8 2 to 7 2 to 7 3 to 6 ethoxylated polyethyleneimine ²⁾ 0.5 to 8 0.5 to 8 0.7 to 6 1 to 4 alkoxylated polyethyleneimine ³⁾ 0.5 to 7 0.5 to 7 0.7 to 5 1 to 3 anionic surfactant ⁴⁾ 18 to 40 18 to 40 18 to 40 24 to 36 fatty acid 4 to 12 4 to 12 4 to 12 6 to 10 non-ionic surfactant ⁵⁾ 12 to 30 12 to 30 12 to 30 18 to 26 Enzyme preparation 0.5 to 7 0.5 to 7 1 to 6 1 to 6 organic solvent 5 to 30 10 to 20 10 to 20 10 to 20 Water 5 to 20 5 to 20 7 to 18 7 to 18 Misc to 100 to 100 to 100 to 100 Formula 61 Formula 62 Formula 63 Formula 64 polyalkoxylated amine ⁶⁾ 1 to 8 2 to 7 2 to 7 3 to 6 ethoxylated polyethyleneimine ²⁾ 0.5 to 8 0.5 to 8 0.7 to 6 1 to 4 alkoxylated polyethyleneimine ⁷⁾ 0.5 to 7 0.5 to 7 0.7 to 5 1 to 3 Surfactant 35 to 60 35 to 60 40 to 55 40 to 55 Misc to 100 to 100 to 100 to 100 Formula 66 Formula 67 Formula 68 Formula 69 polyalkoxylated amine ⁶⁾ 1 to 8 2 to 7 2 to 7 3 to 6 ethoxylated polyethyleneimine ²⁾ 0.5 to 8 0.5 to 8 0.7 to 6 1 to 4 alkoxylated polyethyleneimine ⁷⁾ 0.5 to 7 0.5 to 7 0.7 to 5 1 to 3 anionic surfactant 18 to 40 18 to 40 18 to 40 24 to 36 non-ionic surfactant 12 to 30 12 to 30 12 to 30 18 to 26 Misc to 100 to 100 to 100 to 100 Formula 71 Formula 72 Formula 73 Formula 74 polyalkoxylated amine ⁶⁾ 1 to 8 2 to 7 2 to 7 3 to 6 ethoxylated polyethyleneimine ²⁾ 0.5 to 8 0.5 to 8 0.7 to 6 1 to 4 alkoxylated polyethyleneimine ⁷⁾ 0.5 to 7 0.5 to 7 0.7 to 5 1 to 3 anionic surfactant ⁴⁾ 18 to 40 18 to 40 18 to 40 24 to 36 fatty acid 4 to 12 4 to 12 4 to 12 6 to 10 non-ionic surfactant ⁵⁾ 12 to 30 12 to 30 12 to 30 18 to 26 Misc to 100 to 100 to 100 to 100 Formula 76 Formula 77 Formula 78 Formula 79 polyalkoxylated amine ⁶⁾ 1 to 8 2 to 7 2 to 7 3 to 6 ethoxylated polyethyleneimine ²⁾ 0.5 to 8 0.5 to 8 0.7 to 6 1 to 4 alkoxylated polyethyleneimine ⁷⁾ 0.5 to 7 0.5 to 7 0.7 to 5 1 to 3 anionic surfactant 18 to 40 18 to 40 18 to 40 24 to 36 non-ionic surfactant 12 to 30 12 to 30 12 to 30 18 to 26 organic solvent 5 to 30 10 to 20 10 to 20 10 to 20 Water 5 to 20 5 to 20 7 to 18 7 to 18 Misc to 100 to 100 to 100 to 100 Formula 81 Formula 82 Formula 83 Formula 84 polyalkoxylated amine ⁶⁾ 1 to 8 2 to 7 2 to 7 3 to 6 ethoxylated polyethyleneimine ²⁾ 0.5 to 8 0.5 to 8 0.7 to 6 1 to 4 alkoxylated polyethyleneimine ⁷⁾ 0.5 to 7 0.5 to 7 0.7 to 5 1 to 3 anionic surfactant 18 to 40 18 to 40 18 to 40 24 to 36 non-ionic surfactant 12 to 30 12 to 30 12 to 30 18 to 26 Enzyme preparation 0.5 to 7 0.5 to 7 1 to 6 1 to 6 Misc to 100 to 100 to 100 to 100 Formula 86 Formula 86 Formula 87 Formula 88 polyalkoxylated amine ⁶⁾ 1 to 8 2 to 7 2 to 7 3 to 6 ethoxylated polyethyleneimine ²⁾ 0.5 to 8 0.5 to 8 0.7 to 6 1 to 4 alkoxylated polyethyleneimine ⁷⁾ 0.5 to 7 0.5 to 7 0.7 to 5 1 to 3 anionic surfactant ⁴⁾ 18 to 40 18 to 40 18 to 40 24 to 36 fatty acid 4 to 12 4 to 12 4 to 12 6 to 10 non-ionic surfactant ⁵⁾ 12 to 30 12 to 30 12 to 30 18 to 26 Enzyme preparation 0.5 to 7 0.5 to 7 1 to 6 1 to 6 organic solvent 5 to 30 10 to 20 10 to 20 10 to 20 Water 5 to 20 5 to 20 7 to 18 7 to 18 Misc to 100 to 100 to 100 to 100

1. ¹⁾ polyalkoxylated amine having a weight-average molecular weight M _w in the range from 600 g/mol to 10000 g/mol, which is obtainable by reacting ammonia or primary alkyl or hydroxyalkylamines having a molecular weight below 200 g/mol with alkylene oxides
2. ²⁾ ethoxylated polyethyleneimine with ethylene oxide segments bonded to the nitrogen atoms of the polyethyleneimine
3. ³⁾ alkoxylated polyethyleneimine having alkylene oxide segments bonded to the nitrogen atoms of the polyethyleneimine, wherein the alkylene oxide segments comprise ethylene oxide segments and C ₃ -C ₆ alkylene oxide segments
4. ⁴⁾ anionic surfactant from the group of C _8-18 alkylbenzenesulfonates, preferably from the group of alkanolamine C _8-18 alkylbenzenesulfonates with alkanolamine from the group monoethanolamine, monoisopropanolamine, diisopropanolamine, in particular from the group monoethanolamine
5. ⁵⁾ non-ionic surfactant from the group of ethoxylated primary C _8-18 alcohols
6. ⁶⁾ polyalkoxylated amine having a weight average molecular weight M _w in the range of 600 g/mol to 10000 g/mol, which is obtainable by reacting triethanolamine with ethylene oxide and propylene oxide
7. ⁷⁾ alkoxylated polyethyleneimine having alkylene oxide segments bonded to the nitrogen atoms of the polyethyleneimine, wherein the alkylene oxide segments comprise ethylene oxide segments and C ₃ alkylene oxide segments

1. i) eine Waschmittelzubereitung
2. ii) einen wasserlöslichen Film, welcher die Waschmittelzubereitung vollständig umschließt.

A further preferred subject of this application is a detergent portion unit comprising

1. i) a detergent preparation
2. ii) a water-soluble film which completely encloses the detergent preparation.

The water-soluble film in which the detergent preparation is packaged can comprise one or more structurally different water-soluble polymers. Particularly suitable water-soluble polymers are polymers from the group of (optionally acetalized) polyvinyl alcohols (PVAL) and their copolymers.

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

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

Preferred polyvinyl alcohol copolymers comprise, in addition to vinyl alcohol, an ethylenically unsaturated carboxylic acid, its salt, or its ester. Particularly preferably, such polyvinyl alcohol copolymers contain, in addition to vinyl alcohol, sulfonic acids such as 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS), acrylic acid, methacrylic acid, acrylic esters, methacrylic esters, or mixtures thereof; among the esters, C _1-4 alkyl esters or hydroxyalkyl esters are preferred. Other suitable monomers include ethylenically unsaturated dicarboxylic acids, for example, itaconic acid, maleic acid, fumaric acid, and mixtures thereof.

Suitable water-soluble films for use are sold by MonoSol LLC, for example, under the designation M8630, M8720, M8310, C8400 or M8900.

Also suitable are films called Solublon® PT, Solublon® GA, Solublon® KC or Solublon® KL from Aicello Chemical Europe GmbH or the VF-HP films from Kuraray.

The water-soluble films may contain additional active ingredients or fillers as well as plasticizers and/or solvents, especially water.

The group of other active ingredients includes, for example, materials that protect the ingredients of the preparation enclosed in the film material from decomposition or deactivation by light exposure. Antioxidants, UV absorbers, and fluorescent dyes have proven particularly suitable in this regard.

Plasticizers that can be used include, for example, glycerin, ethylene glycol, diethylene glycol, propanediol, 2-methyl-1,3-propanediol, sorbitol or mixtures thereof.

To reduce its friction coefficient, the surface of the water-soluble film of the detergent dispenser can optionally be dusted with a fine powder. Sodium aluminosilicate, silicon dioxide, talc, and amylose are examples of suitable dusting agents.

Preferred water-soluble films are suitable for processing in a thermoforming apparatus.

The volume of the detergent portion unit is preferably from 12 to 22 ml, in particular from 12 to 20 ml.

Preferred detergent portion units have one to four receiving chambers, preferably three or four receiving chambers. In detergent portion units with two or more receiving chambers, preferably at least one of the receiving chambers, preferably the majority of the receiving chambers, is transparent.

• - Waschmittelportionseinheit mindestens zwei Aufnahmekammern, welche von einem wasserlöslichen Film umgeben sind, wobei eine Aufnahmekammer mit der erfindungsgemäßen Waschmittelzubereitung befüllt ist und die weitere Aufnahmekammer mit einer zweiten, von der erfindungsgemäßen Waschmittelzubereitung verschiedenen Waschmittelzubereitung befüllt ist;
• - Waschmittelportionseinheit mindestens drei Aufnahmekammern, welche von einem wasserlöslichen Film umgeben sind, wobei eine Aufnahmekammer mit der erfindungsgemäßen Waschmittelzubereitung befüllt ist und mit die weiteren zwei Aufnahmekammern voneinander getrennt mit einer zweiten und einer dritten voneinander und von der erfindungsgemäßen Waschmittelzubereitung verschiedenen Waschmittelzubereitung befüllt sind;
• - Waschmittelportionseinheit mindestens vier Aufnahmekammern, welche von einem wasserlöslichen Film umgeben sind, wobei eine Aufnahmekammer mit der erfindungsgemäßen Waschmittelzubereitung befüllt ist und die weiteren drei Aufnahmekammern voneinander getrennt mit einer zweiten und einer dritten und einem vierten voneinander und von der erfindungsgemäßen Waschmittelzubereitung verschiedenen Waschmittelzubereitung befüllt sind.

The following embodiments are particularly preferred:

• - Detergent portion unit at least two receiving chambers which are surrounded by a water-soluble film, wherein one receiving chamber is filled with the detergent preparation according to the invention and the further receiving chamber is filled with a second detergent preparation different from the detergent preparation according to the invention;
• - Detergent portion unit at least three receiving chambers which are surrounded by a water-soluble film, wherein one receiving chamber is filled with the detergent preparation according to the invention and the other two receiving chambers are filled separately with a second and a third detergent preparation which is different from one another and from the detergent preparation according to the invention;
• - Detergent portion unit at least four receiving chambers which are surrounded by a water-soluble film, wherein one receiving chamber is filled with the detergent preparation according to the invention and the other three receiving chambers are filled separately from one another with a second and a third and a fourth detergent preparation which is different from one another and from the detergent preparation according to the invention.

As stated above, the detergent preparation is particularly suitable for cleaning and sustainably scenting textiles during machine textile cleaning. A further subject matter of this application is therefore a textile cleaning method in which a flowable detergent preparation according to the invention or a detergent portion unit according to the invention is introduced into the wash liquor of a textile washing machine.

The mechanical textile cleaning process is preferably carried out at temperatures of 20°C to 60°C, preferably 30°C to 45°C. Preferred textile cleaning processes are used for cleaning cotton fabrics.

1. 1. Waschmittelzubereitung, enthaltend, bezogen auf ihr Gesamtgewicht,
   1. a) 1 bis 8 Gew.-% polyalkoxyliertes Amin mit einem gewichtsmittleren Molekulargewicht M_w im Bereich von 600 g/mol bis 10000 g/mol, das erhältlich ist durch Umsetzung von Ammoniak oder primären Alkyl- oder Hydroxyalkylaminen, die ein Molekulargewicht unter 200 g/mol aufweisen, mit Alkylenoxiden;
   2. b) 0,5 bis 8 Gew.-% ethoxyliertes Polyethylenimin mit Ethylenoxid-Segmenten, die an die Stickstoffatome des Polyethylenimins gebunden sind;
   3. c) 0,5 bis 7 Gew.-% alkoxyliertes Polyethylenimin mit Alkylenoxid-Segmenten, die an die Stickstoffatome des Polyethylenimins gebunden sind, wobei die Alkylenoxid-Segmente Ethylenoxid-Segmenten und C₃-C₆-Alkylenoxid-Segmente umfassen.
2. 2. Waschmittelzubereitung nach Punkt 1, wobei die Waschmittelzubereitung, bezogen auf ihr Gesamtgewicht, 2 bis 7 Gew.-%, vorzugsweise 3 bis 6 Gew.-% polyalkoxyliertes Amin enthält.
3. 3. Waschmittelzubereitung nach einem der vorherigen Punkte, wobei das polyalkoxylierte Amin durch Umsetzung von Triethanolamin mit Alkylenoxiden, vorzugsweise durch Umsetzung von Triethanolamin mit Ethylenoxid und Propylenoxid erhältlich ist.
4. 4. Waschmittelzubereitung nach einem der vorherigen Punkte, wobei das polyalkoxylierte Amin ein gewichtsmittleres Molekulargewicht M_w im Bereich von 1300 g/mol bis 6000 g/mol, insbesondere von 1400 g/mol bis 4500 g/mol aufweist.
5. 5. Waschmittelzubereitung nach einem der vorherigen Punkte, wobei die Waschmittelzubereitung, bezogen auf ihr Gesamtgewicht, 0,7 bis 6 Gew.-%, vorzugsweise 1 bis 4 Gew.-% ethoxyliertes Polyethylenimin b) enthält.
6. 6. Waschmittelzubereitung nach einem der vorherigen Punkte, wobei das ethoxylierte Polyethylenimin b) ein Polyethylenimin-Rückgrat mit einem gewichtsmittleren Molekulargewicht im Bereich von 100 g/mol bis 2000 g/mol, insbesondere von 400 g/mol bis 800 g/mol aufweist.
7. 7. Waschmittelzubereitung nach einem der vorherigen Punkte, wobei das ethoxylierte Polyethylenimin b) ein gewichtsmittleres Molekulargewicht im Bereich von 5000 g/mol bis 20000 g/mol, insbesondere von 8000 g/mol bis 14000 g/mol aufweist.
8. 8. Waschmittelzubereitung nach einem der vorherigen Punkte, wobei die Waschmittelzubereitung, bezogen auf ihr Gesamtgewicht, 0,7 bis 5 Gew.-%, vorzugsweise 1 bis 3 Gew.-% alkoxyliertes Polyethylenimin c) enthält.
9. 9. Waschmittelzubereitung nach einem der vorherigen Punkte, wobei das alkoxylierte Polyethylenimin c) ein Polyethylenimin-Rückgrat mit einem gewichtsmittleren Molekulargewicht im Bereich von 100 g/mol bis 2000 g/mol, insbesondere von 400 g/mol bis 800 g/mol aufweist.
10. 10. Waschmittelzubereitung nach einem der vorherigen Punkte, wobei das alkoxylierte Polyethylenimin c) ein gewichtsmittleres Molekulargewicht im Bereich von 1000 g/mol bis 1000000 g/mol, vorzugsweise von 5000 bis 500000 g/mol und insbesondere von 10000 g/mol bis 50000 g/mol aufweist.
11. 11. Waschmittelzubereitung nach einem der vorherigen Punkte, wobei die Alkylenoxid-Segmente des alkoxylierten Polyethylenimins c) Ethylenoxid-Segmente und C₃-Alkylenoxid-Segmente umfassen.
12. 12. Waschmittelzubereitung nach einem der vorherigen Punkte, wobei die Alkylenoxid-Segmente des alkoxylierten Polyethylenimins c) aus Ethylenoxid-Segmenten und C₃-Alkylenoxid-Segmenten bestehen.
13. 13. Waschmittelzubereitung nach einem der vorherigen Punkte, wobei das ethoxylierte Polyethylenimin b) und das alkoxylierte Polyethylenimin c) in einem Gewichtsverhältnis von 3:2 bis 2:3, vorzugweise von 4:3 bis 3:4 vorliegen.
14. 14. Waschmittelzubereitung nach einem der vorherigen Punkte, wobei das polyalkoxylierte Amin a) und die alkoxylierten Polyethylenimine b) und c) in einem Gewichtsverhältnis von 2:1 bis 1:2, vorzugweise von 3:2 bis 2:3 vorliegen.
15. 15. Waschmittelzubereitung nach einem der vorherigen Punkte, wobei die Waschmittelzubereitung, bezogen auf ihr Gesamtgewicht 35 bis 60 Gew.-%, vorzugsweise 40 bis 55 Gew.-% Tensid enthält.
16. 16. Waschmittelzubereitung nach einem der vorherigen Punkte, wobei die Waschmittelzubereitung, bezogen auf ihr Gesamtgewicht, 18 bis 40 Gew.-%, vorzugsweise 24 bis 36 Gew.-% anionisches Tensid enthält.
17. 17. Waschmittelzubereitung nach einem der vorherigen Punkte, wobei die Waschmittelzubereitung, bezogen auf ihr Gesamtgewicht, 15 bis 35 Gew.-%, vorzugsweise 18 bis 32 Gew.-% anionisches Tensid aus der Gruppe der C₈-₁₈-Alkylbenzolsulfonate enthält.
18. 18. Waschmittelzubereitung nach einem der vorherigen Punkte, wobei die Waschmittelzubereitung, bezogen auf ihr Gesamtgewicht, weniger als 10 Gew.-%, vorzugsweise weniger als 5 Gew,-% besonders bevorzugt weniger als 2 Gew.-% und insbesondere kein anionisches Tensid aus der Gruppe der Alkylethersulfate enthält.
19. 19. Waschmittelzubereitung nach einem der vorherigen Punkte, wobei die Waschmittelzubereitung, bezogen auf ihr Gesamtgewicht, 15 bis 35 Gew.-%, vorzugsweise 18 bis 32 Gew.-% anionisches Tensid aus der Gruppe der Alkanolamin-C_8-18-Alkylbenzolsulfonate, vorzugsweise aus der Gruppe der Alkanolamin-C_8-18-Alkylbenzolsulfonate mit Alkanolamin aus der Gruppe Monoethanolamin, Monoisopropanolamin, Diisopropanolamin, insbesondere aus der Gruppe Monoethanolamin enthält.
20. 20. Waschmittelzubereitung nach einem der vorherigen Punkte, wobei die Waschmittelzubereitung, bezogen auf ihr Gesamtgewicht, 12 bis 30 Gew.-%, vorzugsweise 18 bis 26 Gew.-% nichtionisches Tensid enthält.
21. 21. Waschmittelzubereitung nach einem der vorherigen Punkte, wobei die Waschmittelzubereitung, bezogen auf ihr Gesamtgewicht, 12 bis 30 Gew.-%, vorzugsweise 15 bis 28 Gew.-% und insbesondere 18 bis 26 nichtionisches Tensid aus der Gruppe der ethoxylierten primären C_8-18-Alkohole, vorzugsweise der ethoxylierten primären C_8-18-Alkohole mit einem Alkoxylierungsgrad ≥ 4, besonders bevorzugt der C_12-14-Alkohole mit 4 EO oder 7 EO, der C_9-11-Alkohole mit 7 EO, der C_13-15-Alkohole mit 5 EO, 7 EO oder 8 EO, der C_13-15-Oxoalkohole mit 7 EO, der C_12-18-Alkohole mit 5 EO oder 7 EO, insbesondere der C_12-18-Fettalkohole mit 7 EO oder der C_13-15-Oxoalkohole mit 7 EO enthält.
22. 22. Waschmittelzubereitung nach einem der vorherigen Punkte, wobei die Waschmittelzubereitung nichtionisches Tensid und anionisches Tensid in einem Gewichtsverhältnis von 3:1 bis 1:3, vorzugsweise von 2:1 bis 1:2 und insbesondere von 3:2 bis 2:3 enthält.
23. 23. Waschmittelzubereitung nach einem der vorherigen Punkte, wobei die Waschmittelzubereitung, bezogen auf ihr Gesamtgewicht, 4 bis 12 Gew.-%, vorzugsweise 6 bis 10 Gew.-% Fettsäure enthält.
24. 24. Waschmittelzubereitung nach Punkt 23, wobei die Fettsäure aus der Gruppe der C_12-18 Fettsäuren, vorzugsweise aus der Gruppe Caprylsäure, Caprinsäure, Laurinsäure, Myristinsäure, Palmitinsäure, Stearinsäure, Ölsäure, Linolsäure und deren Mischungen ausgewählt ist.
25. 25. Waschmittelzubereitung nach einem der vorherigen Punkte, wobei die Waschmittelzubereitung, bezogen auf ihr Gesamtgewicht, 5 bis 20 Gew.-%, vorzugsweise 7 bis 18 Gew.-% Wasser enthält.
26. 26. Waschmittelzubereitung nach einem der vorherigen Punkte, wobei die Waschmittelzubereitung, bezogen auf ihr Gesamtgewicht, 5 bis 30 Gew.-%, vorzugsweise 10 bis 20 Gew.-% organisches Lösungsmittel enthält.
27. 27. Waschmittelzubereitung nach Punkt 26, wobei das organisches Lösungsmittel ausgewählt ist aus der Gruppe Ethanol, n-Propanol, i-Propanol, Butanolen, Glykol, Propandiol, Butandiol, Methylpropandiol, Glycerin, Diglykol, Propyldiglycol, Butyldiglykol, Hexylenglycol, Ethylenglykolmethylether, Ethylenglykolethylether, Ethylenglykolpropylether, Ethylenglykolmono-n-butylether, Diethylenglykolmethylether, Diethylenglykolethylether, Propylenglykolmethylether, Propylenglykolethylether, Propylenglykolpropylether, Dipropylenglykolmonomethylether, Dipropy-lenglykolmonoethylether, Methoxytriglykol, Ethoxytriglykol, Butoxytriglykol, 1-Butoxyethoxy-2-propanol, 3-Methyl-3-methoxybutanol, Propylen-glykol-t-butylether, Di-n-octylether sowie deren Mischungen, vorzugsweise aus der Gruppe Propandiol, Glycerin, Monoethanolamin und deren Mischungen.
28. 28. Waschmittelzubereitung nach einem der vorherigen Punkte, wobei die Waschmittelzubereitung, bezogen auf ihr Gesamtgewicht, 0,1 bis 3 Gew.-%, vorzugsweise 0,2 bis 1 Gew.-% Phosphonat enthält.
29. 29. Waschmittelzubereitung nach einem der vorherigen Punkte, wobei die Waschmittelzubereitung Phosphonat enthält und das Phosphonat aus der Gruppe der Hydroxyalkan- und/oder Aminoalkanphosphonate, bevorzugt aus der Gruppe der Aminoalkanphosphonate und insbesondere aus der Gruppe Ethylendiamintetramethylenphosphonat (EDTMP) und Diethylentriaminpentamethylenphosphonat (DTPMP) ausgewählt ist.
30. 30. Waschmittelzubereitung nach einem der vorherigen Punkte, wobei die Waschmittelzubereitung, bezogen auf ihr Gesamtgewicht, 0,5 bis 7 Gew.-%, vorzugsweise 1,0 bis 6 Gew.-% Enzymzubereitungen enthält.
31. 31. Waschmittelzubereitung nach Punkt 30, wobei die Enzym-Zubereitungen, bezogen auf ihr Gesamtgewicht, einen Gewichtsanteil an aktivem Protein von 0,1 und 40 Gew.-%, bevorzugt von 0,2 und 30 Gew.-% aufweisen.
32. 32. Waschmittelzubereitung nach einem der vorherigen Punkte, wobei die Waschmittelzubereitung weiterhin mindestens eine Enzym-Zubereitung, vorzugweise mindestens drei Enzymzubereitungen von Enzymen aus der Gruppe Lipase, Mannanase, Amylase, Protease, Cellulase, Hexosaminidase Zubereitungen eines pektinolytischen Enzyms und Endoglucanase enthält.
33. 33. Waschmittelzubereitung nach einem der vorherigen Punkte, wobei die Waschmittelzubereitung, bezogen auf ihr Gesamtgewicht, 0,1 bis 0,4 Gew.-% und insbesondere 0,2 bis 0,3 Gew.-% Hexosaminidase Zubereitung, besonders bevorzugt β-Hexosaminidase Zubereitung enthält.
34. 34. Waschmittelzubereitung nach einem der vorherigen Punkte, wobei die Waschmittelzubereitung, bezogen auf ihr Gesamtgewicht, 0,1 bis 2 Gew.-%, vorzugsweise 0,2 bis 1 Gew.-% einer Amylase Zubereitung enthält.
35. 35. Waschmittelzubereitung nach einem der vorherigen Punkte, wobei die Waschmittelzubereitung, bezogen auf ihr Gesamtgewicht, 0,2 bis 4 Gew.-%, vorzugsweise 0,4 bis 3 Gew.-% einer Protease Zubereitung enthält.
36. 36. Waschmittelzubereitung nach einem der vorherigen Punkte, wobei die Waschmittelzubereitung, bezogen auf ihr Gesamtgewicht, 0,01 bis 1 Gew.-%, vorzugsweise 0,02 bis 0,3 Gew.-% einer Mannanase Zubereitung enthält.
37. 37. Waschmittelzubereitung nach einem der vorherigen Punkte, wobei die Waschmittelzubereitung, bezogen auf ihr Gesamtgewicht, 0,01 bis 1 Gew.-%, vorzugsweise 0,05 bis 0,3 Gew.-% einer Cellulase Zubereitung enthält.
38. 38. Waschmittelzubereitung nach einem der vorherigen Punkte, wobei die Waschmittelzubereitung, bezogen auf ihr Gesamtgewicht, 0,2 bis 4 Gew.-%, vorzugsweise 0,5 bis 3 Gew.-% Duftstoffzubereitung enthält.
39. 39. Waschmittelzubereitung nach einem der vorherigen Punkte, wobei die Waschmittelzubereitung unter Standardbedingungen (20°C, 1013 mbar) fließfähig ist und vorzugsweise eine Viskosität (21°C, Brookfield Viskosimeter Typ DV-II. Pro, Spindel Nr. 2, 20 rpm) oberhalb 400 mPas, vorzugsweise oberhalb 1000 mPas aufweist.
40. 40. Waschmittelportionseinheit umfassend
    1. i) eine Waschmittelzubereitung nach einem der Punkte 1 bis 39
    2. ii) einen wasserlöslichen Film, welcher die Waschmittelzubereitung vollständig umschließt.
41. 41. Waschmittelportionseinheit nach Punkt 40, wobei die Waschmittelportionseinheit ein Volumen von 12 bis 22 ml, vorzugsweise von 12 bis 20 ml aufweist.
42. 42. Waschmittelportionseinheit nach einem der Punkte 40 oder 41, wobei die Waschmittelportionseinheit eine bis vier Aufnahmekammern, vorzugsweise drei oder vier Aufnahmekammern aufweist.
43. 43. Verfahren zur Textilreinigung, bei welchem eine Waschmittelzubereitung nach einem der Punkte 1 bis 39 oder eine Waschmittelportionseinheit nach einem der Punkte 40 bis 42 in die Waschflotte einer Textilwaschmaschine eingebracht wird.

This registration provides, among other things, the following items:

1. 1. Detergent preparation containing, based on its total weight,
   1. a) 1 to 8 wt.% of polyalkoxylated amine having a weight-average molecular weight M _w in the range from 600 g/mol to 10,000 g/mol, which is obtainable by reacting ammonia or primary alkyl or hydroxyalkylamines having a molecular weight below 200 g/mol with alkylene oxides;
   2. b) 0.5 to 8 wt.% of ethoxylated polyethyleneimine having ethylene oxide segments bonded to the nitrogen atoms of the polyethyleneimine;
   3. c) 0.5 to 7 wt.% of alkoxylated polyethyleneimine having alkylene oxide segments bonded to the nitrogen atoms of the polyethyleneimine, wherein the alkylene oxide segments comprise ethylene oxide segments and C ₃ -C ₆ alkylene oxide segments.
2. 2. Detergent preparation according to item 1, wherein the detergent preparation contains, based on its total weight, 2 to 7 wt.%, preferably 3 to 6 wt.% of polyalkoxylated amine.
3. 3. Detergent preparation according to one of the preceding points, wherein the polyalkoxylated amine is obtainable by reacting triethanolamine with alkylene oxides, preferably by reacting triethanolamine with ethylene oxide and propylene oxide.
4. 4. Detergent preparation according to one of the preceding points, wherein the polyalkoxylated amine has a weight-average molecular weight M _w in the range from 1300 g/mol to 6000 g/mol, in particular from 1400 g/mol to 4500 g/mol.
5. 5. Detergent preparation according to one of the preceding points, wherein the detergent preparation contains, based on its total weight, 0.7 to 6 wt.%, preferably 1 to 4 wt.% of ethoxylated polyethyleneimine b).
6. 6. Detergent preparation according to one of the preceding points, wherein the ethoxylated polyethyleneimine b) has a polyethyleneimine backbone with a weight-average molecular weight in the range from 100 g/mol to 2000 g/mol, in particular from 400 g/mol to 800 g/mol.
7. 7. Detergent preparation according to one of the preceding points, wherein the ethoxylated polyethyleneimine b) has a weight-average molecular weight in the range from 5000 g/mol to 20000 g/mol, in particular from 8000 g/mol to 14000 g/mol.
8. 8. Detergent preparation according to one of the preceding points, wherein the detergent preparation contains, based on its total weight, 0.7 to 5 wt.%, preferably 1 to 3 wt.% of alkoxylated polyethyleneimine c).
9. 9. Detergent preparation according to one of the preceding points, wherein the alkoxylated polyethyleneimine c) has a polyethyleneimine backbone with a weight-average molecular weight in the range from 100 g/mol to 2000 g/mol, in particular from 400 g/mol to 800 g/mol.
10. 10. Detergent preparation according to one of the preceding points, wherein the alkoxylated polyethyleneimine c) has a weight-average molecular weight in the range from 1000 g/mol to 1,000,000 g/mol, preferably from 5,000 to 500,000 g/mol and in particular from 10,000 g/mol to 50,000 g/mol.
11. 11. Detergent preparation according to one of the preceding points, wherein the alkylene oxide segments of the alkoxylated polyethyleneimine c) comprise ethylene oxide segments and C ₃ alkylene oxide segments.
12. 12. Detergent preparation according to one of the preceding points, wherein the alkylene oxide segments of the alkoxylated polyethyleneimine c) consist of ethylene oxide segments and C ₃ alkylene oxide segments.
13. 13. Detergent preparation according to one of the preceding points, wherein the ethoxylated polyethyleneimine b) and the alkoxylated polyethyleneimine c) are present in a weight ratio of 3:2 to 2:3, preferably of 4:3 to 3:4.
14. 14. Detergent preparation according to one of the preceding points, wherein the polyalkoxylated amine a) and the alkoxylated polyethyleneimines b) and c) are present in a weight ratio of 2:1 to 1:2, preferably of 3:2 to 2:3.
15. 15. Detergent preparation according to one of the preceding points, wherein the detergent preparation contains, based on its total weight, 35 to 60 wt.%, preferably 40 to 55 wt.% surfactant.
16. 16. Detergent preparation according to one of the preceding points, wherein the detergent preparation contains, based on its total weight, 18 to 40 wt.%, preferably 24 to 36 wt.% of anionic surfactant.
17. 17. Detergent preparation according to one of the preceding points, wherein the detergent preparation contains, based on its total weight, 15 to 35 wt.%, preferably 18 to 32 wt.% of anionic surfactant from the group of C ₈ - ₁₈ alkylbenzenesulfonates.
18. 18. Detergent preparation according to one of the preceding points, wherein the detergent preparation, based on its total weight, contains less than 10 wt.%, preferably less than 5 wt.%, particularly preferably less than 2 wt.% and in particular no anionic surfactant from the group of alkyl ether sulfates.
19. 19. Detergent preparation according to one of the preceding points, wherein the detergent preparation contains, based on its total weight, 15 to 35% by weight, preferably 18 to 32% by weight of anionic surfactant from the group of alkanolamine-C _8-18 alkylbenzenesulfonates, preferably from the group of alkanolamine-C _8-18 alkylbenzenesulfonates with alkanolamine from the group monoethanolamine, monoisopropanolamine, diisopropanolamine, in particular from the group monoethanolamine.
20. 20. Detergent preparation according to one of the preceding points, wherein the detergent preparation contains, based on its total weight, 12 to 30 wt.%, preferably 18 to 26 wt.% of non-ionic surfactant.
21. 21. Detergent preparation according to one of the preceding points, wherein the detergent preparation, based on its total weight, contains 12 to 30 wt.%, preferably 15 to 28 wt.% and in particular 18 to 26 nonionic surfactant from the group of ethoxylated primary C _8-18 alcohols, preferably ethoxylated primary C _8-18 alcohols with a degree of alkoxylation ≥ 4, particularly preferably C _12-14 alcohols with 4 EO or 7 EO, C _9-11 alcohols with 7 EO, C _13-15 alcohols with 5 EO, 7 EO or 8 EO, C _13-15 oxo alcohols with 7 EO, C _12-18 alcohols with 5 EO or 7 EO, in particular C _12-18 -fatty alcohols with 7 EO or C _13-15 -oxo alcohols with 7 EO.
22. 22. Detergent preparation according to one of the preceding points, wherein the detergent preparation contains nonionic surfactant and anionic surfactant in a weight ratio of 3:1 to 1:3, preferably of 2:1 to 1:2 and in particular of 3:2 to 2:3.
23. 23. Detergent preparation according to one of the preceding points, wherein the detergent preparation contains, based on its total weight, 4 to 12 wt.%, preferably 6 to 10 wt.% fatty acid.
24. 24. Detergent preparation according to item 23, wherein the fatty acid is selected from the group of C _12-18 fatty acids, preferably from the group caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid and mixtures thereof.
25. 25. Detergent preparation according to one of the preceding points, wherein the detergent preparation contains, based on its total weight, 5 to 20 wt.%, preferably 7 to 18 wt.% of water.
26. 26. Detergent preparation according to one of the preceding points, wherein the detergent preparation contains, based on its total weight, 5 to 30 wt.%, preferably 10 to 20 wt.% of organic solvent.
27. 27. Detergent preparation according to item 26, wherein the organic solvent is selected from the group consisting of ethanol, n-propanol, i-propanol, butanols, glycol, propanediol, butanediol, methylpropanediol, glycerin, diglycol, propyl diglycol, butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, methoxytriglycol, ethoxytriglycol, butoxytriglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, Propylene glycol t-butyl ether, di-n-octyl ether and mixtures thereof, preferably from the group propanediol, glycerin, monoethanolamine and mixtures thereof.
28. 28. Detergent preparation according to one of the preceding points, wherein the detergent preparation contains, based on its total weight, 0.1 to 3 wt.%, preferably 0.2 to 1 wt.% of phosphonate.
29. 29. Detergent preparation according to one of the preceding points, wherein the detergent preparation contains phosphonate and the phosphonate is selected from the group of hydroxyalkane and/or aminoalkanephosphonates, preferably from the group of aminoalkanephosphonates and in particular from the group of ethylenediaminetetramethylenephosphonate (EDTMP) and diethylenetriaminepentamethylenephosphonate (DTPMP).
30. 30. Detergent preparation according to one of the preceding points, wherein the detergent preparation contains, based on its total weight, 0.5 to 7 wt.%, preferably 1.0 to 6 wt.% of enzyme preparations.
31. 31. Detergent preparation according to item 30, wherein the enzyme preparations, based on their total weight, have a weight fraction of active protein of 0.1 and 40 wt.%, preferably of 0.2 and 30 wt.%.
32. 32. Detergent preparation according to one of the preceding points, wherein the detergent preparation further contains at least one enzyme preparation, preferably at least three enzyme preparations of enzymes from the group lipase, mannanase, amylase, protease, cellulase, hexosaminidase, preparations of a pectinolytic enzyme and endoglucanase.
33. 33. Detergent preparation according to one of the preceding points, wherein the detergent preparation contains, based on its total weight, 0.1 to 0.4 wt.% and in particular 0.2 to 0.3 wt.% of hexosaminidase preparation, particularly preferably β-hexosaminidase preparation.
34. 34. Detergent preparation according to one of the preceding points, wherein the detergent preparation contains, based on its total weight, 0.1 to 2 wt.%, preferably 0.2 to 1 wt.% of an amylase preparation.
35. 35. Detergent preparation according to one of the preceding points, wherein the detergent preparation contains, based on its total weight, 0.2 to 4 wt.%, preferably 0.4 to 3 wt.% of a protease preparation.
36. 36. Detergent preparation according to one of the preceding points, wherein the detergent preparation contains, based on its total weight, 0.01 to 1 wt.%, preferably 0.02 to 0.3 wt.% of a mannanase preparation.
37. 37. Detergent preparation according to one of the preceding points, wherein the detergent preparation contains, based on its total weight, 0.01 to 1 wt.%, preferably 0.05 to 0.3 wt.% of a cellulase preparation.
38. 38. Detergent preparation according to one of the preceding points, wherein the detergent preparation contains, based on its total weight, 0.2 to 4% by weight, preferably 0.5 to 3% by weight, of fragrance preparation.
39. 39. Detergent preparation according to one of the preceding points, wherein the detergent preparation is flowable under standard conditions (20°C, 1013 mbar) and preferably has a viscosity (21°C, Brookfield viscometer type DV-II. Pro, spindle no. 2, 20 rpm) above 400 mPas, preferably above 1000 mPas.
40. 40. Detergent portion unit comprising
    1. i) a detergent preparation as defined in any of points 1 to 39
    2. ii) a water-soluble film which completely encloses the detergent preparation.
41. 41. Detergent portion unit according to item 40, wherein the detergent portion unit has a volume of 12 to 22 ml, preferably 12 to 20 ml.
42. 42. Detergent portion unit according to one of items 40 or 41, wherein the detergent portion unit has one to four receiving chambers, preferably three or four receiving chambers.
43. 43. A process for textile cleaning, in which a detergent preparation according to one of items 1 to 39 or a detergent portion unit according to one of items 40 to 42 is introduced into the wash liquor of a textile washing machine.

Examples

1. 1) polyalkoxyliertes Amin mit einem gewichtsmittleren Molekulargewicht M_w im Bereich von 600 g/mol bis 10000 g/mol, das erhältlich ist durch von Triethanolamin mit Ethylenoxid und Propylenoxid
2. 2) ethoxyliertes Polyethylenimin mit Ethylenoxid-Segmenten, die an die Stickstoffatome des Polyethylenimins gebunden sind
3. 3) alkoxyliertes Polyethylenimin mit Alkylenoxid-Segmenten, die an die Stickstoffatome des Polyethylenimins gebunden sind, wobei die Alkylenoxid-Segmente Ethylenoxid-Segmenten und C₃-Alkylenoxid-Segmente umfassen

Tabelle 2: Helligkeitswertunterschiede (Y-Werte) Fleck Textil V1 V2 V3 E1 Schminke Baumwolle 65,4 65,4 64,8 65,7 Lippenstift Baumwolle 69,2 69,3 69,4 69,5 Vollei, Carbon Black Baumwolle 64,3 65,2 64,1 65,4 Senf Baumwolle 79,9 79,7 79,6 80,2 Eis, Schokolade Baumwolle 71,8 71,8 71,5 72,1 Balsamico Essid Baumwolle 56,1 56,7 56,5 57,1 Mineralöl, Carbon Black Baumwolle 55,7 56,2 56,1 56,5 Textile fabrics were treated with standardized soiling and subsequently washed at 40°C in wash liquors containing 1 g/l of detergent preparation V1 to V3 or E1. After washing, the textiles were dried. The brightness values of the cleaned textiles were determined. The values given were the averages of five washing tests. Table 1: Detergent compositions (wt.%) V1 V2 V3 E1 C _10-13 alkylbenzenesulfonic acid 21.8 21.8 21.8 21.8 C _12-18 fatty acid 7.0 7.0 7.0 7.0 C _12-18 fatty alcohol ethoxylate, 7 EO 22.4 22.4 22.4 22.4 polyalkoxylated amine ¹⁾ 4.5 4.5 - 4.5 polyalkoxylated polyalkyleneimine ²⁾ 4.5 - 4.5 2.25 polyalkoxylated polyalkyleneimine ³⁾ - 4.5 4.5 2.25 1,2-Propanediol 5.2 5.2 5.2 5.2 Glycerin 9.6 9.6 9.6 9.6 Monoethanolamine 6.0 6.0 6.0 6.0 Phosphonate 0.5 0.5 0.5 0.5 Enzyme preparations 4.0 4.0 4.0 4.0 optical brightener 0.5 0.5 0.5 0.5 Water <20 <20 <20 <20 Misc to 100 to 100 to 100 to 100

1. 1) polyalkoxylated amine with a weight average molecular weight M _w in the range of 600 g/mol to 10000 g/mol, which is obtainable by reacting triethanolamine with ethylene oxide and propylene oxide
2. 2) ethoxylated polyethyleneimine with ethylene oxide segments bonded to the nitrogen atoms of the polyethyleneimine
3. 3) alkoxylated polyethyleneimine having alkylene oxide segments bonded to the nitrogen atoms of the polyethyleneimine, wherein the alkylene oxide segments comprise ethylene oxide segments and C ₃ alkylene oxide segments

Table 2: Brightness value differences (Y-values) spot Textile V1 V2 V3 E1 Makeup Cotton 65.4 65.4 64.8 65.7 lipstick Cotton 69.2 69.3 69.4 69.5 Whole egg, carbon black Cotton 64.3 65.2 64.1 65.4 Mustard Cotton 79.9 79.7 79.6 80.2 ice cream, chocolate Cotton 71.8 71.8 71.5 72.1 Balsamic vinegar Cotton 56.1 56.7 56.5 57.1 Mineral oil, carbon black Cotton 55.7 56.2 56.1 56.5

In a second experiment, the viscosities of the detergent preparations V1 to V3 and E1 were determined (20°C, Brookfield rotational viscometer, spindle 31, 12rpm) V1 V2 V3 E1 Viscosity (mpas) 492 492 510 477

QUOTES CONTAINED IN THE DESCRIPTION

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

Cited patent literature

• WO 2016/191238 A1 [0005]
• WO 2022/063487 [0006]

Claims (10)

Detergent preparation comprising, based on its total weight, a) 1 to 8 wt. % of polyalkoxylated amine having a weight-average molecular weight M _w in the range from 600 g/mol to 10,000 g/mol, which is obtainable by reacting ammonia or primary alkyl or hydroxyalkylamines having a molecular weight below 200 g/mol with alkylene oxides; b) 0.5 to 8 wt. % of ethoxylated polyethyleneimine having ethylene oxide segments bonded to the nitrogen atoms of the polyethyleneimine; c) 0.5 to 7 wt. % of alkoxylated polyethyleneimine having alkylene oxide segments bonded to the nitrogen atoms of the polyethyleneimine, where the alkylene oxide segments comprise ethylene oxide segments and C ₃ -C ₆ alkylene oxide segments. Detergent preparation according to Claim 1 , wherein the detergent preparation contains, based on its total weight, 2 to 7 wt.%, preferably 3 to 6 wt.% of polyalkoxylated amine. Detergent preparation according to one of the preceding claims, wherein the polyalkoxylated amine is obtainable by reacting triethanolamine with alkylene oxides, preferably by reacting triethanolamine with ethylene oxide and propylene oxide. Detergent preparation according to one of the preceding claims, wherein the detergent preparation contains, based on its total weight, 0.7 to 6 wt.%, preferably 1 to 4 wt.% of ethoxylated polyethyleneimine b). Detergent preparation according to one of the preceding claims, wherein the detergent preparation contains, based on its total weight, 0.7 to 5 wt.%, preferably 1 to 3 wt.% of alkoxylated polyethyleneimine c). Detergent preparation according to one of the preceding claims, wherein the alkylene oxide segments of the alkoxylated polyethyleneimine c) comprise ethylene oxide segments and C ₃ alkylene oxide segments. Detergent preparation according to one of the preceding claims, wherein the alkylene oxide segments of the alkoxylated polyethyleneimine c) consist of ethylene oxide segments and C ₃ alkylene oxide segments. Detergent preparation according to one of the preceding claims, wherein the ethoxylated polyethyleneimine b) and the alkoxylated polyethyleneimine c) are present in a weight ratio of 3:2 to 2:3, preferably of 4:3 to 3:4. Detergent portion unit comprising i) a detergent preparation according to one of the Claims 1 until 8 ii) a water-soluble film which completely encloses the detergent preparation. A process for textile cleaning, in which a detergent preparation according to one of the Claims 1 until 8 or a detergent portion unit according to Claim 9 is added to the washing liquor of a textile washing machine.