DE102022116758A1 - Amphiphilic alkoxylated poly(ethylene/propylene)imine copolymers as dirt-repellent polymers - Google Patents

Abstract

The present invention relates to the use of the special copolymers described herein as soil-repellent polymers (soil repellent polymer, SRP) for equipping textiles with soil-repellent properties and corresponding processes for equipping textiles with soil-repellent properties by using the polymers mentioned.

Description

The present invention relates to the use of the special copolymers described herein as soil-repellent polymers (soil repellent polymer, SRP) for equipping textiles with soil-repellent properties and corresponding processes for equipping textiles with soil-repellent properties by using the polymers mentioned.

When it comes to textile detergents, consumers' main focus is on the cleaning performance of the products used. In addition to the primary cleaning performance, the equipment of a textile with dirt-repellent properties also plays a role, which prevents dirt from adhering or enables the dirt to be removed more easily in a later wash cycle. For this purpose, so-called soil repellent polymers (SRPs, dirt-repellent polymers) are increasingly being used today, which are applied to the textile fibers and provide them with a kind of protective film that gives them dirt-repellent properties and makes it easier to remove dirt in future washes.

Although some suitable polymers are known, there is still a need for alternative options for providing high-performance formulations that can be used as detergents even in highly concentrated form, especially in liquid form, and which show good to very good cleaning performance on a wide variety of soils, which are characterized by good dirt-repellent properties Characteristics of the textiles washed with it.

In the present case, this need is met according to the invention by providing the copolymers defined herein, optionally in the form of the component of detergent formulations. The inventors have found that these copolymers act as SRPs and provide textiles treated with them with advantageous dirt-repellent properties. It was also found that these copolymers can be easily formulated into existing detergents and used in this form to achieve the observed effect.

In a first aspect, the invention therefore relates to the use of at least one amphiphilic alkoxylated poly(ethylene/propylene)imine copolymer which comprises repeat units of the monomer (A), optionally monomer (B) and/or optionally monomer (C) in condensed form, wherein

istMonomer (A) is a compound of the formula

is

ist undMonomer (B) is a compound of the formula

is and

ist,
wobei m 1 bis 4 ist, I 1 bis 3 ist, k 0 oder 1 ist, o 0 oder 1 ist und Rein C₁-C₁₈ Alkylrest ist, und wobei jede funktionelle NH-Gruppe über eine kovalente Bindung direkt an eine Alkoxykette der Formel -(A¹O)_a-(A²O)_b-(A³O)_c-R' gebunden ist,
wobei A¹ C₃-C₁₂ Alkylen ist, a 0 bis 2 ist, A² Ethylen ist, b 5 bis 50 ist, A³ 1,2-Propylen ist, c 5 bis 50 ist, R' aus H und C₁-C₄ Alkyl ausgewählt wird und die Alkylenoxid Einheiten vorzugsweise als Blockstrukturen gebunden sind
als schmutzabweisendes Polymer (soil repellent polymer, SRP) um Textilien mit schmutzabweisenden Eigenschaften auszurüsten.Monomer (C) is a compound of the formula

is,
where m is 1 to 4, I is 1 to 3, k is 0 or 1, o is 0 or 1 and Rein is C ₁ -C ₁₈ alkyl, and each NH functional group is directly attached to an alkoxy chain via a covalent bond formula -(A ¹ O) _a -(A ² O) _b -(A ³ O) _c -R' is bound,
where A ¹ is C ₃ -C ₁₂ alkylene, a is 0 to 2, A ² is ethylene, b is 5 to 50, A ³ is 1,2-propylene, c is 5 to 50, R' from H and C ₁ -C ₄ alkyl is selected and the alkylene oxide units are preferably bound as block structures
as a dirt-repellent polymer (soil repellent polymer, SRP) to provide textiles with dirt-repellent properties.

In a further aspect, the present invention also relates to a method for equipping textiles with dirt-repellent properties, characterized in that the textiles are coated with at least one amphiphilic alkoxylated poly(ethylene/propylene)imine copolymer which contains repeating units of the monomer (A), optionally monomer ( B) and/or optionally monomer (C) in condensed form, wherein

istMonomer (A) is a compound of the formula

is

ist undMonomer (B) is a compound of the formula

is and

ist, wobei m 1 bis 4 ist, I 1 bis 3 ist, k 0 oder 1 ist, o 0 oder 1 ist und Rein C₁-C₁₈ Alkylrest ist, und wobei jede funktionelle NH-Gruppe über eine kovalente Bindung direkt an eine Alkoxykette der Formel -(A¹O)_a-(A²O)_b-(A³O)_c-R'
gebunden ist,
wobei A¹ C₃-C₁₂ Alkylen ist, a 0 bis 2 ist, A² Ethylen ist, b 5 bis 50 ist, A³ 1,2-Propylen ist, c 5 bis 50 ist, R' aus H und C₁-C₄ Alkyl ausgewählt wird und die Alkylenoxid Einheiten vorzugsweise als Blockstrukturen gebunden sind,
in Kontakt gebracht werden.Monomer (C) is a compound of the formula

is, where m is 1 to 4, I is 1 to 3, k is 0 or 1, o is 0 or 1 and Rein is C ₁ -C ₁₈ alkyl, and wherein each NH functional group is directly attached to a via a covalent bond Alkoxy chain of the formula -(A ¹ O) _a -(A ² O) _b -(A ³ O) _c -R'
is bound,
where A ¹ is C ₃ -C ₁₂ alkylene, a is 0 to 2, A ² is ethylene, b is 5 to 50, A ³ is 1,2-propylene, c is 5 to 50, R' from H and C ₁ -C ₄ alkyl is selected and the alkylene oxide units are preferably bound as block structures,
be brought into contact.

These and other aspects, features and advantages of the invention will become apparent to those skilled in the art from reading the following detailed description and claims. Any feature from one aspect of the invention can be used in any other aspect of the invention. For example, described features or embodiments of use can also apply to the claimed method ren can be applied and vice versa. Furthermore, it is to be understood that the examples contained herein are intended to describe and illustrate the invention, but not to limit it and in particular the invention is not limited to these examples.

“At least one,” as used herein, refers to 1 or more, for example 2, 3, 4, 5, 6, 7, 8, 9 or more. In connection with components of the compounds described herein, this information does not refer to the absolute amount of molecules, but rather to the type of component. “At least one surfactant” therefore means, for example, that only one type of surfactant or several different types of surfactants can be included, without providing information about the amount of the individual compounds.

Unless otherwise stated, all percentages are % by weight, based on the total weight of the corresponding composition. Numerical ranges specified in the format “from x to y” include the stated values. When multiple preferred numerical ranges are specified in this format, it is understood that any ranges resulting from the combination of the various endpoints will also be captured.

Unless otherwise stated, all quantities given in connection with the compositions described herein refer to % by weight based on the total weight of the composition. Furthermore, such quantities that relate to at least one component always refer to the total amount of this type of component contained in the composition, unless explicitly stated otherwise. This means that such quantities, for example in connection with “at least one surfactant”, refer to the total amount of surfactants contained in the composition, unless explicitly stated otherwise.

Numerical values stated herein without decimal places refer to the full stated value with one decimal place. For example, “99%” stands for “99.0%”.

The expression “approximately,” “approx.” or “approximately,” in connection with a numerical value, refers to a variance of ±10% based on the specified numerical value, preferably ±5%, particularly preferably ±1%, even more preferably less than ± 0.1%.

The term “free from” means that the respective compound was not intentionally added to the agent used according to the invention and is contained either in an undetectable amount or in an amount that is below the effective amount of the respective compound. To the extent that this term refers to lipases, the amount of lipases in the compositions described herein is therefore below 0.001% by weight of active protein, preferably below 0.0001% by weight, more preferably below 0.00001% by weight, most preferably below 0.000001% by weight, based on the total weight of the composition.

Numerical ranges specified in the format "in/from x to y" include the stated values. When multiple preferred numerical ranges are specified in this format, it is understood that any ranges resulting from the combination of the various endpoints will also be captured.

Information about the molecular weight refers to the weight-average molecular weight M _w in g/mol, unless the number-average molecular weight is explicitly stated. Molecular weights are preferably determined by GPC using polystyrene standards.

The terms “composition” and “agent” are used interchangeably herein to refer to the detergent compositions.

“Liquid” as used in the context of the present invention means all liquid compositions (at 20°C, 1.013 bar), including gels and paste-like compositions, as well as non-Newtonian liquids that have a yield point. Gels or gel-like compositions or agents in the context of the present invention are those which have a viscosity of 50 to 5000 mPas, preferably 100 to 4800 mPas. The viscosity can be determined with a Brookfield LVDV II+ laboratory viscometer at 20°C using spindle 31 and 3 or 6 rpm.

Amphiphilic alkoxylated poly(ethylene/propylene)imine copolymer

The uses and methods described herein relate to the use of at least one amphiphilic alkoxylated poly(ethylene/propylene)imine copolymer. The term “amphiphilic” as used in this context means that the copolymer includes both hydrophilic and lipophilic moieties. This may mean that the copolymer is soluble in both polar and non-polar solvents.

The copolymer is a poly(ethylene/propylene)imine. It is also alkoxylated, i.e. it includes alkoxy groups that are typically bonded to the NH groups (imine groups) and replace the hydrogen atom. The alkoxy groups may be (poly)ethylene oxide, (poly)propylene oxide, (poly)butylene oxide or other (poly)alkylene oxides or combinations of such units as defined herein.

istSpecifically, the copolymer comprises repeating units of the monomer (A), optionally monomer (B) and/or optionally monomer (C) in condensed form, wherein monomer (A) comprises a compound of the formula

is

ist undMonomer (B) is a compound of the formula

is and

ist,
wobei m 1 bis 4 ist, I 1 bis 3 ist, k 0 oder 1 ist, o 0 oder 1 ist und Rein C₁-C₁₈ Alkylrest ist, und wobei jede funktionelle NH-Gruppe über eine kovalente Bindung direkt an eine Alkoxykette der Formel -(A¹O)_a-(A²O)_b-(A³O)_c-R'
gebunden ist,
wobei A¹ C₃-C₁₂ Alkylen ist, a 0 bis 2 ist, A² Ethylen ist, b 5 bis 50 ist, A³ 1,2-Propylen ist, c 5 bis 50 ist, R' aus H und C₁-C₄ Alkyl ausgewählt wird und die Alkylenoxid Einheiten vorzugsweise als Blockstrukturen gebunden sind.Monomer (C) is a compound of the formula

is,
where m is 1 to 4, I is 1 to 3, k is 0 or 1, o is 0 or 1 and Rein is C ₁ -C ₁₈ alkyl, and each NH functional group is directly attached to an alkoxy chain via a covalent bond formula -(A ¹ O) _a -(A ² O) _b -(A ³ O) _c -R'
is bound,
where A ¹ is C ₃ -C ₁₂ alkylene, a is 0 to 2, A ² is ethylene, b is 5 to 50, A ³ is 1,2-propylene, c is 5 to 50, R' from H and C ₁ -C ₄ alkyl is selected and the alkylene oxide units are preferably bound as block structures.

The monomers are present as repeating units in “condensed form” in such a way that a hydrogen atom of at least one NH ₂ or NH group of one of the monomers mentioned is replaced by a covalent bond to another monomer, with the corresponding NH ₂ - in the further monomer Group is completely replaced by the bond and NH ₃ is formally split off.

In various embodiments of the invention, the copolymer comprises repeating units of monomer (A) and either monomer (B) or monomer (C) in condensed form. In ver In various further embodiments, the copolymer comprises repeating units of the monomers (A), the monomers (B) and the monomers (C) in condensed form.

In various embodiments of the copolymers, m is 1, 2 or 3, preferably 1. In various embodiments of the copolymers, I = 1. In various embodiments of the copolymers, k = 1. In various embodiments, o = 1. In various embodiments, R is a C1-C4 alkyl radical, preferably methyl. In various embodiments, R' = H. These above-mentioned embodiments can be combined with each other as desired. For example, m can be 1, 2, or 3, preferably 1, and/or I=1 and/or k=1 and/or o=1 and/or R=C1-C4 alkyl, preferably methyl, and/or R' = H

In various embodiments of the copolymers, the weight average molecular weight M _w of the poly(ethylene/propylene)imine backbone without alkoxy chains is at least 300 g/mol, more preferably at least 400 g/mol, even more preferably at least 500 g/mol. In other embodiments, the molecular weight M _w of the poly(ethylene/propylene)imine backbone without alkoxy chains is at least 600 g/mol.

The molecular weight M _w of the backbone is determined using gel permeation chromatography (GPC). To determine the molecular weight of the polyamine starting material using GPC, for example, combinations of the following three columns can be used: HFIP-LG Guard, PL HFIPGEL and PL HFIPGel. Further details on these processes can also be found in the experimental part of the international patent publication WO 2021/254828 A1 be removed.

The molecular weight of the copolymers can be obtained by theoretical calculations using the determined weight average molecular weights of the backbone without alkoxy chains and assuming complete conversion during alkoxylation. Further details of such calculations can be found in the experimental part of the international patent publication WO 2021/254828 A1 refer to.

In various further embodiments of the copolymers, a = 0 and/or b = 10 to 40, preferably 15 to 35, and/or c = 10 to 40, preferably 15 to 35, and/or the molar ratio EO (ethylene oxide units)/PO (propylene oxide units) is >0.8, preferably ≥1.

In various further embodiments of the copolymers, m = 1, k = 1, o = 1, I = 1, R is methyl, R' = H and the amounts of the monomers (A), (B) and (C) in the poly (ethylene/propylene)imine backbone without alkoxy chains is at least 10% by weight and a maximum of 50% by weight.

If the copolymer is a component of a detergent, in various embodiments it is present therein in amounts of 0.2 to 10% by weight, 0.2 to 7.0% by weight, for example at least 0.5 or at least 1.0 % by weight, preferably 1.0 or 2.0 to 4.0 or 4.5% by weight, based on the total weight of the agent.

Ethoxylated polyethyleneimine (PEI)

The detergents may also contain an ethoxylated polyethyleneimine in addition to the copolymer. The ethoxylated polyethyleneimine in the context of the present invention and its individual aspects is a polymer with a backbone containing N atoms, which carries (poly)ethoxy groups ((poly)ethylene oxide groups) on the N atoms. The polyamine has primary amino functions at the ends and preferably both secondary and tertiary amino functions inside; If necessary, it can also only have secondary amino functions inside, so that the result is not a branched-chain, but a linear polyamine. However, the polyamine is preferably branched chain. The ratio of primary to secondary amino groups in the polyamine is preferably in the range from 1:0.5 to 1:1.5, in particular in the range from 1:0.7 to 1:1. The ratio of primary to tertiary amino groups in the polyamine is preferably in the range from 1:0.2 to 1:1, in particular in the range from 1:0.5 to 1:0.8. The polyamine preferably has an average molecular weight M _w in the range from 500 g/mol to 50,000 g/mol, in particular from 550 g/mol to 5,000 g/mol. The N atoms in polyamine are separated from each other by ethylene groups. The primary amino functions in the polyamine can carry 1 or 2 (poly)ethoxy groups and the secondary amino functions can carry 1 (poly)ethoxy group, although not every amino function has to be substituted with ethoxy groups. The average number of ethoxy groups per primary and secondary amino function in the polyethoxylated polyethyleneimine is preferably 1 to 100, in particular 5 to 70. The ethoxy groups in the polyamine are ethoxy groups that are directly bonded to N atoms, and optionally ethoxy groups which are bound to other ethoxy radicals and therefore form polyethoxy groups. The (poly)ethoxylated polyethyleneimines are accessible by reacting polyethyleneimines with ethylene oxide. If desired, the terminal OH function of at least some of the polyethoxy substituents can be replaced by an alkyl ether function with 1 to 10, in particular 1 to 3, carbon atoms.

Such ethoxylated polyethyleneimines (PEls) are known in the art and are commercially available. An ethoxylated PEI which is particularly preferably used in the context of the invention is available under the trade name Sokalan® HP20 (BASF SE, DE).

The ethoxylated polyethyleneimine is typically used in amounts of 1 to 7.5% by weight based on the total weight of the composition, preferably 2.0 to 4.5% by weight.

The total amount of amphiphilic, alkoxylated copolymer and ethoxylated PEI in a detergent as can be used according to the invention is, in various embodiments, 6.5 to 10.0% by weight, preferably 6.5 to 7.5% by weight , based on the total weight of the composition.

Enzymes

In various embodiments, the detergents contain at least one enzyme, optionally with the exception of lipases. In various embodiments of the invention, the detergents used according to the invention are therefore free of lipases. Enzymes useful in the context of the present invention include all those enzymes which are suitable for use in a detergent composition and which are commonly used in such compositions and are accordingly known in the art. Such an enzyme may be a hydrolytic enzyme or another enzyme in a concentration appropriate for the effectiveness of the respective agent.

In this context, preference can be given to all enzymes that can develop a catalytic activity in the detergent, in particular amylase, cutinase, protease, cellulase, mannanase, xanthanase, hemicellulase, tannase, xylanase, xyloglucanase, β-glucosidase, pectinase, carrageenase, perhydrolase , oxidase, or oxidoreductase, and mixtures thereof.

One or more enzymes are advantageously contained in the detergent in an amount of 1 × 10 ^-8 to 5% by weight based on active protein, in particular in an amount of 1 × ^{10 -7 to} 3% by weight, from 0 .00001 to 1% by weight, from 0.00005 to 0.5% by weight, from 0.0001 to 0.1% by weight and particularly preferably from 0.0001 to 0.05% by weight, respectively based on the total weight of the product and based on active protein.

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 ( Gornall et al., 1948, J. Biol. Chem., 177:751-766 ) can be determined. In this regard, the active protein concentration can be determined by titrating the active centers using a suitable irreversible inhibitor and determining the residual activity ( Bender et al., 1966, J. Am. Chem. Soc. 88(24):5890-5913 ) take place.

The enzymes used particularly preferably show synergistic cleaning performance against certain dirt or stains, i.e. the enzymes contained in the agent composition support each other in their cleaning performance. Very particularly preferably, such a synergism occurs between a protease and a further enzyme of an agent used according to the invention, including in particular between a protease and an amylase and/or a mannanase and/or a cellulase and/or a pectinase. Synergistic effects can occur not only between different enzymes, but also between one or more enzymes and other ingredients of the agent used according to the invention.

The enzymes to be used in the context of the present invention can, for example, originally come from microorganisms, for example of the genera Bacillus, Streptomyces, Humicola or Pseudomonas, and/or can be produced by suitable microorganisms using known biotechnological processes, for example by transgenic expression hosts, for example of the genera Escherichia , Bacillus or by filamentous fungi.

All enzymes mentioned in the context of the present invention can also be used in the form of technical enzyme preparations of the respective enzyme, which means that accompanying substances can be present. The enzymes can therefore be prepared and used together with accompanying substances, for example from fermentation or with other stabilizers.

The enzymes are generally not provided in the form of pure protein, but rather in the form of stabilized, storable and transportable preparations. These prefabricated preparations include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, in particular in the case of liquid or gel-like agents, solutions of the enzymes, advantageously as concentrated as possible, with little water and/or mixed with stabilizers or other auxiliaries.

Alternatively, the enzymes can be encapsulated for both the solid and liquid dosage forms, for example by spray drying or extrusion of the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are enclosed as in a solidified gel or in those of the core-shell type, in which an enzyme-containing core is covered with a water-, air- and/or chemical-impermeable protective layer. Additional active ingredients, such as stabilizers, emulsifiers, pigments, bleaches or dyes, can also be applied in superimposed layers. Such capsules are applied using methods known per se, for example by shaking or rolling granulation or in fluid bed processes. Such granules are advantageously low-dust, for example by applying polymeric film formers, and are storage-stable due to the coating.

Furthermore, it is particularly possible to assemble two or more enzymes together so that a single granulate has several enzyme activities, as explained above.

In liquid formulations, the enzymes are preferably used as enzyme liquid formulation(s). In various embodiments, such a liquid enzyme-containing formulation contains at least one organic solvent, preferably selected from alcohols, particularly preferably polyhydric polyhydric alcohols that are liquid under standard conditions (20 ° C, 1013 mbar), in particular glycerol, 1,2-propanediol and sorbitol, as well as mixtures thereof . If these are included, the amount is preferably from 0.1 to 99.9% by weight, more preferably 10 to 90% by weight, based on the total weight of the enzyme-containing formulation. In various embodiments, it may be preferred that the enzymes are used without the addition of borates or boron-containing compounds, which often serve as stabilizers. The compositions according to the invention can therefore be boron-free.

In various embodiments, the pH of such an enzyme preparation is in the range of 5 to 9, preferably in the range of 5.5 to 8.5, more preferably 6.5 to 8.0, most preferably in the range of 7.0 to 7.5.

A broad spectrum of effectiveness can be achieved, for example, by combining different enzymes with one another in such a way that enzymatic effectiveness is provided against a large number of different types of soiling, for example against grass stains, greasy and starchy soiling.

In various embodiments, a detergent used according to the invention contains at least one, preferably at least two, in particular at least three enzyme preparations, in an amount of 0.1 to 5% by weight, preferably 0.1 to 4% by weight, in each case based on the total weight of the means.

In various embodiments, the at least one enzyme preparation contains at least one enzyme selected from the group consisting of amylases, proteases, cellulases, mannanases, xanthanases, and pectinolytic enzymes.

• - 0,1 bis 2 Gew.-%, beispielsweise 0,1, 0,15, 0,2, 0,25, 0,3, 0,35, 0,4, 0,45, 0,5, 0,55, 0,6, 0,65, 0,7, 0,75, 0,8, 0,85, 0,9, 0,95, 1,0, 1,1, 1,2, 1,3, 1,4, 1,5, 1,6, 1,7, 1,8, 1,9, oder 2,0 Gew.-%, vorzugsweise 0,2 bis 1 Gew.-%, einer Amylase-Enzymzubereitung; und/oder
• - 0,2 bis 3 Gew.-%, beispielsweise 0,2, 0,25, 0,3, 0,35, 0,4, 0,45, 0,5, 0,55, 0,6, 0,65, 0,7, 0,75, 0,8, 0,85, 0,9, 0,95, 1,0, 1,1, 1,2, 1,3, 1,4, 1,5, 1,6, 1,7, 1,8, 1,9, 2,0, 2,1, 2,2, 2,3, 2,4, 2,5, 2,6, 2,7, 2,8, 2,9, oder 3,0 Gew.-%, vorzugsweise 0,4 bis 2 Gew.-%, einer Protease-Enzymzubereitung; und/oder
• - 0,01 bis 1 Gew.-%, beispielsweise 0,01, 0,03, 0,05, 0,1, 0,15, 0,2, 0,25, 0,3, 0,35, 0,4, 0,45, 0,5, 0,55, 0,6, 0,65, 0,7, 0,75, 0,8, 0,85, 0,9, 0,95 oder 1,0 Gew.-%, vorzugsweise 0,05 bis 0,3 Gew.-%, einer Cellulase-Enzymzubereitung.

In various embodiments, a detergent used according to the invention contains, based on the total weight of the agent,

• - 0.1 to 2% by weight, for example 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0, 55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, or 2.0% by weight, preferably 0.2 to 1% by weight, of an amylase enzyme preparation; and or
• - 0.2 to 3% by weight, for example 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0, 65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2, 8, 2.9, or 3.0% by weight, preferably 0.4 to 2% by weight, of a protease enzyme preparation; and or
• - 0.01 to 1% by weight, for example 0.01, 0.03, 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0, 4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95 or 1.0 wt .-%, preferably 0.05 to 0.3% by weight, of a cellulase enzyme preparation.

Aminocarboxylic acids

In various embodiments, the detergents may contain at least one aminocarboxylic acid. In the context of the present invention, aminocarboxylic acids are understood to mean those organic compounds which have a tertiary amino group which has one or two CH ₂ -COOH groups. Aminocarboxylic acids suitable in the context of the present invention may be present as a free acid or in partially or completely neutralized form, ie as a salt. Suitable counterions are, for example, inorganic cations, for example ammonium, alkali or alkaline earth metal, for example Mg ²⁺ , Na ⁺ , K ⁺ , or organic cations, including preferably ammonium substituted with one or more organic radicals, in particular triethanolammonium, N,N-diethanolammonium, N-Mono-C1-C4-alkyldiethanolammonium, for example N-methyldiethanolammonium or Nn-butyldiethanolammonium, and N,N-di-C1-alkylethanolammonium.

Aminocarboxylic acids suitable according to the invention also include polyaminocarboxylic acids. In the context of the present invention, polyaminocarboxylic acids are understood to mean those organic compounds which have at least two tertiary amino groups, which independently of one another each have one or two CH ₂ -COOH groups, which, as mentioned above, can be partially or completely neutralized.

Aminocarboxylic acids suitable according to the invention can also be selected from derivatives of aminocarboxylates and polyaminocarboxylates, for example from methyl or ethyl esters.

In some embodiments of the present invention, the at least one aminocarboxylic acid is selected from organic compounds that have a secondary amino group that has one or two CH(COOH)CH ₂ -COOH groups, which, as mentioned above, are partially or completely can be neutralized. In a further embodiment of the present invention, polyaminocarboxylic acids are selected from those organic compounds which have at least two secondary amino groups, each of which has a CH(COOH)CH ₂ -COOH group, which, as mentioned above, can be partially or completely neutralized.

Polyaminocarboxylic acids suitable in the context of the present invention are selected from the group consisting of 1,2-diaminoethanetetraacetic acid, tetraacetylmethylenediamine, tetraacetylhexylenediamine, iminodisuccinate (IDS), diethylenetriaminepentaacetic acid (DTPA), hydroxyethylenediaminetriacetic acid (HEDTA) and their respective salts, particularly preferably alkali metal salts, in particular the sodium salts .

In various embodiments, preferred are those aminocarboxylic acids, including polyaminocarboxylic acids, which have an amino acid-based structure whose amino group(s) have one or two CH ₂ -COOH groups and are tertiary amino groups.

In this context, amino acids can be selected from L-amino acids, R-amino acids and enantiomer mixtures of amino acids, for example the racemates.

Particularly preferred representatives are methylglycinediacetic acid (MGDA) or its salts and glutamic diacetic acid (GLDA) or its salts or ethylenediaminediacetic acid or its salts (EDDS), with sodium salts being preferred in the context of the present invention. Also suitable are iminodisuccinic acid (IDS) and iminodiacetic acid (IDA).

In various embodiments, the at least one aminocarboxylic acid is appropriately selected from the group consisting of methylglycinediacetic acid (MGDA) and its salts, glutamicdiacetic acid (GLDA) and its salts, ethylenediaminediacetic acid (EDDS) and its salts, iminodisuccinic acid (IDS) and its salts and iminodiacetic acid (IDA ) and their salts.

In various embodiments, the at least one aminocarboxylic acid is methylglycinediacetic acid (MGDA) or its salts, with the trisodium salt being preferred.

In various embodiments, detergents used according to the invention contain at least one aminocarboxylic acid, as defined and described above, in an amount of approximately 0.1 to 5% by weight, for example in an amount of 0.1, 0.2, 0.3, 0 ,4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6 , 1.7, 1.8, 1.9, 2.0, 2.3, 2.5, 2.7, 2.9, 3.0, 3.2, 3.5, 3.8, 4 ,0, 4.2, 4.5, 4.7, 4.9, or 5.0% by weight, for example, according to some embodiments, in an amount of 0.1 to 4% by weight, preferably in an amount of 0.2 to 3% by weight, based in each case on the total weight of the composition.

The at least one aminocarboxylic acid, as defined and described above, can be used together with other builders.

Builders

A detergent used according to the invention can, in various embodiments, contain at least one water-soluble and/or water-insoluble, organic and/or inorganic builder (builder), which differs from the at least one aminocarboxylic acid, as defined and described above. This can also be used independently of aminocarboxylic acids.

The generally usable builders include, in particular, zeolites, silicates, carbonates, organic (co)builders and - where there are no ecological prejudices against their use - also phosphates. However, according to preferred embodiments, the agents are essentially phosphate-free. In particularly preferred embodiments, the agents used according to the invention contain no phosphate at all.

Phosphonates are also builders that can be used in detergents. In various embodiments, an agent used according to the invention contains phosphonate in an amount of 0.01 to 10.0% by weight, for example in an amount of 0.1 to 5.0% by weight, based in each case on the total weight of the composition.

Phosphonates useful in the context of the present invention include phosphonates selected from the group consisting of hydroxyalkane and/or aminoalkane phosphonates. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance. The preferred aminoalkane phosphonates are ethylenediaminetetramethylene phosphonate (EDTMP), diethylenetriaminepentamethylene phosphonate (DTPMP) and their higher homologues. Accordingly, an agent used according to the invention contains, in various embodiments, at least one phosphonate selected from the group consisting of 1-hydroxyethane-1,1-diphosphonate (HEDP), ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologues, preferably selected from the group consisting of 1-hydroxyethane-1,1-diphosphonate (HEDP), ethylenediaminetetramethylenephosphonate (EDTMP) and diethylenetriaminepentamethylenephosphonate (DTPMP).

Other suitable builders are the alkali carriers. Alkaline carriers include, for example, alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogen carbonates, alkali metal sesquicarbonates, alkali metal silicates, alkali metasilicates, and mixtures of the aforementioned substances, with preference being given to using the alkali metal carbonates, in particular sodium carbonate, sodium hydrogen carbonate or sodium sesquicarbonate, for the purposes of this invention. Due to their low chemical compatibility with some other ingredients of detergents compared to other builder substances, the optional alkali metal hydroxides are preferably used only in small amounts, preferably in amounts below 10% by weight, preferably below 6% by weight, particularly preferably below 4% by weight. -% and in particular below 2% by weight, based on the total weight of the agent. Particular preference is given to agents which, based on their total weight, contain less than 0.5% by weight and in particular no alkali metal hydroxides.

Particular preference is given to using carbonate(s) and/or bicarbonate(s), preferably alkali metal carbonate(s), particularly preferably sodium carbonate, in amounts of 2 to 50% by weight, for example 5 to 40% by weight.

Particular organic builders that should be mentioned are polycarboxylates/polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins and other organic cobuilders. These substance classes are described below.

Useful organic builders are, for example, the polycarboxylic acids that can be used in the form of the free acid and/or their sodium salts, whereby polycarboxylic acids are understood to mean those carboxylic acids that carry more than one acid function. For example, these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, nitrilotriacetic acid (NTA), provided such use is not objectionable for ecological reasons, as well as mixtures of these. In addition to their builder effect, the free acids typically also have the properties of an acidifying component and therefore also serve to set a lower and milder pH value. In particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures of these should be mentioned.

Such further builders can, optionally in addition to one or more phosphonates, in an amount of approximately 0.1 to 10% by weight, preferably in an amount of 0.1 to 5% by weight, for example in an amount of 0. 1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5 or 5.0% by weight may be contained in agents used according to the invention, in each case based on the total weight of the agent.

Surfactants

In various embodiments of the invention, the agents according to the invention contain at least one surfactant. The at least one surfactant can be an anionic surfactant, a nonionic surfactant, an amphoteric or zwitterionic surfactant or a cationic surfactant, with anionic and/or nonionic surfactants being preferred in detergents and particularly preferably being used together. Non-ionic surfactants, in particular, can also be used in cleaning agents, optionally again in combination with anionic surfactants.

In various embodiments, the agent contains at least one anionic surfactant, for example in an amount of 5 to 35% by weight, for example in an amount of 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 , 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34 or 35% by weight, each based on the total weight of the means.

In various embodiments, the at least one anionic surfactant is contained in the agent according to the invention in an amount of 6 to 35% by weight, preferably in an amount of 7 to 25% by weight, based in each case on the total weight of the detergent and/or Detergent composition.

Suitable compounds from the class of anionic surfactants are those of the formula (I) R- _SO3 ^- X ⁺ (I)

In this formula (I), R represents a linear or branched unsubstituted alkylaryl radical. X stands for a single-quality cation or the n-ten part of an N-quality cation, preferably the alkali metal ions and below Na ⁺ or K ⁺ , where Na ⁺ is extremely preferred. _Further ^{cations _ _ _ _ _}

“Alkylaryl,” as used herein, refers to organic radicals consisting of an alkyl radical and an aromatic radical. Typical examples of such radicals include, but are not limited to, alkylbenzene radicals such as benzyl, butylbenzene radicals, nonylbenzene radicals, decylbenzene radicals, undecylbenzene radicals, dodecylbenzene radicals, tridecylbenzene radicals and the like.

in der R' und R'' zusammen 9 bis 19, vorzugsweise 11 bis 15 und insbesondere 11 bis 13 C-Atome enthalten, dargestellt. Ein ganz besonders bevorzugter Vertreter lässt sich durch die Formel A-1a beschreiben:

In verschiedenen Ausführungsformen handelt es sich bei der Verbindung der Formel (I) vorzugsweise um das Natriumsalz eines linearen Alkylbenzolsulfonats.In various embodiments, such surfactants are selected from linear or branched alkylbenzene sulfonates of the formula A-1:

in which R' and R'' together contain 9 to 19, preferably 11 to 15 and in particular 11 to 13 carbon atoms. A particularly preferred representative can be described by the formula A-1a:

In various embodiments, the compound of formula (I) is preferably the sodium salt of a linear alkylbenzene sulfonate.

Further preferred anionic surfactants are those of the formula (II) R ¹ -O ^- (AO) _n -SO3 ^- X ⁺ (II).

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 are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl radicals and mixtures thereof, the representatives having an even number of C Atoms are preferred. Particularly preferred radicals R ¹ are derived from C ₁₂ -C ₁₈ fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or from C ₁₀ -C ₂₀ oxo alcohols. X stands for a single-quality cation or the n-ten part of an N-quality cation, preferably the alkali metal ions and below Na ⁺ or K ⁺ , where Na ⁺ is extremely preferred. _Further ^{cations _ _ _ _ _}

AO represents an ethylene oxide (EO) or propylene oxide (PO) group, preferably an ethylene oxide group. The index n represents an integer from 1 to 50, preferably from 1 to 20 and in particular from 2 to 10. Very particularly preferably n represents the numbers 2, 3, 4, 5, 6, 7 or 8 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 _ _ _ _}

mit k = 11 bis 19, n = 2, 3, 4, 5, 6, 7 oder 8. Besonders bevorzugte Vertreter sind Na-C_12-14 Fettalkoholethersulfate mit 2 EO (k = 11-13, n = 2 in Formel II-1).In summary, agents in various embodiments can therefore contain at least one anionic surfactant selected from fatty alcohol ether sulfates of the formula II-1

with k = 11 to 19, n = 2, 3, 4, 5, 6, 7 or 8. Particularly preferred representatives are Na-C _12-14 fatty alcohol ether sulfates with 2 EO (k = 11-13, n = 2 in formula II -1).

Other anionic surfactants that can be used with preference are the alkyl sulfates of the formula R ² -O-SO ₃ - X ⁺ (III).

In this formula (III), R ² 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 ² are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl radicals and mixtures thereof, the representatives having an even number of C Atoms are preferred. Particularly preferred radicals R ² are derived from C ₁₂ -C ₁₈ fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or from C ₁₀ -C ₂₀ oxo alcohols. X stands for a single-quality cation or the n-ten part of an N-quality cation, preferably the alkali metal ions and below Na ⁺ or K ⁺ , where Na ⁺ is extremely preferred. _Further ^{cations _ _ _ _ _}

mit k = 11 bis 19. Ganz besonders bevorzugte Vertreter sind Na-C_12-14 Fettalkoholsulfate (k = 11-13 in Formel III-1).In various embodiments, these surfactants are selected from fatty alcohol sulfates of the formula III-1

with k = 11 to 19. Very particularly preferred representatives are Na-C _12-14 fatty alcohol sulfates (k = 11-13 in formula III-1).

Other anionic surfactants that can be used are the alkyl ester sulfonates, in particular those of the formula IV: R ¹ -CH(SO ₃ X ⁺ )-C(O)-OR ² (IV).

In this formula (IV), R ¹ represents a linear or branched, substituted or unsubstituted alkyl radical, preferably a linear, unsubstituted alkyl radical. Preferred radicals R ¹ are selected from nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl radicals and mixtures thereof, the representatives with an odd number of carbon atoms are preferred. Particularly preferred radicals R ¹ -CH are derived from C ₁₂ -C ₁₈ fatty acids, for example from lauryl, myristyl, cetyl or stearyl acid. R ² represents a linear or branched, substituted or unsubstituted alkyl radical, preferably a linear, unsubstituted alkyl radical. Preferred radicals R ² are C _1-6 alkyl radicals, especially methyl (=methyl ester sulfonates). X stands for a single-quality cation or the n-ten part of an N-quality cation, preferably the alkali metal ions and below Na ⁺ or K ⁺ , where Na ⁺ is extremely preferred. _Further ^{cations _ _ _ _ _}

The secondary alkanesulfonates are also suitable as anionic surfactants. These have, for example, the formula (V) R ¹ CH(SO ₃ X ⁺ ) R ² (V) on, where each R ¹ and R ² independently is a linear or branched alkyl with 1 to 20 carbon atoms and with the carbon atom to which they are bonded form a linear or branched alkyl, preferably with 10 to 30 carbon atoms, preferably with 10 to ₂₀ ^{carbon atoms and _ _ _ _ _ _}

In various preferred embodiments, the at least one secondary alkane sulfonate has the following formula (V-1): H ₃ C-(CH2) _n -CH(SO ₃ -X ⁺ )-(CH ₂ ) _m -CH ₃ (V-1) where m and n are independently an integer between 0 and 20. Preferably m + n is an integer between 7 and 17, preferably 10 to 14 and X ⁺ is selected from the group Na ⁺ , K ⁺ , NH ₄ ⁺ , ½ Zn ²⁺ , ½ Mg ²⁺ , ½ Ca ²⁺ , ½ Mn ²⁺ and mixtures thereof, preferably Na ⁺ . In a particularly preferred embodiment, the at least one secondary alkane sulfonate is secondary C _14-17 sodium alkane sulfonate. Such a secondary C _14-17 sodium alkane sulfonate is sold, for example, by the Clariant company under the trade name “Hostapur SAS60”.

In various embodiments, the at least one anionic surfactant is selected from the group of C _8-18 alkylbenzene sulfonates and is contained in an amount of 5 to 30% by weight, for example in an amount of 10 to 30% by weight, respectively based on the total weight of the detergent and/or cleaning agent composition.

Soaps can also be considered as a special form of anionic surfactants. Saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, as well as soap mixtures derived in particular from natural fatty acids, for example coconut, palm kernel or tallow fatty acids, are suitable.

The soaps can be in the form of their sodium, potassium or ammonium salts as well as soluble salts of organic bases such as mono-, di- or triethanolamine. The anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.

In various embodiments, an agent according to the invention contains at least one soap. In various embodiments, the fatty acid of the at least one soap is selected from the group consisting of caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid. Mixtures of the aforementioned fatty acids are also suitable.

In various embodiments, an agent according to the invention accordingly contains at least one soap, the soap comprising a fatty acid selected from the group consisting of caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid and mixtures thereof.

The amount of this at least one soap is, in various embodiments, from 0.2 to 10% by weight, for example 0.2, 0.5, 1.0, 1.5, 2.0, 2.5, 3, 0, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, or 8.0 wt. &, preferably 0, 4 to 7% by weight, based on the total weight of the agent according to the invention. The amount of soap can be included in addition to the total amount of anionic surfactant stated above.

In various embodiments, the at least one soap, as described above, is contained in the compositions according to the invention in combination with at least one further anionic surfactant, preferably in combination with one or more surfactants selected from the group of C _8-18 alkyl benzene sulfonates and alkyl ether sulfates, such as described above.

Furthermore, in various embodiments, an agent according to the invention contains at least one nonionic surfactant, for example in an amount of 3 to 40% by weight, for example in an amount of 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39 or 40% by weight, each based on the total weight of the agent.

In various embodiments, the at least one nonionic surfactant is contained in an amount of 5 to 35% by weight, preferably in an amount of 10 to 30% by weight, based in each case on the total weight of the agent according to the invention.

R3

für einen linearen oder verzweigten, substituierten oder unsubstituierten Alkylrest,

AO

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

m

für ganze Zahlen von 1 bis 50 stehen.

Fatty alcohol alkoxylates are particularly suitable as nonionic surfactants. In various embodiments, the agents therefore contain at least one nonionic surfactant of the formula R ³ -O-(AO) _m -H (VI), in the

R3

for a linear or branched, substituted or unsubstituted alkyl radical,

AO

for an ethylene oxide (EO) or propylene oxide (PO) group,

m

stand for integers from 1 to 50.

In the formula (VI) mentioned above, R ³ 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 ² are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl radicals and the like Mixtures, with representatives with an even number of carbon atoms being preferred. Particularly preferred radicals R ³ are derived from C ₁₂ -C ₁₈ fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or from C ₁₀ -C ₂₀ oxo alcohols.

AO represents an ethylene oxide (EO) or propylene oxide (PO) group, preferably an ethylene oxide group. The index m stands for an integer from 1 to 50, preferably from 1 to 20 and in particular from 2 to 10. Most preferably m stands for the numbers 2, 3, 4, 5, 6, 7 or 8.

mit k = 11 bis 19, m = 2, 3, 4, 5, 6, 7 oder 8. Ganz besonders bevorzugte Vertreter sind C_12-18 Fettalkohole mit 7 EO (k = 11-17, m = 7 in Formel (VI-1)).In summary, fatty alcohol alkoxylates to be preferably used are compounds of the formula

with k = 11 to 19, m = 2, 3, 4, 5, 6, 7 or 8. Very particularly preferred representatives are C _12-18 fatty alcohols with 7 EO (k = 11-17, m = 7 in formula (VI -1)).

Amine oxides, for example, are also suitable as nonionic surfactants. In principle, all amine oxides established in the prior art for these purposes, i.e. compounds which have the formula R ¹ R ² R ³ NO, in which each R ¹ , R ² and R ³ independently of the others are an optionally substituted, for example hydroxy- substituted, C ₁ -C ₃₀ hydrocarbon chain can be used. Particularly preferred amine oxides used are those in which R ¹ is C ₁₂ -C ₁₈ alkyl and R ² and R ³ are each independently C ₁ -C ₄ alkyl, in particular C ₁₂ -C ₁₈ alkyldimethylamine oxides. Examples of suitable amine oxides are N-cocoalkyl-N,N-dimethylamine oxide, N-tallow alkyl-N,N-dihydroxyethylamine oxide, myristyl/cetyldimethylamine oxide or lauryldimethylamine oxide.

Further nonionic surfactants that can be contained in the agents described in the sense of the present invention include, but are not limited to, alkyl glycosides, alkoxylated fatty acid alkyl esters, fatty acid alkanolamides, hydroxy mixed ethers, sorbitan fatty acid esters, polyhydroxy fatty acid amides and alkoxylated alcohols. Such surfactants are known in the art.

Suitable alkyl (poly) glycosides are, for example, those of the formula R ² O-[G] _p , in which R ² is a es or branched alkyl with 12 to 16 carbon atoms, G is a sugar residue with 5 or 6 carbon atoms, in particular glucose, and the index p is 1 to 10.

In various _embodiments , the at least one nonionic surfactant is selected 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, the C _12-18 - Alcohols with 5 EO or 7 EO, in particular the C _12-18 fatty alcohols with 7 EO or the C _13-15 oxo alcohols with 7 EO, and is in an amount of 3 to 30% by weight, in each case based on the total weight of the agent according to the invention, contained in this.

In various embodiments, an agent according to the invention contains the at least one anionic surfactant and the at least one nonionic surfactant, as defined and described above, for example in a weight ratio of 2:1 to 2:3.

In various embodiments, an agent according to the invention may contain, in addition to at least one anionic surfactant and/or at least one nonionic surfactant, as defined and described above, or independently thereof, at least one other surfactant selected from the group consisting of cationic and amphoteric surfactants.

Suitable amphoteric surfactants are, for example, betaines of the formula (R ⁱⁱⁱ )(R ^iv )(R ^v )N ⁺ CH ₂ COO ^- , in which R ⁱⁱⁱ is an alkyl radical with 8 to 25, preferably 10 to 21, carbon atoms, optionally interrupted by heteroatoms or heteroatom groups, and R ^iv and R ^v represent similar or different alkyl radicals with 1 to 3 carbon atoms, in particular C ₁₀ -C ₁₈ -alkyldimethylcarboxymethylbetaine and C ₁₁ -C ₁₇ -alkylamidopropyl-dimethylcarboxymethylbetaine.

Suitable cationic surfactants include the quaternary ammonium compounds of the formula (R ^vi )(R ^vii )( ^{R viii} ) ⁽ R ^{ix )} N ⁺ short-chain ^, alkyl radicals and Other suitable cationic surfactants are the quaternary surface-active compounds, in particular with a sulfonium, phosphonium, iodonium or arsonium group, which are also known as antimicrobial active ingredients. By using quaternary surface-active compounds with an antimicrobial effect, the agent can be designed with an antimicrobial effect or its antimicrobial effect, which may already be present due to other ingredients, can be improved.

Preferred cationic surfactants are the quaternary surface-active compounds, in particular with an ammonium, sulfonium, phosphonium, iodonium or arsonium group, which are also known as antimicrobial agents. By using quaternary surface-active compounds with an antimicrobial effect, the agent can be designed with an antimicrobial effect or its antimicrobial effect, which may already be present due to other ingredients, can be improved.

To avoid possible incompatibilities between the cationic surfactants and the anionic surfactants contained, as much anionic surfactant-compatible and/or as little cationic surfactant as possible is used or, in a special embodiment of the invention, cationic surfactants are dispensed with entirely.

In various embodiments, the total amount of surfactants, based on the total weight of the agent, is 8 to 60% by weight, for example 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20 , 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35 ,36 3.7 38, 39, 40, 41, 42, 43, 44, 45 , 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59 or 60% by weight, preferably 10 to 55% by weight, in each case based on the total weight of the product according to the invention Means.

Water

In various embodiments of the invention, the agents used according to the invention can contain water. In various embodiments, the agents can also be concentrates that are low in water to anhydrous, i.e. water in an amount of less than 20% by weight, preferably less than 15% by weight, less than 12% by weight. % or less than 10% by weight based on the total weight of a respective agent.

Other ingredients

The agents used according to the invention can contain further ingredients, for example at least one further component, preferably at least two further components, which further improve the application-related and/or aesthetic properties of the agent. These include, for example, non-aqueous solvents, fragrances, skin-care active ingredients, as well as additives for adjusting the viscosity and/or for stabilization, as well as other auxiliaries and additives common in detergents, such as UV stabilizers, dyes, pearlescent agents, preservatives, bitter substances, organic salts , disinfectants, anti-redeposition polymers, structuring polymers, soil release polymers, color transfer inhibitors, defoamers and pH adjusters.

The amount of correspondingly suitable components in compositions used according to the invention depends on the respective intended use of the composition and the trained specialist is generally familiar with suitable dosages of these components or is able to find appropriate quantities in the literature.

Non-aqueous solvents

In various embodiments, an agent used according to the invention can contain one or more non-aqueous solvents. Suitable non-aqueous solvents include organic solvents from the group of mono- or polyhydric alcohols, alkanolamines and glycol ethers, provided they are miscible with water in the specified concentration range. In various embodiments, an agent used according to the invention contains at least one organic solvent 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 of these solvents, in particular selected from the group consisting of propanediol, glycerol, ethanol and mixtures thereof.

The one or more non-aqueous solvents is/are, in various embodiments, in an amount of 3 to 20% by weight, for example in an amount of 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14.1 5, 16, 17, 18, 19 or 20% by weight, preferably in an amount of 4 to 18% by weight, in each case based on the total weight of the agent used according to the invention.

Fragrances and skin-care active ingredients

In various embodiments, an agent as described herein further comprises at least one fragrance.

In various embodiments, an agent used according to the invention contains at least one fragrance in an amount of 0.2 to 4% by weight, for example in an amount of 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, 1.0, 1, 1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3, 4, 3.5, 3, 6, 3.7, 3.8, 39, or 4.0% by weight, preferably in an amount of 0.5 to 3% by weight, based in each case on the total weight of the agent.

All known substances and mixtures can be used as fragrances or fragrances or perfume oils. For the purposes of this invention, the terms “fragrance(s)”, “fragrances” and “perfume oil(s)” are used synonymously. This refers in particular to all those substances or their mixtures that are perceived by humans and animals as an odor, in particular by humans as a pleasant smell.

Perfumes, perfume oils or perfume oil components can be used as fragrance components. According to the invention, perfume oils or fragrances can contain individual fragrance compounds, e.g. B. the synthetic products can be of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type.

1. (a) Textilpflegestoffe, wie vorzugsweise Silikonöle, und/oder
2. (b) Hautpflegestoffe, wie vorzugsweise Vitamin E, natürliche Öle und/oder kosmetische Öle.

A perfume oil can also be contained in the form of a perfume oil preparation and, for example, comprise at least one further active ingredient in oil form. In this context, suitable active ingredients in oil form are those which are suitable for washing, cleaning, care and/or finishing purposes, in particular

1. (a) Textile care substances, such as preferably silicone oils, and/or
2. (b) skin care ingredients, such as preferably vitamin E, natural oils and/or cosmetic oils.

1. a) Wachse wie beispielsweise Carnauba, Spermaceti, Bienenwachs, Lanolin und/oder Derivate derselben und andere.
2. b) Hydrophobe Pflanzenextrakte
3. c) Kohlenwasserstoffe wie beispielsweise Squalene und/oder Squalane
4. d) Höhere Fettsäuren, vorzugsweise solche mit wenigstens 12 Kohlenstoffatomen, beispielsweise Laurinsäure, Stearinsäure, Behensäure, Myristinsäure, Palmitinsäure, Ölsäure, Linolsäure, Linolensäure, Isostearinsäure und/oder mehrfach ungesättigte Fettsäuren und andere.
5. e) Höhere Fettalkohole, vorzugsweise solche mit wenigstens 12 Kohlenstoffatomen, beispielsweise Laurylalkohol, Cetylalkohol, Stearylalkohol, Oleylalkohol, Behenylalkohol, Cholesterol und/oder 2-Hexadecanaol und andere.
6. f) Ester, vorzugsweise solche wie Cetyloctanoate, Lauryllactate, Myristyllactate, Cetyllactate, Isopropylmyristate, Myristylmyristate, Isopropylpalmitate, Isopropyladipate, Butylstearate, Decyloleate, Cholesterolisostearate, Glycerolmonostearate, Glyceroldistearate, Glyceroltristearate, Alkyllactate, Alkylcitrate und/oder Alkyltartrate und andere.
7. g) Lipide wie beispielsweise Cholesterol, Ceramide und/oder Saccharoseester und andere.
8. h) Vitamine wie beispielsweise die Vitamine A, C und E, Vitaminalkylester, einschließlich Vitamin-C-Alkylester und andere.
9. i) Sonnenschutzmittel
10. j) Phospholipide
11. k) Derivate von alpha-Hydroxysäuren
12. l) Germizide für den kosmetischen Gebrauch, sowohl synthetische wie beispielsweise Salicylsäure und/oder andere als auch natürliche wie beispielsweise Neemöl und/oder andere.
13. m) Silikone
14. n) Natürliche Öle, z.B. Mandelöl

sowie Mischungen jeglicher vorgenannter Komponenten.Skin care active ingredients are all those active ingredients that provide the skin with a sensory and/or cosmetic benefit. Skin-care active ingredients are preferably selected from the following substances:

1. a) Waxes such as carnauba, spermaceti, beeswax, lanolin and/or derivatives thereof and others.
2. b) Hydrophobic plant extracts
3. c) Hydrocarbons such as squalene and/or squalane
4. d) Higher fatty acids, preferably those with at least 12 carbon atoms, for example lauric acid, stearic acid, behenic acid, myristic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid, isostearic acid and / or polyunsaturated fatty acids and others.
5. e) Higher fatty alcohols, preferably those with at least 12 carbon atoms, for example lauryl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, behenyl alcohol, cholesterol and/or 2-hexadecanaol and others.
6. f) Esters, preferably those such as cetyl octanoates, lauryl lactates, myristyl lactates, cetyl lactates, isopropyl myristates, myristyl myristates, isopropyl palmitates, isopropyl adipates, butyl stearates, decyl oleates, cholesterol isostearates, glycerol monostearates, glycerol distearates, glycerol tristearates, alkyl lactates, alkyl citrates and/or alkyl tart rate and others.
7. g) Lipids such as cholesterol, ceramides and/or sucrose esters and others.
8. h) Vitamins such as vitamins A, C and E, vitamin alkyl esters, including vitamin C alkyl esters and others.
9. i) Sunscreen
10. j) Phospholipids
11. k) Derivatives of alpha-hydroxy acids
12. l) Germicides for cosmetic use, both synthetic, such as salicylic acid and/or others, and natural, such as neem oil and/or others.
13. m) silicones
14. n) Natural oils, e.g. almond oil

as well as mixtures of any of the aforementioned components.

In various embodiments, the content of the at least one fragrance, which can also be in the form of a perfume oil or as a component of a perfume oil composition, as described above, is preferably between approximately 0.0001 to 5% by weight, in particular between approximately 0.005 and 3.0 % by weight, preferably between about 0.01 and 1.5% by weight, more preferably between about 0.05 and 1.0% by weight, based on the total weight of a respective agent.

It may be desirable to keep sensitive beneficial agents/active ingredients, such as perfumes and fragrances, as described above, spatially separated from other components of the detergent until they are used. An elegant method for incorporating such sensitive, chemically or physically incompatible or volatile ingredients is to use microcapsules in which these ingredients are enclosed in a storage and transport-stable manner and from which they are released mechanically, chemically, thermally or enzymatically for or during use .

In a preferred embodiment, a fragrance, as defined above, and possibly also other components, such as additional fragrances and skin feeling-improving active ingredients, are incorporated wholly or partially into microcapsules. Suitable microcapsules are known in the art and are commercially available.

Other polymers

The agents can also contain other polymers that differ from the copolymer used and optionally the ethoxylated PEI.

Polymers suitable as additives are, in particular, maleic acid-acrylic acid copolymer Na salt (for example the commercially available Sokalan® CP 5 (BASF SE, DE)), modified polyacrylic acid Na salt (for example the commercially available Sokalan® CP 10 (BASF SE , DE)), modified polycarboxylate Na salt (for example the commercially available Sokalan® HP 25 (BASF SE, DE)), polyalkylene oxide, modified heptamethyltrisiloxane (for example the commercially available Silwet® L-77 (BASF SE, DE)), Polyalkylene oxide, modified heptamethyltrisiloxane (for example the commercially available Silwet® L-7608 (BASF SE, DE)) and polyethersiloxanes (copolymers of polymethylsiloxanes with ethylene oxide/propylene oxide segments (polyether blocks)), preferably water-soluble linear polyethersiloxanes with terminal polyether blocks such as the commercially available compounds Tegopren ® 5840, Tegopren® 5843, Tegopren® 5847, Tegopren® 5851, Tegopren® 5863 or Tegopren® 5878 (Evonik, DE). In a special embodiment of the invention, the polymers mentioned are dispensed with.

Antiredeposition polymers suitable in principle in the context of the present invention include carboxymethylcellulose (CMC), polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP), polyoxyethylene and/or polyethylene glycol (PEG), homopolymers of acrylic acid, and copolymers of acrylic acid and maleic acid. Also suitable are cellulose-based soil release polymers, which can also function as anti-redeposition agents. Suitable cellulose polymers include cellulose, cellulose ethers, cellulose esters, cellulose amides and mixtures thereof. Suitable cellulosic polymers include anionically modified cellulose, nonionically modified cellulose, cationically modified cellulose, zwitterionically modified cellulose and mixtures thereof. Suitable examples include, but are not limited to on, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, ester carboxymethyl cellulose and mixtures thereof.

Other suitable polymers are soil release polymers (SRPs), in particular terephthalate-based copolymers, for example poly(oxy)ethylene or poly(oxy)propylene terephthalates or combinations of such polymers. Examples of suitable SRPs include the products available under the trade name Texcare® (Clariant, DE), such as Texcare SRN 170.

The polymers mentioned above can be used, for example, in amounts of 1 to 10% by weight, for example 1 to 8% by weight or 1 to 7% by weight, based on the total weight of the agent. However, the total amount of polymers together with the copolymer used according to the invention and, optionally, PEls is preferably not more than 15% by weight, more preferably not more than 10% by weight, based on the total weight of the composition.

Polymeric thickeners which can also be contained in the agent are the polycarboxylates which have a thickening effect as polyelectrolytes, preferably homo- and copolymers of acrylic acid, in particular acrylic acid copolymers such as acrylic acid-methacrylic acid copolymers, and the polysaccharides, in particular heteropolysaccharides, as well as other common thickeners Polymers. However, in various embodiments no such thickeners are included.

Optical brightener

An optical brightener is preferably made from the substance classes of distyrylbiphenyls, stilbenes, 4,4'-diamino-2,2'-stilbenedisulfonic acids, coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, naphthalamides, benzoxazole systems, the benzisoxazole systems, the benzimidazole systems, the pyrene derivatives substituted by heterocycles and mixtures thereof.

Particularly preferred suitable optical brighteners include disodium 4,4'-bis-(2-morpholino-4-anilino-s-triazine-6-ylamino)stilbenedisulfonate (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'disulfonic 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) (available for example as Tinopal® SFP from BASF SE), 2, 2'-(2,5-thiophenediyl)bis[5-1,1-dimethylethyl)benzoxazole (available for example as Tinopal® SFP from BASF SE) and/or 2,5-bis(benzoxazol-2-yl)thiophene.

Dye transfer inhibitors

Suitable dye transfer inhibitors include polymers and copolymers of cyclic amines such as vinylpyrrolidone and/or vinylimidazole. Polymers suitable as a color transfer inhibitor 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. Polyvinylpyrrolidone (PVP), polyvinylimidazole (PVI) or copolymers of vinylpyrrolidone and vinylimidazole (PVP/PVI) are particularly preferably used as color transfer inhibitors. 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. A PVP/PVI copolymer is commercially available, for example from BASF under the name Sokalan® HP 56. Another extremely preferably usable color transfer inhibitor are polyethylene glycol-modified copolymers of vinylpyrrolidone and vinylimidazole, which are available, for example, from BASF under the name Sokalan® HP 66 are.

pH adjusting agent

In general, the pH value of the agents used according to the invention can be adjusted using conventional pH regulators. In various embodiments, the pH value of agents used according to the invention is in a range from 6.5 to 12, preferably 7.0 to 11.5, preferably greater than 7. Acids and/or alkalis, preferably alkalis, serve as pH adjusting agents. Suitable acids are, in particular, organic acids such as acetic acid, citric acid, glycolic acid, lactic acid, succinic acid, adipic acid, malic acid, tartaric acid and gluconic acid or amidosulfonic acid. In addition, the mineral acids hydrochloric acid, sulfuric acid and nitric acid or mixtures thereof can also be used. Suitable bases come from the group of alkali and alkaline earth metal hydroxides and carbonates, in particular alkali metal hydroxides, of which potassium hydroxide is preferred. The alkali source described above is particularly preferably used to adjust the pH value. Volatile alkali, for example in the form of ammonia and/or alkanolamines, which can contain up to 9 carbon atoms in the molecule, can also be used to adjust the pH, whereby the alkanolamine can be selected, for example, from the group consisting of mono -, di-, triethanol- and -propanolamine and their mixtures. Monoethanolamine is particularly preferably used in the agents used according to the invention.

To adjust and/or stabilize the pH value, an agent used according to the invention can further contain one or more buffer substances (INCI buffering agents), usually in amounts of 0.001 to 5% by weight. Buffer substances that are also complexing agents or even chelating agents (chelators, INCI chelating agents) are preferred. Particularly preferred buffer substances are citric acid or citrates, in particular sodium and potassium citrates, for example trisodium citrate·2H ₂ O and tripotassium citrate·H ₂ O.

assembly

In some embodiments, the detergents described herein can be prepackaged into dosage units. These dosing units preferably include the amount of washing or care-active substances necessary for a cleaning cycle. In some embodiments, suitable dosage units have a weight of between 12 and 30 g, for example. The volume of the aforementioned dosing units and their spatial shape are particularly preferably chosen so that the pre-assembled units can be dosed via the dosing chamber of a washing machine. The volume of the dosing unit is therefore preferably between 10 and 35 ml, preferably between 12 and 30 ml.

In various embodiments, agents as described herein, in particular the prefabricated dosage units, may have a water-soluble coating. In some embodiments, an agent as described herein is in the form of a unit dose as described above. In preferred embodiments, such an agent used according to the invention is in particular encased in a water-soluble film.

The water-soluble covering is preferably formed from a water-soluble film material selected from the group consisting of polymers or polymer mixtures. The wrapping may be formed from one or two or more layers of the water-soluble film material. The water-soluble film material of the first layer and the additional layers, if present, can be the same or different. Films that can be glued and/or sealed to form packaging such as tubes or pillows after they have been filled with an agent are particularly preferred. In various embodiments, the films have the shape of multi-chamber pouches.

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

Suitable water-soluble films for producing the water-soluble coating are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer, the molecular weight of which 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 .

Polyvinyl alcohol is usually produced by hydrolysis of polyvinyl acetate, as the direct synthesis route is not possible. The same applies to polyvinyl alcohol copolymers, which are made from polyvinyl acetate copolymers. It is preferred if at least one layer of the water-soluble coating comprises a polyvinyl alcohol, the degree of hydrolysis of which is 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%.

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

In addition to vinyl alcohol, preferred polyvinyl alcohol copolymers include dicarboxylic acids as further monomers. Suitable dicarboxylic acids are itaconic acid, malonic acid, succinic acid and mixtures thereof, with itaconic acid being preferred.

In addition to vinyl alcohol, also preferred polyvinyl alcohol copolymers include an ethylenically unsaturated carboxylic acid, its salt or its ester. In addition to vinyl alcohol, such polyvinyl alcohol copolymers particularly preferably contain acrylic acid, methacrylic acid, acrylic acid esters, methacrylic acid esters or mixtures thereof.

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

Suitable water-soluble films for use in the water-soluble wrappings of the water-soluble packaging according to the invention are films sold by MonoSol LLC, for example under the names M8630, C8400 or M8900. Other suitable films include films called Solublon® PT, Solublon® GA, Solublon® KC or Solublon® KL from Aicello Chemical Europe GmbH or the VF-HP films from Kuraray.

In various embodiments, the agents used according to the invention are liquid agents, in particular liquid (textile) detergents.

Use and procedure

The use of the copolymer as described above may be in the form of a detergent which may contain the additional ingredients described above. Such detergents are used to clean textiles, although the use according to the invention uses them to give textiles dirt-repellent properties, which are caused by the copolymer used. The present invention covers uses in which an agent as described herein is used in the washing machine or in a manual textile washing process.

Another subject of the invention is a manual or mechanical process for providing textiles with dirt-repellent properties, in which a copolymer as described herein is brought into contact with the textiles in at least one process step. This can be done as part of a standard textile washing process in a washing machine or manually.

In particular, the present invention relates to a method in which the agent, as described herein, is placed together with the textiles in a household washing machine or an industrial washing machine and subjected to a washing program, or in which the detergent is transferred to the textiles via the washing liquor in a manual washing process can.

In general, in such processes, the textiles to be cleaned come into contact with a copolymer or a composition containing it, optionally in diluted form with water, in one process step.

In principle, an agent as described here can also be used advantageously in combination with other textile detergents and/or care agents in corresponding processes. In various embodiments, the present invention also relates to processes in which, in addition to at least one copolymer or detergent as described herein, a textile conditioning agent is also used.

All facts, objects and embodiments that are described for the uses according to the invention are also applicable to the above methods and vice versa.

Examples

Table 1: Detergent formulations (V(x) = comparison formulation; E(x) = according to the invention) V1 E1 E2 ingredients copolymer* - 1.37 4.0 Ethoxylated polyethyleneimine*** 4.8 4.8 2.4 Nonionic surfactant 22.7 22.7 22.7 anionic surfactant 22.1 22.1 22.1 Soap 7.2 7.2 7.2 Monoethanolamine 6.1 6.1 6.1 1,2-propanediol 5.9 5.6 5.7 Ethanol 3.5 3.5 3.5 Glycerin 10.7 10.1 10.3 Phosphonate 0.7 0.7 0.7 Amylase, protease, cellulase, mannanase** 1.7 1.7 1.7 Coloring agents, bitter substances, disulfite, opacifying agents 0.2 0.2 0.2 Optical brightener 0.5 0.5 0.5 Perfume 1.5 1.5 1.5 water, demin. ad 100 ad 100 ad 100 * Amphiphilic, alkoxylated poly(ethylene/propylene)imine copolymer according to the invention ** commercially available enzyme formulations *** Sokalan HP20 (ex BASF)

The amounts of all ingredients are given in% by weight of active substance (except enzyme formulations).

Definished polyester and cotton fabric was pre-washed 3 times with the formulation to be tested without filling. The raw fabrics were washed 3 times at 40 ° C with washing liquors each containing 1.47 g / l of a detergent V1, E1 or E2 on the same day and then hanging dried. It was washed in a Miele WCI 360 WTL washing machine at 40°C. The duration of the wash cycle was 119 minutes, with the main wash cycle taking 74 minutes.

The fabrics pretreated in this way were now soiled with defined amounts of different types of soiling. The spots were aged for 7 days.

The fabrics pretreated and soiled in this way were washed at 40 ° C with washing liquors containing 1.47 g / l each of V1, E1 or E2 and then dried. It was washed in the same washing machine on the same program as described above in the pre-treatment.

The water hardness was 16°dH and it was washed with 17L of water with 5 repetitions/washing cycles and then the brightness values of the soiling (Y values, the higher the better the cleaning performance) were determined as average values from 5 measurements. The results are shown in Table 2. Table 2: Washing tests (Y values) V1 V1 E1 E2 Soiling material Lard (blue) PES 54.3 55.2 lipstick PES 35.8 43.6 Sebum (blue) PES 54.3 65.4 Shoe polish (black) PES 39.7 47.1 Lard (blue) Co 51.2 53.8 Make-up 1 PES 67.2 68.6 Collar and hem PES 60.1 66.3 Lard (blue) PES 54.3 55.7 lipstick PES 35.8 47.6 Make-up 2 PES 56.6 64.7 Sebum (blue) PES 54.3 65.6 Shoe polish (black) PES 39.7 49.8 Lard (blue) PES 55.2 55.7 lipstick PES 43.6 47.6 Shoe polish (black) PES 47.1 49.8 CO = cotton; PES = Polyester

The first set of experiments shows the soil release effect of the copolymer used on greasy soils.

The second sentence shows that by varying the polymer content in the formula, the performance on greasy soils in the soil release performance can be increased even further, while at the same time the proportion of ethoxylated PEI can be reduced.

The third sentence shows that by increasing the proportion of copolymer in the polymer mixture of the formula, the performance on greasy soils could be increased even further.

QUOTES INCLUDED IN THE DESCRIPTION

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

Cited patent literature

• WO 2021254828 A1 [0033, 0034]

Non-patent literature cited

• Gornall et al., 1948, J. Biol. Chem., 177:751-766 [0045]
• Bender et al., 1966, J. Am. Chem. Soc. 88(24):5890-5913 [0045]

Claims (10)

Use of at least one amphiphilic alkoxylated poly(ethylene/propylene)imine copolymer which comprises repeat units of the monomer (A), optionally monomer (B) and/or optionally monomer (C) in condensed form, wherein monomer (A) is a compound of the formula

Monomer (B) is a compound of the formula

is and monomer (C) is a compound of the formula

is, where m is 1 to 4, I is 1 to 3, k is 0 or 1, o is 0 or 1 and Rein is C ₁ -C ₁₈ alkyl, and wherein each NH functional group is directly attached to a via a covalent bond Alkoxy chain of the formula -(A ¹ O) _a -(A ² O) _b -(A ³ O) _c -R' is bonded, where A ¹ is C ₃ -C ₁₂ alkylene, a is 0 to 2, A ² is ethylene, b is 5 to 50, A ³ is 1,2-propylene, c is 5 to 50, R 'from H and C ₁ -C ₄ alkyl is selected and the alkylene oxide units are preferably bound as block structures, as a soil repellent polymer (SRP) in order to provide textiles with dirt-repellent properties. Process for equipping textiles with dirt-repellent properties, characterized in that the textiles are coated with at least one amphiphilic alkoxylated poly(ethylene/propylene)imine copolymer, which contains repeating units of the monomer (A), optionally monomer (B) and/or optionally monomer (C) in condensed form, wherein monomer (A) is a compound of the formula

Monomer (B) is a compound of the formula

is and monomer (C) is a compound of the formula

is, where m is 1 to 4, I is 1 to 3, k is 0 or 1, o is 0 or 1 and Rein is C ₁ -C ₁₈ alkyl, and wherein each NH functional group is directly attached to a via a covalent bond Alkoxy chain of the formula -(A ¹ O) _a -(A ² O) _b -(A ³ O) _c -R' is bonded, where A ¹ is C ₃ -C ₁₂ alkylene, a is 0 to 2, A ² is ethylene, b is 5 to 50, A ³ is 1,2-propylene, c is 5 to 50, R 'from H and C ₁ -C ₄ alkyl is selected and the alkylene oxide units are preferably bound as block structures, are brought into contact. Use according to Claim 1 or procedures in accordance with Claim 2 , characterized in that the at least one copolymer is part of a (textile) detergent. Use or method according to any of the Claims 1 until 3 , characterized in that the at least one copolymer is brought into contact with the textiles in a washing process in order to equip them with dirt-repellent properties. Use or method according to any of the Claims 1 until 4 , characterized in that the at least one amphiphilic alkoxylated poly(ethylene/propylene)imine copolymer repeating units of the monomer (A) and either the monomer (B) or the monomer (C), preferably the monomer (A) and the monomer (B) in condensed form. Use or method according to any of the Claims 1 until 5 , characterized in that the at least one amphiphilic alkoxylated poly(ethylene/propylene)imine copolymer comprises repeating units of the monomer (A), the monomer (B) and the monomer (C) in condensed form. Use or method according to any of the Claims 1 until 6 , characterized in that in the at least one amphiphilic alkoxylated poly(ethylene/propylene)imine copolymer m is 1, 2 or 3, preferably 1, and/or I is 1 and/or k is 1 and/or o is 1 and/ or R is a C ₁ -C ₄ alkyl radical, preferably methyl, and/or R' is H. Use or method according to any of the Claims 1 until 7 , characterized in that the at least one amphiphilic alkoxylated poly(ethylene/propylene)imine copolymer has a weight-average molecular weight Mw of the poly(ethylene/propylene)imine backbone without alkoxy chains of at least 300 g/mol, preferably at least 500 g/mol. Use or method according to any of the Claims 1 until 8th , characterized in that in the at least one amphiphilic alkoxylated poly(ethylene/propylene)imine copolymer a is 0 and/or b is 10 to 40, preferably 15 to 35, and/or c is 5 to 40, preferably 10 to 35, and/or the molar ratio EO/PO is >0.8, preferably ≥1. Use or method according to any of the Claims 6 until 9 , characterized in that in the at least one amphiphilic alkoxylated poly(ethylene/propylene)imine copolymer m is 1, k is 1, o is 1, I is 1, R is methyl, R' is H and where the amount of monomers ( A), (B) and (C) in the poly(ethylene/propylene)imine backbone without alkoxy chains is each at least 10% by weight but a maximum of 50% by weight.