Polymeric soil-dispersing agents

Abstract

The aim of the invention is to improve the cleaning performance and / or anti-greying performance of detergents when washing textiles. This is substantially achieved by the use of copolymers obtainable by i) free-radical polymerization of cyclic ketene acetals with a (meth)acrylic acid monomer having a protecting group, and ii) subsequent removal of said protecting group.

Description

[0001] Henkel AG & Co. KGaA 2024P00251 WO

[0002] Polymer dirt-dispersing agents

[0003] The present invention relates to the use of certain copolymers of ketene derivatives and monoethylene unsaturated comonomers to enhance the cleaning performance of detergents when washing textiles.

[0004] Washing and cleaning agents must demonstrate good cleaning performance across a wide range of soils. This spectrum ranges from polar soils such as proteins, clays, and inorganic compounds to nonpolar soils such as soot and organic compounds.

[0005] Due to the ever-decreasing washing temperatures, shorter wash cycle durations, and reduced water consumption, it is essential that dirt is easily and quickly removed from textiles and that the loosened dirt is quickly and stably dissolved or dispersed in the wash water. Furthermore, it is necessary to keep the suspended dirt stable in the wash water so that it can be carried away when the wash water is removed.

[0006] The same applies to water-insoluble salts, such as calcium carbonate or magnesium carbonate, which form when washing with hard water. These water-insoluble salts are deposited on the washed textiles and cause them to grey.

[0007] EP 760846 A1 therefore describes compositions with improved dirt dispersing properties that contain uncharged, alkoxylated polyalkylenamine polymers as dirt dispersants. Furthermore, charged, alkoxylated polyalkylenamine polymers are known from EP 917562 A1.

[0008] Surprisingly, polymers accessible from ketene derivatives and (meth)acrylic acid were found to have a dirt-dispersing effect.

[0009] The invention relates to the use of copolymers obtainable by i) radical polymerization of cyclic ketene acetals with a protecting group-provided (meth)acrylic acid monomer and ii) subsequent removal of the protecting group to enhance the cleaning performance of detergents when washing textiles.

[0010] In the radical polymerization of cyclic ketene acetals, the acetal ring opens, giving rise to ester functionalities that can improve the biodegradability of the resulting polymer. This improved biodegradability is considered a further advantage of the invention. Preferably, the copolymers used according to the invention are composed of 5 mol% to 50 mol%, in particular 35 mol% to 15 mol%, of at least one cyclic ketene acetal monomer and 50 mol% to 95 mol%, in particular 65 mol% to 85 mol%, of at least one (meth)acrylic acid monomer. Apart from components originating from radical initiators or radical terminators, the copolymers preferably contain no components derived from other monomers. The copolymers preferably exist as a statistically determined structure, but can also contain a gradient or be structured as block copolymers.

[0011] The ketene acetal is preferably selected from 2-methylene-1,3-dioxolane, 2-methylene-1,3-dioxane, 2-methylene-1,3-dioxepane (MDO), 2-methylene-1,3,6-trioxocan (MTC), 2-methylene-1,3,6-dioxazocane, which may optionally be substituted in the acetal ring or at the nitrogen atom, such as 4,5,-Di-Ci-i2-alkyl-2-methylene-1,3-dioxolane, 4-Ci-i2-alkyl-2-methylene-1,3-dioxolane, 5-Ci-i2-alkyl-2-methylene-1,3-dioxepane, 5,6-Di-Ci-i2-alkyl-2-methylene-1,3-dioxepane. 4-Ci-i2-Alkyl-2-methylene-1,3-dioxane, 4,6-Di-Ci-i2-Alkyl-2-methylene-1,3-dioxolane and 5,6-Benzo-2-methylene-1,3-dioxepane, 4-Phenyl-2-methylene-1,3-dioxolane, 4,5-Di-phenyl-2-methylene-1,3-dioxolane, 4-Phenyl-2-methylene-1,3-dioxane, 4,6-Di-phenyl-2-methylene-1,3-dioxolane, 4-Phenyl-2-methylene-1,3-dioxepane, 4,7-Di-phenyl-2-methylene-1,3-dioxepane and A / -4,8-Tri-Ci-i2-Alkyl-2-methylene-1 ,3,6-dioxazocane and its mixtures.

[0012] The ketene acetal preferably comprises 2-methylene-1,3-dioxepane (MDO). The ketene acetal 2-methylene-1,3-dioxepane (MDO) is particularly preferred.

[0013] In an alternative, also particularly preferred embodiment, the ketene acetal comprises 2-methylene-1,3,6-trioxocan (MTC). The ketene acetal 2-methylene-1,3,6-trioxocan (MTC) is particularly preferred.

[0014] The protecting group-modified (meth)acrylic acid monomer is preferably selected from acrylic acid esters and / or methacrylic acid esters. It is particularly selected from te / y-butyl acrylate, te / y-butyl methacrylate, and mixtures thereof. It is especially preferred that the protecting group-modified (meth)acrylic acid monomer comprises te / y-butyl acrylate (tBA or tert-butyl acrylate). It is highly preferred that the protecting group-modified (meth)acrylic acid monomer is te / y-butyl acrylate.

[0015] The removal of the protecting group, in particular a te / Y.-butyl protecting group, can be achieved by the action of acid, for example by acid hydrolysis. It is particularly preferred that the copolymer be obtained by i) radical polymerization of cyclic ketene acetals comprising ketene acetal 2-methylene-1,3-dioxepane (MDO), with a protecting (meth)acrylic acid monomer comprising acrylic acid te / Y.-butyl ester, and ii) subsequent removal of the protecting group by acid.

[0016] It is also particularly preferred that the copolymer is obtainable by i) radical polymerization of cyclic ketene acetals comprising ketene acetal 2-methylene-1,3,6-trioxocan (MTC) with a protecting group-equipped (meth)acrylic acid monomer comprising acrylic acid te / Y.-butyl ester, and ii) subsequent removal of the protecting group by acid.

[0017] Another aspect of the invention is a method for washing textiles, in which a detergent and a dirt-dispersing agent in the form of a copolymer as defined above are used. These methods can be carried out manually or, optionally, with the aid of a conventional household washing machine. It is advantageous to apply the detergent and the dirt-dispersing agent simultaneously. This simultaneous application is particularly advantageous when using a detergent that contains the dirt-dispersing agent.

[0018] The process essentially consists of bringing a textile in need of cleaning, or at least the soiled part of its surface, into contact with an aqueous preparation containing the copolymer defined above, allowing the aqueous preparation to act on the textile, or at least the soiled part of its surface, for a certain period of time, and removing the aqueous preparation, for example by rinsing the textile with water.

[0019] In the presence of the copolymers essential to the invention during the washing process, there is less redeposition of dirt already removed from the textile and / or less deposition of water-insoluble salts formed during the washing process onto the cleaned textile, so that textiles washed in the presence of a copolymer essential to the invention gray significantly less than those washed in its absence. A further object of the invention is therefore the use of the copolymers defined above to reduce the graying of textiles, in particular textiles made of or containing cotton, during washing.

[0020] The uses according to the invention can be carried out within the framework of a washing process by adding the dirt-dispersing active ingredient to a detergent-containing bath or, preferably, by introducing the active ingredient as a component of a detergent into the bath containing the object to be cleaned or which is brought into contact with it. A further aspect of the invention is therefore a detergent containing the copolymers defined above.

[0021] The washing process is preferably carried out at a temperature of 15 °C to 60 °C, particularly preferably at a temperature of 20 °C to 40 °C. The washing process is further preferably carried out at a pH value of 6 to 1, particularly preferably at a pH value of 7.5 to 9.5. The concentration of the copolymer in the washing liquor is preferably 0.0001 g / l to 5 g / l, particularly 0.001 g / l to 0.5 g / l.

[0022] Detergents containing an active ingredient to be used according to the invention in the form of the said copolymer, or used together with it or employed in processes according to the invention, may contain all other usual components of such agents that do not interact in an undesirable way with the active ingredient essential to the invention, in particular surfactant.

[0023] Preferably, the active ingredient defined above is used in amounts of 0.01 wt.% to 15 wt.%, particularly preferably from 0.1 wt.% to 10 wt.%, wherein these and the following quantities refer to the entire composition unless otherwise specified. Preferably, a composition according to the invention, or used in the process according to the invention, or used within the scope of the use according to the invention, is aqueous and liquid; it contains in particular 2 wt.% to 92 wt.%, particularly preferably 3 wt.% to 85 wt.% water.

[0024] In a preferred embodiment, an agent used in the invention or employed in the process according to the invention contains a non-ionic surfactant selected from fatty alkyl polyglycosides, fatty alkyl polyalkoxylates, in particular ethoxylates and / or propoxylates, fatty acid polyhydroxyamides and / or ethoxylation and / or propoxylation products of fatty alkylamines, vicinal diols, fatty acid alkyl esters and / or fatty acid amides, as well as mixtures thereof, in particular in an amount in the range of 2 wt.% to 25 wt.%.

[0025] Another embodiment of such agents comprises the presence of synthetic anionic surfactant of the sulfate and / or sulfonate type, in particular fatty alkyl sulfate, fatty alkyl ether sulfate, sulfofatty acid esters, and / or sulfofatty acid disalts, especially in an amount in the range of 2 wt.% to 25 wt.%. Preferably, the anionic surfactant is selected from the alkyl or alkenyl sulfates and / or the alkyl or alkenyl ether sulfates in which the alkyl or alkenyl group has 8 to 22, in particular 12 to 18, carbon atoms. These are usually not single substances, but rather cuts or mixtures. Among these, those whose proportion of compounds with longer-chain residues in the range of 16 to 18 carbon atoms exceeds 20 wt.% are preferred.Suitable nonionic surfactants include alkoxylates, in particular ethoxylates and / or propoxylates of saturated or mono- to polyunsaturated linear or branched-chain alcohols with 10 to 22 carbon atoms, preferably 12 to 18 carbon atoms. The degree of alkoxylation of the alcohols is generally between 1 and 20, preferably between 3 and 10. They can be prepared in a known manner by reacting the corresponding alcohols with the corresponding alkylene oxides. Derivatives of fatty alcohols are particularly suitable, although their branched-chain isomers, especially so-called oxo alcohols, can also be used to produce usable alkoxylates. Accordingly, alkoxylates, especially ethoxylates, of primary alcohols with linear, in particular dodecyl, tetradecyl, hexadecyl, or octadecyl, residues, as well as mixtures thereof, are suitable.Furthermore, corresponding alkoxylation products of alkylamines, vicinal diols, and carboxylic acid amides, which correspond to the aforementioned alcohols with respect to the alkyl moiety, can be used. In addition, the ethylene oxide and / or propylene oxide insertion products of fatty acid alkyl esters as well as fatty acid polyhydroxyamides are suitable. So-called alkyl polyglycosides suitable for incorporation into the compositions according to the invention are compounds of the general formula (G). n -OR 12 , in the R 12 an alkyl or alkenyl group with 8 to 22 carbon atoms, G a glucose unit, and n a number between 1 and 10. In the case of the glycoside component (G) nThese are oligo- or polymers of naturally occurring aldose or ketose monomers, which include in particular glucose, mannose, fructose, galactose, talose, gulose, altrose, allose, idose, ribose, arabinose, xylose, and lyxose. The oligomers consisting of such glycosidically linked monomers are characterized not only by the type of sugars they contain but also by their number, the so-called degree of oligomerization. The degree of oligomerization n, as a quantity to be determined analytically, generally takes on fractional values; it lies between 1 and 10, and for the preferably used glycosides, below a value of 1.5, particularly between 1.2 and 1.4. Glucose is the preferred monomer building block due to its good availability. The alkyl or alkenyl moiety R 12The glycosides are preferably also derived from readily available derivatives of renewable raw materials, especially fatty alcohols, although their branched-chain isomers, particularly so-called oxo alcohols, can also be used to produce usable glycosides. Accordingly, primary alcohols with linear octyl, decyl, dodecyl, tetradecyl, hexadecyl, or octadecyl groups, as well as mixtures thereof, are particularly suitable. Particularly preferred alkyl glycosides contain a coconut fatty acid alkyl group, i.e., mixtures with essentially R 12 =Dodecyl and R 12 =Tetradecyl.

[0026] Non-ionic surfactant is present in compositions containing, used according to the invention, or employed in the process according to the invention, preferably in amounts of 1 wt.% to 30 wt.%, and in particular from 1 wt.% to 25 wt.%, wherein amounts in the upper part of this range are more likely to be found in liquid detergents, and particulate detergents preferably contain lower amounts of up to 5 wt.%. The compositions may instead or additionally contain further surfactants, preferably synthetic anionic surfactants of the sulfate or sulfonate type, such as alkylbenzenesulfonates, in amounts preferably not exceeding 20 wt.%, and in particular from 0.1 wt.% to 18 wt.%, in each case based on the total composition.Particularly suitable synthetic anionic surfactants for use in such agents include alkyl and / or alkenyl sulfates with 8 to 22 carbon atoms, bearing an alkali, ammonium, or alkyl / hydroxyalkyl-substituted ammonium ion as a countercation. Derivatives of fatty alcohols, especially those with 12 to 18 carbon atoms, and their branched-chain analogs, the so-called oxo alcohols, are preferred. The alkyl and alkenyl sulfates can be prepared in a known manner by reacting the corresponding alcohol component with a conventional sulfating reagent, particularly sulfur trioxide or chlorosulfonic acid, followed by neutralization with alkali, ammonium, or alkyl / hydroxyalkyl-substituted ammonium bases. The sulfated alkoxylation products of the aforementioned alcohols, so-called ether sulfates, are also among the sulfate-type surfactants that can be used.Preferably, such ether sulfates contain 2 to 30, in particular 4 to 10, ethylene glycol groups per molecule. Suitable anionic surfactants of the sulfonate type include the α-sulfoesters obtainable by reacting fatty acid esters with sulfur trioxide and subsequent neutralization, in particular the sulfonation products derived from fatty acids with 8 to 22 carbon atoms, preferably 12 to 18 carbon atoms, and linear alcohols with 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, as well as the sulfofatty acids obtained from these by formal saponification.

[0027] Soaps are also considered as optional surfactant ingredients, including saturated fatty acid soaps such as the salts of lauric, myristic, palmitic, or stearic acid, as well as soaps derived from natural fatty acid mixtures, for example, coconut, palm kernel, or tallow fatty acids. Soap mixtures are particularly preferred that consist of 50 wt.% to 100 wt.% saturated Ci₂-Ci₈ fatty acid soaps and up to 50 wt.% oleic acid soap. Preferably, soap is present in amounts of 0.1 wt.% to 5 wt.%. However, especially in liquid compositions containing a polymer used according to the invention, higher amounts of soap, generally up to 20 wt.%, may also be present.

[0028] In a further embodiment, the agent contains water-soluble and / or water-insoluble builder, in particular selected from alkali aluminosilicate, crystalline alkali silicate with a modulus above 1, monomeric polycarboxylate, polymeric polycarboxylate and mixtures thereof, in particular in amounts in the range of 2.5 wt.% to 60 wt.%.

[0029] The composition preferably contains 20 wt.% to 55 wt.% water-soluble and / or water-insoluble, organic and / or inorganic builders. The water-soluble organic builders include, in particular, those from the class of polycarboxylic acids, especially citric acid and sugar acids, as well as polymeric (poly)carboxylic acids, especially polycarboxylates accessible by oxidation of polysaccharides, polymeric acrylic acids, methacrylic acids, maleic acids, and copolymers of these, which may also contain small amounts of polymerizable substances without carboxylic acid functionality. Suitable, though less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ethers, vinyl esters, ethylene, propylene, and styrene, in which the acid content is at least 50 wt.%.Water-soluble organic builder substances can also include terpolymers which contain two carboxylic acids and / or their salts as monomers and vinyl alcohol and / or a vinyl alcohol derivative or a carbohydrate as a third monomer.

[0030] Such organic builder substances are preferably present in amounts up to 40 wt.%, particularly up to 25 wt.%, and most preferably from 1 wt.% to 5 wt.%. Amounts close to the aforementioned upper limit are preferably used in paste-like or liquid, particularly aqueous, agents.

[0031] Water-insoluble, water-dispersible inorganic builder materials, particularly crystalline or amorphous alkali aluminosilicates, are used in amounts of up to 50 wt.%, preferably not exceeding 40 wt.%, and in liquid form, especially from 1 wt.% to 5 wt.%. Among these, crystalline aluminosilicates of detergent quality, especially zeolite NaA and optionally NaX, are preferred. Amounts close to the aforementioned upper limit are preferably used in solid, particulate form. Suitable substitutes or partial substitutes for the aforementioned aluminosilicate are crystalline alkali silicates, which can be present alone or in mixtures with amorphous silicates.

[0032] In addition to the aforementioned inorganic builder, further water-soluble or water-insoluble inorganic substances may be contained in the compositions, used together with an active ingredient according to the invention, or employed in processes according to the invention. Suitable substances in this context are alkali carbonates, alkali hydrogen carbonates, and alkali sulfates, as well as mixtures thereof. Such additional inorganic material may be present in amounts up to 70% by weight.

[0033] In addition, the compositions may contain other components commonly found in detergents and cleaning agents. These optional components include, in particular, enzymes, enzyme stabilizers, bleaching agents, bleach activators, complexing agents for heavy metals, for example, aminopolycarboxylic acids, aminohydroxypolycarboxylic acids, polyphosphonic acids and / or aminopolyphosphonic acids, foam inhibitors, solvents, and optical brighteners. Solvents that can be used, especially in liquid compositions, are preferably those that are water-miscible, in addition to water. These include lower alcohols, for example, ethanol, propanol, isopropanol, and the isomeric butanols, glycerol, lower glycols, for example, ethylene and propylene glycol, and ethers derived from the aforementioned classes of compounds. In such liquid compositions, the active ingredients used according to the invention are generally present in dissolved or suspended form.

[0034] Any enzymes present are preferably selected from the group comprising protease, amylase, lipase, cellulase, hemicellulase, oxidase, peroxidase or mixtures thereof.

[0035] In a preferred embodiment, a composition in which the active ingredient to be used according to the invention is incorporated is particulate and contains up to 25 wt.%, in particular 4 wt.% to 20 wt.% bleaching agent, in particular alkali percarbonate, up to 15 wt.%, in particular 1 wt.% to 10 wt.% bleach activator, 20 wt.% to 55 wt.% inorganic builder, up to 10 wt.%, in particular 2 wt.% to 8 wt.% water-soluble organic builder, 10 wt.% to 25 wt.% synthetic anionic surfactant, 1 wt.% to 5 wt.% non-ionic surfactant and up to 25 wt.%, in particular 0.1 wt.% to 25 wt.% inorganic salts, in particular alkali carbonate and / or hydrogen carbonate.

[0036] In a further preferred embodiment, a composition in which the active ingredient to be used according to the invention is incorporated is liquid and contains 1 wt.% to 25 wt.%, in particular 5 wt.% to 15 wt.% non-ionic surfactant, up to 10 wt.%, in particular 0.5 wt.% to 8 wt.% synthetic anionic surfactant, 3 wt.% to 15 wt.%, in particular 5 wt.% to 10 wt.% soap, 0.5 wt.% to 5 wt.%, in particular 1 wt.% to 4 wt.% organic builder, in particular polycarboxylate such as citrate, up to 1.5 wt.%, in particular 0.1 wt.% to 1 wt.% complexing agent for heavy metals, such as phosphonate, and, in addition to any enzyme, enzyme stabilizer, coloring and / or fragrance, water and / or water-miscible solvent.

[0037] The dirt-dispersing copolymers are preferably water-soluble, whereby the term "water-soluble" is understood to mean a solubility of at least 0.01 g, preferably at least 0.1 g of the polymer per liter of water at room temperature and pH 8. However, the polymers preferably used exhibit a solubility of at least 1 g per liter, and in particular at least 10 g per liter, under these conditions. Examples

[0038] Example 1: Production of poly(MDO-co-AA) (17:83 mol%) (Polymer P1)

[0039] To 3.88 mL of MDO (25 mol%) and 14.25 mL of te / Y-butyl acrylate (tBA) (75 mol%, tBA) (together 33 wt% in toluene), 38 mL of dry toluene and 0.51 mL of tert-butyl peroxide (2 mol% to MDO and tBA) were added. The mixture was degassed by freeze-pump-thaw and then stirred at 100 °C for 3 h. To stop the reaction, the mixture was rapidly cooled in liquid nitrogen and then precipitated in 350 mL of a cold 1:11 water:methanol solution. 12.24 g of the dried polymer P1 were dissolved in 65 mL of dichloromethane and treated with 30 mL of trifluoroacetic acid (5 eq). The mixture was stirred for 24 hours at 25 °C, then precipitated in 350 mL of cold water and dried.

[0040] MDO is present at 17 mol% in the copolymer P1, determined by 1 H-NMR spectroscopy.

[0041] Molecular weight range of copolymer P1: 5000-200,000 Da

[0042] Example 2: Production of poly(MDO-co-AA) (40:60 mol%) (Polymer P2)

[0043] To 9.31 mL of MDO (45 mol%) and 9.08 mL of te / Y-butyl acrylate (tBA) (55 mol%, tBA) (together 33 wt% in toluene), 40 mL of dry toluene and 0.51 mL of tert-butyl peroxide (2 mol% to MDO and tBA) were added. The mixture was degassed by freeze-pump-thaw and then stirred at 100 °C for 3 h. To stop the reaction, the mixture was rapidly cooled in liquid nitrogen and then precipitated in 400 mL of a cold 1:11 water:methanol solution. 9.85 g of the dried polymer P2 were dissolved in 45 mL of dichloromethane and treated with 20 mL of trifluoroacetic acid (5 eq). The mixture was stirred for 24 hours at 25 °C, then precipitated in 500 mL of cold water and dried.

[0044] MDO is present at 40 mol% in the copolymer P2, determined by 1 H-NMR spectroscopy.

[0045] Molecular weight range of copolymer P2: 5000-200,000 Da

[0046] Example 3: Production of poly(MTC-co-AA) (45:55 mol%) (Polymer P3)

[0047] To 7.00 mL of 2-methylene-1,3,6-trioxocane (75 mol%, MTC) and 2.80 mL of te / Y-butyl acrylate (tBA) (25 mol%, tBA) (together 33 wt% in toluene), 23 mL of dry toluene and 0.28 mL of tert-butyl peroxide (2 mol% to MTC and tBA) were added. The mixture was stirred at 100 °C for 3 h. To stop the reaction, the mixture was rapidly cooled in liquid nitrogen and the toluene was then removed under vacuum. The mixture was dissolved in 6 mL of dichloromethane and precipitated in 400 mL of a cold 1:3 water:methanol solution. 3.49 g of the dried polymer P3 were dissolved in 34 mL of dichloromethane and treated with 5.8 mL of trifluoroacetic acid (5 eq). The mixture was stirred for 24 h at 25 °C, after which the dichloromethane was removed under vacuum. After the addition of 10 mL of dioxane, the mixture was freeze-dried.

[0048] MTC is present at 45 mol% in the copolymer P3, determined by 1 H-NMR spectroscopy.

[0049] Molecular weight range: 500-50,000 Da

[0050] Example 4: Production of poly(MTC-co-AA) (30:70 mol%) (Polymer P4)

[0051] To 3.0 mL of MTC (50 mol%) and 3.6 mL of te / Y-butyl acrylate (tBA) (50 mol%) (together 33 wt% in toluene), 14 mL of dry toluene and 0.18 mL of tert-butyl peroxide (2 mol% to MTC and tBA) were added. The mixture was stirred at 100 °C for 3 h. To stop the reaction, the mixture was rapidly cooled in liquid nitrogen, and the toluene was then removed under vacuum. The mixture was dissolved in 4 mL of DCM and precipitated in 300 mL of a cold 1:3 water:methanol solution. 3.77 g of the dried polymer were dissolved in 46 mL of DCM and treated with 7.8 mL of trifluoroacetic acid (5 eq). The mixture was stirred at 25 °C for 24 h, and the DCM was then removed under vacuum. After the addition of 15 mL of dioxane, the mixture was freeze-dried.

[0052] MTC is present at 30 mol% in the copolymer P4, determined by 1 H-NMR spectroscopy.

[0053] Molecular weight range: 1000-100,000 Da

[0054] Example 5: Dispersing properties of polymers P1 to P4

[0055] A wash solution was prepared from a builder-free powder detergent W1 or W2 (3.59 g / L). 100 mL of this wash solution was heated to 60 °C, and 4.97 mL of a CaCl₂ solution (20.641 g / L) and 4.97 mL of a MgSO₄ solution (1.537 g / L) were added dropwise at a rate of 0.5 mL / min. The turbidity was determined photometrically until the end of the titration. For comparison, wash solutions W1 were tested together with polymers P1 and P2 (0.105 g / L), and W2 together with polymers P3 and P4 (0.105 g / L) were tested under the same conditions.

[0056] The titration was performed using a Metrohm 905 Titrando, and the addition was carried out using a Metrohm 800 Dosino and a Metrohm 801 stirrer. A Metrohm 662 photometer and a Metrohm 856 conductivity module were used for measurements. At the end of the titration, the water hardness was 35°dH. Table 1: Transparency (in %) at different water hardnesses when using polymers P1 and P1.

[0057] P2

[0058] Table 2: Transparency (in %) at different water hardness levels when using polymers P3 and

[0059] P4

[0060] It can be seen that polymers P1 to P4 effectively prevent the precipitation of calcium and magnesium carbonate, silicate, and sulfate, as well as mixed precipitates, even at high hardness levels, resulting in a solution with less turbidity than without their use. Because the metal ions are kept in solution and do not precipitate, their deposition on textiles is also prevented.

Claims

Patent claims 1. Use of copolymers obtainable by i) radical polymerization of cyclic ketene acetals with a protecting group-equipped (meth)acrylic acid monomer and ii) subsequent removal of the protecting group to enhance the cleaning performance of detergents when washing textiles.

2. Use of copolymers obtainable by i) radical polymerization of cyclic ketene acetals with a protecting group-equipped (meth)acrylic acid monomer and ii) subsequent removal of the protecting group to reduce the greying of textiles during washing.

3. A method for washing textiles comprising a detergent and a copolymer obtainable by i) radical polymerization of cyclic ketene acetals with a protecting group-equipped (meth)acrylic acid monomer and ii) subsequent removal of the protecting group.

4. Method according to claim 3, characterized in that the concentration of the copolymer used in the washing liquor is 0.0001 g / l to 5 g / l, in particular 0.001 g / l to 0.5 g / l.

5. Method according to claim 3 or 4, characterized in that it is carried out using a detergent containing the copolymer.

6. Detergents containing a copolymer obtainable by i) radical polymerization of cyclic ketene acetals with a protecting group-protected (meth)acrylic acid monomer and ii) subsequent removal of the protecting group.

7. Composition according to claim 6, characterized in that it contains the copolymer in amounts of 0.01 wt.% to 15 wt.%, in particular from 0.1 wt.% to 10 wt.%.

8. Use according to one of claims 1 or 2, method according to one of claims 3 to 5 or agent according to claim 6 or 7, characterized in that the copolymer is composed of 5 mol% to 50 mol%, in particular 15 mol% to 35 mol%, at least one cyclic ketene acetal monomer and 50 mol% to 95 mol%, in particular 65 mol% to 85 mol%, at least one (meth)acrylic acid monomer.

9. Use according to one of claims 1 or 2, method according to one of claims 3 to 5 or agent according to claim 6 or 7, characterized in that the ketene acetal is selected from 2-methylene-1,3-dioxepane (MDO), 2-methylene-1,3,6-trioxocan (MTC) and their mixtures.

10. Use according to one of claims 1 or 2, method according to one of claims 3 to 4. 5 or composition according to claim 6 or 7, characterized in that the (meth)acrylic acid monomer provided with a protecting group comprises acrylic acid te / Y.-butyl ester.

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