Textile washing method

Abstract

Washing process for textiles in a domestic washing machine, comprising the steps: a) providing a washing machine with a washing program, comprising a main wash cycle of duration tw, and activating this washing program; b) placing textiles into the washing chamber of the washing machine; c) introducing an aqueous liquor into the washing chamber of the washing machine; d) introducing a first detergent composition, comprising at least one surfactant, into the washing chamber of the washing machine during the main wash cycle at a time between 0 and 10% tw; e) introducing a second detergent composition, comprising peroxycarboxylic acid and surfactant, into the aqueous liquor of the main wash cycle at a time between 11 and 99% tw.

Description

[0001] The present invention relates to a textile washing process. In particular, the application relates to a multi-stage machine-based textile washing process in the course of which washing and cleaning active substances are dosed at different times.

[0002] While currently less than a third of humanity has access to a textile washing machine, machine textile cleaning has been the standard procedure for removing dirt and refreshing laundry in some regions of the world since the 1970s.

[0003] Both the machinery and the detergents used in machine-based textile cleaning processes have been continuously developed and improved in terms of performance and environmental footprint over the past decades. While initial development efforts focused on improving individual components of the washing process, such as the washing machine and its mechanics and programs, or the detergent itself, more recently the focus has shifted to improving the interaction between these components.

[0004] International application WO 2021 / 048911 A1 describes a washing process using a textile washing machine, in the course of which the textiles are sprayed with a rinsing solution in a rinsing cycle.

[0005] European patent EP 3 428 336 B1 discloses washing processes with a minimum duration of 110 minutes, in which detergents containing rejuvenating agents are added to the washing liquid.

[0006] The European patent EP 2 711 413 B1 relates to washing processes which are characterized by a time-staggered dosage of different washing-active substances.

[0007] European patent EP 2 566 943 B1 discloses the sensor-controlled time-delayed dosing of washing-active substances, for example peroxocarboxylic acids, into the interior of a textile washing machine.

[0008] Even in light of previous developments, the technical challenge of improving the washing performance of textile detergents in textile washing machines remains.

[0009] To solve this task, a washing procedure for textiles in a household washing machine is suitable, which includes the following steps: a) Providing a washing machine with a washing program comprising a main wash cycle of duration tw and activating this washing program; b) Placing textiles into the washing machine's treatment chamber; c) Placing an aqueous liquor into the washing machine's treatment chamber; d) Placing a first detergent composition comprising at least one surfactant into the washing machine's treatment chamber during the main wash cycle at a time between 0 and 10% tw; e) Placing a second detergent composition comprising peroxycarboxylic acid and surfactant into the aqueous liquor of the main wash cycle at a time between 11 and 99% tw.

[0010] A washing machine is a motor-driven device for cleaning textiles. Drum washing machines with a drum rotatable about a horizontal axis are particularly preferred. The method according to the invention is especially suitable for implementation in a household washing machine with a tub, a drum located inside the tub (serving as a laundry treatment chamber), and a draining device designed to pump out aqueous solution from the tub.

[0011] In step a) of the procedure, a washing machine with a washing program comprising a main wash cycle of duration tw is provided. Conventional washing machines typically have multiple washing programs designed for cleaning different textiles, which, in addition to a main wash cycle, may include pre-rinse, rinse, and / or spin cycles. Preferred washing programs include a main wash cycle, at least one rinse cycle, and at least one spin cycle. Alternative washing programs include at least one pre-wash cycle, a main wash cycle, at least one rinse cycle, and at least one spin cycle.

[0012] In addition to the mechanical forces acting on the laundry, the detergent used, and the temperature of the wash liquor, the duration of the wash cycle, particularly the main wash cycle, influences the cleaning performance achieved. Preferably, the duration tw of the main wash cycle used in the washing process is 15 to 400 minutes, more preferably 30 to 240 minutes, and particularly 60 to 180 minutes.

[0013] The textiles brought into the laundry treatment room in step b) can be, for example, cotton or synthetic textiles, but also blended fabrics.

[0014] The aqueous liquor introduced into the laundry treatment room in step c) preferably has a volume of 3 to 40 l, preferably 6 to 30 l and particularly 8 to 20 l.

[0015] The loading of the washing machine with textiles in step b) and the volume of the aqueous liquor introduced in step c) are preferably coordinated such that the weight ratio of aqueous liquor to textiles in step c) is above 1:1, preferably above 2:1 and in particular above 5:2.

[0016] In step c), the aqueous liquor preferably has a temperature T1 of 18 to 25°C.

[0017] The first detergent composition is introduced into the laundry treatment chamber in step d) at a time between 0 and 10% of the duration tw. In other words, the first detergent composition is already in the laundry treatment chamber at the beginning of the main wash cycle (time 0 tw) or is introduced into the laundry treatment chamber within a period of 10% of the duration tw of the main wash cycle.

[0018] In one process variant, the aqueous solution is introduced into the washing machine's laundry treatment chamber before the first detergent mixture is added. Such a process variant can be implemented, for example, by means of a pre-rinse cycle, during which the textiles are pre-rinsed and / or soaked with water but not yet cleaned with the actual detergent mixture.

[0019] A second method involves the simultaneous introduction of the aqueous liquor and the first detergent composition into the washing machine's treatment chamber. If, for example, the aqueous liquor is introduced into the treatment chamber via the washing machine's dispenser drawer (which is already filled with the first detergent composition) when a pre-rinse cycle is omitted, then the introduction of both the aqueous liquor and the first detergent composition into the treatment chamber occurs simultaneously.

[0020] Finally, it is also possible that the aqueous solution is introduced into the washing machine's laundry treatment chamber after the first detergent composition, for example by applying the first detergent composition in pre-portioned form or using a dosing aid directly to the textiles before the start of the washing program.

[0021] The first detergent composition introduced into the laundry treatment chamber preferably comprises at least one anionic surfactant. Preferred first detergent compositions contain, based on their total weight, 12 to 40 wt.%, preferably 15 to 30 wt.%, and particularly 18 to 25 wt.% anionic surfactant.

[0022] The anionic surfactant is preferably selected from the group comprising C9-C13 alkylbenzenesulfonates, olefin sulfonates, C12-C18 alkanesulfonates, ester sulfonates, alk(en)yl sulfates, fatty alcohol ether sulfates, and mixtures thereof. Compositions comprising C9-C13 alkylbenzenesulfonates and fatty alcohol ether sulfates as the anionic surfactant exhibit particularly good dispersing properties. Suitable sulfonate-type surfactants include preferably C9-C13 alkylbenzenesulfonates, olefin sulfonates (i.e., mixtures of alkene and hydroxyalkanesulfonates), and disulfonates, such as those obtained, for example, from C12-C18 monoolefins with terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.Also suitable are C 12 -C 18 -alkanesulfonates and the esters of α-sulfofaticial acids (estersulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.

[0023] It is particularly preferred if the first detergent composition contains at least one anionic surfactant of formula (I), in which R' and R" are independent H or alkyl and together contain 9 to 19, preferably 9 to 15 and in particular 9 to 13 C atoms, and Y +< denotes a monovalent cation or the nth part of an n-valent cation (in particular monoethanolamine).

[0024] The group of alkyl ether sulfates includes fatty alcohol ether sulfates, for example, the sulfuric acid monoesters of straight-chain or branched C₇-C₂₁ alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C₉-C₁₁₁ alcohols with an average of 3.5 mol of ethylene oxide (EO) or C₁₂₁₈ fatty alcohols with 1 to 4 EO. Alkyl ether sulfates with the formula (II) R₁<-O-(AO)ₙ-SO₃<X+< (II) are preferred.

[0025] In this formula (II), R<1> represents a linear or branched, substituted or unsubstituted alkyl group, preferably a linear, unsubstituted alkyl group, and particularly preferably a fatty alcohol group. Preferred R<1> groups of formula (II) are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, and eicosyl groups and mixtures thereof, with those having an even number of carbon atoms being preferred. Particularly preferred R<1> groups of formula (II) are derived from fatty alcohols with 12 to 18 carbon atoms, for example, coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl, or stearyl alcohol, or from oxo alcohols with 10 to 20 carbon atoms.

[0026] In formula (II), AO represents an ethylene oxide (EO) or propylene oxide (PO) group, preferably an ethylene oxide group. The index n in formula (I) is an integer from 1 to 50, preferably from 1 to 20, and particularly from 2 to 10. n 2, 3, 4, 5, 6, 7, or 8 is most preferred. X is a monovalent cation or the nth part of an n-valent cation, preferably the alkali metal ions, including Na⁺ or K⁺, with Na⁺ being most preferred. Further cations X⁺ can be selected from NH₄⁺, ½ Zn²⁺, ½ Mg²⁺, ½ Ca²⁺, ½ Mn²⁺, and mixtures thereof, as well as primary and secondary amines, particularly monoethanolamine.

[0027] Particularly preferred first detergent compositions contain an alkyl ether sulfate selected from fatty alcohol ether sulfates of formula (III) with k = 11 to 19, n = 2, 3, 4, 5, 6, 7, or 8. Particularly preferred representatives are Na fatty alcohol ether sulfates with 12 to 18 carbon atoms and 2 EOs (k = 11 to 13, n = 2 in Formula III). The stated degree of ethoxylation represents a statistical average, which may be a whole number or a fraction for a specific product. The stated degrees of alkoxylation represent statistical averages, which may be a whole number or a fraction for a specific product. Preferred alkoxylates / ethoxylates exhibit a narrow range of homologs (narrow range ethoxylates, NRE).

[0028] In summary, preferred first detergent compositions contain, based on their total weight, 12 to 40 wt.%, preferably 15 to 30 wt.% and in particular 18 to 25 wt.% anionic surfactant from the group of C 9-19 alkylbenzenesulfonates and alkyl ether sulfates, preferably from the group of C 9-19 alkylbenzenesulfonates.

[0029] The use of fatty acids has proven advantageous for stability and cleaning performance. Preferred first detergent compositions therefore contain 4 to 12 wt.%, preferably 6 to 10 wt.%, fatty acids based on their total weight. Particularly preferred fatty acids are 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. For the purposes of this application, the fatty acids are not classified as anionic surfactants.

[0030] The first detergent composition also includes at least one non-ionic surfactant as a further preferred component.

[0031] The use of a non-ionic surfactant from the group of alkyl ethoxylates is particularly preferred, wherein preferred alkyl ethoxylates are selected from the group of ethoxylated primary C 6-18 alcohols, preferably the ethoxylated primary C 8-18 alcohols with a degree of alkoxylation ≥ 2, particularly preferably the C 12-14 alcohols with 4 EO or 7 EO, the C9-11 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.

[0032] Preferred first detergent compositions contain, based on their total weight, 12 to 40 wt.%, preferably 15 to 30 wt.%, and particularly 18 to 25 wt.% non-ionic surfactant from the group of ethoxylated primary C 8-18 alcohols, preferably ethoxylated primary C 8-18 alcohols with a degree of alkoxylation ≥ 2, particularly preferably C 12-14 alcohols with 4 EO or 7 EO, C 9-11 alcohols with 7 EO, C 13-15 alcohols with 5 EO, 7 EO or 8 EO, C 13-15 oxo alcohols with 7 EO, C 12-18 alcohols with 5 EO or 7 EO, in particular C 12-18 fatty alcohols with 7 EO or the C 13-15 -Oxo alcohols with 7 EO.

[0033] As a further preferred optional component, the first detergent composition comprises at least one enzyme preparation, preferably at least three enzyme preparations of enzymes from the group consisting of lipase, amylase, protease, cellulase, mannanase, and hexosaminidase. Due to their improved cleaning effect, first detergent compositions containing 2 to 8 wt.%, preferably 3 to 6 wt.%, of enzyme preparation based on their total weight are preferred.

[0034] According to the invention, it is preferred if the first detergent composition contains at least one lipase preparation. Preferred lipases according to the invention are selected from at least one enzyme of the group consisting of triacylglycerol lipase (EC 3.1.1.3), lipoprotein lipase (EC 3.1.1.34), and monoglyceride lipase (EC 3.1.1.23).

[0035] Preferred lipase preparations according to the invention are the commercial products marketed by Amano Pharmaceuticals under the names Lipase M-AP10®, Lipase LE®, and Lipase F® (also Lipase JV®). Lipase F® is, for example, naturally present in Rhizopus oryzae. Lipase M-AP10® is, for example, naturally present in Mucor javanicus.

[0036] The first detergent composition preferably contains at least one amylase, in particular an α-amylase. α-Amylases (EC 3.2.1.1) act as enzymes to hydrolyze internal α-1,4-glycosidic bonds of starch and starch-like polymers. Examples include α-amylases from Bacillus licheniformis, B. amyloliquefaciens, and B. stearothermophilus, as well as their improved formulations for use in detergents or cleaning agents. The enzyme from B. licheniformis is available from Novozymes under the trade name Termamyl® and from Genencor under the trade name Purastar® ST. Further developmental products of these α-amylases are available from Novozymes under the trade names Duramyl® and Termamyl® ultra, from Genencor under the name Purastar® OxAm, and from Daiwa Seiko Inc., Tokyo, Japan, as Keistase®. The α-amylase of B.Amyloliquefaciens is marketed by Novozymes under the name BAN®<, and derivatives of the α-amylase from B. stearothermophilus are marketed under the names BSG®< and Novamyl®<, also by Novozymes. Examples of α-amylases from other organisms include the further developments of α-amylase from Aspergillus niger and A. oryzae, available from Novozymes under the trade names Fungamyl®<.

[0037] According to the invention, it is preferred if the first detergent composition contains at least one protease as an enzyme. A protease is an enzyme that cleaves peptide bonds by hydrolysis. According to the invention, each of the enzymes from class EC 3.4 falls under this category (comprising each of the thirteen subclasses included therein). "Protease activity" is present according to the invention if the enzyme possesses proteolytic activity (EC 3.4). Various types of protease activity are known: The three main types are: trypsin-like, wherein cleavage of the amide substrate occurs along the amino acids Arg or Lys at P1; chymotrypsin-like, wherein cleavage occurs along one of the hydrophobic amino acids at P1; and elastase-like, wherein cleavage of the amide substrate occurs along the Ala at P1.

[0038] As a further preferred optional component, the first detergent composition contains a cellulase preparation. Synonymous terms can be used for cellulases, in particular endoglucanase, endo-1,4-beta-glucanase, carboxymethylcellulase, endo-1,4-beta-D-glucanase, beta-1,4-glucanase, beta-1,4-endoglucan hydrolase, celludextrinase, or avicelase. The decisive factor in determining whether an enzyme is a cellulase within the meaning of the invention is its ability to hydrolyze 1,4-β-D-glucosidic bonds in cellulose.

[0039] Suitable cellulases (endoglucanases, EG) according to the invention include, for example, fungal endoglucanase (EG)-rich compositions offered by Novozymes under the trade name Celluzyme®. The products Endolase® and Carezyme®, also available from Novozymes, are based on the 50 kDa EG and 43 kDa EG from Humicola insolens DSM 1800, respectively. Other usable trade products from this company are Cellusoft®, Renozyme®, and Celluclean®. Also suitable are, for example, cellulases available from AB Enzymes, Finland, under the trade names Ecostone® and Biotouch®, which are at least partially based on the 20 kDa EG from Melanocarpus. Other cellulases from AB Enzymes are Econase® and Ecopulp®. Other suitable cellulases are from Bacillus sp. CBS 670.93 and CBS 669.93, with the one from Bacillus sp. CBS 670 being the most suitable.93 is available from Danisco / Genencor under the trade name Puradax®. Other usable commercial products from Danisco / Genencor are "Genencor detergent cellulase L" and IndiAge® Neutra.

[0040] The first detergent composition contains a mannanase preparation as a preferred ingredient.

[0041] A mannanase catalyzes the hydrolysis of 1,4-beta-D-mannosidic bonds in mannans, galactomannans, glucomannan, and galactoglucomannan. These mannanases are classified as EC 3.2.1.78 according to enzyme nomenclature.

[0042] The term "hexosaminidase" refers to a polypeptide with hexosaminidase activity (hexosaminidases) and includes enzymes that catalyze the hydrolysis of N-acetyl-D-hexosamine or N-acetyl-glucosamine polymers.

[0043] Polypeptides with hexosaminidase activity include dispersins such as dispersin B (DspB), which are β-N-acetylglucosamininidases belonging to the glycoside hydrolase 20 family. Dispersins are produced by the periodontal pathogen Aggregatibacter actinomycetemcomitans, a Gram-negative oral bacterium. Dispersin B is a β-hexosaminidase that specifically hydrolyzes β-1,6-glycosidic bonds of acetylglucosamine polymers. The use of hexosaminidases from the β-hexosaminidase group is preferred.

[0044] An enzyme preparation comprises, in addition to the actual enzyme protein, other components such as enzyme stabilizers, carrier materials, or fillers. The enzyme protein typically constitutes only a fraction of the total weight of the enzyme preparation. Preferably, enzyme preparations contain between 0.1 and 40 wt.%, preferably between 0.2 and 30 wt.%, more preferably between 0.4 and 20 wt.%, and most preferably between 0.8 and 10 wt.% of the enzyme protein. In such compositions, an enzyme stabilizer may be present in an amount of 0.05 to 35 wt.%, preferably between 0.05 and 10 wt.%, based on the total weight in the enzyme composition.

[0045] Protein concentration can be determined using established methods, such as the BCA method (bicinchoninic acid; 2,2'-bicinolyl-4,4'-dicarboxylic acid) or the biuret method. The determination of the active protein concentration is carried out by titrating the active sites using a suitable irreversible inhibitor (for proteases, for example, phenylmethylsulfonylfluoride (PMSF)) and determining the residual activity.

[0046] In one process variant, the first detergent composition is preferably introduced into the laundry treatment chamber of the washing machine at a time 0 tw in step d).

[0047] It is more preferable that the first detergent composition in step d) is introduced into the laundry treatment chamber of the washing machine at a time >0 to 10% tw , preferably >0 to 5% tw.

[0048] In contrast, the peroxycarboxylic acid and the surfactant of the second detergent composition are introduced into the aqueous liquor in step e) at a time 30 to 99% tw, preferably at a time 50 to 99% tw, particularly preferably at a time 70 to 99% tw and especially at a time 80 to 96 tw.

[0049] The term "second detergent composition" encompasses all active ingredients that are introduced into the aqueous solution at a time between 11 and 99% tw, preferably at a time between 30 and 99% tw, particularly preferably at a time between 50 and 99% tw, most preferably at a time between 70 and 99% tw, and particularly preferably at a time between 80 and 96 tw. The components of the second detergent composition can be introduced into the aqueous solution simultaneously or at different times. It is particularly preferred that the peroxycarboxylic acid and the surfactant, as essential components of the second detergent composition, are introduced into the aqueous solution within a period of five minutes, particularly preferably within two minutes, and particularly within one minute.

[0050] In step e) of the process, a peroxycarboxylic acid is introduced into the aqueous bath. Preferred peroxycarboxylic acids are in particular i) Mono- and diperoxocarboxylic acids such as peraformic acid, peracetic acid, decanediperoxoic acid, dodecanediperoxoic acid, ii) Mono- and diperphthalic acids, iii) Mono- and diperterephthalic acids, iv) Imidoperoxocarboxylic acids such as 6-phthalimidoperoxocaproic acid (PAP).

[0051] Preferably, the peroxocarboxylic acid is solid at room temperature and atmospheric pressure; in this case, the peroxocarboxylic acid is used as a suspension or dispersion, preferably containing water. The use of 6-phthalimidoperoxocaproic acid (PAP) is particularly preferred.

[0052] In step e), the peroxycarboxylic acid is preferably introduced into the washing liquor in the form of a preparation containing 5 to 45 wt.%, preferably 10 to 30 wt.% peroxycarboxylic acid. The wt. fraction of the peroxycarboxylic acid in the total weight of the second detergent composition is preferably 4 to 25 wt.%, particularly preferably 6 to 20 wt.%, and especially 8 to 15 wt.%.

[0053] The surfactant introduced into the aqueous solution in step e) can be identical to or different from the surfactant contained in the first detergent composition. Using an identical surfactant reduces formulation complexity, while using a surfactant with a different structure enriches the aqueous solution with an active ingredient whose cleaning profile differs from those already present in the solution. For this latter reason, it is preferred that the surfactant introduced in step e) differs from the surfactant introduced in step d).

[0054] The weight fraction of the surfactant, preferably the non-ionic surfactant, in the total weight of the second detergent composition is preferably 10 to 70 wt.%, particularly preferably 20 to 65 wt.% and particularly 30 to 60 wt.%.

[0055] Preferably, the surfactant in step e) is selected from the group of non-ionic surfactants, in particular non-ionic surfactants from the group of alkoxylated primary C 8-18 alcohols, preferably from the group of ethoxylated primary C 8-18 alcohols with a degree of ethoxylation ≥ 4 and the ethoxylated and propoxylated C 8-18 alcohols with a degree of ethoxylation ≥ 4 and a degree of propoxylation ≥ 2, particularly preferably from the group of ethoxylated primary C 12-14 alcohols with a degree of ethoxylation ≥ 6 and the ethoxylated and propoxylated C 16-18 alcohols with a degree of ethoxylation ≥ 4 and a degree of propoxylation ≥ 2.

[0056] Washing processes in which the surfactant in step e) is selected from the group of non-ionic surfactants of the general formula CH 3 (CH 2 ) n OEO x PO y with n = 5 to 21, x = 2 to 10 and y = 2 to 10 are particularly preferred, with non-ionic surfactants of the general formula CH 3 (CH 2 ) n OEO x PO y with n = 15 to 17, x = 4 to 8 and y = 2 to 6 being especially preferred.

[0057] In step e), the use of non-ionic surfactants from the group of ethoxylated primary C 8-18 alcohols with a degree of ethoxylation ≥ 4, in particular from the group of ethoxylated primary C 10-14 alcohols with a degree of ethoxylation of 6 to 10, is particularly preferred.

[0058] Alternatively, but preferably in combination with the aforementioned nonionic surfactants, a surfactant selected from the group of amine oxides, preferably from the group of alkylamine oxides, in particular alkyldimethylamine oxides, alkylamidoamine oxides and alkoxyalkylamine oxides, particularly preferably from the group of amine oxides of formula (1a) or (1b) R 6< R 7< R 8< N +< -O -< (1a) R 6< -[CO-NH-(CH 2 ) w ] z -N +< (R 7< )(R 8< )-O -< (1b) in the R 6< is a saturated or unsaturated C 6-22 alkyl group, preferably a C 8-18 alkyl group, in particular a saturated C 10-16 alkyl group, for example a saturated C 12-14 alkyl group, which in the alkylamidoamine oxides is bonded to the nitrogen atom N via a carbonylamidoalkylene group -CO-NH-(CH 2 ) z- and in the alkoxyalkylamine oxides via an oxaalkylene group -O-(CH 2 ) z-, wherein z is, for a number of 1 to 10, preferably 2 to 5, in particular 3, R 7< , R 8< independently of each other a C 1-4 alkyl group, optionally hydroxy-substituted such as a hydroxyethyl group, in particular a methyl group.

[0059] It is particularly preferred to use in step e) surfactants selected from the group of amine oxides, in particular from the group of cocoalkyldimethylamine oxide, myristyldimethylamine oxide, cetyldimethylamine oxide, lauryldimethylamine oxide and stearyldimethylamine oxide.

[0060] The use of the aforementioned surfactants from the group of non-ionic and amphoteric surfactants has proven advantageous for the cleaning performance achieved in the washing process.

[0061] For the cleaning performance achieved, it has also proven advantageous if the peroxycarboxylic acid and the surfactant are introduced into the aqueous liquor in step e) in a weight ratio of 2:1 to 1:12, preferably from 3:2 to 1:10 and particularly from 1:1 to 1:8.

[0062] In a preferred method variant, in step e) a polyalkoxylated polyalkylenemine, which is obtainable by reacting polyalkylenemines with alkylene oxides, is introduced into the aqueous liquor.

[0063] The polyalkoxylated polyalkylenemine is a polymer with a polyalkylenemine backbone bearing polyalkoxy groups at the nitrogen atoms. It preferably has a weight-average molecular weight (Mw) in the range of 5000 g / mol to 60000 g / mol, particularly from 10000 g / mol to 22500 g / mol. The polyalkylenemine has primary amino groups at its ends and preferably both secondary and tertiary amino groups in its interior; optionally, it may also have only secondary amino groups in its interior, resulting in a linear rather than a branched-chain polyalkylenemine. The ratio of primary to secondary amino groups in the polyalkylenemine is preferably in the range of 1:0.5 to 1:1.5, particularly in the range of 1:0.7 to 1:1. The ratio of primary to tertiary amino groups in the polyalkylenemine is preferably in the range of 1:0.2 to 1:1, particularly in the range of 1:0.5 to 1:0.8.Preferably, the polyalkylenemine has a weight-average molecular weight in the range of 500 g / mol to 50,000 g / mol, particularly from 550 g / mol to 2,000 g / mol. The nitrogen atoms in the polyalkylenemine are preferably separated from one another by alkylene groups with 2 to 12 carbon atoms, particularly 2 to 6 carbon atoms, whereby not all alkylene groups need to have the same number of carbon atoms. Ethylene groups, 1,2-propylene groups, 1,3-propylene groups, and mixtures thereof are particularly preferred. The primary amino groups in the polyalkylenemine can bear 1 or 2 polyalkoxy groups, and the secondary amino groups can bear 1 polyalkoxy group, whereby not every amino group needs to be alkoxy substituted. The average number of alkoxy groups per primary and secondary amino function in the polyalkoxylated polyalkyenimine is preferably 5 to 100, particularly 10 to 50.The alkoxy groups in the polyalkoxylated polyalkylenemine are preferably ethoxy, propoxy, or butoxy groups, or mixtures thereof. Polyethoxylated polyethyleneimines are particularly preferred. The polyalkoxylated polyalkylenemines are accessible by reacting the polyalkylenemines with the alkoxy groups of corresponding epoxides. Optionally, the terminal OH function of at least some of the polyalkoxy substituents can be replaced by an alkyl ether function with 1 to 10, in particular 1 to 3, carbon atoms. The polyalkoxylated polyalkylenemine can be partially quaternized.

[0064] The composition of some preferred first and second detergent compositions for use in the process according to the invention can be found in the following tables (values ​​in wt.% based on the total weight of the gel body or the coating substance unless otherwise specified). formula 1 Formula 2 Formula 3 Formula 4 First detergent composition Anionic surfactant 12 to 40 15 to 30 15 to 30 18 to 25 Niotenside 12 to 40 15 to 30 15 to 30 18 to 25 Enzyme preparation 2 to 8 2 to 8 3 to 6 3 to 6 Misc ad 100 ad 100 ad 100 ad 100 Second detergent composition Peroxycarboxylic acid 4 to 25 6 to 20 6 to 20 8 to 15 surfactant 10 to 70 20 to 65 30 to 60 30 to 60 Formula 5 Formula 6 Formula 7 Formula 8 First detergent composition Anionic surfactant 12 to 40 15 to 30 15 to 30 18 to 25 Niotenside 12 to 40 15 to 30 15 to 30 18 to 25 Enzyme preparation 2 to 8 2 to 8 3 to 6 3 to 6 Misc ad 100 ad 100 ad 100 ad 100 Second detergent composition 6-phthalimidoperoxocaproic acid (PAP) 4 to 25 6 to 20 6 to 20 8 to 15 surfactant 10 to 70 20 to 65 30 to 60 30 to 60 Formula 11 Formula 12 Formula 13 Formula 14 First detergent composition Anionic surfactant 12 to 40 15 to 30 15 to 30 18 to 25 Niotenside 12 to 40 15 to 30 15 to 30 18 to 25 Enzyme preparation 2 to 8 2 to 8 3 to 6 3 to 6 Misc ad 100 ad 100 ad 100 ad 100 Second detergent composition Peroxycarboxylic acid 4 to 25 6 to 20 6 to 20 8 to 15 Niotenside * 10 to 70 20 to 65 30 to 60 30 to 60 Formula 15 Formula 16 Formula 17 Formula 18 First detergent composition Anionic surfactant 12 to 40 15 to 30 15 to 30 18 to 25 Niotenside 12 to 40 15 to 30 15 to 30 18 to 25 Enzyme preparation 2 to 8 2 to 8 3 to 6 3 to 6 Misc ad 100 ad 100 ad 100 ad 100 Second detergent composition 6-phthalimidoperoxocaproic acid (PAP) 4 to 25 6 to 20 6 to 20 8 to 15 Niotenside * 10 to 70 20 to 65 30 to 60 30 to 60 Formula 21 Formula 22 Formula 23 Formula 24 First detergent composition Anionic surfactant 12 to 40 15 to 30 15 to 30 18 to 25 Niotenside 1 12 to 40 15 to 30 15 to 30 18 to 25 Enzyme preparation 2 to 8 2 to 8 3 to 6 3 to 6 Misc ad 100 ad 100 ad 100 ad 100 Second detergent composition Peroxycarboxylic acid 4 to 25 6 to 20 6 to 20 8 to 15 Niotenside 2 ** 10 to 70 20 to 65 30 to 60 30 to 60 Formula 25 Formula 26 Formula 27 Formula 28 First detergent composition Anionic surfactant 12 to 40 15 to 30 15 to 30 18 to 25 Niotenside 1 12 to 40 15 to 30 15 to 30 18 to 25 Enzyme preparation 2 to 8 2 to 8 3 to 6 3 to 6 Misc ad 100 ad 100 ad 100 ad 100 Second detergent composition 6-phthalimidoperoxocaproic acid (PAP) 4 to 25 6 to 20 6 to 20 8 to 15 Niotenside 2 ** 10 to 70 20 to 65 30 to 60 30 to 60 * Ethoxylated and propoxylated C 8-18 alcohol with a degree of ethoxylation ≥ 4 and a degree of propoxylation ≥ 2 ** Niotenside 2 differs from Niotenside 1 and is selected from the group of ethoxylated and propoxylated C 8-18 alcohols with a degree of ethoxylation ≥ 4 and a degree of propoxylation ≥ 2

[0065] The peroxycarboxylic acid and the surfactant can be introduced into the aqueous solution simultaneously or at different times in step e), with simultaneous introduction of the peroxycarboxylic acid and surfactant into the aqueous solution proving particularly advantageous for the cleaning effect. For this reason, it is also preferred, for example, to introduce the peroxycarboxylic acid and the surfactant into the aqueous solution in step e) as a mixture.

[0066] As a preferred optional active ingredient, a phosphonate is further introduced into the aqueous solution in step e), wherein the weight ratio of peroxycarboxylic acid to phosphonate is preferably 1:2 to 1:20, and in particular 1:4 to 1:12. Again, it is preferred to introduce the peroxycarboxylic acid and the phosphonate into the aqueous solution simultaneously in step e).

[0067] In step e) of the washing process, preferably no water softeners from the group of polymeric builders, complexing agents and sequestrants are introduced into the aqueous liquor.

[0068] The temperature T2 of the aqueous solution in step e) is preferably 26 to 45°C. After the addition of the peroxycarboxylic acid, the pH of the aqueous solution preferably reaches 7 to 9, particularly 7.5 to 8.5.

[0069] After completion of the main wash cycle at time 100% tw, the aqueous liquor is preferably pumped out of the laundry treatment room.

[0070] This registration will provide, among other things, the following items: 1. Washing process for textiles in a domestic washing machine, comprising the steps: a) providing a washing machine with a washing program comprising a main wash cycle of duration tw; b) introducing textiles into the washing machine's treatment chamber; c) introducing an aqueous liquor into the washing machine's treatment chamber; d) introducing a first detergent composition, comprising at least one surfactant, into the washing machine's treatment chamber during the main wash cycle at a time between 0 and 10% tw; e) introducing a second detergent composition, comprising peroxycarboxylic acid and surfactant, into the aqueous liquor of the main wash cycle at a time between 11 and 99% tw. 2. Washing process according to point 1, wherein the domestic washing machine comprises a tub, a drum installed within the tub as the treatment chamber, and a draining device configured for draining aqueous liquor from the tub.3. Washing method according to any of the preceding points, wherein the washing program comprises a main wash cycle, at least one rinse cycle, and at least one spin cycle. 4. Washing method according to any of the preceding points, wherein the washing program comprises at least one pre-wash cycle, a main wash cycle, at least one rinse cycle, and at least one spin cycle. 5. Washing method according to any of the preceding points, wherein the duration tw of the main wash cycle is 15 to 400 minutes, preferably 30 to 240 minutes, and particularly 60 to 180 minutes. 6. Washing method according to any of the preceding points, wherein the aqueous liquor in step c) has a volume of 3 to 40 l, preferably 6 to 30 l, and particularly 8 to 20 l. 7. Washing method according to any of the preceding points, wherein the weight ratio of aqueous liquor to textiles in step c) is greater than 1:1.preferably above 2:1 and particularly above 5:2. 8. Washing process according to any of the preceding points, wherein the aqueous liquor in step c) has a temperature T1 of 18 to 25°C. 9. Washing process according to any of the preceding points, wherein the aqueous liquor is introduced into the laundry treatment chamber of the washing machine before the first detergent composition. 10. Washing process according to any of the preceding points, wherein the aqueous liquor is introduced into the laundry treatment chamber of the washing machine simultaneously with the first detergent composition. 11. Washing process according to any of the preceding points, wherein the aqueous liquor is introduced into the laundry treatment chamber of the washing machine after the first detergent composition. 12. Washing process according to any of the preceding points, wherein the first detergent composition comprises at least one anionic surfactant. 13. Washing process according to any of the preceding points,wherein the first detergent composition comprises at least one anionic surfactant selected from the group consisting of C 9-13 alkylbenzenesulfonates, olefin sulfonates, C 12-18 alkanesulfonates, ester sulfonates, alk(en)yl sulfates, and fatty alcohol ether sulfates. 14. Washing process according to any of the preceding points, wherein the first detergent composition comprises at least one nonionic surfactant. 15. Washing process according to any of the preceding points, wherein the first detergent composition comprises at least one nonionic surfactant selected from the group of ethoxylated primary C 6-18 alcohols, preferably ethoxylated primary C 8-18 alcohols with a degree of alkoxylation ≥ 2, particularly preferably C 12-14 alcohols with 4 EO or 7 EO, C 9-11 alcohols with 7 EO, C 13-15 alcohols with 5 EO, 7 EO or 8 EO, C 13-15 oxo alcohols with 7 EO, C 12-18 alcohols with 5 EO or 7 EO,in particular the C 12-18 fatty alcohols with 7 EO or the C 13-15 oxo alcohols with 7 EO. 16. Washing process according to any of the preceding points, wherein the first detergent composition comprises at least one enzyme preparation, preferably at least three enzyme preparations of enzymes from the group consisting of lipase, amylase, protease, cellulase, mannanase, and hexosaminidase. 17. Washing process according to any of the preceding points, wherein the first detergent composition is introduced into the laundry treatment chamber of the washing machine at time 0 tw in step d). 18. Washing process according to any of the preceding points, wherein the first detergent composition is introduced into the laundry treatment chamber of the washing machine at time >0 to 10% tw, preferably >0 to 5% tw. 19. Washing process according to one of the previous steps, wherein the peroxycarboxylic acid in step e) is selected from the group i) of mono- and diperoxycarboxylic acids such as peraformic acid,Peracetic acid, decanediperoxoic acid, dodecanediperoxoic acid, ii) mono- and diperphthalic acids, iii) mono- and diperterephthalic acids, iv) imidoperoxocarboxylic acids such as 6-phthalimidoperoxocaproic acid (PAP). 20. Washing process according to any one of the preceding points, wherein the peroxycarboxylic acid in step e) is selected from the group consisting of 6-phthalimidoperoxocaproic acid (PAP). 21. Washing process according to any one of the preceding points, wherein the peroxycarboxylic acid in step e) is introduced into the washing liquor in the form of a preparation containing a weight fraction of 5 to 45 wt.%, preferably 10 to 30 wt.% peroxycarboxylic acid. 22. Washing process according to any one of the preceding points, wherein the weight fraction of the peroxycarboxylic acid in the total weight of the second washing composition is 4 to 25 wt.%, particularly preferably 6 to 20 wt.% and particularly 8 to 15 wt.%. 23. Washing process according to any one of the preceding points,wherein the surfactant introduced in step e) differs from the surfactant introduced in step d). 24. Washing process according to any of the preceding points, wherein the weight fraction of the surfactant in the total weight of the second detergent composition is 10 to 70 wt.%, preferably 20 to 65 wt.%, and particularly 30 to 60 wt.%. 25. Washing process according to any of the preceding points, wherein the surfactant in step e) is selected from the group of non-ionic surfactants, in particular non-ionic surfactants from the group of alkoxylated primary C8-18 alcohols, preferably from the group of ethoxylated primary C8-18 alcohols with a degree of ethoxylation ≥ 4 and ethoxylated and propoxylated C8-18 alcohols with a degree of ethoxylation ≥ 4 and a degree of propoxylation ≥ 2.particularly preferably from the group of ethoxylated primary C 12-14 alcohols with a degree of ethoxylation ≥ 6 and the ethoxylated and propoxylated C 16-18 alcohols with a degree of ethoxylation ≥ 4 and a degree of propoxylation ≥ 2. 26. Washing process according to any one of the preceding steps, wherein the surfactant in step e) is selected from the group of nonionic surfactants of the general formula CH 3 (CH 2 ) n OEO x PO y with n = 5 to 21, x = 2 to 10 and y = 2 to 10. 27. Washing process according to any one of the preceding steps, wherein the surfactant in step e) is selected from the group of nonionic surfactants of the general formula CH 3 (CH 2 ) n OEO x PO y with n = 15 to 17, x = 4 to 8 and y = 2 to 6. 28. Washing process according to one of the preceding points, wherein the surfactant in step e) is selected from the group of amine oxides, preferably from the group of alkylamine oxides, in particular alkyldimethylamine oxides, alkylamidoamine oxides and alkoxyalkylamine oxides,particularly preferably from the group of amine oxides of formula (1a) or (1b), R 6< R 7< R 8< N +< -O -< (1a) R 6< -[CO-NH-(CH 2 ) w ] z -N +< (R 7< )(R 8< )-O -< (1b) in which R 6< is a saturated or unsaturated C 6-22 alkyl group, preferably a C 8-18 alkyl group, in particular a saturated C 10 - 16 alkyl group, for example a saturated C 12-14 alkyl group, which in the alkylamidoamine oxides is bonded to the nitrogen atom N via a carbonylamidoalkylene group -CO-NH-(CH 2 ) z - and in the alkoxyalkylamine oxides via an oxaalkylene group -O-(CH 2 ) z -, wherein z is in each case for a number from 1 to 10, preferably 2 to 5, in particular 3, R 7< , R 8< independently of each other is a C 1-4 alkyl group, optionally hydroxy-substituted such as a hydroxyethyl group, in particular a methyl group. 29. Washing process according to one of the preceding steps, wherein the surfactant in step e) is selected from the group consisting of amine oxides,preferably from the group consisting of cocoalkyldimethylamine oxide, myristyldimethylamine oxide, cetyldimethylamine oxide, lauryldimethylamine oxide, and stearyldimethylamine oxide. 30. Washing process according to any one of the preceding points, wherein the peroxycarboxylic acid and the surfactant are introduced into the aqueous liquor in step e) in a weight ratio of 2:1 to 1:12, preferably 3:2 to 1:10, and particularly 1:1 to 1:8. 31. Washing process according to any one of the preceding points, wherein the peroxycarboxylic acid and the surfactant are introduced into the aqueous liquor in step e) within a period of five minutes, particularly preferably two minutes, and particularly one minute. 32. Washing process according to any one of the preceding points, wherein in step e) a polyalkoxylated polyalkylenemine, obtainable by reacting polyalkylenemines with alkylene oxides,Preferably, a polyethoxylated polyethyleneimine is introduced into the aqueous bath. 33. Washing process according to any of the preceding steps, wherein the peroxycarboxylic acid and the surfactant are introduced into the aqueous bath simultaneously in step e). 34. Washing process according to any of the preceding steps, wherein the peroxycarboxylic acid and the surfactant are introduced into the aqueous bath in step e) as a mixture. 35. Washing process according to any of the preceding steps, wherein no water softeners from the group of polymeric builders, complexing agents, and sequestrants are introduced into the aqueous bath in step e). 36. Washing process according to any of the preceding steps, wherein the aqueous bath has a temperature T2 of 26 to 45°C in step e). 37. Washing process according to one of the preceding steps, wherein the peroxycarboxylic acid and the surfactant in step e) at a time 30 to 99% tw , preferably at a time 50 to 99% tw ,38. Washing process according to any one of the preceding points, wherein in step e) a phosphonate is further introduced into the aqueous liquor and the weight ratio of peroxycarboxylic acid to phosphonate is preferably 1:2 to 1:20, more preferably 1:4 to 1:12. 39. Washing process according to any one of the preceding points, wherein the peroxycarboxylic acid and the phosphonate are introduced into the aqueous liquor simultaneously in step e). 40. Washing process according to any one of the preceding points, wherein the aqueous liquor reaches a pH of 7 to 9, preferably 7.5 to 8.5, after the introduction of the peroxycarboxylic acid. 41. Washing process according to any one of the preceding points, wherein the aqueous liquor is pumped out of the washing treatment chamber at 100% tw after completion of the main washing cycle. , Examples

[0071] A washing machine (Bosch WAV28E41) was loaded with the test laundry (75% of the nominal load capacity = 6.75 kg of a mixed load of cotton and synthetic textiles in a ratio of 2:1), dirt ballast and an evaluable stain monitor (GCS stain set).

[0072] Then, 70 ml of a detergent gel was dosed directly onto the laundry and the washing program (cotton, cold, Speed ​​Perfect Modifier, 83 min cycle, 1400 rpm final spin) was started. The detergent gel had the following composition: Active ingredient % by weight Water 37 % C 10-13 -Alkylbenzenesulfonate 22 % C 12-14 fatty alcohol ether sulfate 2EO 5,2 % C 12-18 fatty alcohol ethoxylate 7EO 10 % 1,2-Propanediol 11 % Monoethanolamine 2,3 % C12-18 fatty acid 1,8 % Trisodium citrate 4,2 % HEDP-Na4 1,4 % Glycerin 0,6 % Sorbitol 0,3 % Fragrance 0,3 % rest ad 100

[0073] In washing test V2, at the beginning of the main washing cycle, an additional 6g of a bleach dispersion (Eureco LX 17; 17% 6-phthalimidoperoxocaproic acid suspension) and 5g of Marlox RT 64 (C 16-18 alcohol with degree of ethoxylation 6 and degree of propoxylation 4) were dosed directly into the washing container.

[0074] In washing test E1, 6g of a bleach dispersion (Eureco LX 17; 17% 6-phthalimidoperoxocaproic acid suspension) and 5g of Marlox RT 64 (C 16-18 alcohol with degree of ethoxylation 6 and degree of propoxylation 4) were added directly to the washing container 10 minutes before the end of the main washing cycle.

[0075] Once the program has finished, the laundry is removed, the stain monitor is flattened, and the results are evaluated. The results of this evaluation can be found in the following table. stains V1 V2 E1 tea 55 65 66 Blackcurrant 54 56 64 blueberry 54 60 64 Blood (aged) 33 29 47 Whole egg / pigment 52 60 73 cocoa 46 55 57 chocolate ice cream 59 64 70 Salad dressing (blackened) 66 59 71 Olive oil (soot) 31 35 46 Sebum (soot) 34 36 45 Mayonnaise (activated charcoal) 28 36 45 Liquid make-up 54 55 59 lipstick, red 47 52 59 Beef tallow (colored) 56 49 59

Claims

1. Washing method for textiles in a household washing machine, comprising the steps a) providing a washing machine with a washing program comprising a main wash cycle of duration t w and activate this washing program; b) introduce textiles into the washing machine's treatment chamber; c) introduce an aqueous liquor into the washing machine's treatment chamber; d) introduce a first detergent composition, comprising at least one surfactant, into the washing machine's treatment chamber during the main wash cycle at a time between 0 and 10% of the time. w ; e) Introducing a peroxycarboxylic acid and a surfactant into the aqueous bath of the main wash step at a time between 11 and 99% t w .

2. Washing method according to claim 1, wherein the washing program comprises a main wash cycle, at least one rinse cycle and at least one spin cycle.

3. Washing method according to one of the preceding claims, wherein the duration tw The main wash cycle lasts 15 to 400 minutes, preferably 30 to 240 minutes and particularly 60 to 180 minutes.

4. Washing process according to any of the preceding claims, wherein the peroxycarboxylic acid in step e) is selected from the group i) of mono- and diperoxocarboxylic acids such as peraformic acid, peracetic acid, decanediperoxoic acid, dodecanediperoxoic acid, ii) of mono- and diperphthalic acids, iii) of mono- and diperterephthalic acids, iv) of imidoperoxocarboxylic acids such as 6-phthalimidoperoxocaproic acid (PAP).

5. Washing process according to any of the preceding claims, wherein the peroxycarboxylic acid in step e) is selected from the group 6-phthalimidoperoxocaproic acid (PAP).

6. Washing process according to one of the preceding claims, wherein the peroxycarboxylic acid is introduced into the washing liquor in step e) in the form of a preparation with a weight fraction of 5 to 45 wt.%, preferably of 10 to 30 wt.% peroxycarboxylic acid.

7. Washing method according to one of the preceding claims, wherein the surfactant introduced in step e) differs from the surfactant introduced in step d).

8. Washing method according to one of the preceding claims, wherein the surfactant in step e) is selected from the group of non-ionic surfactants, in particular the non-ionic surfactants from the group of alkoxylated primary C 8-18 -Alcohols, preferably from the group of ethoxylated primary C 8-18 -Alcohols with a degree of ethoxylation ≥ 4 and the ethoxylated and propoxylated C 8-18 -Alcohols with an ethoxylation degree ≥ 4 and a propoxylation degree ≥ 2, particularly preferably from the group of ethoxylated primary C 12-14 -Alcohols with a degree of ethoxylation ≥ 6 and the ethoxylated and propoxylated C 16-18 -Alcohols with an ethoxylation degree ≥ 4 and a propoxylation degree ≥ 2.

9. Washing process according to one of the preceding claims, wherein the peroxycarboxylic acid and the surfactant are introduced into the aqueous liquor in step e) in the form of a mixture.

10. Washing process according to one of the preceding claims, wherein the peroxycarboxylic acid and the surfactant are added in step e) at a time 30 to 99% t w , preferably at a time between 50 and 99% t w , particularly preferably at a time between 70 and 99% t w and especially at a time between 80 and 96 tons w be introduced into the aqueous fleet.

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