Fabric washing method

Abstract

The invention relates to a method for washing fabrics in a domestic washing machine, comprising the following steps: a) providing a washing machine with a washing program and starting the washing program, the washing program comprising a main washing cycle with a duration tw; b) introducing the fabric into a laundry treatment chamber of the washing machine; c) introducing an aqueous liquid into the laundry treatment chamber of the washing machine; d) during the main wash cycle, introducing a first detergent composition comprising at least one surfactant into the laundry treatment chamber of the washing machine at a point in time of 0 to 10% tw; e) introducing a second detergent composition comprising a peroxycarboxylic acid and a surfactant into the aqueous liquid of the main wash cycle at a point in time of 11% to 99% tw.

Description

[0001] The present invention relates to a fabric washing process. In particular, the present application relates to a multi-stage machine fabric washing process in which the detergent and cleaning active materials are metered in a staggered manner.

[0002] Although fewer than one third of the population today has access to a fabric washing machine, in some parts of the world machine fabric cleaning has been the standard method for removing soil and for making clothes look new since the 1970s.

[0003] Over the past decades, both machine technology and the detergents used in machine cleaning processes for fabrics have been continuously developed and improved in terms of their performance and ecological footprint. While development work was initially directed to improvements in individual components of the washing process (e.g., fabric washing machines and their mechanical parts and programs, or fabric detergents), more recently interest has focused on improving the interactions of these components.

[0004] In the international application WO 2021 / 048911 A1, a washing method using a fabric washing machine is described, during which the fabrics are sprayed with a rinsing solution during the rinse cycle.

[0005] In European patent EP 3 428 336 B1, a washing process with a minimum duration of 110 minutes is disclosed, during which a detergent containing a regenerating agent is added to the washing liquid.

[0006] European patent EP 2 711 413 B1 relates to a washing process characterized by staggered metering of different washing active substances.

[0007] European patent EP 2 566 943 B1 discloses the sensor-controlled staggered metering of detergent active substances (eg peroxycarboxylic acids) into the interior of a textile washing machine.

[0008] Against the background of previous developments, there is also the technical object of improving the washing performance of fabric detergents in fabric washing machines.

[0009] To achieve this object, a method for washing fabrics in a domestic washing machine having the following steps is suitable:

[0010] a) providing a washing machine having a washing program and starting the washing program, the washing program comprising a washing machine having a duration t w Main wash cycle;

[0011] b) introducing fabric into a laundry treatment chamber of a washing machine;

[0012] c) introducing an aqueous liquid into a laundry treatment chamber of a washing machine;

[0013] d) During the main wash cycle, between 0 and 10% t w introducing a first detergent composition comprising at least one surfactant into a laundry treatment chamber of a washing machine at a time point;

[0014] e) 11% to 99% t w A second detergent composition comprising a peroxycarboxylic acid and a surfactant is introduced into the aqueous liquor of the main wash cycle at a point in time.

[0015] Motor-driven devices for cleaning fabrics are called washing machines. Particularly preferred are rotary washing machines having an inner drum rotatable about a horizontal axis. The method according to the invention is particularly suitable for being performed in a domestic washing machine having an outer drum, an inner drum attached inside the outer drum as a laundry treatment chamber, and a pumping device configured to pump an aqueous liquid out of the outer drum.

[0016] In step a) of the method, a washing machine is provided which has a washing program comprising a washing cycle having a duration t w A conventional washing machine generally has a plurality of washing programs provided for cleaning different fabrics, and the washing program may also have a pre-rinsing cycle, a rinsing cycle, and / or a spin-drying cycle in addition to the main washing cycle. A preferred washing program comprises a main wash cycle, at least one rinse cycle and at least one spin dry cycle. An alternative washing program has at least one pre-wash cycle, a main wash cycle, at least one rinse cycle and at least one spin dry cycle.

[0017] In addition to the mechanical forces acting on the laundry, the detergent used and the liquid temperature reached in the wash liquid, the duration of the wash cycle, in particular the main wash cycle, has an influence on the cleaning performance achieved. The duration t of the main wash cycle used in the washing method w It is preferably from 15 to 400 minutes, preferably from 30 to 240 minutes, in particular from 60 to 180 minutes.

[0018] The fabric introduced into the laundry treatment chamber in step b) may be, for example, a cotton fabric or a synthetic fabric, but also a blended fabric.

[0019] The volume of aqueous liquid introduced into the laundry treatment chamber in step c) is preferably from 3 to 40 1, preferably from 6 to 30 1, in particular from 8 to 20 1.

[0020] The loading of the washing machine with fabrics in step b) and the volume of aqueous liquor introduced in step c) are preferably coordinated with each other in such a way that the weight ratio of aqueous liquor to fabrics in step c) is higher than 1:1, preferably higher than 2:1 and in particular higher than 5:2.

[0021] In step c), the temperature T1 of the aqueous liquid is preferably from 18 to 25°C.

[0022] In step d), at 0 to 10% t w In other words, the first detergent composition is introduced into the laundry treatment chamber at the beginning of the main wash cycle (0t w t) is already in the laundry treatment chamber, or during the duration t of the main wash cycle w 10% of the time period is introduced into the laundry treatment chamber.

[0023] In a first method variant, the aqueous liquid is introduced into the laundry treatment chamber of the washing machine before the first detergent composition. Such a method variant can be realized, for example, with the aid of a pre-rinse cycle, during which the fabrics are pre-rinsed and / or soaked with water, but not yet cleaned with the aid of the actual detergent composition.

[0024] A second method variant provides for introducing the aqueous liquid and the first detergent composition simultaneously into the laundry treatment chamber of the washing machine. If the aqueous liquid is introduced into the laundry treatment chamber without a pre-rinse cycle, for example through a dispensing drawer of the washing machine filled with the first detergent composition, the aqueous liquid and the first detergent composition are introduced into the laundry treatment chamber simultaneously.

[0025] Finally, the aqueous liquid can also be introduced into the laundry treatment chamber of the washing machine after the first detergent composition, for example by applying the first detergent composition directly to the fabrics before the start of the washing program in pre-dispensed form or with the aid of a dosing aid.

[0026] The first detergent composition introduced into the laundry treatment chamber preferably comprises at least one anionic surfactant. Preferred first detergent compositions comprise 12 to 40 wt. %, preferably 15 to 30 wt. %, in particular 18 to 25 wt. % of anionic surfactants, based on their total weight.

[0027] Anionic surfactants are preferably selected from C9-C 13 Alkylbenzene sulfonate, olefin sulfonate, C 12 -C 18 Alkane sulfonates, ester sulfonates, alkyl (alkenyl) sulfates, fatty alcohol ether sulfates, and mixtures thereof. 13 The combination of alkylbenzene sulfonate and fatty alcohol ether sulfate as anionic surfactant has particularly good dispersing properties. In this case, C9-C 13 Alkylbenzene sulfonates, olefin sulfonates (i.e., mixtures of olefin and hydroxyalkane sulfonates, and disulfonates, are obtained, for example, by reacting C 2+ with terminal or internal double bonds with gaseous sulfur trioxide. 12 -C18 Sulfonation of monoolefins and subsequent alkaline or acid hydrolysis of the sulfonated products can be used as sulfonate-type surfactants. 12 -C 18 Also suitable are alkanesulfonates and esters of α-sulfofatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut oil, palm kernel oil or tallow fatty acids.

[0028] It is very particularly preferred that the first detergent composition comprises at least one anionic surfactant of the formula (I):

[0029]

[0030] in

[0031] R' and R" are independently H or alkyl and together contain 9 to 19, preferably 9 to 15, in particular 9 to 13 C atoms, and Y + It represents a monovalent cation or the n-th part of an n-valent cation (particularly monoethanolamine).

[0032] The group of alkyl ether sulfates includes fatty alcohol ether sulfates, for example linear or branched C7-C 21 Alcohols, such as 2-methyl branched C 9-11 Alcohol or C with 1-4 EO 12-18 Sulfate monoesters of fatty alcohols. Preferably, alkyl ether sulfates of formula (II):

[0033] R 1 -O-(AO) n -SO3 - X + (II).

[0034] In the formula (II), R 1 is a linear or branched, substituted or unsubstituted alkyl functional group, preferably a linear unsubstituted alkyl functional group, and particularly preferably a fatty alcohol functional group. 1 The functional group is selected from the group consisting of decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl functional groups, and mixtures thereof, representatives with an even number of C atoms being preferred. Particularly preferred functional groups R of formula (II) are 1 Derived from fatty alcohols having 12 to 18 C atoms, for example from coconut alcohol, tallow alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol or stearyl alcohol, or from oxo alcohols having 10 to 20 C atoms.

[0035] AO in formula (II) represents an ethylene oxide (EO) or propylene oxide (PO) group, preferably an ethylene oxide group. The subscript n in formula (II) is an integer from 1 to 50, preferably from 1 to 20, in particular from 2 to 10. Very particularly preferably, n is 2, 3, 4, 5, 6, 7 or 8. X is a monovalent cation or the nth part of an n-valent cation, in which case an alkali metal ion (including Na + or K + ) is preferred, wherein Na + is the most preferred. Other cations X + Can be selected from NH4 + 、1 / 2Zn 2+ 、1 / 2Mg 2+ 、1 / 2Ca 2+ 、1 / 2Mn 2+ , and mixtures thereof, and primary and secondary amines, especially monoethanolamine.

[0036] Particularly preferred first detergent compositions comprise an alkyl ether sulfate selected from fatty alcohol ether sulfates of formula (III):

[0037]

[0038] wherein k=11 to 19 and n=2, 3, 4, 5, 6, 7 or 8. Very particularly preferred representatives are sodium fatty alcohol ether sulfates with 12 to 18 C atoms and 2 EO (k=11 to 13, n=2 in formula III). The indicated degrees of ethoxylation represent statistical averages, which for a specific product may correspond to integers or fractions. The indicated degrees of alkoxylation represent statistical averages, which for a specific product may correspond to integers or fractions. Preferred alkoxylates / ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).

[0039] In general, the preferred first detergent composition comprises, based on its total weight, 12 to 40 wt%, preferably 15 to 30 wt%, in particular 18 to 25 wt% of anionic surfactant selected from C 9-19 Alkylbenzene sulfonates and alkyl ether sulfates, preferably selected from C 9-19 Alkylbenzene sulfonate.

[0040] The use of fatty acids has been shown to be beneficial to stability and cleaning performance. Therefore, the preferred first detergent composition comprises 4 to 12 wt %, preferably 6 to 10 wt % of fatty acids based on its total weight. Particularly preferred fatty acids are selected from caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, and mixtures thereof. In the context of the present application, fatty acids do not belong to the group of anionic surfactants.

[0041] As a further preferred ingredient, the first detergent composition comprises at least one nonionic surfactant.

[0042] Particularly preferred is the use of nonionic surfactants selected from the group consisting of alkyl ethoxylates, preferably alkyl ethoxylates selected from the group consisting of: ethoxylated C 6-18 Primary alcohol; preferably ethoxylated C with a degree of alkoxylation ≥ 2 8-18 Primary alcohol; particularly preferably C with 4 EO or 7 EO 12-14 Alcohol, C with 7 EO 9-11 Alcohols, C with 5 EO, 7 EO or 8 EO 13-15 Alcohol, C with 7 EO 13-15 Oxo alcohols, C with 5 EO or 7 EO 12-18 Alcohols; especially C with 7 EO 12-18 Fatty alcohol or C with 7 EO 13-15 Oxo alcohols.

[0043] The preferred first detergent composition comprises, based on its total weight, 12 to 40% by weight, preferably 15 to 30% by weight, in particular 18 to 25% by weight of a nonionic surfactant selected from: ethoxylated C 8-18 Primary alcohol; preferably ethoxylated C with a degree of alkoxylation ≥ 2 8-18 Primary alcohol; particularly preferably C with 4 EO or 7 EO 12-14 Alcohol, C with 7 EO 9-11 Alcohols, C with 5 EO, 7 EO or 8 EO 13-15 Alcohol, C with 7 EO 13-15 Oxo alcohols, C with 5 EO or 7 EO 12-18 Alcohols; especially C with 7 EO 12-18 Fatty alcohol or C with 7 EO 13-15 Oxo alcohols.

[0044] As a further preferred optional component, the first detergent composition comprises at least one enzyme preparation, preferably at least three enzyme preparations, selected from the following enzymes: lipase, amylase, protease, cellulase, mannanase and hexosaminidase. Due to its improved cleaning effect, a first detergent composition comprising 2 to 8 wt. %, preferably 3 to 6 wt. % of an enzyme preparation based on its total weight is preferred.

[0045] According to the present invention, it is preferred that the first detergent composition comprises at least one lipase preparation.Preferred lipases according to the present invention are at least one enzyme selected from the group consisting of triacylglycerol lipases (EC3.1.1.3), lipoprotein lipases (EC3.1.1.34) and monoglyceride lipases (EC3.1.1.23).

[0046] A preferred lipase preparation according to the invention is produced by Amano Pharmaceuticals under the name Lipase Lipase and Lipase (And Lipase ) are commercial products sold by the market. For example, Lipase It occurs naturally in Rhizopus oryzae. It occurs naturally in Mucor javanicus.

[0047] The first detergent composition preferably comprises at least one amylase, in particular an alpha-amylase. Alpha-amylases (EC 3.2.1.1) act as enzymes to hydrolyze internal alpha-1,4-glycosidic bonds of starch and starch-like polymers. Examples that may be mentioned are alpha-amylases from Bacillus licheniformis, from Bacillus amyloliquefaciens and from Bacillus stearothermophilus, and developments thereof that are improved for use in detergents or cleaning agents. The enzyme from Bacillus licheniformis is available from Novozymes under the trade name and from Genencor under the trade name ST. These α-amylase development products are available from Novozymes under the trade name and ultra, from Genencor under the trade name OxAm, and from Daiwa Seiko Inc., Tokyo, Japan Alpha-amylase from Bacillus amyloliquefaciens is produced by Novozymes under the name A derivative variant of the alpha-amylase from Bacillus stearothermophilus is also marketed by Novozymes under the name and Examples of alpha-amylases from other organisms are those from Aspergillus niger and Aspergillus oryzae available from Novozymes under the trade name The development results of α-amylase obtained.

[0048] According to the present invention, it is preferred that the first detergent composition comprises at least one protease as enzyme. A protease is an enzyme that cleaves peptide bonds by hydrolysis. Each enzyme in the enzyme from category EC3.4 according to the present invention belongs thereunder (including each of the thirteen subclasses belonging thereunder). According to the present invention, if an enzyme has proteolytic activity (EC 3.4), "protease activity" is present. Different types of protease activity are known. Three main types are: trypsin-like, in which an amide substrate is cleaved after the amino acid Arg or Lys at P1; chymotrypsin-like, in which cleavage occurs after one of the hydrophobic amino acids at P1; and elastase-like, in which an amide substrate is cleaved after Ala at P1.

[0049] As a further preferred optional component, the first detergent composition comprises a cellulase preparation. Synonymous terms may be used for cellulases, in particular endoglucanases, endo-1,4-β-glucanases, carboxymethylcellulases, endo-1,4-β-D-glucanases, β-1,4-glucanases, β-1,4-endoglucanohydrolases, cellulose dextrinase or avicelase. Within the meaning of the present invention, whether an enzyme is a cellulase depends on its ability to hydrolyze 1,4-β-D-glycosidic bonds in cellulose.

[0050] Suitable cellulases (endoglucanases, EG) according to the present invention include, for example, fungal compositions enriched with endoglucanases (EG), which are marketed by Novozymes under the trade name Available. Also available from Novozymes and Based on 50 kD-EG and 43 kD-EG from Humicola insolens DSM 1800, respectively. Further commercial products from this company that can be used are and Cellulases may also be used, for example, which are available from AB Enzymes, Finland under the trade name and and is based at least in part on 20 kD-EG from Melanocarpus. Additional cellulases from AB Enzymes are and Additional suitable cellulases are derived from Bacillus sp. CBS 670.93 and CBS 669.93, wherein the cellulase derived from Bacillus sp. CBS 670.93 is available from Danisco / Genencor under the trade name Other commercial products from Danisco / Genencor that can be used are "Genencor detergent cellulase L" and Neutra.

[0051] As a preferred ingredient, the first detergent composition comprises a mannanase preparation.

[0052] Mannanase catalyzes the hydrolysis of 1,4-β-D-mannosidic bonds in mannans, galactomannans, glucomannans and galactoglucomannans. The mannanase is classified according to enzyme nomenclature as EC 3.2.1.78.

[0053] The term "hexosaminidase" refers to polypeptides having hexosaminidase activity (hexosaminidase class) and includes enzymes that catalyze the hydrolysis of N-acetyl-D-hexosamine polymers or N-acetylglucosamine polymers.

[0054] Polypeptides with hexosaminidase activity include dispersin (e.g., dispersin B, DspB), which is a β-N-acetylglucosaminidase belonging to glycoside hydrolase family 20. Dispersin is produced by the periodontal pathogen Aggregatibacter actinomycetemcomitans, a gram-negative oral bacterium. Dispersin B is a β-hexosaminidase that specifically hydrolyzes the β-1,6-glycosidic bonds of acetylglucosamine polymers. It is preferred to use a hexosaminidase from the group of β-hexosaminidase.

[0055] Except enzyme protein itself, enzyme preparation also comprises other components, such as enzyme stabilizer, carrier material or filler.In this case, enzyme protein only forms a part of the gross weight of enzyme preparation usually.Preferred enzyme preparation used comprises 0.1 to 40 % by weight, preferably 0.2 to 30 % by weight, more preferably 0.4 to 20 % by weight, most preferably 0.8 to 10 % by weight of enzyme protein.In such composition, based on the gross weight of enzyme composition, the content of enzyme stabilizer can be 0.05 to 35 % by weight, preferably 0.05 to 10 % by weight.

[0056] The protein concentration can be determined using known methods, such as the BCA method (bicinchoninic acid; 2,2'-bicinchoniyl-4,4'-dicarboxylic acid) or the biuret method. In this regard, the active protein concentration is determined by titrating the active center with a suitable irreversible inhibitor (for proteases, for example, phenylmethylsulfonyl fluoride (PMSF)) and determining the residual activity.

[0057] In a process variant, preferably in step d), at 0t w The first detergent composition is introduced into the laundry treatment chamber of the washing machine at a point in time.

[0058] More preferably, in step d), at >0 to 10% t w , preferably >0 to 5% t w The first detergent composition is introduced into the laundry treatment chamber of the washing machine at a point in time.

[0059] In contrast, in step e), at 30% to 99% t w time point, preferably between 50% and 99% t w time point, particularly preferably between 70% and 99% t w The time point, especially at 80% to 96% t w The peroxycarboxylic acid and surfactant of the second detergent composition are introduced into the aqueous liquid at a point in time.

[0060] The term "second detergent composition" comprises from 11% to 99% t w time point, preferably between 30% and 99% t w time point, particularly preferably between 50% and 99% t w time point, very particularly preferably between 70% and 99% t w time point, particularly preferably at 80% to 96% t w The components of the second detergent composition can be introduced into the aqueous liquid simultaneously, but can also be introduced into the aqueous liquid in a staggered manner. It is particularly preferred that the peroxycarboxylic acid and the surfactant, which are essential components of the second detergent composition, are introduced into the aqueous liquid within a period of 5 minutes, particularly preferably 2 minutes, and in particular 1 minute.

[0061] In step e) of the process, a peroxycarboxylic acid is introduced into the aqueous liquid. Preferred peroxycarboxylic acids are in particular:

[0062] i) monoperoxycarboxylic acids and diperoxycarboxylic acids, such as performic acid, peracetic acid, sebacic acid, dodecanedioic acid,

[0063] ii) monoperoxyphthalic acid and diperoxyphthalic acid,

[0064] iii) Mono- and Di-peroxyterephthalic acid ),

[0065] iv) Imidoperoxycarboxylic acids, such as 6-phthalimidoperoxycaproic acid (6- PAP).

[0066] The peroxycarboxylic acid is preferably solid at room temperature and atmospheric pressure; in this case, the peroxycarboxylic acid is preferably used as an aqueous suspension or dispersion. Particular preference is given to using 6-phthalimidocaproic acid (PAP).

[0067] In step e), the peroxycarboxylic acid is preferably introduced into the washing liquid in the form of a preparation having a weight proportion of 5 to 45% by weight, preferably 10 to 30% by weight, of peroxycarboxylic acid. The weight proportion of the peroxycarboxylic acid, relative to the total weight of the second detergent composition, is preferably 4 to 25% by weight, particularly preferably 6 to 20% by weight and in particular 8 to 15% by weight.

[0068] The surfactant introduced into the aqueous liquid in step e) may be the same or different from the surfactant present in the first detergent composition. The use of the same surfactant reduces formulation complexity, whereas the use of a surfactant with a different structure enriches the aqueous liquid with active substances having cleaning properties different from those present in the liquid so far. For the latter reason, it is preferred that the surfactant introduced in step e) is different from the surfactant introduced in step d).

[0069] The weight proportion of the surfactant, preferably the nonionic surfactant, relative to the total weight of the second detergent composition is preferably 10 to 70% by weight, particularly preferably 20 to 65% by weight, and in particular 30 to 60% by weight.

[0070] The surfactant in step e) is preferably selected from nonionic surfactants, in particular from alkoxylated C 8-18 Primary alcohols, preferably selected from ethoxylated C 8-18 Primary alcohols and ethoxylated and propoxylated C 8-18 Alcohols, particularly preferably selected from ethoxylated C 12-14 Primary alcohols and ethoxylated and propoxylated C 16-18 Alcohol-based nonionic surfactant.

[0071] Particularly preferred is the following washing method: wherein the surfactant in step e) is selected from the general formula CH3(CH2)n OEO x PO y (where n=5 to 21, x=2 to 10, and y=2 to 10), among which very particular preference is given to nonionic surfactants of the general formula CH3(CH2) n OEO x PO y (wherein n=15 to 17, x=4 to 8, and y=2 to 6) a nonionic surfactant.

[0072] In step e), it is also particularly preferred to use ethoxylated C 8-18 Primary alcohols, in particular selected from ethoxylated C 10-14 Nonionic surfactant based on primary alcohol.

[0073] Alternatively, but preferably in combination with the above nonionic surfactants, a surfactant is used in step e) which is selected from amine oxides, preferably from alkylamine oxides, in particular from alkyldimethylamine oxides, alkylamidoamine oxides and alkoxyalkylamine oxides, particularly preferably from amine oxides of formula (Ia) or (Ib):

[0074] R 6 R 7 R 8 N + -O - (Ia)

[0075] R 6 -[CO-NH-(CH2) w ] z -N + (R 7 )(R 8 )-O - (Ib)

[0076] Where R 6 Is saturated or unsaturated C 6-22 Alkyl, preferably C 8-18 Alkyl, especially saturated C 10-16 Alkyl, such as saturated C 12-14 Alkyl, which is via the carbonylamidoalkylene group -CO-NH-(CH2) z -bonded to the nitrogen atom N in the alkylamidoamine oxide and via the oxaalkylene group -O-(CH2) z - is bonded to the nitrogen atom N of an alkoxyalkylamine oxide, wherein z in each case represents a number from 1 to 10, preferably from 2 to 5, in particular 3,

[0077] R 7and R 8 are independently C 1-4 Alkyl groups such as hydroxyethyl and especially methyl.

[0078] Very particular preference is given to using in step e) a surfactant selected from the group consisting of amine oxides, in particular selected from the group consisting of cocoalkyldimethylamine oxide, myristyldimethylamine oxide, cetyldimethylamine oxide, lauryldimethylamine oxide and stearyldimethylamine oxide.

[0079] The use of the above-mentioned surfactants selected from nonionic surfactants and amphoteric surfactants has proven to be advantageous for the cleaning performance achieved in the washing method.

[0080] For the cleaning performance achieved, it has also proven advantageous if, in step e), peroxycarboxylic acid and surfactant are introduced into the aqueous liquid in a weight ratio of 2:1 to 1:12, preferably 3:2 to 1:10, in particular 1:1 to 1:8.

[0081] In a preferred process variant, in step e), the polyalkoxylated polyalkyleneimine obtained by reacting a polyalkyleneimine with an alkylene oxide is introduced into the aqueous liquid.

[0082] Polyalkyleneimines are polymers having a polyalkyleneimine backbone which carries polyalkoxy groups on the N atoms. The weight average molecular weight Mw is preferably in the range of 5000 g / mol to 60000 g / mol, in particular in the range of 10000 g / mol to 22500 g / mol. The polyalkyleneimines have primary amino functional groups at the ends and preferably both secondary and tertiary amino functional groups in the interior, and optionally they may also have only secondary amino functional groups in the interior so that the result is not a branched but a linear polyalkyleneimines. The ratio of primary to secondary amino groups in the polyalkyleneimines is preferably in the range of 1:0.5 to 1:1.5, in particular in the range of 1:0.7 to 1:1. The ratio of primary to tertiary amino groups in the polyalkyleneimines is preferably in the range of 1:0.2 to 1:1, in particular in the range of 1:0.5 to 1:0.8. The weight average molecular weight of the polyalkylene imine is preferably in the range of 500 g / mol to 50000 g / mol, in particular 550 g / mol to 2000 g / mol. The N atoms in the polyalkylene imine are preferably separated from each other by alkylene groups having 2-12 C atoms, in particular 2-6 C atoms, but not all alkylene groups have the same number of C atoms. Particularly preferred are ethylene, 1,2-propylene, 1,3-propylene, and mixtures thereof. The primary amino functional group in the polyalkylene imine may carry 1 or 2 polyalkoxy groups, and the secondary amino functional group may carry 1 polyalkoxy group, not every amino functional group must be substituted by an alkoxy group. The average number of alkoxy groups per primary and secondary amino functional group in the polyalkoxylated polyalkylene imine is preferably 5 to 100, in particular 10 to 50. The alkoxy group in the polyalkoxylated polyalkylene imine is preferably ethoxy, propoxy, or butoxy, or a mixture thereof. Polyethoxylated polyethyleneimines are particularly preferred. Polyalkoxylated polyalkyleneimines can be obtained by reacting polyalkyleneimines with epoxides corresponding to the alkoxy groups. If desired, the terminal OH functions of at least some of the polyalkoxy substituents can be replaced by alkyl ether functions having 1 to 10, in particular 1 to 3, C atoms. The polyalkoxylated polyalkyleneimines may be partially quaternized.

[0083] The compositions of some preferred first and second detergent compositions for use in the process according to the invention can be found in the table below (unless otherwise stated, the amounts are given in % by weight, based on the total weight of the solid gel or shell substance).

[0084]

[0085]

[0086]

[0087] * Ethoxylated and propoxylated C 8-18 alcohol

[0088] **Nonionic surfactant 2 is different from nonionic surfactant 1 and is selected from ethoxylated and propoxylated C 8-18 alcohol.

[0089] In step e), the peroxycarboxylic acid and the surfactant can be introduced into the aqueous liquid simultaneously or in a staggered manner, wherein the simultaneous introduction of the peroxycarboxylic acid and the surfactant into the aqueous liquid has proven to be particularly advantageous for the cleaning effect. For this reason, it is also preferred that, for example, in step e), the peroxycarboxylic acid and the surfactant are introduced into the aqueous liquid in the form of a mixture.

[0090] In step e), a phosphonate is also introduced as a preferred optionally present active substance into the aqueous liquid, wherein the weight ratio of peroxycarboxylic acid to phosphonate is preferably 1:2 to 1:20, in particular 1:4 to 1:12. Furthermore, it is preferred that peroxycarboxylic acid and phosphonate are introduced simultaneously into the aqueous liquid in step e).

[0091] Preferably, in step e) of the washing process no water-softening agent selected from polymeric builders, complexing agents and chelating agents is introduced into the aqueous liquid.

[0092] In step e), the temperature T2 of the aqueous liquid is preferably from 26 to 45° C. After the peroxycarboxylic acid has been introduced, a pH of from 7 to 9, in particular from 7.5 to 8.5, is preferably established in the aqueous liquid.

[0093] At 100% t w After completion of the main wash cycle at a point in time, the aqueous liquid is preferably pumped out of the laundry treatment chamber.

[0094] This application provides, among other things, the following topics:

[0095] 1. A method for washing fabrics in a domestic washing machine, the method comprising the following steps:

[0096] a) providing a washing machine having a washing program, the washing program comprising a washing cycle having a duration t w Main wash cycle;

[0097] b) introducing fabrics into a laundry treatment chamber of said washing machine;

[0098] c) introducing an aqueous liquid into the laundry treatment chamber of the washing machine;

[0099] d) during the main wash cycle, between 0 and 10% t w introducing a first detergent composition comprising at least one surfactant into the laundry treatment chamber of the washing machine at a time point;

[0100] e) 11% to 99% t w A second detergent composition comprising a peroxycarboxylic acid and a surfactant is introduced into the aqueous liquor of the main wash cycle at a point in time.

[0101] 2. The washing method according to clause 1, wherein the household washing machine comprises an outer drum, an inner drum attached within the outer drum as a laundry treatment chamber, and a pumping device configured to pump aqueous liquid out of the outer drum.

[0102] 3. Washing method according to one of the preceding clauses, wherein the washing program comprises a main washing cycle, at least one rinse cycle and at least one spin-drying cycle.

[0103] 4. Washing method according to one of the preceding clauses, 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-drying cycle.

[0104] 5. The washing method according to one of the preceding clauses, wherein the duration t of the main washing cycle w It is 15 to 400 minutes, preferably 30 to 240 minutes, and particularly 60 to 180 minutes.

[0105] 6. Washing method according to one of the preceding clauses, wherein the volume of the aqueous liquid in step c) is from 3 to 40 1, preferably from 6 to 30 1, in particular from 8 to 20 1.

[0106] 7. Washing method according to one of the preceding clauses, wherein the weight ratio of aqueous liquid to fabric in step c) is higher than 1:1, preferably higher than 2:1 and in particular higher than 5:2.

[0107] 8. Washing method according to one of the preceding clauses, wherein the temperature T1 of the aqueous liquid in step c) is from 18 to 25°C.

[0108] 9. Washing method according to one of the preceding clauses, wherein the aqueous liquid is introduced into the laundry treatment chamber of the washing machine before the first detergent composition.

[0109] 10. Washing method according to one of the preceding clauses, wherein the aqueous liquid is introduced into the laundry treatment chamber of the washing machine simultaneously with the first detergent composition.

[0110] 11. Washing method according to one of the preceding clauses, wherein the aqueous liquid is introduced into the laundry treatment chamber of the washing machine after the first detergent composition.

[0111] 12. Washing method according to one of the preceding clauses, wherein the first detergent composition comprises at least one anionic surfactant.

[0112] 13. A washing method according to one of the preceding clauses, wherein the first detergent composition comprises at least one anionic surfactant selected from C 9-13 Alkylbenzene sulfonate, olefin sulfonate, C 12-18 Alkane sulfonates, ester sulfonates, alkyl (alkenyl) sulfates and fatty alcohol ether sulfates.

[0113] 14. Washing method according to one of the preceding clauses, wherein the first detergent composition comprises at least one nonionic surfactant.

[0114] 15. The washing method according to one of the preceding clauses, wherein the first detergent composition comprises at least one nonionic surfactant selected from: ethoxylated C 6-18 Primary alcohol; preferably ethoxylated C with a degree of alkoxylation ≥ 2 8-18 Primary alcohol; particularly preferably C with 4 EO or 7 EO 12-14 Alcohol, C with 7 EO 9-11 Alcohols, C with 5 EO, 7 EO or 8 EO 13-15 Alcohol, C with 7 EO 13-15 Oxo alcohols, C with 5 EO or 7 EO 12-18 Alcohols; especially C with 7 EO 12-18 Fatty alcohol or C with 7 EO 13-15 Oxo alcohols.

[0115] 16. Washing method according to one of the preceding clauses, wherein the first detergent composition comprises at least one enzyme preparation, preferably at least three enzyme preparations, selected from the group consisting of lipase, amylase, protease, cellulase, mannanase and hexosaminidase.

[0116] 17. The washing method according to one of the preceding clauses, wherein, in step d), at 0t w The first detergent composition is introduced into the laundry treatment chamber of the washing machine at a time point of

[0117] 18. The washing process according to one of the preceding clauses, wherein, in step d), thew , preferably >0 to 5% t w The first detergent composition is introduced into the laundry treatment chamber of the washing machine at a time point of

[0118] 19. The washing method according to one of the preceding clauses, wherein the peroxycarboxylic acid in step e) is selected from:

[0119] i) monoperoxycarboxylic acids and diperoxycarboxylic acids, such as performic acid, peracetic acid, sebacic acid, dodecanedioic acid,

[0120] ii) monoperoxyphthalic acid and diperoxyphthalic acid,

[0121] iii) monoperoxyterephthalic acid and diperoxyterephthalic acid,

[0122] iv) Imidoperoxycarboxylic acids, such as 6-phthalimidocaproic acid (PAP).

[0123] 20. The washing process according to one of the preceding clauses, wherein the peroxycarboxylic acid in step e) is selected from 6-phthalimidoperoxycaproic acid (PAP).

[0124] 21. Washing process according to one of the preceding clauses, wherein, in step e), the peroxycarboxylic acid is introduced into the washing liquid in the form of a preparation having a weight proportion of 5 to 45% by weight, preferably 10 to 30% by weight, of peroxycarboxylic acid.

[0125] 22. Washing method according to one of the preceding clauses, wherein the weight proportion of the peroxycarboxylic acid is 4 to 25 wt. %, preferably 6 to 20 wt. %, in particular 8 to 15 wt. %, relative to the total weight of the second detergent composition.

[0126] 23. Washing process according to one of the preceding clauses, wherein the surfactant introduced in step e) is different from the surfactant introduced in step d).

[0127] 24. The washing method according to one of the preceding clauses, wherein the weight proportion of the surfactant is 10 to 70 wt. %, preferably 20 to 65 wt. %, in particular 30 to 60 wt. %, relative to the total weight of the second detergent composition.

[0128] 25. The washing method according to one of the preceding clauses, wherein the surfactant in step e) is selected from nonionic surfactants, in particular from alkoxylated C 8-18 Primary alcohols, preferably selected from ethoxylated C 8-18Primary alcohols and ethoxylated and propoxylated C 8-18 Alcohols, particularly preferably selected from ethoxylated C 12-14 Primary alcohols and ethoxylated and propoxylated C 16-18 Alcohol-based nonionic surfactant.

[0129] 26. The washing method according to one of the preceding clauses, wherein the surfactant in step e) is selected from the group consisting of the general formula CH3(CH2) n OEO x PO y A nonionic surfactant wherein n=5 to 21, x=2 to 10, and y=2 to 10.

[0130] 27. The washing method according to one of the preceding clauses, wherein the surfactant in step e) is selected from the group consisting of: n OEO x PO y A nonionic surfactant wherein n=15 to 17, x=4 to 8, and y=2 to 6.

[0131] 28. A washing method according to one of the preceding clauses, wherein the surfactant in step e) is selected from amine oxides, preferably from alkylamine oxides, in particular alkyldimethylamine oxides, alkylamidoamine oxides and alkoxyalkylamine oxides, particularly preferably from amine oxides of formula (Ia) or (Ib),

[0132] R 6 R 7 R 8 N + -O - (Ia)

[0133] R 6 -[CO-NH-(CH2) w ] z -N + (R 7 )(R 8 )-O - (Ib)

[0134] Where R 6 Is saturated or unsaturated C 6-22 Alkyl, preferably C 8-18 Alkyl, especially saturated C 10-16 Alkyl, such as saturated C 12-14 Alkyl, which is via the carbonylamidoalkylene group -CO-NH-(CH2) z-bonded to the nitrogen atom N in the alkylamidoamine oxide and via the oxaalkylene group -O-(CH2) z - is bonded to the nitrogen atom N of an alkoxyalkylamine oxide, wherein z in each case represents a number from 1 to 10, preferably from 2 to 5, in particular 3,

[0135] R 7 and R 8 are independently C 1-4 Alkyl groups such as hydroxyethyl and especially methyl.

[0136] 29. A washing method according to one of the preceding clauses, wherein the surfactant in step e) is selected from amine oxides, preferably selected from coconut oil alkyl dimethyl amine oxide, myristyl dimethyl amine oxide, cetyl dimethyl amine oxide, lauryl dimethyl amine oxide and stearyl dimethyl amine oxide.

[0137] 30. Washing method according to one of the preceding clauses, wherein, in step e), the peroxycarboxylic acid and the surfactant are introduced into the aqueous liquid in a weight ratio of 2:1 to 1:12, preferably 3:2 to 1:10, in particular 1:1 to 1:8.

[0138] 31. The washing method according to one of the preceding clauses, wherein, in step e), the peroxycarboxylic acid and the surfactant are introduced into the aqueous liquid within a period of 5 minutes, particularly preferably 2 minutes, in particular 1 minute.

[0139] 32. Washing process according to one of the preceding clauses, wherein, in step e), a polyalkoxylated polyalkyleneimine, preferably a polyethoxylated polyethyleneimine, obtained by reacting a polyalkyleneimine with an alkylene oxide is introduced into the aqueous liquid.

[0140] 33. Washing process according to one of the preceding clauses, wherein, in step e), the peroxycarboxylic acid and the surfactant are introduced simultaneously into the aqueous liquid.

[0141] 34. Washing process according to one of the preceding clauses, wherein, in step e), the peroxycarboxylic acid and the surfactant are introduced into the aqueous liquid in the form of a mixture.

[0142] 35. Washing process according to one of the preceding clauses, wherein, in step e), no water-softening agent selected from polymeric builders, complexing agents and chelating agents is introduced into the aqueous liquid.

[0143] 36. Washing method according to one of the preceding clauses, wherein the temperature T2 of the aqueous liquid in step e) is from 26 to 45°C.

[0144] 37. The washing method according to one of the preceding clauses, wherein, in step e), the w time point, preferably between 50% and 99% t w time point, particularly preferably between 70% and 99% t w The time point, especially at 80% to 96% t w The peroxycarboxylic acid and the surfactant are introduced into the aqueous liquid at a point in time.

[0145] 38. Washing process according to one of the preceding clauses, wherein, in step e), a phosphonate is also introduced into the aqueous liquid and the weight ratio of peroxycarboxylic acid to phosphonate is preferably from 1:2 to 1:20, preferably from 1:4 to 1:12.

[0146] 39. The washing process according to one of the preceding clauses, wherein, in step e), the peroxycarboxylic acid and the phosphonate are introduced simultaneously into the aqueous liquid.

[0147] 40. Washing process according to one of the preceding clauses, wherein, after the introduction of the peroxycarboxylic acid, a pH of 7 to 9, preferably 7.5 to 8.5, is established in the aqueous liquid.

[0148] 41. The washing method according to one of the preceding clauses, wherein at 100% t w After the main wash cycle is completed at a certain point in time, the aqueous liquid is pumped out of the laundry treatment chamber. Example

[0149] The washing machine (Bosch WAV28E41) was loaded with test laundry (75% of the nominal load = 6.75 kg of a mixed batch of cotton and synthetic fabrics in a ratio of 2:1), a soil ballast (Schmutzballast) and an evaluable stain monitor (GCS stain panel, GCS Fleckensatz).

[0150] Then, 70 ml of detergent gel were metered directly onto the laundry and the wash program was started (cotton, cold, Speed ​​Perfect Modifier, 83 min run time, 1400 rpm final spin). The detergent gel had the following composition:

[0151] Active substances weight% water 37％ <![CDATA[C 10-13 Alkylbenzene sulfonate]]> 22％ <![CDATA[C 12-14 Fatty alcohol ether sulfate, 2EO]]> 5.2％ <![CDATA[C 12-18 Fatty alcohol ethoxylate, 7EO]]> 10％ 1,2-Propanediol 11％ Monoethanolamine 2.3％ <![CDATA[C 12-18 Fatty Acids]]> 1.8％ Trisodium Citrate 4.2％ HEDP-Na4 1.4％ glycerin 0.6％ Sorbitol 0.3％ spices 0.3％ the remaining Replenish to 100

[0152] In washing test V2, at the beginning of the main wash cycle, 6 g of bleach dispersion (Eureco LX 17; 17% 6-phthalimidoperoxycaproic acid suspension) and 5 g of Marlox RT 64 (C 600 with a degree of ethoxylation of 6 and a degree of propoxylation of 4) were additionally added. 16-18 Alcohol) is metered directly into the wash tank.

[0153] In the washing test E1, 10 minutes before the end of the main wash cycle, 6 g of bleach dispersion (Eureco LX 17; 17% 6-phthalimidoperoxycaproic acid suspension) and 5 g of Marlox RT 64 (C 600 with a degree of ethoxylation of 6 and a degree of propoxylation of 4) were additionally added. 16-18 Alcohol) is metered directly into the wash tank.

[0154] After the program is finished, the laundry is removed and the stain monitor is flattened and evaluated. The results of this evaluation can be found in the table below.

[0155] Stains V1 V2 E1 Tea 55 65 66 Blackcurrant 54 56 64 blueberry 54 60 64 Blood (old) 33 29 47 Whole egg / coloring 52 60 73 cocoa 46 55 57 Chocolate Ice Cream 59 64 70 Salad Dressing (Blackened) 66 59 71 Olive oil (soot, Ruβ) 31 35 46 Sebum (soot) 34 36 45 Mayonnaise (activated charcoal, Aktivkohle) 28 36 45 Cosmetics (liquid) 54 55 59 Red lipstick 47 52 59 Butter (dyed) 56 49 59

Claims

1. A method for washing fabrics in a domestic washing machine, the method comprising the following steps: a) providing a washing machine having a washing program and starting the washing program, the washing program comprising a washing machine having a duration t w Main wash cycle; b) introducing fabrics into a laundry treatment chamber of said washing machine; c) introducing an aqueous liquid into the laundry treatment chamber of the washing machine; d) during the main wash cycle, between 0 and 10% t w introducing a first detergent composition comprising at least one surfactant into the laundry treatment chamber of the washing machine at a time point; e) 11% to 99% t w The peroxycarboxylic acid and surfactant are introduced into the aqueous liquid of the main wash cycle at a point in time. 2 . The washing method according to claim 1 , wherein the washing program includes a main washing cycle, at least one rinsing cycle and at least one spin-drying cycle.

3. The washing method according to claim 1, wherein the duration t of the main washing cycle is w It is 15 to 400 minutes, preferably 30 to 240 minutes, and particularly 60 to 180 minutes.

4. The washing method according to claim 1, wherein the peroxycarboxylic acid in step e) is selected from: i) monoperoxycarboxylic acids and diperoxycarboxylic acids, such as performic acid, peracetic acid, sebacic acid, dodecanedioic acid, ii) monoperoxyphthalic acid and diperoxyphthalic acid, iii) monoperoxyterephthalic acid and diperoxyterephthalic acid, iv) Imidoperoxycarboxylic acids, such as 6-phthalimidocaproic acid (PAP).

5. The washing process according to one of the preceding claims, wherein the peroxycarboxylic acid in step e) is selected from 6-phthalimidoperoxycaproic acid (PAP).

6. Washing method according to one of the preceding claims, wherein: In step e), the peroxycarboxylic acid is introduced into the washing liquor in the form of a preparation having a weight proportion of 5 to 45% by weight, preferably 10 to 30% by weight, of peroxycarboxylic acid.

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

8. The washing method according to claim 1, wherein the surfactant in step e) is selected from nonionic surfactants, in particular from alkoxylated C 8-18 Primary alcohols, preferably selected from ethoxylated C 8-18 Primary alcohols and ethoxylated and propoxylated C 8-18 Alcohols, particularly preferably selected from ethoxylated C 12-14 Primary alcohols and ethoxylated and propoxylated C 16-18 Alcohol-based nonionic surfactant.

9. The washing method according to claim 1, wherein: In step e), the peroxycarboxylic acid and the surfactant are introduced into the aqueous liquid in the form of a mixture.

10. The washing method according to claim 1, wherein: In step e), at 30% to 99% t w time point, preferably between 50% and 99% t w time point, particularly preferably between 70% and 99% t w The time point, especially at 80% to 96% t w The peroxycarboxylic acid and the surfactant are introduced into the aqueous liquid at a point in time.

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