Textile washing method

Abstract

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

Description

[0001] .Textile washing process

[0002] The present invention relates to a textile washing process. In particular, the application relates to a multi-stage machine textile washing process in which washing and cleaning agents are dosed at different times.

[0003] While currently less than a third of the world's population has access to a washing machine, machine-based textile cleaning has been the standard method for removing soiling and freshening laundry in some regions of the world since the 1970s.

[0004] Both the machine technology and the detergents used in machine textile cleaning processes have been continuously developed over the past decades and improved in terms of their performance and ecological footprint. While development efforts were initially focused on improving the individual components of the washing process, such as the textile washing machine and its mechanics and programs, or the textile detergent, recent attention has also focused on improving the interaction between these components.

[0005] The international application WO 2021 / 048911 A1 describes a washing process using a textile washing machine, during which the textiles are sprayed with a rinsing solution in a rinse cycle.

[0006] European patent EP 3 428 336 B1 discloses washing processes with a minimum duration of 110 minutes, during which detergents containing rejuvenating agents are added to the washing liquid.

[0007] The European patent EP 2 711 413 B1 relates to washing processes which are characterized by a time-delayed dosing of different detergent substances.

[0008] European patent EP 2 566 943 B1 discloses the sensor-controlled, time-delayed dosing of detergent substances, for example peroxocarboxylic acids, into the interior of a textile washing machine.

[0009] Even in light of previous developments, the technical challenge of improving the washing performance of textile detergents in textile washing machines still remains.

[0010] To achieve this object, a washing method for textiles in a household washing machine is suitable, which comprises 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) introducing textiles into the laundry treatment chamber of the washing machine; c) introducing an aqueous liquor into the laundry treatment chamber of the washing machine; d) introducing a first detergent composition, comprising at least one surfactant, into the laundry treatment chamber of the washing machine in the main wash cycle at a time 0 to 10% t w ; e) introducing a second detergent composition comprising peroxycarboxylic acid and surfactant into the aqueous liquor of the main wash cycle at a time 11 to 99% tw.

[0011] A washing machine is a motor-driven appliance for cleaning textiles. Drum washing machines with a laundry drum rotatable about a horizontal axis are particularly preferred. The method according to the invention is particularly suitable for implementation in a household washing machine with a tub, a laundry drum mounted within the tub as the laundry treatment chamber, and a pumping device designed to pump aqueous liquor from the tub.

[0012] In step a) of the method, a washing machine with a washing program comprising a main wash cycle of duration t wStandard washing machines generally have several washing programs designed for cleaning different fabrics. These programs may include a main wash cycle, pre-wash, rinse, and / or spin cycles in addition to a main wash cycle. 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.

[0013] In addition to the mechanical forces acting on the laundry, the detergent used, and the temperature reached in the wash liquor, the duration of the wash cycle, especially the main wash cycle, influences the cleaning performance achieved. The duration tw of the main wash cycle used in the washing process is preferably 15 to 400 minutes, preferably 30 to 240 minutes, and especially 60 to 180 minutes.

[0014] The textiles introduced into the laundry treatment room in step b) can be, for example, cotton or synthetic textiles, but also mixed fabrics.

[0015] The aqueous liquor introduced into the laundry treatment room in step c) preferably has a volume of 3 to 40 l, preferably of 6 to 30 l and in particular of 8 to 20 l.

[0016] 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. The aqueous liquor in step c) preferably has a temperature Ti of 18 to 25°C.

[0017] The first detergent composition is introduced into the laundry treatment room in step d) at a time 0 to 10% tw. In other words, the first

[0018] Detergent composition already at the beginning of the main wash cycle in the

[0019] Laundry treatment room (time 0 tw) or is introduced into the laundry treatment room within a period of 10% of the duration tw of the main wash cycle.

[0020] In a first process variant, the aqueous liquor is introduced into the laundry treatment chamber of the washing machine before the first detergent composition. Such a process variant can be implemented, for example, using a pre-rinse cycle, during which the textiles are pre-rinsed and / or soaked with water but are not yet cleaned with the actual detergent composition.

[0021] A second process variant provides for the simultaneous introduction of the aqueous liquor and the first detergent composition into the laundry treatment chamber of the washing machine. If the aqueous liquor is fed into the laundry treatment chamber, for example, through the washing machine's dispenser drawer filled with the first detergent composition, without a pre-rinse cycle, the aqueous liquor and the first detergent composition are introduced into the laundry treatment chamber simultaneously.

[0022] Finally, it is also possible for the aqueous liquor to be introduced into the laundry treatment chamber of the washing machine after the first detergent composition, for example by applying the first detergent composition in pre-portioned form or by means of a dosing aid directly to the textiles before the start of the washing program.

[0023] The first detergent composition introduced into the laundry treatment room 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 in particular 18 to 25 wt.% of anionic surfactant.

[0024] The anionic surfactant is preferably selected from the group comprising C9-C13 alkylbenzenesulfonates, olefinsulfonates, C12-C18 alkanesulfonates, estersulfonates, alk(en)yl sulfates, fatty alcohol ether sulfates, and mixtures thereof. Compositions comprising C8-C13 alkylbenzenesulfonates and fatty alcohol ether sulfates as anionic surfactant have particularly good dispersing properties. Suitable sulfonate-type surfactants are preferably C9-C13 alkylbenzenesulfonates, olefinsulfonates, i.e., mixtures of alkene and hydroxyalkanesulfonates, and disulfonates, such as those obtained, for example, from C12-C18 monoolefins with a terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.Also suitable are C12-C18 alkanesulfonates and the esters of a-sulfofatty acids (estersulfonates), for example the a-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.

[0025] It is very particularly preferred if the first detergent composition contains at least one anionic surfactant of the formula (I), in the

[0026] R' and R" are independently H or alkyl and together contain 9 to 19, preferably 9 to 15 and especially 9 to 13 C atoms, and Y + a monovalent cation or the nth part of an n-valent cation (in particular monoethanolamine).

[0027] The group of alkyl ether sulfates includes fatty alcohol ether sulfates, for example the sulfuric acid monoesters of straight-chain or branched C7-C2i alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C8-n 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) are preferred.

[0028] R 1 -O-(AO) n -SO3- X + (II)

[0029] In this formula (II) R 1 represents a linear or branched, substituted or unsubstituted alkyl radical, preferably a linear, unsubstituted alkyl radical, particularly preferably a fatty alcohol radical. Preferred radicals R 1of formula (II) are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl radicals and mixtures thereof, with the representatives having an even number of carbon atoms being preferred. Particularly preferred radicals R 1 of formula (II) are derived from fatty alcohols with 12 to 18 C atoms, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or from oxo alcohols with 10 to 20 C atoms.

[0030] 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 in particular from 2 to 10. n is most preferably 2, 3, 4, 5, 6, 7, or 8. X is a monovalent cation or the nth part of an n-valent cation, preferred being the alkali metal ions, and among these, Na + or K+ , where Na + is highly preferred. Further cations X+ can be selected from NHT, % Zn 2+ ,% Mg 2+ ,% Ca 2+ ,% Mn 2+ , and mixtures thereof as well as primary and secondary amines, in particular monoethanolamine.

[0031] Particularly preferred first detergent compositions contain an alkyl ether sulfate selected from fatty alcohol ether sulfates of the formula (III) where k = 1, 1 to 19, n = 2, 3, 4, 5, 6, 7, or 8. Very particularly preferred representatives are Na fatty alcohol ether sulfates having 12 to 18 C atoms and 2 EO (k = 11 to 13, n = 2 in formula III). The stated degree of ethoxylation represents a statistical mean, which can be a whole or fractional number for a specific product. The stated degrees of alkoxylation represent statistical mean, which can be a whole or fractional number for a specific product. Preferred alkoxylates / ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).

[0032] 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.% of anionic surfactant from the group of Cg-19-alkylbenzenesulfonates and alkyl ether sulfates, preferably from the group of Cg-18-alkylbenzenesulfonates.

[0033] The use of fatty acids has proven advantageous for stability and cleaning performance. Preferred first detergent compositions therefore contain, based on their total weight, 4 to 12 wt.%, preferably 6 to 10 wt.% fatty acid. Particularly preferred fatty acids are selected from the group of caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, and mixtures thereof. The fatty acids are not classified as anionic surfactants in the context of this application.

[0034] As a further preferred component, the first detergent composition comprises at least one nonionic surfactant.

[0035] In particular, the use of non-ionic surfactants from the group of alkyl ethoxylates is preferred, with preferred alkyl ethoxylates being selected from the group of ethoxylated primary C1-C18 alcohols, preferably ethoxylated primary C5-C18 alcohols with a degree of alkoxylation > 2, particularly preferably C12-C14 alcohols with 4 EO or 7 EO, C9-C11 alcohols with 7 EO, C5-C5 alcohols with 5 EO, 7 EO or 8 EO, C5-C5 oxo alcohols with 7 EO, C5-C5 alcohols with 5 EO or 7 EO, in particular C12-C18 fatty alcohols with 7 EO or C5-C5 oxo alcohols with 7 EO.

[0036] 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.% of nonionic surfactant from the group of ethoxylated primary Cs-is alcohols, preferably the ethoxylated primary Cs-is alcohols with a degree of alkoxylation > 2, particularly preferably the C12-14 alcohols with 4 EO or 7 EO, the Cg-n alcohols with 7 EO, the C18-is alcohols with 5 EO, 7 EO or 8 EO, the Cs-oxo alcohols with 7 EO, the Cs-alcohols with 5 EO or 7 EO, in particular the Cs-fatty alcohols with 7 EO or the C13-15 oxo alcohols with 7 EO. As a further preferred optional component, the first detergent composition comprises at least one enzyme preparation, preferably at least 3 enzyme preparations of enzymes from the group lipase, amylase, protease, cellulase, mannanase and hexosaminidase.Due to their improved cleaning effect, first detergent compositions are preferred which contain, based on their total weight, 2 to 8 wt.%, preferably 3 to 6 wt.% enzyme preparation.

[0037] According to the invention, it is preferred if the first detergent composition contains at least one lipase preparation. Lipases preferred according to the invention are selected from at least one enzyme from the group consisting of triacylglycerol lipase (EC 3.1.1.3), lipoprotein lipase (EC 3.1.1.34), and monoglyceride lipase (EC 3.1.1.23).

[0038] Preferred lipase preparations according to the invention are the commercial products marketed by Amano Pharmaceuticals under the names Lipase M-AP10®, Lipase LE®, and Lipase F® (also Lipase JV®). Lipase F®, for example, is naturally present in Rhizopus oryzae. Lipase M-AP10®, for example, is naturally present in Mucor javanicus.

[0039] 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 the α-amylases from Bacillus licheniformis, from B. amyloliquefaciens, and from B. stearothermophilus, as well as their improved further developments for use in detergents or cleaning agents. The enzyme from B. licheniformis is available from Novozymes under the trade name Termamyl® and from Genencor under the trade name Purastar®ST. Further developments of these α-amylases are available from Novozymes under the trade names Duramyl® and Termamyl®ultra, from Genencor under the name Purastar®OxAm, and from Daiwa Seiko Inc., Tokyo, Japan, as Keistase®. The a-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 are the further developments of the α-amylase from Aspergillus niger and A. oryzae, available from Novozymes under the trade name Fungamyl®.

[0040] 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, any of the enzymes from class EC 3.4 falls within this category (comprising each of the thirteen subclasses falling within it). According to the invention, "protease activity" is present when the enzyme possesses proteolytic activity (EC 3.4). Various types of protease activity are known: The three main types are: trypsin-like, in which cleavage of the amide substrate occurs after the amino acids Arg or Lys at P1; chymotrypsin-like, in which cleavage occurs after one of the hydrophobic amino acids at P1; and elastase-like, in which cleavage of the amide substrate occurs after Ala at P1.

[0041] As a further preferred optional ingredient, 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-endoglucanhydrolase, celludextrinase, or avicelase. The decisive factor for whether an enzyme is a cellulase within the meaning of the invention is its ability to hydrolyze 1,4-ß-D-glucosidic bonds in cellulose.

[0042] Cellulases (endoglucanases, EG) suitable according to the invention include, for example, fungal, endoglucanase (EG)-rich compositions which are offered by the company Novozymes under the trade name Celluzyme®. The products Endolase® and Carezyme®, also available from Novozymes, are based on the 50 kD EG and the 43 kD EG from Humicola insolens DSM 1800, respectively. Other commercial products from this company that can be used are Cellusoft®, Renozyme® and Celluclean®. Also suitable are cellulases available from AB Enzymes, Finland, under the trade names Ecostone® and Biotouch®, which are based at least in part on the 20 kD EG from Melanocarpus. Other cellulases from AB Enzymes are Econase® and Ecopulp®. Other suitable cellulases are those from Bacillus sp. CBS 670.93 and CBS 669.93, with the one from Bacillus sp. CBS 670.93 is available from Danisco / Genencor under the trade name Puradax®. Other commercial products available from Danisco / Genencor are "Genencor detergent cellulase L" and lndiAge®Neutra.

[0043] As a preferred ingredient, the first detergent composition contains a mannanase preparation.

[0044] A mannanase catalyzes the hydrolysis of 1,4-beta-D-mannosidic bonds in mannans, galactomannans, glucomannans, and galactoglucomannans. These mannanases are classified as EC 3.2.1.78 according to enzyme nomenclature.

[0045] 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.

[0046] Polypeptides with hexosaminidase activity include dispersins such as Dispersin B (DspB), which are ß-N-acetylglucosamine glycerides 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 ß-hexosaminidase that specifically hydrolyzes ß-1,6-glycosidic bonds of acetylglucosamine polymers. The use of hexosaminidases from the ß-hexosaminidase group is preferred.

[0047] In addition to the actual enzyme protein, an enzyme preparation comprises 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 used enzyme preparations contain between 0.1 and 40 wt.%, preferably between 0.2 and 30 wt.%, more preferably between 0.4 and 20 wt.%, and most preferably between 0.8 and 10 wt.% of the enzyme protein. In such compositions, an enzyme stabilizer can be present in an amount of 0.05 to 35 wt.%, preferably 0.05 to 10 wt.%, based on the total weight of the enzyme composition.

[0048] The protein concentration can be determined using known methods, for example, the BCA method (bicinchoninic acid; 2,2'-biquinolyl-4,4'-dicarboxylic acid) or the biuret method. The active protein concentration is determined by titrating the active sites using a suitable irreversible inhibitor (for proteases, for example, phenylmethylsulfonyl fluoride (PMSF)) and determining the residual activity.

[0049] In a process variant in step d), the first detergent composition is preferably introduced into the laundry treatment chamber of the washing machine at a time 0 tw.

[0050] More preferably, 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.

[0051] 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 in particular at a time 80 to 96 tw.

[0052] The term “second detergent composition” encompasses all those active ingredients which are introduced into the aqueous liquor at a time from 11 to 99% dw, preferably at a time from 30 to 99% dw, more preferably at a time from 50 to 99% dw, very particularly preferably at a time from 70 to 99% dw and especially preferably at a time from 80 to 96 dw. The constituents of the second detergent composition can enter the aqueous liquor at the same time or at different times. It is particularly preferred if the peroxycarboxylic acid and the surfactant, as essential constituents of the second detergent composition, are introduced into the aqueous liquor within a period of five minutes, more preferably 2 minutes and in particular 1 minute. In step e) of the process, a peroxycarboxylic acid is introduced into the aqueous liquor.Preferred peroxycarboxylic acids are in particular i) mono- and diperoxocarboxylic acids such as performic acid, peracetic acid, decane diperoxo acid, dodecane diperoxo acid, ii) mono- and di-perphthalic acids, iii) mono- and di-perterephthalic acids, iv) imidoperoxocarboxylic acids such as 6-phthalimidoperoxocaproic acid (PAP).

[0053] The peroxocarboxylic acid is preferably solid at room temperature and atmospheric pressure; in this case, the peroxocarboxylic acid is used as a preferably water-containing suspension or dispersion. The use of 6-phthalimidoperoxocaproic acid (PAP) is particularly preferred.

[0054] The peroxycarboxylic acid is preferably introduced into the wash liquor in step e) in the form of a preparation with a weight fraction of 5 to 45 wt.%, preferably 10 to 30 wt.% peroxycarboxylic acid. The weight 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 in particular 8 to 15 wt.%

[0055] The surfactant introduced into the aqueous liquor in step e) can be identical to or different from the surfactant contained in the first detergent composition. The use of an identical surfactant reduces formulation complexity, while the use of a surfactant with a different structure enriches the aqueous liquor with an active ingredient with a cleaning profile different from the active ingredients previously contained in the liquor. For this reason, it is preferred if the surfactant introduced in step e) differs from the surfactant introduced in step d).

[0056] The weight proportion 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 in particular 30 to 60 wt.%.

[0057] The surfactant in step e) is preferably selected from the group of non-ionic surfactants, in particular the non-ionic surfactants from the group of alkoxylated primary Cs-18 alcohols, preferably from the group of ethoxylated primary Cs-18 alcohols with a degree of ethoxylation > 4 and the ethoxylated and propoxylated Cs-18 alcohols with a degree of ethoxylation > 4 and a degree of propoxylation > 2, particularly preferably from the group of ethoxylated primary C12-14 alcohols with a degree of ethoxylation > 6 and the ethoxylated and propoxylated C16-18 alcohols with a degree of ethoxylation > 4 and a degree of propoxylation > 2.

[0058] Particularly preferred washing processes are those in which the surfactant in step e) is selected from the group of non-ionic surfactants of the general formula CH3(CH2)nOEOxPO y with n = 5 to 21, x = 2 to 10 and y = 2 to 10, wherein nonionic surfactants of the general formula CH3(CH2)nOEOxPO ywith n = 15 to 17, x = 4 to 8 and y = 2 to 6 are particularly preferred.

[0059] In step e), the use of nonionic surfactants from the group of ethoxylated primary Ca-14 alcohols with a degree of ethoxylation > 4, in particular from the group of ethoxylated primary Cio-14 alcohols with a degree of ethoxylation of 6 to 10, is also particularly preferred.

[0060] Alternatively, but preferably in combination with the aforementioned non-ionic 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 the formula (Ia) or (Ib) R 6 R 7 R 8 N + -O _ (la)

[0061] R 6 -[CO-NH-(CH2)W]ZN + (R 7 )(R 8 )-O- (Ib) in the R 6a saturated or unsaturated C 1-22 alkyl radical, preferably C 1-16 alkyl radical, in particular a saturated C 10-16 alkyl radical, for example a saturated C 12-14 alkyl radical, which in the alkylamidoamine oxides is bonded to the nitrogen atom N via a carbonylamidoalkylene group -CO-NH-(CH 2) 2 - and in the alkoxyalkylamine oxides via an oxaalkylene group -O-(CH 2) 2 -, where z is in each case a number from 1 to 10, preferably 2 to 5, in particular 3,

[0062] R 7 , R 8 independently of one another is a Ci-4-alkyl radical, optionally hydroxy-substituted such as a hydroxyethyl radical, in particular a methyl radical.

[0063] It is very particularly preferred to use 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, in step e).

[0064] The use of the aforementioned surfactants from the group of non-ionic surfactants and amphoteric surfactants has proven to be advantageous for the cleaning performance achieved in the washing process.

[0065] For the cleaning performance achieved, it has further 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 of 3:2 to 1:10 and in particular of 1:1 to 1:8.

[0066] In a preferred process variant, in step e) a polyalkoxylated polyalkyleneimine, which is obtainable by reacting polyalkyleneimines with alkylene oxides, is introduced into the aqueous liquor.

[0067] The polyalkoxylated polyalkyleneimine is a polymer with a polyalkyleneimine backbone bearing polyalkoxy groups on the nitrogen atoms. It preferably has a weight-average molecular weight Mw in the range from 5000 g / mol to 60000 g / mol, in particular from 10000 g / mol to 22500 g / mol. The polyalkyleneimine has primary amino functions at the ends and preferably both secondary and tertiary amino functions in the interior; optionally, it can also have only secondary amino functions in the interior, resulting in a linear rather than a branched-chain polyalkyleneimine. The ratio of primary to secondary amino groups in the polyalkyleneimine is preferably in the range from 1:0.5 to 1:1.5, in particular in the range from 1:0.7 to 1:1. The ratio of primary to tertiary amino groups in the polyalkyleneimine is preferably in the range from 1:0.2 to 1:1, in particular in the range from 1:0.5 to 1:0.8.The polyalkyleneimine preferably has a weight-average molecular weight in the range from 500 g / mol to 50,000 g / mol, in particular from 550 g / mol to 2,000 g / mol. The N atoms in the polyalkyleneimine are preferably separated from one another by alkylene groups having 2 to 12 C atoms, in particular 2 to 6 C atoms, although not all alkylene groups need to have the same number of C atoms. Ethylene groups, 1,2-propylene groups, 1,3-propylene groups, and mixtures thereof are particularly preferred. The primary amino functions in the polyalkyleneimine can carry 1 or 2 polyalkoxy groups, and the secondary amino functions can carry 1 polyalkoxy group, although not every amino function needs to be alkoxy-substituted. The average number of alkoxy groups per primary and secondary amino function in the polyalkoxylated polyalkylenimine is preferably 5 to 100, in particular 10 to 50.The alkoxy groups in the polyalkoxylated polyalkyleneimine are preferably ethoxy, propoxy, or butoxy groups, or mixtures thereof. Polyethoxylated polyethyleneimines are particularly preferred. The polyalkoxylated polyalkyleneimines are obtainable by reacting the polyalkyleneimines with the alkoxy groups of corresponding epoxides. If desired, the terminal OH function of at least some of the polyalkoxy substituents can be replaced by an alkyl ether function having 1 to 10, in particular 1 to 3, carbon atoms. The polyalkoxylated polyalkyleneimine can be partially quaternized.

[0068] 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 (data in wt.% based on the total weight of the gel body or the coating substance unless otherwise stated).

[0069]

[0070] ethoxylated and propoxylated Ca -is alcohol with a degree of ethoxylation > 4 and a

[0071] Degree of propoxylation > 2

[0072] ** Nonionic surfactant 2 differs from nonionic surfactant 1 and is selected from the group of ethoxylated and propoxylated Ca -is alcohols with a degree of ethoxylation > 4 and a degree of propoxylation > 2

[0073] The peroxycarboxylic acid and the surfactant can be introduced into the aqueous liquor in step e) simultaneously or at different times, with simultaneous introduction of the peroxycarboxylic acid and the surfactant into the aqueous liquor having proven 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 liquor in step e) in the form of a mixture.

[0074] As a preferred optional active ingredient, a phosphonate is further introduced into the aqueous liquor in step e), wherein the weight ratio of peroxycarboxylic acid to phosphonate is preferably 1:2 to 1:20, in particular 1:4 to 1:12. Again, it is preferred to introduce the peroxycarboxylic acid and the phosphonate into the aqueous liquor simultaneously in step e).

[0075] In step e) of the washing process, preferably no water softeners from the group of polymeric builders, complexing agents and sequestering agents are introduced into the aqueous liquor.

[0076] The temperature T2 of the aqueous liquor in step e) is preferably 26 to 45°C. After addition of the peroxycarboxylic acid, the aqueous liquor preferably reaches a pH of 7 to 9, in particular 7.5 to 8.5.

[0077] After completion of the main wash cycle at time 100% t wThe aqueous liquor is preferably pumped out of the laundry treatment room.

[0078] This registration provides, among other things, the following items:

[0079] 1. A washing method for textiles in a household washing machine, comprising the steps of a) providing a washing machine with a washing program comprising a main wash cycle of duration t w ; b) introducing textiles into the laundry treatment chamber of the washing machine; c) introducing an aqueous liquor into the laundry treatment chamber of the washing machine; d) introducing a first detergent composition comprising at least one surfactant into the laundry treatment chamber of the washing machine in the main wash cycle at a time 0 to 10% t w; e) introducing a second detergent composition comprising peroxycarboxylic acid and surfactant into the aqueous liquor of the main wash cycle at a time 11 to 99% tw. Washing method according to point 1, wherein the household washing machine comprises a suds container, a laundry drum mounted inside the suds container, as a laundry treatment chamber, and a pumping device designed to pump aqueous liquor out of the suds container. Washing method according to one of the preceding points, wherein the washing program comprises a main wash cycle, at least one rinse cycle, and at least one spin cycle. Washing method according to one 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.Washing process according to one of the preceding points, wherein the duration tw of the main wash cycle is 15 to 400 minutes, preferably 30 to 240 minutes and in particular 60 to 180 minutes. Washing process according to one 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 in particular 8 to 20 l. Washing process according to one of the preceding points, wherein 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. Washing process according to one of the preceding points, wherein the aqueous liquor in step c) has a temperature Ti of 18 to 25°C. Washing process according to one of the preceding points, wherein the aqueous liquor is introduced into the laundry treatment chamber of the washing machine before the first detergent composition.Washing method according to one 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. Washing method according to one of the preceding points, wherein the aqueous liquor is introduced into the laundry treatment chamber of the washing machine after the first detergent composition. Washing method according to one of the preceding points, wherein the first detergent composition comprises at least one anionic surfactant. Washing method according to one of the preceding points, wherein the first detergent composition comprises at least one anionic surfactant selected from the group of C9-13 alkylbenzenesulfonates, olefinsulfonates, C12-18 alkanesulfonates, estersulfonates, alk(en)yl sulfates, and fatty alcohol ether sulfates. Washing method according to one of the preceding points, wherein the first detergent composition comprises at least one nonionic surfactant.Washing method according to one of the preceding points, wherein the first detergent composition comprises at least one nonionic surfactant selected from the group of ethoxylated primary C1-C18 alcohols, preferably ethoxylated primary C5-C18 alcohols with a degree of alkoxylation > 2, particularly preferably C12-C14 alcohols with 4 EO or 7 EO, C9-C11 alcohols with 7 EO, C5-C18 alcohols with 5 EO, 7 EO or 8 EO, C13-C15 oxo alcohols with 7 EO, C12-C18 alcohols with 5 EO or 7 EO, in particular C5-C18 fatty alcohols with 7 EO or C13-C15 oxo alcohols with 7 EO. Washing method according to one of the preceding points, wherein the first detergent composition comprises at least one enzyme preparation, preferably at least 3 enzyme preparations of enzymes from the group lipase, amylase, protease, cellulase, mannanase and hexosaminidase.Washing method according to one of the preceding points, wherein the first detergent composition in step d) is introduced into the laundry treatment chamber of the washing machine at a time 0 tw. Washing method according to one of the preceding points, wherein 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. Washing method according to one of the preceding points, wherein the peroxycarboxylic acid in step e) is selected from the group i) mono- and diperoxocarboxylic acids such as performic acid, peracetic acid, decane diperoxo acid, dodecane diperoxo acid, ii) mono- and di-perphthalic acids, iii) mono- and di-perterephthalic acids, iv) imidoperoxocarboxylic acids such as 6-phthalimidoperoxocaproic acid (PAP). Washing process according to one of the previous points, wherein the peroxycarboxylic acid in step e) is selected from the group 6-phthalimidoperoxocaproic acid (PAP).Washing process according to one of the preceding points, wherein the peroxycarboxylic acid is introduced into the wash liquor in step e) in the form of a preparation with a weight fraction of 5 to 45 wt.%, preferably 10 to 30 wt.% peroxycarboxylic acid. Washing process according to one of the preceding points, wherein the weight fraction of the peroxycarboxylic acid in the total weight of the second detergent composition is 4 to 25 wt.%, particularly preferably 6 to 20 wt.% and in particular 8 to 15 wt.%. Washing process according to one of the preceding points, wherein the surfactant introduced in step e) differs from the surfactant introduced in step d). Washing process according to one 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 in particular 30 to 60 wt.%.Washing process according to one of the preceding points, 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 Cs-18 alcohols, preferably from the group of ethoxylated primary Cs-18 alcohols with a degree of ethoxylation > 4 and the ethoxylated and propoxylated Cs-18 alcohols with a degree of ethoxylation > 4 and a degree of propoxylation > 2, particularly preferably from the group of ethoxylated primary Cs-12-14 alcohols with a degree of ethoxylation > 6 and the ethoxylated and propoxylated Cs-16-18 alcohols with a degree of ethoxylation > 4 and a degree of propoxylation > 2. Washing process according to one of the preceding points, wherein the surfactant in step e) is selected from the group of non-ionic surfactants of the general formula CH3(CH2)nOEOxPO. ywith n = 5 to 21, x = 2 to 10 and y = 2 to 10. Washing process according to one of the previous points, wherein the surfactant in step e) is selected from the group of non-ionic surfactants of the general formula CH3(CH2)nOEOxPO y with n = 15 to 17, x = 4 to 8 and y = 2 to 6. 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 the formula (Ia) or (Ib), R 6 R 7 R 8 N + -O _ (la)

[0080] R 6 -[CO-NH-(CH2)W]ZN + (R 7 )(R 8 )-O- (lb) in the R 6a saturated or unsaturated C 1-22 alkyl radical, preferably C 1-16 alkyl radical, in particular a saturated C 10-16 alkyl radical, for example a saturated C 12-14 alkyl radical, which in the alkylamidoamine oxides is bonded to the nitrogen atom N via a carbonylamidoalkylene group -CO-NH-(CH2)Z- and in the alkoxyalkylamine oxides via an oxaalkylene group -O-(CH2)Z-, where z is in each case a number from 1 to 10, preferably 2 to 5, in particular 3,

[0081] R 7 , R 8independently of one another is a C 1-4 alkyl radical, optionally hydroxy-substituted, such as a hydroxyethyl radical, in particular a methyl radical. 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 cocoalkyldimethylamine oxide, myristyldimethylamine oxide, cetyldimethylamine oxide, lauryldimethylamine oxide and stearyldimethylamine oxide. Washing process according to one of the preceding points, wherein the peroxycarboxylic acid and the surfactant in step e) are introduced into the aqueous liquor in a weight ratio of 2:1 to 1:12, preferably of 3:2 to 1:10 and in particular of 1:1 to 1:8. Washing process according to one of the preceding points, wherein the peroxycarboxylic acid and the surfactant in step e) are introduced into the aqueous liquor within a period of five minutes, particularly preferably of 2 minutes and in particular of 1 minute.Washing process according to one of the preceding points, wherein in step e) a polyalkoxylated polyalkyleneimine, which is obtainable by reacting polyalkyleneimines with alkylene oxides, preferably a polyethoxylated polyethyleneimine, is introduced into the aqueous liquor. Washing process according to one of the preceding points, wherein the peroxycarboxylic acid and the surfactant are introduced into the aqueous liquor simultaneously in step e). Washing process according to one of the preceding points, wherein the peroxycarboxylic acid and the surfactant are introduced into the aqueous liquor in step e) in the form of a mixture. Washing process according to one of the preceding points, wherein in step e) no water softeners from the group of polymeric builders, complexing agents and sequestering agents are introduced into the aqueous liquor. Washing process according to one of the preceding points, wherein the aqueous liquor in step e) has a temperature T2 of 26 to 45°C.Washing process according to one of the preceding points, wherein the peroxycarboxylic acid and the surfactant are introduced into the aqueous liquor in step e) at a time of 30 to 99% tw, preferably at a time of 50 to 99% tw, particularly preferably at a time of 70 to 99% tw and in particular at a time of 80 to 96 tw. Washing process according to 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, preferably 1:4 to 1:12. Washing process according to one of the preceding points, wherein the peroxycarboxylic acid and the phosphonate are introduced into the aqueous liquor at the same time in step e). Washing process according to one of the preceding points, wherein a pH value of 7 to 9, preferably 7.5 to 8.5, is established in the aqueous liquor after introduction of the peroxycarboxylic acid.Washing process according to one of the preceding points, wherein the aqueous liquor is pumped out of the laundry treatment room after completion of the main wash cycle at the time 100% tw.

[0082] Examples

[0083] A washing machine (Bosch WAV28E41) was loaded with the test laundry (75% of the nominal load = 6.75 kg of a mixed batch of cotton and synthetic textiles in a ratio of 2:1), dirt ballast and an evaluable stain monitor (GCS stain set).

[0084] Then, 70 ml of a detergent gel was applied directly to the laundry and the wash program (cold cotton with Speed ​​Perfect Modifier, 83 minutes run time, 1400 rpm final spin) was started. The detergent gel had the following composition:

[0085] In washing test V2, at the beginning of the main wash cycle, an additional 6g of a bleaching agent dispersion (Eureco LX 17; 17% 6-phthalimidoperoxocaproic acid suspension) and 5g of Marlox RT 64 (Ci6-18 alcohol with ethoxylation degree 6 and propoxylation degree 4) were dosed directly into the washing container.

[0086] In wash test E1, 10 minutes before the end of the main wash cycle, an additional 6g of a bleaching agent dispersion (Eureco LX 17; 17% 6-phthalimidoperoxocaproic acid suspension) and 5g of Marlox RT 64 (Ci6-18 alcohol with ethoxylation degree 6 and propoxylation degree 4) were added directly to the wash tub. After the end of the program, the laundry was removed, and the stain monitor was ironed and evaluated. The results of this evaluation can be found in the following table.

Claims

Patent 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 cycle at a time 1 to 99% tw. 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. Washing method according to any of the preceding claims, 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. Washing method according to one 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 method 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 non-ionic surfactants from the group of alkoxylated primary Cs-is alcohols, preferably from the group of ethoxylated primary Cs-is alcohols with a degree of ethoxylation > 4 and of ethoxylated and propoxylated Cs-is alcohols with a degree of ethoxylation > 4 and a degree of propoxylation > 2, especially preferably from the group consisting of ethoxylated primary Ci2-14 alcohols with a degree of ethoxylation > 6 and ethoxylated and propoxylated Ci6-18 alcohols with a degree of ethoxylation > 4 and a degree of propoxylation > 2. Washing process according to any one of the preceding claims, wherein the peroxycarboxylic acid and the surfactant are introduced into the aqueous bath in step e) in the form of a mixture. Washing process according to any one of the preceding claims, wherein the peroxycarboxylic acid and the surfactant are introduced into the aqueous bath in step e) at a time point of 30 to 99% tw, preferably at a time point of 50 to 99% tw, particularly preferably at a time point of 70 to 99% tw, and particularly preferably at a time point of 80 to 96 tw.

Images