Textile washing method

Abstract

The invention relates to a method for washing textiles in a drum washing machine, comprising the following steps: a) providing a washing procedure for the washing machine, comprising a main washing cycle of duration tw; b) introducing the textile into the laundry treatment chamber of the washing machine; c) introducing the aqueous liquid 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 at a point in time of 0 to 10% tw during the main wash cycle; and e) introducing a second detergent composition into the aqueous liquid of the main wash cycle at a point in time of from 11% to 99% tw, where the second detergent composition comprises i) at least 4 wt.% of an active protease protein and ii) at least 80 wt.% of a liquid carrier, based on the total weight of the second detergent composition.

Description

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

[0002] Although fewer than a third of the population today has access to a textile washing machine, machine textile cleaning has been the standard method for removing dirt and freshening clothes in certain parts of the world since the 1970s.

[0003] In recent decades, both the machine technology and the detergents used in machine-based textile cleaning methods have been continuously developed and improved, both in terms of their performance and their ecological footprint. While development work initially focused on improving individual components of the washing process, such as textile washing machines and their mechanical aspects and procedures or textile detergents, for some time now the focus has also been on improving the interactions between these components.

[0004] International application WO 2012 / 048911 A1 describes a washing method using a textile washing machine, during which the textiles are sprayed with a rinsing solution in 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 liquor.

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

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

[0008] In the context of previous developments, a further technical goal was to improve the washing performance of textile detergents in textile washing machines.

[0009] To achieve this object, the present invention proposes a method for washing textiles in a drum washing machine, which comprises the following steps:

[0010] a) Provide a washing program for the washing machine, including a duration t w Main wash cycle;

[0011] b) introducing textiles into the laundry treatment chamber of the washing machine;

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

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

[0014] e) 11% to 99% t w At a time point of , a second detergent composition is introduced into the aqueous liquid of the main wash cycle, wherein the second detergent composition comprises, based on the total weight of the second detergent composition,

[0015] i) at least 4 wt.% active protease protein

[0016] ii) at least 80 wt.% of a liquid carrier.

[0017] Electric devices for cleaning textiles 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 drum washing machine having an outer drum, an inner drum attached to the outer drum as a laundry treatment chamber, and a pumping device configured to pump an aqueous liquid out of the outer drum.

[0018] In step a) of the method, a washing machine is provided which has a washing program comprising a washing cycle of duration t w A conventional washing machine generally has a plurality of washing programs for cleaning different textiles, which washing programs may also have pre-rinse, rinse and / or spin cycles in addition to the main wash cycle. A preferred washing program comprises a main wash cycle, at least one rinse cycle and at least one spin 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 cycle.

[0019] In addition to the mechanical forces acting on the laundry, the detergent used and the liquid temperature reached by the washing liquid, the duration of the washing cycle, in particular the main washing cycle, also has an influence on the cleaning performance achieved. The duration t of the main washing cycle used in the washing method w It is preferably from 15 to 400 minutes, preferably from 30 to 240 minutes, and particularly from 60 to 180 minutes.

[0020] The textile placed in the laundry treatment chamber in step b) can be, for example, cotton or synthetic textiles, or mixed fabrics.

[0021] In a preferred embodiment of the washing method, the drum washing machine has a device for detecting the weight of the textiles placed in step b).

[0022] In an exemplary embodiment, the drum washing machine has a load sensor as a means for detecting the weight of textiles. Using such a sensor, the weight of the textiles placed in the laundry treatment chamber of the washing machine can be directly determined in step b).

[0023] In a preferred embodiment of the method, the weight of the textiles placed in the laundry treatment chamber of the washing machine in step b) is determined by a load sensor, and the treatment parameter is determined based on this weight information and (if applicable) further information (preferably information detected by the sensor). The treatment parameter can be, for example, the duration of a washing program or a program step thereof, such as a pre-wash cycle, a main wash cycle or a rinse cycle. Alternatively, the treatment parameter is related to the temperature of the aqueous liquid, preferably to the temperature of the aqueous liquid in the main wash cycle. It is particularly preferred that the treatment parameter is related to the amount of the first or second detergent composition introduced in step d) and / or e).

[0024] Preferably, the wash program is configured such that the weight of the textiles detected by the device influences the amount of second detergent composition introduced in step e).

[0025] The treatment parameters can be determined by comparing the determined textile weight with reference values ​​and the treatment parameters assigned to these reference values. The corresponding reference values ​​can be stored in a database.

[0026] Determined treatment parameters are available for users. Treatment parameters can be output to users on a display, or can trigger corresponding output, such as output (particularly in text form) on a screen, and / or voice output (such as verbal notification). Then the user can process. Alternatively or additionally, in one embodiment of the method, treatment parameters can be output to a washing machine. For example, treatment parameters can represent at least one parameter of the washing program output to a washing machine, so that the washing machine, for example, adopts corresponding washing programs as presets, and the user only needs to start cleaning devices. It is also conceivable that the washing machine automatically performs washing programs by output. The washing machine can, for example, have a metering device for a detergent composition, so that the amount of the first and / or second detergent composition is automatically provided. This makes the method therefore more user-friendly.

[0027] The aqueous liquid introduced into the laundry treatment chamber in step c) has a volume of preferably 3 to 40 liters, preferably 6 to 30 liters and in particular 8 to 20 liters.

[0028] Since the washing method according to the invention achieves above-average cleaning results, in particular at high water hardnesses, the water hardness of the aqueous liquid introduced in step c) is preferably greater than 14° dH, preferably greater than 17° dH, in particular greater than 21° dH.

[0029] In a preferred embodiment of the washing method, the drum washing machine has a device for detecting the water hardness of the aqueous liquid used in step c). In an exemplary embodiment, the drum washing machine has a sensor for determining the water hardness as a means for determining the water hardness. The use of such a sensor makes it possible to directly determine the hardness of the aqueous liquid introduced into the laundry treatment chamber of the washing machine in step c).

[0030] In an alternative embodiment, the hardness of the aqueous liquid introduced into the laundry treatment chamber of the washing machine in step c) is determined indirectly. An indirect way of determining the water hardness is, for example, to determine the geographical location of the drum washing machine and to compare this location data with the water hardness values ​​of different locations stored in a database. The location data may be input by a user, for example in the form of coordinates or information equivalent to coordinates, such as a postal code, or may be determined automatically by the washing machine itself, for example by means of a GPS positioning system.

[0031] In a preferred embodiment of the method, the water hardness of the aqueous liquid introduced into the laundry treatment chamber of the washing machine in step c) is determined by means of a device for determining the water hardness, and the treatment parameter is determined based on this water hardness information and, if applicable, further information, preferably information acquired by a sensor. The treatment parameter can be, for example, the duration of a washing program or a program step thereof, such as a pre-wash cycle, a main wash cycle or a rinse cycle. Alternatively, the treatment parameter is related to the temperature of the aqueous liquid, preferably to the temperature of the aqueous liquid in the main wash cycle. It is particularly preferred if the treatment parameter is related to the amount of the first or second detergent composition introduced in step d) and / or e).

[0032] Preferably, the wash program is configured such that the water hardness detected by the device influences the amount of second detergent composition introduced in step e).

[0033] The treatment parameters can be determined by comparing the determined water hardness with reference values ​​and the treatment parameters assigned to these reference values. The corresponding comparison values ​​can be stored in a database.

[0034] Determined treatment parameters are available for users. Treatment parameters can be output to users on a display, or can trigger corresponding output, such as output (particularly in text form) on a screen, and / or voice output (such as verbal notification). Then the user can process. Alternatively or additionally, in one embodiment of the method, treatment parameters can be output to a washing machine. For example, treatment parameters can represent at least one parameter of the washing program output to a washing machine, so that the washing machine, for example, adopts corresponding washing programs as presets, and the user only needs to start cleaning devices. It is also conceivable that the washing machine automatically performs washing programs by output. The washing machine can, for example, have a metering device for a detergent composition, so that the amount of the first and / or second detergent composition is automatically provided. This makes the method therefore more user-friendly.

[0035] A preferred subject of the present application is a method for washing textiles in a drum washing machine, which comprises the following steps:

[0036] a) Provide a washing program for the washing machine, including a duration t w Main wash cycle;

[0037] b) introducing textiles into the laundry treatment chamber of the washing machine;

[0038] c) introducing an aqueous liquid into a laundry treatment chamber of the washing machine;

[0039] d) 0 to 10% t during the main wash cycle w At a time point, introducing a first detergent composition comprising at least one surfactant into a laundry treatment chamber of a washing machine;

[0040] e) 11% to 99% t w At a time point of , a second detergent composition is introduced into the aqueous liquid of the main wash cycle, wherein the second detergent composition comprises, based on the total weight of the second detergent composition,

[0041] i) at least 4 wt.% active protease protein

[0042] ii) at least 80 wt.% of a liquid carrier.

[0043] Therein, the water hardness of the aqueous liquid introduced into the laundry treatment chamber of the washing machine in step c) is determined by means of a device for determining the water hardness, and treatment parameters are determined by comparing the determined water hardness with reference values ​​and treatment parameters assigned to these reference values, the treatment parameters being related to the amount of the first or second detergent composition introduced in step d) and / or step e), and the first detergent composition is introduced in step d) and / or the second detergent composition is introduced in step e) in an amount corresponding to the determined treatment parameters.

[0044] A particularly preferred subject of the present application is a method for washing textiles in a drum washing machine, which comprises the following steps:

[0045] a) Provide a washing program for the washing machine, including a duration t w Main wash cycle;

[0046] b) introducing textiles into the laundry treatment chamber of the washing machine;

[0047] c) introducing an aqueous liquid into a laundry treatment chamber of the washing machine;

[0048] d) 0 to 10% t during the main wash cycle w At a time point, introducing a first detergent composition comprising at least one surfactant into a laundry treatment chamber of a washing machine;

[0049] e) 11% to 99% t w At a time point of , a second detergent composition is introduced into the aqueous liquid of the main wash cycle, wherein the second detergent composition comprises, based on the total weight of the second detergent composition,

[0050] i) at least 4 wt.% active protease protein

[0051] ii) at least 80 wt.% of a liquid carrier.

[0052] Therein, the water hardness of the aqueous liquid introduced into the laundry treatment chamber of the washing machine in step c) is determined by means of a device for determining the water hardness, and treatment parameters are determined by comparing the determined water hardness with reference values ​​and treatment parameters assigned to these reference values, the treatment parameters being related to the amount of the second detergent composition introduced in step e), and the second detergent composition is introduced in step e) in an amount corresponding to the determined treatment parameters.

[0053] In step c), the aqueous liquid preferably has a temperature T1 of 18 to 25°C.

[0054] The load of textiles in the washing machine in step b) and the volume of aqueous liquid introduced in step c) are preferably coordinated with one another in such a way that the weight ratio of aqueous liquid to textiles in step c) is greater than 1:1, preferably greater than 2:1, in particular greater than 5:2.

[0055] In step d), at 0 to 10% t w The first detergent composition is introduced into the laundry treatment chamber at a time point of 0t. 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 main wash cycle duration t w 10% of the time period is introduced into the laundry treatment chamber.

[0056] In a first method variant, the aqueous liquid is introduced into the laundry treatment chamber of the washing machine before the first detergent composition. This method variant can be achieved, for example, by a pre-rinse cycle, during which the textiles are pre-rinsed and / or soaked with water, but have not yet been cleaned by the actual detergent composition.

[0057] A second method variant is to introduce 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 washing machine dispensing drawer filled with the first detergent composition, the aqueous liquid and the first detergent composition are introduced into the laundry treatment chamber simultaneously.

[0058] 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 textiles in pre-dispensed form or via a dosing aid before the start of the washing program.

[0059] The first surfactant-containing detergent composition used in step d) is preferably highly concentrated and comprises, based on its total weight,

[0060] i) 50 to 95 wt.% of a surfactant

[0061] ii) less than 10 wt.% water.

[0062] In a particularly preferred embodiment, the surfactant-containing first detergent composition contains 55 to 92 wt%, especially 60 to 88 wt% of surfactant.

[0063] The surfactant-containing first detergent composition used in step d) is preferably metered from a container integrated in the washing machine, which container contains a multiple of the amount of first detergent composition required to run a washing program.

[0064] The group of surfactants includes nonionic surfactants, anionic surfactants, cationic surfactants and amphoteric surfactants. The composition of the present invention may contain one or more of the mentioned surfactants. Particularly preferred compositions contain surfactants from the group of anionic surfactants and nonionic surfactants.

[0065] Anionic surfactants are preferably selected from the group consisting of C 9-13 Alkylbenzene sulfonic acid, olefin sulfonic acid, C 12-18 The group consisting of alkyl sulfonic acid, ester sulfonic acid, alkyl (alkenyl) sulfonic acid, fatty alcohol ether sulfonic acid and mixtures thereof. 9-13The combination of alkylbenzene sulfonic acid and fatty alcohol ether sulfonic acid as anionic surfactant has particularly good dispersibility. The sulfonic acid surfactant that can be used is preferably C 9-13 Alkylbenzenesulfonic acids, olefinsulfonic acids (i.e., mixtures of olefin and hydroxyalkanesulfonic acids) and disulfonic acids, e.g., C 12-18 Monoolefins are obtained by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation product. 12-18 Also suitable are esters of alkylsulfonic acids and α-sulfofatty acids (ester sulfonic acids), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.

[0066] In a particularly preferred washing method, the first detergent composition comprises 8-18 Anionic surfactants from the alkylbenzenesulfonic acid group are particularly preferred. 9-15 Alkylbenzenesulfonic acid, especially C 9-13 Alkylbenzenesulfonic acid.

[0067] Alternatively, but preferably in combination with the alkylbenzene sulfonic acid, the first detergent composition comprises an anionic surfactant selected from the group of alkyl ether sulfonic acids.

[0068] Preferably, the compound has the formula R1-O-(AO) n -SO3H alkyl ether sulfonic acid, wherein

[0069] - R1 represents a linear or branched, substituted or unsubstituted alkyl radical, preferably a linear, unsubstituted alkyl radical, particularly preferably a fatty alcohol radical. Preferred radicals R1 are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl radicals and mixtures thereof, wherein preference is given to representatives with an even number of C atoms. Particularly preferred radicals R1 are derived from fatty alcohols having 12 to 18 C atoms, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol or stearyl alcohol, or from oxo alcohols having 10 to 20 C atoms.

[0070] -AO represents an ethylene oxide (EO) or propylene oxide (PO) group, preferably an ethylene oxide group. The index n in the formula 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.

[0071] As another optional component preferably present in the first detergent composition in combination with the aforementioned alkylbenzene sulfonic acid and alkyl ether sulfonic acid, the first detergent composition contains an anionic surfactant from the group of fatty acids. 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.

[0072] The preferred first detergent composition used in step d) of the process contains 30 to 90 wt.%, preferably 40 to 80 wt.%, in particular 45 to 70 wt.% of anionic surfactant, based on its total weight. The weight proportion of the anionic surfactant is determined as the weight proportion of the anionic surfactant acid, regardless of the degree of neutralization of the anionic surfactant in the detergent composition.

[0073] As a further optional component, the first detergent composition contains a nonionic surfactant, preferably a nonionic surfactant from the group of ethoxylated C6-18 primary alcohols, preferably an ethoxylated C6-18 primary alcohol with a degree of alkoxylation ≥ 2, particularly preferably a C12-14 alcohol with 4EO or 7EO, a C9-11 alcohol with 7EO, a C13-15 alcohol with 5EO, 7EO or 8EO, a C13-15 oxo alcohol with 7EO, a C12-18 alcohol with 5EO or 7EO, in particular a C12-18 fatty alcohol with 7EO or a C13-15 oxo alcohol with 7EO.

[0074] The preferred first detergent composition used in step d) of the process contains 7 to 50 wt.%, preferably 12 to 40 wt.%, especially 15 to 30 wt.% of nonionic surfactant, based on its total weight.

[0075] One group of optional components of the first detergent composition is formed by polyalkoxylated amines having a weight average molecular weight Mw in the range of 600 g / mol to 10000 g / mol, which are obtained by reacting ammonia or a primary alkylamine or hydroxyalkylamine having a molecular weight of less than 200 g / mol with an alkylene oxide. The weight proportion of these polyalkoxylated amines relative to the total weight of the first detergent composition is preferably 0.5 to 10 wt.%, particularly preferably 1 to 8 wt.%, and especially 2 to 6 wt.%.

[0076] Preferred polyalkoxylated amines have a weight average molecular weight M in the range of 1300 g / mol to 6000 g / mol, in particular 1400 g / mol to 4500 g / mol. w (The average molecular weight indicated here, and the average molecular weight that may be used for other polymers later, is the weight average molecular weight M w, which can in principle be determined by gel permeation chromatography with the aid of an R1 detector, the measurement being conveniently carried out on the basis of an external standard. ) To prepare them, it is possible in a known manner to start from ammonia, monoalkylamines, monoalkylmonoalkanolamines or monoalkyldialkanolamines or monoalkanolamines, dialkanolamines or trialkanolamines, for example triethanolamine, methyl-, ethyl-, propyl- and isopropyl-diethanolamine, methyl-, ethyl-, propyl- and isopropyl-diisopropanolamine, tripropanolamine, triisopropanolamine, N,N-di-(2-hydroxyethyl)cyclohexylamine, N,N-di-(2-hydroxypropyl)cyclohexylamine, n-butylamine, n-hexylamine, n-octylamine, isopropylamine, sec-butylamine, tert-butylamine, cyclohexylamine, 2-ethylhexylamine, 2-phenylethylamine and mixtures thereof, which are reacted with alkylene oxides, in particular selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide and mixtures thereof, in particular with mixtures containing propylene oxide and preferably ethylene oxide, particularly preferably with propylene oxide. The polyalkoxylated amines thus obtained may be block structures or random structures. Particularly preferred among them are polyalkoxylated amines obtained by propoxylation of triethanolamine, preferably with a length of three side arms of 15 propylene oxide units in each case. Also preferred are polyalkoxylated amines obtained by propoxylation of triisopropanolamine, preferably with a length of three side arms of 15 propylene oxide units in each case. Polyalkoxylated monoalkylamines with linear, branched or cyclic alkyl groups are likewise suitable, wherein the alkylene oxide selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide and mixtures thereof is alkoxylated, preferably with a mixture containing propylene oxide, more preferably with propylene oxide. Also preferred are polyalkoxylated amines obtained by propoxylation of tert-butylamine, preferably with a length of two side arms of 12 propylene oxide units in each case.

[0077] Preferred polyalkoxylated amines satisfy the general formula

[0078]

[0079] wherein R represents a linear, optionally branched or optionally cyclic alkyl group having 1 to 12 C atoms, or a group -(CH2CHR'O) n” -(CH2CHR'O) m” -H group,

[0080] R' and R" independently represent H, CH3 or CH2CH3,

[0081] n, n' and n" independently of one another represent values ​​from 0 to 30, preferably from 0 to 10, in particular from 0 to 5, and

[0082] m, m' and m" independently of one another represent values ​​from 0 to 30, preferably from 5 to 20, in particular from 12 to 16,

[0083] Provided that the sum of n+n'+n"+m+m'+m" is at least 14, preferably in the range of 18 to 100, in particular in the range of 20 to 70. Preferably, in the compounds of formula I, at least one of the functional groups R' and R" is a CH3 group.

[0084] As a further optional component, the first detergent composition contains polyalkoxylated polyalkyleneimine, which can be obtained by reacting polyalkyleneimine with alkylene oxide, preferably in a weight ratio of 0.5 to 10 wt.%, preferably 1 to 8 wt.%, especially 2 to 6 wt.%, based on the total weight of the first detergent composition.

[0085] Polyalkoxylated polyalkyleneimines are polymers with a polyalkyleneimine backbone, which carry polyalkoxy groups on the N atoms. They preferably have a weight average molecular weight Mw in the range of 5000 g / mol to 60000 g / mol, in particular 10000 g / mol to 22500 g / mol. The polyalkyleneimines have primary amino functional groups at the ends, and preferably have secondary and tertiary amino functional groups in the interior, and optionally it can 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 amino to secondary amino functional 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 amino to tertiary amino functional 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 polyalkyleneimines preferably have a weight average molecular weight 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 polyalkyleneimines are preferably separated from each other by alkylene groups having 2 to 12 C atoms, in particular 2 to 6 C atoms, although all alkylene groups do not necessarily have the same number of C atoms. Particularly preferred are vinyl groups, 1,2-propenyl groups, 1,3-propenyl groups and mixtures thereof. The primary amino functional groups in the polyalkyleneimines may carry 1 or 2 polyalkoxy groups, and the tertiary amino functional groups may carry 1 polyalkoxy group, but 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 polyalkyleneimines is preferably 5 to 100, in particular 10 to 50. The alkoxy groups in the polyalkoxylated polyalkyleneimines are preferably ethoxy, propoxy or butoxy groups or mixtures thereof. Polyalkoxylated polyalkyleneimines are particularly preferred. Polyalkoxylated polyalkyleneimines are obtainable by reacting polyalkyleneimines with epoxides corresponding to the alkoxy groups. If desired, at least some of the terminal OH functions of the polyalkoxy substituents can be replaced by alkyl ether functions having 1 to 10, in particular 1 to 3, C atoms.

[0086] It is preferred to provide a detergent composition with the lowest possible proportion of inactive ingredients for the washing method according to the invention. It is therefore preferred if the first detergent composition contains less than 10 wt.%, preferably less than 6 wt.%, in particular less than 2 wt.% of water. As the proportion of inactive ingredients decreases, not only the amount of resources required for packaging, storing and transporting the first detergent composition decreases, but at the same time the volume of the first detergent composition used per washing method also decreases, thereby increasing the range of storage containers (e.g. storage containers integrated in washing machines).

[0087] For the operability of the first detergent composition, in particular its dosage, a weight proportion of 0.5 to 29 wt.%, preferably 4.5 to 27 wt.%, and in particular 10 to 24 wt.% of the organic solvent, based on the total weight of the first detergent composition, has proven to be advantageous. The cleaning enhancement effect in the washing method can be attributed to the organic solvent. This is particularly applicable when an organic solvent from the class of organic amines (preferably monoethanolamine) is used. Its use not only has an enhanced cleaning effect, but also can partially or completely neutralize any anionic surfactant acid present in the first detergent composition.

[0088] In a preferred embodiment of the washing method, the first detergent composition comprises a 8-18 Anionic surfactants of the group consisting of alkylbenzenesulfonic acid, alkylethersulfonic acid and fatty acid, and an organic amine in a stoichiometric amount relative to the anionic surfactant, preferably monoethanolamine.

[0089] In general, a washing method is preferred in which the first detergent composition in step d) contains, based on its total weight,

[0090] i) 30 to 90 wt.%, preferably 40 to 80 wt.%, especially 45 to 70 wt.% of selected from C 8-18 Anionic surfactants of alkylbenzene sulfonic acid, alkyl ether sulfonic acid and fatty acid,

[0091] ii) 7 to 50 wt.%, preferably 12 to 40 wt.%, in particular 15 to 30 wt.% of a nonionic surfactant derived from ethoxylated C6-18 primary alcohols,

[0092] iii) 0.5 to 29 wt.%, preferably 4.5 to 27 wt.%, in particular 10 to 24 wt.% of an organic solvent from the group consisting of organic amines,

[0093] iv) less than 10 wt.%, preferably less than 6 wt.%, in particular less than 2 wt.% of water.

[0094] In a process variant, preferably in step d) 0tw At a certain point in time, the first detergent composition is introduced into the laundry treatment chamber of the washing machine.

[0095] More preferably, in step d) >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 time point of

[0096] In contrast, in step e), at 20% to 70% t w time point, preferably between 25% and 65% t w time point, particularly preferably between 30% and 60% t w The second detergent composition is introduced into the aqueous liquid at a point in time.

[0097] The second detergent composition is highly concentrated with respect to its active protease content and comprises at least 4 wt.% active protease protein and at least 80 wt.% liquid carrier, based on its total weight.

[0098] Proteases are one of the most important enzymes in technology. For detergents and cleaning agents, they are the longest-lived enzymes, and are contained in almost all modern high-performance detergents and cleaning agents. They can cause protein stains on the items to be cleaned to be degraded. In turn, subtilisin type proteases (subtilases, subtilisin, EC 3.4.21.62) are particularly important, and these proteases become serine proteases due to catalytically active amino acids. They act as non-specific endopeptidases and hydrolyze any amide bonds in peptides or proteins. Their optimal pH values ​​are usually in a significantly alkaline range. Subtilases are naturally formed by microorganisms. Specifically, subtilisin formed and secreted by Bacillus species is the most important class of subtilases.

[0099] Examples of subtilisin-type proteases preferably used in detergents and cleaners are subtilisin BPN' and Carlsberg, protease PB92, subtilisin 147 and 309, alkaline proteases from Bacillus lentus (especially Bacillus lentus DSM 5483), subtilisin DY and thermitase, proteinase K and proteases TW3 and TW7 (which should be classified as subtilases, but no longer subtilisin in the narrow sense), as well as variants of the proteases, which have an altered amino acid sequence compared to the starting protease. Proteases are modified in a targeted or random manner by methods known in the prior art, thereby optimizing their use, for example, in detergents and cleaners. This includes point mutagenesis, deletion or insertion mutagenesis, or fusion with other proteins or protein parts. Thus, for most proteases known in the prior art, appropriately optimized variants are known.

[0100] In a preferred embodiment of the method, the second detergent composition comprises 4 to 18 wt.%, preferably 5 to 15 wt.%, and in particular 7 to 12 wt.% of active protease protein based on its total weight. Thus, the concentration of active protease protein in the second detergent composition is 10 to 40 times higher than the concentration of active protease protein in conventional commercial detergent compositions.

[0101] Preferred proteases include

[0102] a) a protease having proteolytic activity and comprising at least 70% identity over its entire length to the amino acid sequence given in SEQ ID NO: 1, and increasingly preferably at least 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90.5%, 91%, 91.5%, 92%, 92.5%, 93%, 93.5%, 94%, 94.5%, 95.5%, 96%, 96.5%, 97%, 97.5%, 98%, 98.5% or 98.8% identical amino acid sequence and having, in each case based on the numbering according to SEQ ID NO:3: (i) at the position corresponding to position 101, the amino acid substitution R101E, and (ii) at least one amino acid substitution selected from the group consisting of S3T, V4I, R45E, at at least one position corresponding to positions 3, 4, 45, 55, 58, 59, 61, 87, 97, 98, 106, 117, 120, 124, 129, 136, 137, 143, 156, 161, 163, 171, 172, 185, 199, 205, 209, 222, 238, 244, 261 and 262: , R45D, R45Q, P55N, T58W, T58Y, T58L, Q59D, Q59M, Q59N, Q59T, G61D, G61R, S87E, G97S, A98D, A98E, A98R, S106A, S106W, N117E , H120V, H120D, H120K, H120N, S124M, P129D, E136Q, Q137H, S143W, S156D, S161T, S163A, S163G, Y171L, A172S, N185Q, V199M, V205I, Y209W, M222Q, N238H, V244T, N261T and L262N, L262Q, L262D, L262E; wherein the amino acid substitution combination of group (ii) is preferably selected from the group consisting of: N238E-L262E, S156D-L262E, S3T-V4I-V205I, S3T-V4I-A228V, G195E-V199M, H120D-S163G-N261D, N76D-A228V-N261D, S3T-N76D-S156D-Y209W , Q137H-S141H-R145H-N238E-L262E, Q137H-S141H-R145H-S156D-L262E, N76D-Q137H-S141H-R145H-A228V-N261D, N76D-Q1 37H-S141H-R145H-S163G-N238E, H120D-Q137H-S141H-R145H-S163G-N261D, S3T-N76D-Q137H-S141H-R145H-S156D-Y209W;.

[0103] b) a protease having proteolytic activity and comprising an amino acid sequence that is at least 70% identical over its entire length, and increasingly preferably at least 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 90.5%, 91%, 91.5%, 92%, 92.5%, 93%, 93.5%, 94%, 94.5%, 95%, 95.5%, 96%, 96.5%, 97%, 97.5% or 98% identical to the amino acid sequence given in SEQ ID NO: 2, and in each case based on the amino acid sequence according to SEQ ID NO:3, having: (i) at positions corresponding to positions 9, 130, 133, 144, 217, 252, and 271, at least one amino acid substitution selected from the group consisting of P9T, N130D, N130V, T133A, N144K, Y217M, N252T, and Q271E, and (ii) at positions corresponding to positions 6, 61, 62, 63, 89, 99, 101, 131, 156, 166, 170, 187, 188, 189 9, 211 and 224, at least one amino acid substitution selected from the group consisting of Y6F, Y6W, F61G, Q62N, S63Q, S89A, S89G, N99H, D101S, D101E, D101A, G131H, G131Y, G131F, S156R, G166A, G166M, G166L, G166I, K170R, K170G, N187D, N188G, S189T, S189 9L, S189I, S189R, S211N, S211Q, S224A, S224G; wherein the protease preferably has an amino acid substitution combination selected from the group consisting of: P9T-N130D-T133A-N144K-G166M-S189T-Y217M-N252T-Q271E, P9T-N130D-T133A-N144K-G166M-S189T-Y217M-S224A-N252T-Q27 1E, P9T-N130D-T133A-N144K-G166M-S211N-Y217M-N252T-Q271E, P9T-S89A-N130D-G131H-T133A-N144K -S189T-Y217M-S224A-N252T-Q271E, P9T-S89A-N130D-T133A-N144K-S189T-Y217M-S224A-N252T-Q271E,<h2 style=";text-align:left;direction:ltr">P9T-S89A-N130D-T133A-N144K-S189T-Y217M-S224A-N252T-Q271E、P9 T-S89A-N130D-T133A-N144K-N187D-Y217M-S224A-N252T-Q271E、P9T-S 89A-N130D-T133A-N144K-S189R-Y217M-S224A-N252T-Q271E, P9T-S89A-N130D-T133A-N144K-N187D-S189R-Y217M-S224A-N252T-Q271E, P9T-S89A-D101S-N130D-T133A-N144K-S189T-Y217M-S224A-N252T-Q271E, P9T-S89A-D101E-N130D-T133A-N144K-S189T-Y217M-S224A-N252T-Q27 1E、P9T-S89A-D101A-N130D-T133A-N144K-S189T-Y217M-S224A-N252T-Q271E、P9T-S89A-N99H-N130D-T133A-N144K-K170R-S189T-Y217M-S22 4A-N252T-Q271E、P9T-S89A-N130D-T133A-N144K-S156R-S189T-Y217M -S224A-N252T-Q271E、P9T-S63Q-S89A-N130D-T133A-N144K-G166A-S18 9T-Y217M-S224A-N252T-Q271E、P9T-F61G-Q62-N-S89A-N130D-T133A-N144K-N188G-S189T-Y217M-S224A-N252T-Q271E、Y6W-P9T-N130D-T133 A-N144K-S189T-Y217M-S224A-N252T-Q271E、Y6W-P9T-S89A-N130D-T1 33A-N144K-S189T-Y217M-S224A-N252T-Q271E、Y6W-P9T-F61G-Q62N-S8 9A-N130D-T133A-N144K-S189T-Y217M-S224A-N252T-Q271E、Y6W-P9T-S89A-N130D-T133A-N144K-N188G-S189T-Y217M-S224A-N252T-Q271E;、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0104] c) a protease having proteolytic activity and comprising an amino acid sequence that is at least 70% identical over its entire length, and increasingly preferably at least 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90.5%, 91%, 91.5%, 92%, 92.5%, 93%, 93.5%, 94%, 94.5%, 95.5%, 96%, 96.5%, 97%, 97.5%, 98%, 98.5% or 98.8% identical to the amino acid sequence given in SEQ ID NO: 3, and in each case based on the amino acid sequence according to SEQ ID NO:3, having: (i) at positions corresponding to positions 3, 4, 101 and 205, the amino acid substitutions S3T, V4I, R101E and V205I, and (ii) at least one amino acid substitution selected from the group consisting of N76D, N76D, N76D, N76D, N76D, N76D, N76D, N76D, N76D, N76D, N76D, N76D, N76D, N76D, N76D, N76D, N76D, N76D, N76D, N76D, N76D, N76D, N76D, N76D, N76D, N76D, N76D, N76D, N76D, N76D, N76D, N76D, N76D, N76D, 6E, N76Q, A138Q, R145L, R145W, R145Y, S156D, S156Q, S166G, Y167T, A169G, V177L, A187D, F189R, Q191R, Q206A, Q206L, Q206S, Q206T, Y209K, Y209V, Y209W, A215K, A215W, N218S, N218T, L262D, L262E, and L262Q;wherein the protease preferably has an amino acid substitution combination selected from the group consisting of: S3T-V4I-R101E-V205I-Q206L-Y209W, S3T-V4I-R101E-V205I-N218S, S3T-V4I-R101E-V205I-N76D, S3T-V4I-R101E-V205I-S156D-L262E, S3T-V4I-R101E-V205I-Q206L-Y209W-S156D-L262E, S3T-V4I-R101E-V205I-N76D-Q206 L-Y209W, S3T-V4I-R101E-V205I-N76D-S156D-Q206L-Y209W-L262E, S3T-V4I-R101E-V205I-N76D-N218S, S3T-V4I-R101E-V205I-N 76D-S156D-Y209W-L262E, S3T-V4I-R101E-V205I-N76D-Y209W, S3T-V4I-R101E-V205I-N76D-S156D-Q206L-L262E, S3T-V4I-R101E -V205I-N76D-Q206L, S3T-V4I-R101E-V205I-S156D-Q206L-Y209W, S3T-V4I-R101E-V205I-Q206L-Y209W-L262E, S3T-V4I-R101E-V 205I-A138Q-R145W-Y167T-Q206L, S3T-V4I-R101E-V205I-N76D-R145Y-A215W-N218S-L262E, S3T-V4I-R101E-V205I-N76D-S156D- Y209W-L262E; S3T-V4I-R101E-V205I-Q206L-Y209W-A215K-S156D-L262E, S3T-V4I-R101E-V205I-S156D-S166G-Q191R-Q206L-Y209W-L262E, S3T-V4I-R101E-V205I-S156D-A187D-F189R-Q206L-Y209W-L262E and S3T-V4I-R101E-V205I-A138Q-S156D-V171L-Q206L. ;

[0105] With regard to the cleaning performance achieved, in particular even at high water hardness or high loads, it has proven to be advantageous if the active protease protein has proteolytic activity and comprises an amino acid sequence which has at least 70% sequence identity to the amino acid sequence given in SEQ ID NO: 1 over its entire length and, in each case based on the numbering according to SEQ ID NO: 3: (i) at least two amino acid substitutions, preferably three amino acid substitutions, selected from the group consisting of the amino acid substitutions S3T, V4I, R101E and V205I at at least two, preferably three, of the positions corresponding to positions 3, 4, 101 or 205, and (ii) at least one further amino acid substitution at at least one of the positions corresponding to positions 76, 138, 145, 156, 166, 167, 169, 177, 187, 189, 191, 206, 209, 215, 218 or 262, in particular In some embodiments, the present invention further comprises at least one additional amino acid substitution selected from the group consisting of N76D, N76E, N76Q, A138Q, R145L, R145W, R145Y, S156D, S156Q, S166G, Y167T, A169G, V177L, A187D, F189R, Q191R, Q206A, Q206L, Q206S, Q206T, Y209K, Y209V, Y209W, A215K, A215W, N218S, N218T, L262D, L262E, and L262Q.

[0106] Proteases according to the present invention exhibit enzymatic activity, i.e. they are able to hydrolyze peptides and proteins, in particular in detergents or cleaning agents. Therefore, proteases according to the present invention are enzymes which catalyze the hydrolysis of amide / peptide bonds in protein / peptide substrates and are thus able to cleave proteins or peptides. In addition, proteases according to the present invention are preferably mature proteases, i.e. catalytically active molecules without one or more signal peptides / signal peptides and / or one or more propeptides. Unless otherwise indicated, the sequences shown also refer to mature (processed) enzymes in each case.

[0107] Methods for determining protease activity are familiar to those skilled in the art of enzyme technology and are routinely used. For example, such methods are disclosed in Tenside, Vol. 7 (1970), pp. 125-132. Alternatively, protease activity can be determined by releasing the chromophore p-nitroaniline (pNA) from the substrate suc-L-Ala-L-Ala-L-Pro-L-Phe-p-nitroaniline (AAPF). The protease cleaves the substrate and releases pNA. The release of pNA results in an increase in absorbance at 410 nm, the time curve of which is a measure of enzyme activity (see Del Mar et al., 1979). The measurement is carried out at a temperature of 25 ° C, a pH of 8.6 and a wavelength of 410 nm. The measurement time is 5 minutes and the measurement interval is 20 seconds to 60 seconds. Protease activity is usually expressed in protease units (PU). Suitable protease activity is, for example, close to 2.25, 5 or 10 PE per ml of washing liquid. However, protease activity is not equal to zero.

[0108] An alternative test for determining the proteolytic activity of the protease according to the invention is an optical measurement method, preferably a photometric determination method. A test suitable for this purpose comprises the protease-dependent cleavage of the substrate protein casein. Casein is cleaved into a plurality of smaller partial products by the protease. The entirety of these partial products has an increased absorbance at 290 nm relative to uncleaved casein, wherein a photometer can be used to determine this increased absorbance, and thus conclusions about the enzymatic activity of the protease can be drawn.

[0109] The protein concentration can be determined using known methods, such as the BCA method (bicinchoninic acid; 2,2'-biquinoline-4,4'-dicarboxylic acid) or the biuret method (Gornall et al., J. Biol. Chem. 177 (1948): 751-766). In this regard, the active protein concentration can be determined by titrating the active center with a suitable irreversible inhibitor and determining the residual activity (see Bender et al., J. Am. Chem. Soc. 88, 24 (1966): 5890-5913).

[0110] In various embodiments of the present invention, protease is a free enzyme. This means that the protease can directly act on all components of the medicament, and if the medicament is a liquid medicament, the protease directly contacts the solvent (e.g., water) of the medicament. In other embodiments, the medicament may contain a protease that forms an interaction complex with other molecules or contains a "coating". In this case, one or more protease molecules can be separated from the other components of the medicament by the structure around them. This separation structure can be produced by a vesicle (e.g., micelle or liposome), but is not limited thereto. However, the surrounding structure can also be a viral particle, a bacterial cell, or a eukaryotic cell. In various embodiments, the medicament can contain a cell of Bacillus pumilus or Bacillus subtilis expressing a protease according to the present invention, or a cell culture supernatant of such a cell.

[0111] In connection with the present invention, a protease characterized by a given substitution means that it contains a (given) substitution at the relevant position, i.e. at least the given position has not been otherwise mutated or deleted - for example, by fragmentation of the protease. In various embodiments, the proteases described herein have the sequence of SEQ ID NO: 1 except for the explicitly mentioned substitutions, i.e., they are 100% identical to the sequence according to SEQ ID NO: 1 except for the substituted positions.

[0112] The identity of nucleic acid or amino acid sequence is determined by sequence comparison. The sequence is relatively based on the BLAST algorithm commonly used in the prior art (see, for example, Altschul et al. (1990) "Basic local alignment search tool," J. Mol. Biol., 215: 403-410, and Altschul et al. (1997): "Gapped BLAST and PSI-BLAST: a new generation of protein database search programs," Nucleic Acids Res., 25: 3389-3402), and in principle occurs by assigning similar nucleotides or amino acid sequences to each other in nucleic acid or amino acid sequences. The table assignment of the relevant position is called alignment. Another available algorithm in the prior art is the FASTA algorithm. Sequence comparison (alignment), particularly multiple sequence comparison, is created using a computer program. For example, the Clustal series (see, for example, Chenna et al. (2003): "Multiple sequence alignment with the Clustal series of programs," Nucleic Acid Res. 31: 3497-3500), T-Coffee (see, for example, Notredame et al. (2000): "T-Coffee: A novel method for multiple sequence alignments," J. Mol. Biol., 302: 205-217) or programs based on these programs or algorithms are often used. There are also programs using the computer program Vector Suite 10.3 (Invitrogen Corporation, 1600 Faraday Avenue, Carlsbad, California, USA) using specified standard parameters for sequence comparison (alignment), wherein the AlignX module for sequence comparison is based on ClustalW or Clone Manager 10 (using the scoring matrix BLOSUM 62 for amino acid level sequence alignment). Unless otherwise stated, the sequence identities indicated herein are determined using the BLAST algorithm.

[0113] Such comparison also allows to draw conclusions about the similarity of the compared sequences to each other. It is usually given as a percentage identity, i.e. the ratio of the same nucleotide or amino acid group in the same position or corresponding position in the comparison. In the case of amino acid sequences, the broader concept of homology takes into account conservative amino acid exchanges, i.e. amino acids with similar chemical activity, because these amino acids usually play similar chemical activities in proteins. Therefore, the similarity of the compared sequences can also be expressed as a percentage homology or percentage similarity. Identity and / or homology information about the entire polypeptide or gene or only about individual regions can be provided. Therefore, the homology or identical regions of different nucleic acids or amino acid sequences are defined by sequence matching. These regions usually have the same function. They can be very small and contain only a few nucleotides or amino acids. Generally, these small regions play a vital function for the overall activity of the protein. Therefore, it may be advantageous to associate sequence matching only with individual optional small regions. However, unless otherwise specified, the identity or homology information in this application relates to the entire length of the indicated specific nucleic acid or amino acid sequence.

[0114] In the context of the present invention, the indication that an amino acid position corresponds to a numerically designated position in SEQ ID NO:1 therefore means that the corresponding position is related to the numerically designated position in SEQ ID NO:1 in the alignment as defined above. In addition, the assignment of the positions is based on the mature protein. This assignment is also particularly useful when the amino acid sequence of the protease according to the invention comprises a higher number of amino acid groups than the protease according to SEQ ID NO:1. Starting from the stated positions in the amino acid sequence of the protease according to SEQ ID NO:1, the altered positions in the protease according to the invention are those positions which are assigned to the stated positions in the alignment. In the present application, unless otherwise indicated, the numbering of any sequence variations is based on the numbering according to SEQ ID NO:3.

[0115] In addition to the amino acid changes described above, the protease according to the present invention can also have other amino acid changes, particularly amino acid substitutions, insertions or deletions. Such proteases are, for example, developed by targeted genetic modification, i.e., by mutagenesis methods, and are optimized for specific purposes of use or specific characteristics (e.g., with respect to its catalytic activity, stability, etc.). In addition, nucleic acids according to the present invention can be introduced into recombinant methods and are therefore used to produce brand-new proteases or other polypeptides. The purpose is to introduce targeted mutations in known molecules, such as substitutions, insertions or deletions, so as to, for example, improve the cleaning performance of the enzyme according to the present invention. For this purpose, the surface charge and / or isoelectric point of the molecule can be particularly changed, thereby changing their interaction with the substrate. For example, the net charge of the enzyme can be changed to affect substrate binding, particularly for washing and detergents. Alternatively or additionally, the stability or catalytic activity of the protease can be increased by one or more corresponding mutations, thereby improving its cleaning performance. The favorable properties of individual mutations (e.g., individual substitutions) can complement each other. Therefore, in the context of the present invention, additional development can be performed for certain characteristics (e.g., with respect to its stability during storage) The optimized protease.

[0116] For the description of substitutions (amino acid exchanges) involving exactly one amino acid position, the following convention is adopted herein: first, the naturally occurring amino acid is mentioned in the form of the internationally used single-letter code, then the relevant sequence position and finally the inserted amino acid. Several or alternative exchanges within the same polypeptide chain are separated by slashes. Thus "130D / V" means that position 130 has been mutated to D or V. In the case of an insertion, the additional amino acid is named according to the sequence position. In the case of a deletion, the missing amino acid is replaced by a symbol (e.g. an asterisk or a dash) or Δ is indicated before the corresponding position. For example, P9T describes a substitution of the proline at position 9 by threonine, P9TH describes an insertion of a histidine after the amino acid threonine at position 9, and P9* or ΔP9 describes a deletion of the proline at position 9. This nomenclature is known to those skilled in the art in the field of enzyme technology.

[0117] In addition to the active protease protein, the second detergent composition also comprises a liquid carrier as another necessary component. The weight proportion of the liquid carrier relative to the total weight of the second detergent composition is 80 to 96 wt.%, preferably 85 to 95 wt.%, especially 85 to 90 wt.% based on the total weight of the second detergent composition.

[0118] The aqueous carrier of the second detergent composition preferably comprises a water-organic solvent mixture. It is particularly preferred to use an organic solvent from the group consisting of ethanol, n-propanol, isopropanol, butanol, ethylene glycol, propylene glycol, butylene glycol, methylpropylene glycol, glycerine, diethylene glycol, propyl diglycol, butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, methoxytriglycol, ethoxytriglycol, butoxytriglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol tert-butyl ether, di-n-octyl ether and mixtures thereof, in particular an organic solvent from the group consisting of propylene glycol, glycerine and ethanol.

[0119] The active protease protein in the second detergent composition can be combined with at least one reversible inhibitor compound selected from the group consisting of polyols, especially glycerol and 1,2-propylene glycol, benzamidine hydrochloride, borax, boric acids, boronic acids or their salts or esters or derivatives, especially phenylboronic acid derivatives or 4-formylphenylboronic acid (4-FPBA), compounds of formula (I) or (II)

[0120]

[0121] wherein R is in each case selected from -COOH, C 1-6 Alkyl substituted or unsubstituted C 2-6 Dicarboxylic acid, C 1-6 Alkyl substituted or unsubstituted C 2-6 Carboxylic acid and -OOC-NR 2 2, where R 2 The same or different and selected from C 1-6 Alkyl or H, and salts, esters or derivatives thereof, preferably benzoic acid, phenylmalonic acid, benzylmalonic acid, phenylsuccinic acid, benzylsuccinic acid, methyl 3-benzoylpropionate, (S)-3-phenylbutyric acid and benzyl carbamate, and combinations thereof, to further improve the stability of the protease in detergents and cleaners.

[0122] The term "phenylboronic acid derivatives" is understood to mean compounds of formula (III).

[0123]

[0124] Where R is hydrogen, hydroxyl group, C 1-6 Alkyl groups, substituted C 1-6 Alkyl group, C 1-6 Alkenyl or substituted C 1-6Preferably, the functional group R in the phenylboronic acid derivative is C 1-6 Alkyl groups, among which -CH3, -CH3CH2 or -CH3CH2CH2 are more preferred. More preferably, the functional group R in the phenylboronic acid derivative is hydrogen. Particularly preferably, the phenylboronic acid derivative is 4-formylphenylboronic acid (4-FPBA).

[0125] The reversible inhibitor compound used may be a boronic acid.

[0126] The reversible inhibitor compound used may be a compound of formula (I) or (II).

[0127]

[0128] wherein R is in each case selected from the group consisting of -COOH, C 1-6 Alkyl substituted or unsubstituted C 2-6 Dicarboxylic acid, C 1-6 Alkyl substituted or unsubstituted C 2-6 Carboxylic acid and -OOC-NR 2 2 groups, where R 2 The same or different and selected from C 1-6 The alkyl group or H, and salts, esters or derivatives thereof, and combinations thereof, are preferably selected from the group consisting of benzoic acid, phenylmalonic acid, benzylmalonic acid, phenylsuccinic acid, benzylsuccinic acid, methyl 3-benzoylpropionate, (S)-3-phenylbutyric acid and benzylcarbamate.

[0129] The second detergent composition preferably contains essentially no boron-containing compounds. "Essentially free of boron-containing compounds" in this context means that the second detergent composition contains less than 2 wt.%, preferably less than 1 wt.%, more preferably less than 0.5 wt.%, and particularly preferably less than 0.1 wt.% of boron-containing compounds based on its total weight. In a very particularly preferred embodiment, the second detergent composition contains no boron-containing compounds, i.e. in particular it does not contain any boron-containing compounds, in particular no boric acid and / or phenylboronic acid derivatives.

[0130] In step e) of the method, the second detergent composition is preferably metered from a container integrated in the washing machine, which container contains a multiple of the amount of second detergent composition required for carrying out the washing program.

[0131] In step e), the second detergent composition is preferably metered in such a way that it is introduced into the aqueous liquid within 5 minutes, particularly preferably within 2 minutes and in particular within 1 minute.

[0132] In step e), the aqueous liquid preferably has a temperature of 26 to 64°C.

[0133] In a preferred embodiment of the method, no bleaching agent or detergent composition containing bleaching agent is introduced into the laundry treatment chamber of the washing machine before step e). It has been shown that metering bleaching agent or detergent composition containing bleaching agent before step e) is detrimental to the cleaning effect or at least irrelevant to the cleaning effect.

[0134] Bleaching agents are particularly understood to be compounds that provide hydrogen peroxide in aqueous media. Among the compounds used as bleaching agents that provide H2O2 in water, sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are particularly important. Other bleaching agents that can be used are, for example, peroxypyrophosphates, citrate perhydrates, and persalts or peracids (e.g., persulfates or persulfuric acid) that provide H2O2. Also useful are urea peroxohydrate percarbamides, which are described by the formula H2N-CO-NH2H2O2. Particularly when the agent is used to clean hard surfaces, for example, for automatic dishwashing, the detergent part unit may also contain bleaching agents from the group of organic bleaches as required, although they can also be used in agents for washing fabrics in principle. Typical organic bleaches are diacyl peroxides, such as dibenzoyl peroxide. Other typical organic bleaches are peroxyacids, wherein alkyl peroxyacids and aryl peroxyacids are particularly mentioned as examples. Preferred representatives are (a) peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, also peroxy-α-naphthoic acid and magnesium monoperphthalate, (b) aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ε-phthalimidoperoxycaproic acid (phthaloiminoperoxyhexanoic acid (PAP)), o-carboxybenzoimidoperoxycaproic acid, N-nonenylamidoperoxycaproic acid (nonenylamidoperoxycaproic acid) (c) aliphatic and araliphatic peroxydicarboxylic acids, for example 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperoxysebacic acid, diperoxytridecanedioic acid, diperoxyphthalic acid, 2-decyldiperoxybutane-1,4-dioic acid, N,N-terephthaloyl-di(6-aminoperhexanoic acid). Preferred oxygen bleaches are formulated in the form of particles, wherein the particles have a coating.

[0135] At 100% t w After the main wash cycle has been completed at a point in time, the aqueous liquid is preferably pumped out of the laundry treatment chamber.

[0136] The compositions of some preferred first and second detergent compositions for use in the process according to the invention can be found in the following table (unless otherwise stated, amounts are given in wt. % based on the total weight of the solid gel or shell material).

[0137]

[0138]

[0139] * wherein the active protease protein has proteolytic activity and comprises an amino acid sequence which over its entire length has at least 70% sequence identity with the amino acid sequence given in SEQ ID NO: 1 and has (i) at least two amino acid substitutions, preferably three amino acid substitutions, selected from the group consisting of amino acid substitutions 3T, 4I, 99E and 199I at at least two positions, preferably three positions corresponding to positions 3, 4, 99 or 199, and (ii) at least two amino acid substitutions, preferably three amino acid substitutions, selected from the group consisting of amino acid substitutions 3T, 4I, 99E and 199I at at least two positions, preferably three positions corresponding to positions 74, 136, 143, 154, 160, 161, 163, 171, 181, 183, 185, 200, 203, 209, 212, or 256, at least one additional amino acid substitution, particularly selected from N74D / E / Q, A136Q, R143L / W / Y, S154D / Q, S160G, Y161T, A163G, V171L, A181D, F183R, Q185R, Q200A / L / S / T, Y203K / V / W, A209K / W, N212S / T and L256D / E / Q.

[0140] This application provides, among other things, the following topics:

[0141] 1. A method for washing textiles in a drum washing machine, comprising the following steps

[0142] a) Provide a washing program for the washing machine, including a duration t w Main wash cycle;

[0143] b) introducing textiles into the laundry treatment chamber of the washing machine;

[0144] c) introducing an aqueous liquid into a laundry treatment chamber of the washing machine;

[0145] d) 0 to 10% t during the main wash cycle w At a time point, introducing a first detergent composition comprising at least one surfactant into a laundry treatment chamber of a washing machine;

[0146] e) 11% to 99% t w At a time point of , a second detergent composition is introduced into the aqueous liquid of the main wash cycle, wherein the second detergent composition comprises, based on the total weight of the second detergent composition,

[0147] i) at least 4 wt.% active protease protein

[0148] ii) at least 80 wt.% of a liquid carrier.

[0149] 2. The washing method according to item 1, wherein the drum washing machine comprises an outer tub, an inner tub attached to the outer tub as a laundry treatment chamber, and a pumping device configured to pump the aqueous liquid out of the outer tub.

[0150] 3. The washing method according to one of the preceding points, wherein the washing program comprises a main washing cycle, at least one rinse cycle and at least one spin cycle.

[0151] 4. The 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.

[0152] 5. The washing method according to one of the preceding points, wherein the duration of the main washing cycle is t w It is 15 to 400 minutes, preferably 30 to 240 minutes, and particularly 60 to 180 minutes.

[0153] 6. The washing method according to one of the preceding points, wherein the aqueous liquid in step c) has a volume of 3 to 40 liters, preferably 6 to 30 liters, in particular 8 to 20 liters.

[0154] 7. Washing method according to one of the preceding points, wherein the aqueous liquid in step c) has a water hardness higher than 14° dH, preferably higher than 17° dH, in particular higher than 21° dH.

[0155] 8. A washing method according to one of the preceding points, wherein the drum washing machine has a device for detecting the water hardness of the aqueous liquid used in step c), wherein the washing program is preferably configured so that the water hardness detected by the device preferably affects the amount of the second detergent composition introduced in step e).

[0156] 9. A washing method according to any of the preceding points, wherein the water hardness of the aqueous liquid introduced into the laundry treatment chamber of the washing machine in step c) is determined by means of a device for determining the water hardness, and the treatment parameters are determined by comparing the determined water hardness with reference values ​​and the treatment parameters assigned to these reference values, the treatment parameters being related to the amount of the first or second detergent composition introduced in step d) and / or step e), and the first detergent composition is introduced in step d) and / or the second detergent composition is introduced in step e) in an amount corresponding to the determined treatment parameters.

[0157] 10. Washing method according to one of the preceding points, wherein the water hardness of the aqueous liquid introduced into the laundry treatment chamber of the washing machine in step c) is determined by means of a device for determining the water hardness, and treatment parameters are determined by comparing the determined water hardness with reference values ​​and treatment parameters assigned to these reference values, the treatment parameters being related to the amount of the second detergent composition introduced in step e), and the second detergent composition is introduced in step e) in an amount corresponding to the determined treatment parameters.

[0158] 11. The washing method according to one of the preceding points, wherein the weight ratio of aqueous liquid to textile in step c) is greater than 1:1, preferably greater than 2:1, in particular greater than 5:2.

[0159] 12. A washing method according to one of the preceding points, wherein the drum washing machine has a device for detecting the weight of the textile introduced in step b), wherein the washing program is preferably configured so that the weight of the textile detected by the device affects the amount of the second detergent composition introduced in step e).

[0160] 13. Washing method according to one of the preceding points, wherein the aqueous liquid in step c) has a temperature T1 of 18 to 25°C.

[0161] 14. Washing method according to one of the preceding points, wherein the aqueous liquid is introduced into the laundry treatment chamber of the washing machine before the first detergent composition.

[0162] 15. Washing method according to one of the preceding points, wherein the aqueous liquid is introduced into the laundry treatment chamber of the washing machine simultaneously with the first detergent composition.

[0163] 16. Washing method according to one of the preceding points, wherein the aqueous liquid is introduced into the laundry treatment chamber of the washing machine after the first detergent composition.

[0164] 17. The washing method according to any one of the preceding points, wherein the first detergent composition contains, based on its total weight,

[0165] i) 50 to 95 wt.% of a surfactant

[0166] ii) less than 10 wt.% water.

[0167] 18. The washing method according to one of the preceding points, wherein the first detergent composition contains 55 to 92 wt.%, preferably 60 to 88 wt.% of surfactant, based on its total weight.

[0168] 19. The washing method according to any one of the preceding points, wherein the first detergent composition contains 8-18Anionic surfactants of the alkylbenzenesulfonic acid group.

[0169] 20. The washing method according to one of the preceding points, wherein the first detergent composition contains an anionic surfactant from the group of alkyl ether sulfonic acids.

[0170] 21. The washing method according to one of the preceding points, wherein the first detergent composition contains an anionic surfactant from the group of fatty acids.

[0171] 22. The washing method according to one of the preceding points, wherein the first detergent composition contains 30 to 90 wt.%, preferably 40 to 80 wt.%, in particular 45 to 70 wt.% of anionic surfactant based on its total weight.

[0172] 23. The washing method according to one of the preceding points, wherein the first detergent composition contains a nonionic surfactant from the group of ethoxylated C6-18 primary alcohols, preferably ethoxylated C6-18 primary alcohols with a degree of alkoxylation ≥ 2, particularly preferably C12-14 alcohols with 4EO or 7EO, C9-11 alcohols with 7EO, C13-15 alcohols with 5EO, 7EO or 8EO, C13-15 oxo alcohols with 7EO, C12-18 alcohols with 5EO or 7EO, in particular C12-18 fatty alcohols with 7EO or C13-15 oxo alcohols with 7EO.

[0173] 24. The washing method according to one of the preceding points, wherein the first detergent composition contains 7 to 50 wt.%, preferably 12 to 40 wt.%, in particular 15 to 30 wt.% of a nonionic surfactant based on its total weight.

[0174] 25. A washing method according to one of the preceding points, wherein the first detergent composition contains a polyalkoxylated amine having a weight average molecular weight Mw in the range of 600 g / mol to 10,000 g / mol, which is obtained by reacting ammonia or a primary alkylamine or hydroxyalkylamine having a molecular weight of less than 200 g / mol with an alkylene oxide, preferably in a weight ratio of 0.5 to 10 wt.%, preferably 1 to 8 wt.%, in particular 2 to 6 wt.%.

[0175] 26. The washing method according to one of the preceding points, wherein the first detergent composition contains a polyalkoxylated polyalkyleneimine obtainable by reacting a polyalkyleneimine with an alkylene oxide, preferably in a weight ratio of 0.5 to 10 wt.%, preferably 1 to 8 wt.%, in particular 2 to 6 wt.%.

[0176] 27. The washing method according to one of the preceding points, wherein the first detergent composition contains less than 6 wt.%, in particular less than 2 wt.% of water.

[0177] 28. The washing method according to one of the preceding points, wherein the first detergent composition contains 0.5 to 29 wt.%, preferably 4.5 to 27 wt.%, in particular 10 to 24 wt.% of organic solvent, based on its total weight.

[0178] 29. The washing method according to one of the preceding points, wherein the first detergent composition contains an organic solvent from the class of organic amines, preferably monoethanolamine.

[0179] 30. A washing method according to any one of the preceding points, wherein the first detergent composition contains based on its total weight

[0180] i) 30 to 90 wt.%, preferably 40 to 80 wt.%, in particular 45 to 70 wt.% of C 8-18 Anionic surfactants from the group of alkylbenzenesulfonic acid, alkylethersulfonic acid and fatty acid,

[0181] ii) 7 to 50 wt.%, preferably 12 to 40 wt.%, in particular 15 to 30 wt.% of ethoxylated C 6-18 Nonionic surfactants of primary alcohol group,

[0182] iii) 0.5 to 29 wt.%, preferably 4.5 to 27 wt.%, in particular 10 to 24 wt.% of an organic solvent from the group consisting of organic amines,

[0183] iv) less than 10 wt.%, preferably less than 6 wt.%, in particular less than 2 wt.% of water.

[0184] 31. The washing method according to one of the preceding points, wherein the first detergent composition does not contain enzymes.

[0185] 32. Washing method according to one of the preceding points, wherein in step d) the first detergent composition is metered from a container integrated in the washing machine, which container contains a multiple of the amount of first detergent composition required for running a washing program.

[0186] 33. A washing method according to one of the preceding points, wherein in step d), at 0t w At a certain point in time, the first detergent composition is introduced into the laundry treatment chamber of the washing machine.

[0187] 34. The washing method according to one of the preceding points, wherein in step d), at >0 to 10% t w , preferably >0 to 5% tw The first detergent composition is introduced into the laundry treatment chamber of the washing machine at a time point of

[0188] 35. The washing method according to one of the preceding points, wherein the second detergent composition comprises 4 to 18 wt.%, preferably 5 to 15 wt.%, in particular 7 to 12 wt.% of active protease protein based on its total weight.

[0189] 36. A washing method according to any of the preceding points, wherein the active protease protein has proteolytic activity and comprises an amino acid sequence which, over its entire length, has at least 70% sequence identity with the amino acid sequence given in SEQ ID NO: 1 and, in each case based on the numbering according to SEQ ID NO: 1, has (i) at least two amino acid substitutions, preferably three amino acid substitutions selected from the group consisting of amino acid substitutions 3T, 4I, 99E and 199I at at least two positions, preferably three positions corresponding to positions 3, 4, 99 or 199, and (ii) at least two amino acid substitutions, preferably three amino acid substitutions, selected from the group consisting of amino acid substitutions 3T, 4I, 99E and 199I at at least two positions, preferably three positions corresponding to positions 74, 136, 143, 154, 160, 161, 163, 171, 181, 183, 185, 200, 203, 209, 212 or 213. At least one additional amino acid substitution is made at at least one position of 56, particularly an amino acid substitution selected from the group consisting of N74D / E / Q, A136Q, R143L / W / Y, S154D / Q, S160G, Y161T, A163G, V171L, A181D, F183R, Q185R, Q200A / L / S / T, Y203K / V / W, A209K / W, N212S / T and L256D / E / Q.

[0190] 37. The washing method according to one of the preceding points, wherein the second detergent composition comprises 80 to 96 wt.%, preferably 85 to 95 wt.%, in particular 85 to 90 wt.% of the liquid carrier, based on its total weight.

[0191] 38. The washing method according to one of the preceding points, wherein the second detergent composition comprises a water-organic solvent mixture as liquid carrier.

[0192] 39. The washing method according to any one of the preceding points, wherein the liquid carrier of the second detergent composition comprises an organic solvent from the following group: ethanol, n-propanol, isopropanol, butanol, ethylene glycol, propylene glycol, butylene glycol, methylpropylene glycol, glycerol, diethylene glycol, propyl diglycol, butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, methoxytriglycol, ethoxytriglycol, butoxytriglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol tert-butyl ether, di-n-octyl ether and mixtures thereof, preferably from the group of propylene glycol, glycerol and ethanol.

[0193] 40. The washing method according to one of the preceding points, wherein the second detergent composition is substantially free of boron-containing compounds, and preferably free of boron-containing compounds.

[0194] 41. Washing method according to one of the preceding points, wherein in step e) the second detergent composition is metered from a container integrated in the washing machine, which container contains several times the amount of the second detergent composition required for running a washing program.

[0195] 42. The washing method according to one of the preceding points, wherein in step e), at 20% to 70% t w time point, preferably between 25% and 65% t w time point, particularly preferably between 30% and 60% t w The second detergent composition is introduced into the aqueous liquid at a point in time.

[0196] 43. The washing method according to one of the preceding points, wherein in step e), the second detergent composition is introduced into the aqueous liquid within five minutes, particularly preferably within 2 minutes, in particular within 1 minute.

[0197] 44. Washing method according to one of the preceding points, wherein the aqueous liquid in step e) has a temperature of 26 to 64°C.

[0198] 45. The washing method according to one of the preceding points, wherein no bleaching agent and no detergent composition containing bleaching agent are introduced into the laundry treatment chamber of the washing machine before step e).

Claims

1. A method for washing textiles in a drum washing machine, wherein The following steps are included a) Provide a washing program for the washing machine, including a duration t w Main wash cycle; b) introducing textiles into the laundry treatment chamber of the washing machine; c) introducing an aqueous liquid into a laundry treatment chamber of the washing machine; d) 0 to 10% t during the main wash cycle w At a time point, introducing a first detergent composition comprising at least one surfactant into a laundry treatment chamber of a washing machine; e) 11% to 99% t w At a time point of , a second detergent composition is introduced into the aqueous liquid of the main wash cycle, wherein the second detergent composition comprises, based on the total weight of the second detergent composition, i) at least 4 wt.% active protease protein, ii) at least 80 wt.% of a liquid carrier.

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

3. Washing method according to one of the preceding claims, wherein the aqueous liquid in step c) has a water hardness higher than 14° dH, preferably higher than 17° dH, in particular higher than 21° dH.

4. Washing method according to one of the preceding claims, wherein the water hardness of the aqueous liquid introduced into the laundry treatment chamber of the washing machine in step c) is determined by means of a device for determining the water hardness, and treatment parameters are determined by comparing the determined water hardness with reference values ​​and the treatment parameters assigned to these reference values, the treatment parameters being related to the amount of the second detergent composition introduced in step e), and the second detergent composition is introduced in step e) in an amount corresponding to the determined treatment parameters.

5. A washing method according to claim 1, wherein the first detergent composition contains, based on its total weight, i) 50 to 95 wt.% of a surfactant, ii) Less than 10 wt.% water.

6. A washing method according to claim 1, wherein the first detergent composition comprises, based on its total weight, i) 30 to 90 wt.%, preferably 40 to 80 wt.%, in particular 45 to 70 wt.% of C 8-18 Anionic surfactants from the group of alkylbenzenesulfonic acid, alkylethersulfonic acid and fatty acid, ii) 7 to 50 wt.%, preferably 12 to 40 wt.%, in particular 15 to 30 wt.% of ethoxylated C 6-18 Nonionic surfactants of primary alcohol group, iii) 0.5 to 29 wt.%, preferably 4.5 to 27 wt.%, in particular 10 to 24 wt.% of an organic solvent from the group consisting of organic amines, iv) less than 10 wt.%, preferably less than 6 wt.%, in particular less than 2 wt.% of water.

7. Washing method according to one of the preceding claims, wherein in step d) the first detergent composition is metered from a container integrated in the washing machine, which container contains a multiple of the amount of first detergent composition required for running a washing program.

8. Washing method according to one of the preceding claims, wherein the second detergent composition comprises 4 to 18 wt.%, preferably 5 to 15 wt.%, in particular 7 to 12 wt.% of active protease protein, based on its total weight.

9. The washing method according to claim 1 , wherein the active protease protein has proteolytic activity and comprises an amino acid sequence which has at least 70% sequence identity over its entire length to the amino acid sequence given in SEQ ID NO: 1 and has (i) at least two amino acid substitutions, preferably three amino acid substitutions selected from the group consisting of amino acid substitutions 3T, 4I, 99E and 199I at at least two positions, preferably three positions corresponding to positions 3, 4, 99 or 199, and (ii) at least one amino acid substitution at at least one position corresponding to positions 74, 136, 143, 154, 160, 161, 163, 171, 181, 183, 185, 200, 203, 209, 212 or 256, Additional amino acid substitutions, in particular amino acid substitutions selected from N74D / E / Q, A136Q, R143L / W / Y, S154D / Q, S160G, Y161T, A163G, V171L, A181D, F183R, Q185R, Q200A / L / S / T, Y203K / V / W, A209K / W, N212S / T and L256D / E / Q, are preferably in an amount of 0.0001 to 1 wt.%, based on the total weight of the washing and cleaning agent.

10. Washing method according to one of the preceding claims, wherein the second detergent composition comprises 80 to 96 wt.%, preferably 85 to 95 wt.%, in particular 85 to 90 wt.% of liquid carrier, based on its total weight.

11. Washing method according to one of the preceding claims, wherein the second detergent composition comprises a water-organic solvent mixture as liquid carrier.

12. The washing method according to one of the preceding claims, wherein the liquid carrier of the second detergent composition comprises an organic solvent from the following group: ethanol, n-propanol, isopropanol, butanol, ethylene glycol, propylene glycol, butylene glycol, methylpropylene glycol, glycerol, diethylene glycol, propyl diglycol, butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, methoxytriglycol, ethoxytriglycol, butoxytriglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol tert-butyl ether, di-n-octyl ether and mixtures thereof, preferably from the group of propylene glycol, glycerol and ethanol.

13. Washing method according to one of the preceding claims, wherein the second detergent composition is substantially free of boron containing compounds, and preferably free of boron containing compounds.

14. Washing method according to one of the preceding claims, wherein in step e) the second detergent composition is metered from a container integrated in the washing machine, which container contains a multiple of the amount of second detergent composition required for running a washing program.

15. The washing method according to claim 1, wherein in step e), at 20% to 70% t w time point, preferably between 25% and 65% t w time point, particularly preferably between 30% and 60% t w The second detergent composition is introduced into the aqueous liquid at a point in time.

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