Textile washing method

Abstract

The invention relates to a method for washing textiles in a drum-type washing machine, having the steps of a) providing a washing machine with a wash program with a duration tw; 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 at a point in time of 1 to 50% of tw; and e) introducing a second detergent composition, comprising, based on the total weight thereof, i) at least 0.0005 wt.% of an active cellulase protein, and ii) at least 40 wt.% of an organic liquid carrier, into the aqueous liquor at a point in time of 50 to 99% tw.

Description

[0001] Henkel AG & Co. KGaA

[0002] ATD / BLO

[0003] May 26, 2025

[0004] “Textile washing process”

[0005] The present invention relates to a textile washing process. In particular, the application relates to a multi-stage machine-based textile washing process in the course of which washing and cleaning active substances are dosed at different times.

[0006] While currently less than a third of humanity has access to a textile washing machine, machine textile cleaning has been the standard procedure for removing dirt and refreshing laundry in some regions of the world since the 1970s.

[0007] Both the machinery and the detergents used in machine-based textile cleaning processes have been continuously developed and improved in terms of performance and environmental footprint over the past decades. While initial development efforts focused on improving individual components of the washing process, such as the washing machine and its mechanics and programs, or the detergent itself, more recently the focus has shifted to improving the interaction between these components.

[0008] International application WO 2012 / 048911 A1 describes a washing process using a textile washing machine, in the course of which the textiles are sprayed with a rinsing solution in a rinsing cycle.

[0009] European patent EP 3 428 336 B1 discloses washing processes with a minimum duration of 110 minutes, in which detergents containing rejuvenating agents are added to the washing liquid.

[0010] The European patent EP 2 711 413 B1 relates to washing processes which are characterized by a time-staggered dosage of different washing-active substances.

[0011] European patent EP 2 566 943 B1 discloses the sensor-controlled, time-delayed dosing of washing-active substances, for example peroxocarboxylic acids, into the interior of a

[0012] Textile washing machine.

[0013] Even in light of previous developments, the technical challenge of improving the washing performance of textile detergents in textile washing machines remains. 2023P00411WG

[0014] 2

[0015] To solve this problem, a washing procedure for textiles in a drum washing machine is suitable, which comprises the following steps: a) providing a washing machine which is set up to carry out a washing program with a duration of tw; b) placing textiles into the washing machine's treatment chamber and starting the washing program with a duration of t w c) Introducing an aqueous solution into the washing machine's treatment chamber; d) Introducing a first detergent composition comprising at least one surfactant into the washing machine's treatment chamber at a time between 1 and 50% t w ; e) Introducing a second detergent composition comprising, based on its total weight, i) at least 0.0005 wt.% active cellulase protein ii) at least 40 wt.% of a liquid organic carrier into the aqueous bath at a time between 50% and 99% tw.

[0016] A washing machine is a motor-driven device for cleaning textiles. Drum washing machines with a drum rotatable about a horizontal axis are particularly preferred. The method according to the invention is especially suitable for implementation in a drum washing machine with a tub, a drum located inside the tub (serving as a laundry treatment chamber), and a draining device designed to pump out aqueous solution from the tub.

[0017] In step a) of the method, a washing machine is provided which is configured to execute a wash program with a duration of tw. Conventional washing machines typically have several pre-programmed wash programs designed for cleaning different textiles, which, in addition to a main wash cycle, may include pre-rinse, rinse, and / or spin cycles. In alternative embodiments of the method, in step a), a washing machine is provided in which wash programs are generated on a case-by-case basis depending on input data, for example, sensor data concerning the amount of laundry and / or the type of textiles and / or the type of stain and / or user preferences.

[0018] Preferred washing programs include a main wash cycle, at least one rinse cycle, and at least one spin cycle.

[0019] Alternative washing programs include at least one pre-wash cycle, one main wash cycle, at least one rinse cycle and at least one spin cycle.

[0020] According to the invention, it is particularly preferred to provide washing programs with a main wash cycle, at least two rinse cycles, and at least one spin cycle. 2023P00411WG

[0021] 3

[0022] Besides the mechanical forces acting on the laundry, the detergent used, and the temperature of the wash liquor, the duration of the wash cycle, especially the main wash cycle, influences the cleaning performance achieved. Preferably, the duration t w The washing program lasts 15 to 400 minutes, preferably 30 to 240 minutes and particularly 60 to 180 minutes.

[0023] With regard to the textile cleaning effect, it has proven particularly advantageous to introduce the first detergent composition into the aqueous liquor during the main wash cycle.

[0024] For textile care, it is advantageous if the washing program includes one rinse cycle and the second detergent composition is introduced into the aqueous solution during this rinse cycle. If the washing program includes two or more rinse cycles, the second detergent composition is preferably introduced into the aqueous solution during the second rinse cycle. Alternatively, in washing programs with two or more rinse cycles, the second detergent composition can also be introduced into the aqueous solution during the final rinse cycle.

[0025] The textiles introduced into the laundry treatment room in step b) can be, for example, pure cotton or synthetic textiles, but also blended fabrics. Preferably, the textiles introduced into the laundry treatment room in step b) consist at least partially of cotton or polyester, since the unexpected cleaning and care effects were particularly noticeable on these textiles.

[0026] The aqueous liquor introduced into the laundry treatment room in step c) preferably has a volume of 3 to 40 l, preferably 6 to 30 l and particularly 8 to 20 l.

[0027] 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.

[0028] In step c), the aqueous liquor preferably has a temperature Ti of 18 to 25°C.

[0029] The first detergent composition is introduced into the laundry treatment chamber in step d) at a time between 1% and 50% of the wash cycle duration (tw). In other words, the first detergent composition is already present in the laundry treatment chamber shortly after the start of the wash program (at 1% tw) or is introduced within a period of 50% of the wash program duration (tw). It has proven particularly advantageous to introduce the first detergent composition into the washing machine's laundry treatment chamber at a time between 1% and 35% tw, preferably between 1% and 20% tw. 2023P00411WG

[0030] 4

[0031] In one process variant, the aqueous solution is introduced into the washing machine's laundry treatment chamber before the first detergent mixture is added. Such a process variant can be implemented, for example, by means of a pre-rinse cycle, during which the textiles are pre-rinsed and / or soaked with water but not yet cleaned with the actual detergent mixture.

[0032] A second method involves the simultaneous introduction of the aqueous liquor and the first detergent composition into the washing machine's treatment chamber. If, for example, the aqueous liquor is dosed into the incoming wash liquor using a dosing device when a pre-rinse cycle is omitted, the introduction of both the aqueous liquor and the first detergent composition into the treatment chamber occurs simultaneously.

[0033] Finally, it is also possible that the aqueous solution is introduced into the washing machine's laundry treatment chamber after the first detergent composition, for example by applying the first detergent composition in pre-portioned form, or by means of a dosing aid, or by means of a dosing device integrated into the washing machine directly onto the textiles before the start of the washing program.

[0034] In step d), the first detergent composition is introduced into the aqueous solution. Although the detergent composition can, in principle, be introduced in a single dose or in portions, it is preferable, with regard to the dissolution behavior and cleaning effect of the first detergent composition, to introduce the total quantity of the first detergent composition into the washing machine's laundry treatment chamber in portions.

[0035] The first detergent composition introduced into the laundry treatment chamber of the washing machine in step d) contains at least one surfactant.

[0036] The surfactant-containing first detergent composition used in step d) is preferably dosed from one or more containers integrated into the washing machine, which is / are filled with several times the amount of the first detergent composition required to carry out a washing program.

[0037] The group of surfactants includes nonionic, anionic, cationic, and amphoteric surfactants. The first detergent composition may comprise one or more of these surfactants. Particularly preferred first detergent compositions contain surfactants from the anionic and nonionic surfactant groups.

[0038] The anionic surfactant is preferably selected from the group comprising C9-13 alkylbenzenesulfonic acids, olefinsulfonic acids, C₆s-alkanesulfonic acids, estersulfonic acids, alk(en)ylsulfonic acids, fatty alcohol ethersulfonic acids, and mixtures thereof. Compositions, 2023P00411WÖ

[0039] 5. Anionic surfactants comprising Cg- alkylbenzenesulfonic acids and fatty alcohol ethersulfonic acids exhibit particularly good dispersing properties. Suitable sulfonic acid-type surfactants include preferably Cg- alkylbenzenesulfonic acids, olefinsulfonic acids (i.e., mixtures of alkene and hydroxyalkanesulfonic acids), and disulfonic acids, such as those obtained, for example, from C12-18 monoolefins with terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Also suitable are Cs-alkanesulfonic acids and the esters of α-sulfofaticial acids (estersulfonates), for example, the α-sulfonated methyl esters of hydrogenated coconut, palm kernel, or tallow fatty acids.

[0040] In particularly preferred washing processes, the first detergent composition contains an anionic surfactant from the group of Cs-15 alkylbenzenesulfonic acids. The use of alkylbenzenesulfonic acids from the group of C9-15 alkylbenzenesulfonic acids, especially Cg-15 alkylbenzenesulfonic acids, is particularly preferred.

[0041] Alternatively, but preferably in combination with the alkylbenzenesulfonic acid, the first detergent composition comprises an anionic surfactant from the group of alkyl ethersulfonic acids.

[0042] Preferably, alkyl ethersulfonic acids with the formula Ri-O-(AO) are used. n -SO3H

[0043] Ri represents a linear or branched, substituted or unsubstituted alkyl group, preferably a linear, unsubstituted alkyl group, and particularly preferably a fatty alcohol group. Preferred groups Ri are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, and eicosyl groups and mixtures thereof, with those having an even number of carbon atoms being preferred. Particularly preferred groups Ri are derived from fatty alcohols with 12 to 18 carbon atoms, for example, coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl, or stearyl alcohol, or from oxo alcohols with 10 to 20 carbon atoms.

[0044] AO stands for an ethylene oxide (EO) or propylene oxide (PO) group, preferably for an ethylene oxide group. The index n in the formula is an integer from 1 to 50, preferably from 1 to 20, and particularly from 2 to 10. Most preferably, n is 2, 3, 4, 5, 6, 7, or 8.

[0045] As a further optional component, which is preferably present in the first detergent composition in combination with the aforementioned alkylbenzenesulfonic acids and alkyl ethersulfonic acids, the first detergent composition contains an anionic surfactant from the group of fatty acids. Particularly preferred fatty acids are selected from the group consisting of caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, and mixtures thereof. 2023P00411WG

[0046] 6

[0047] Preferred first detergent compositions used in step d) of the process contain, based on their total weight, 30 to 90 wt.%, preferably 40 to 80 wt.%, and particularly 45 to 70 wt.% anionic surfactant. The weight fraction of the anionic surfactant is determined, irrespective of the degree of neutralization of the anionic surfactant in the first detergent composition, as the weight fraction of the anionic surfactant acid.

[0048] As a further optional component, the first detergent composition contains a non-ionic surfactant, preferably a non-ionic surfactant from the group of ethoxylated primary C6-18 alcohols, preferably the ethoxylated primary C6-18 alcohols with a degree of alkoxylation > 2, particularly preferably the C12-14 alcohols with 4 EO or 7 EO, the C9-11 alcohols with 7 EO, the C13-15 alcohols with 5 EO, 7 EO or 8 EO, the C13-15 oxo alcohols with 7 EO, the C12-18 alcohols with 5 EO or 7 EO, in particular the C12-18 fatty alcohols with 7 EO or the C13-15 oxo alcohols with 7 EO.

[0049] Preferred first detergent compositions used in step d) of the process contain, based on their total weight, 7 to 50 wt.%, preferably 12 to 40 wt.% and in particular 15 to 30 wt.% non-ionic surfactant.

[0050] As a further preferred optional component, the first detergent composition comprises at least one enzyme preparation, preferably at least two enzyme preparations of enzymes from the group lipase, amylase, protease and mannanase.

[0051] According to the invention, it is preferred if the first detergent composition contains at least one lipase preparation. Preferred lipases according to the invention are selected from at least one enzyme of the group consisting of triacylglycerol lipase (EC 3.1.1.3), lipoprotein lipase (EC 3.1.1.34), and monoglyceride lipase (EC 3.1.1.23).

[0052] Preferred lipase preparations according to the invention are the commercial products marketed by Amano Pharmaceuticals under the names Lipase M-AP10®, Lipase LE®, and Lipase F® (also Lipase JV®). Lipase F® is naturally present, for example, in Rhizopus oryzae. Lipase M-AP10® is naturally present, for example, in Mucor javanicus.

[0053] 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, B. amyloliquefaciens, and B. stearothermophilus, as well as their improved formulations for use in detergents or cleaning agents. The enzyme from B. licheniformis is available from Novozymes under the trade name Termamyl® and from Genencor under the trade name Purastar®ST. Further developments of these α-amylases are available from Novozymes under the trade names Duramyl® and Termamyl®ultra, and from Genencor under the name 2023P00411WG.

[0054] 7

[0055] Purastar®OxAm and Keistase® are available from Daiwa Seiko Inc., Tokyo, Japan. The α-amylase from *B. amyloliquefaciens* is marketed by Novozymes under the name BAN®, and derivatives of the α-amylase from *B. stearothermophilus* are marketed under the names BSG® and Novamyl®, also by Novozymes. Examples of α-amylases from other organisms include the further developments of α-amylase from *Aspergillus niger* and *A. oryzae*, available from Novozymes under the trade names Fungamyl®.

[0056] According to the invention, it is preferred if the first detergent composition contains at least one protease as an enzyme. A protease is an enzyme that cleaves peptide bonds by hydrolysis. According to the invention, each of the enzymes from class EC 3.4 falls under this category (comprising each of the thirteen subclasses included therein). According to the invention, “protease activity” is present if the enzyme possesses proteolytic activity (EC 3.4). Various types of protease activity are known: The three main types are: trypsin-like, wherein cleavage of the amide substrate occurs along the amino acids Arg or Lys at P1; chymotrypsin-like, wherein cleavage occurs along the amino acids Arg or Lys at P1; and elastase-like, wherein cleavage of the amide substrate occurs along the amino acid Ala at P1.

[0057] The first detergent composition contains a mannanase preparation as a preferred ingredient.

[0058] A mannanase catalyzes the hydrolysis of 1,4-beta-D-mannosidic bonds in mannans, galactomannans, glucomannan, and galactoglucomannan. These mannanases are classified as EC 3.2.1.78 according to enzyme nomenclature.

[0059] An enzyme preparation comprises, in addition to the actual enzyme protein, other components such as enzyme stabilizers, carrier materials, or fillers. The enzyme protein typically constitutes only a fraction of the total weight of the enzyme preparation. Preferably, enzyme preparations contain between 0.1 and 40 wt.%, preferably between 0.2 and 30 wt.%, more preferably between 0.4 and 20 wt.%, and most preferably between 0.8 and 10 wt.% of the enzyme protein. In such compositions, an enzyme stabilizer may be present in an amount of 0.05 to 35 wt.%, preferably 0.05 to 10 wt.%, based on the total weight in the enzyme composition.

[0060] Protein concentration can be determined using established methods, such as the BCA method (bicinchoninic acid; 2,2'-bicinolyl-4,4'-dicarboxylic acid) or the biuret method. The determination of the active protein concentration is carried out by titration of the active sites using a suitable irreversible inhibitor (for proteases, for example, phenylmethylsulfonylfluoride (PMSF)) and determination of the residual activity. 2023P00411WG

[0061] 8

[0062] The first detergent composition and the second detergent composition preferably differ with respect to the enzymes they contain. Preferably, the first detergent composition is in particular free of active cellulase protein.

[0063] As a preferred optional active ingredient, a builder is further introduced into the aqueous bath in step d). Preferred washing processes are characterized in that the first detergent composition contains a builder from the group of hydroxyalkane and / or aminoalkane phosphonates, preferably from the group of aminoalkane phosphonates and in particular from the group of ethylenediaminetetramethylenephosphonate (EDTMP) and diethylenetriaminepentamethylenephosphonate (DTPMP), especially from the group of diethylenetriaminepentamethylenephosphonate (DTPMP).

[0064] Alternatively to the hydroxyalkane and / or aminoalkane phosphonates described above, or in combination with them, the first detergent composition in a further preferred embodiment contains a structural material from the group of aminocarboxylic acids and their salts, particularly preferably from the group consisting of methylglycine diacetic acid (MGDA) and its salts, glutamic diacetic acid (GLDA) and its salts, ethylenediamine diacetic acid (EDDS) and its salts, iminodisuccinic acid (IDS) and its salts, and iminodiacetic acid (IDA) and its salts.

[0065] A group of optional components of the first detergent composition consists of polyalkoxylated amines with a weight-average molecular weight (Mw) in the range of 600 g / mol to 10,000 g / mol, which are obtainable by reacting ammonia or primary alkyl or hydroxyalkylamines having a molecular weight below 200 g / mol with alkylene oxides. The weight fraction of these polyalkoxylated amines in 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.%.

[0066] Preferred polyalkoxylated amines have a weight-average molecular weight Mw in the range of 1300 g / mol to 6000 g / mol, particularly from 1400 g / mol to 4500 g / mol. (The mean molecular weights given here and subsequently, if applicable, for other polymers, are weight-average molecular weights Mw, which can generally be determined by gel permeation chromatography using an Rl detector, the measurement being expediently carried out against an external standard.)) For their preparation, one can start with ammonia, a monoalkylamine, a monoalkyl monoalkanolamine, a monoalkyl dialkanolamine, or a mono-, di-, or trialanolamine, for example, triethanolamine, methyl-, ethyl-, propyl-, and isopropyldiethanolamine, methyl-, ethyl-, propyl-, and isopropyldiisopropanolamine, 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, in a known manner, using an alkylene oxide, in particular selected from the group consisting of ethylene oxide, propylene oxide, and butylene oxide. and mixtures thereof, is reacted, in particular with a mixture containing propylene oxide and 2023P00411WG.

[0067] 9. Preferably ethylene oxide, particularly preferably with propylene oxide. The polyalkoxylated amines thus obtained can be block or random structures. Particularly preferred is, among others, a polyalkoxylated amine obtainable by propoxylation of triethanolamine, preferably with a length of 15 propylene oxide units for each of the three side arms. Also preferred is a polyalkoxylated amine obtainable by propoxylation of triisopropanolamine, preferably with a length of 15 propylene oxide units for each of the three side arms. Also suitable are polyalkoxylated monoalkylamines with a linear, branched, or cyclic alkyl group, wherein alkoxylation is performed with an alkylene oxide selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, and mixtures thereof, preferably with a mixture containing propylene oxide, particularly preferably with propylene oxide.A polyalkoxylated amine obtainable by propoxylation of tert-butylamine is also preferred, preferably with a length of the two side arms of 12 propylene oxide units each.

[0068] Preferred polyalkoxylated amines satisfy the general formula, in the R for a linear, optionally branched or optionally cyclic alkyl group with 1 to 12 C atoms or a group -(CH2CHR'O) n -(CH2CHR“O) m -H stands,

[0069] R' and R" independently represent H, CH3 or CH2CH3, n, n' and n" independently represent numbers from 0 to 30, preferably from 0 to 10 and particularly from 0 to 5, and m, m' and m" independently represent numbers from 0 to 30, preferably from 5 to 20 and particularly from 12 to 16, provided that the sum n + n' + n" + m + m' + m" is at least 14, preferably in the range of 18 to 100 and particularly in the range of 20 to 70. Preferably, in the compounds of formula I, at least one of the residues R' and R" is a CHs group.

[0070] As a further optional component, the first detergent composition contains a polyalkoxylated polyalkylenemine, which is obtainable by reacting polyalkylenemines with alkylene oxides, wherein weight fractions of the total weight of the first detergent composition of 0.5 to 10 wt.%, preferably of 1 to 8 wt.% and particularly of 2 to 6 wt.% are preferred.

[0071] The polyalkoxylated polyalkylenemine is a polymer with a polyalkylenemine backbone bearing polyalkoxy groups at the nitrogen atoms. It preferably has a weight-average molecular weight (Mw) in the range of 5000 g / mol to 60000 g / mol, particularly from 10000 g / mol to 22500 g / mol. The polyalkylenemine has primary amino groups at its ends and preferably both secondary and tertiary amino groups in its interior; optionally, it may also have only secondary amino groups in its interior, so that a branched-chain structure is not formed. 2023P00411WG

[0072] 10, but rather a linear polyalkylenemine. The ratio of primary to secondary amino groups in the polyalkylenemine is preferably in the range of 1:0.5 to 1:1.5, particularly in the range of 1:0.7 to 1:1. The ratio of primary to tertiary amino groups in the polyalkylenemine is preferably in the range of 1:0.2 to 1:1, particularly in the range of 1:0.5 to 1:0.8. Preferably, the polyalkylenemine has a weight-average molecular weight in the range of 500 g / mol to 50,000 g / mol, particularly from 550 g / mol to 2,000 g / mol. The nitrogen atoms in the polyalkylenemine are preferably separated from each other by alkylene groups with 2 to 12 carbon atoms, particularly 2 to 6 carbon atoms, whereby not all alkylene groups need to have the same number of carbon atoms. Ethylene groups, 1,2-propylene groups, 1,3-propylene groups, and mixtures thereof are particularly preferred.The primary amino groups in the polyalkylenemine can bear one or two polyalkoxy groups, and the secondary amino groups one polyalkoxy group, although not every amino group needs to be alkoxy substituted. The average number of alkoxy groups per primary and secondary amino group in the polyalkoxylated polyalkylenemine is preferably 5 to 100, and more particularly 10 to 50. The alkoxy groups in the polyalkoxylated polyalkylenemine are preferably ethoxy, propoxy, or butoxy groups, or mixtures thereof. Polyethoxylated polyethyleneimines are particularly preferred. The polyalkoxylated polyalkylenemines are accessible by reacting the polyalkylenemines with the epoxides corresponding to the alkoxy groups. If desired, the terminal OH function of at least some of the polyalkoxy substituents can be replaced by an alkyl ether function with 1 to 10, in particular 1 to 3, carbon atoms.

[0073] For use in the washing process according to the invention, detergent compositions with the lowest possible proportion of inactive ingredients are preferably provided. Consequently, it is preferred if the first detergent composition contains less than 10 wt.%, preferably less than 6 wt.%, and particularly less than 2 wt.% water. With a decreasing proportion of inactive ingredients, not only does the amount of resources required for packaging, storage, and transport of the first detergent composition decrease, but the volume of the first detergent composition used per washing process also decreases, thus increasing the range of a supply container, for example, a supply container integrated into the washing machine.

[0074] In step e), the second detergent composition is added to the aqueous solution. The second detergent composition differs from the first detergent composition. It differs from the first detergent composition in terms of the active ingredients it contains.

[0075] The second detergent composition used in step e) is preferably dosed from one or more containers integrated into the washing machine, which contain several times the amount of the second detergent composition required to carry out a wash program.

[0076] Detergent composition is filled. 2023P00411WG

[0077] 11

[0078] The second detergent composition comprises, based on its total weight, i) at least 0.0005 wt.% active cellulase protein; ii) at least 40 wt.% of a liquid organic carrier.

[0079] Cellulases are proteins capable of hydrolyzing 1,4-β-D-glucosidic bonds in cellulose. Synonymous terms for cellulases found in the literature include endoglucanase, endo-1,4-β-glucanase, carboxymethylcellulase, endo-1,4-β-D-glucanase, β-1,4-glucanase, β-1,4-endoglucanhydrolase, celludextrinase, and avicelase.

[0080] Suitable cellulases (endoglucanases, EG) according to the invention include, for example, fungal endoglucanase (EG)-rich compositions offered by Novozymes under the trade name Celluzyme®. The products Endolase® and Carezyme®, also available from Novozymes, are based on the 50 kDa EG and 43 kDa EG from Humicola insolens DSM 1800, respectively. Other usable commercial products from this company are Cellusoft®, Renozyme®, and Celluclean®. Also suitable are, for example, cellulases available from AB Enzymes, Finland, under the trade names Ecostone® and Biotouch®, which are at least partially based on the 20 kDa EG from Melanocarpus. Other cellulases from AB Enzymes are Econase® and Ecopulp®. Further suitable cellulases are derived from Bacillus sp. CBS 670.93 and CBS 669.93, the latter being from Bacillus sp. CBS 670.93 is available from Danisco / Genencor under the trade name Puradax®. Other usable commercial products from Danisco / Genencor are "Genencor detergent cellulase L" and IndiAge®Neutra.

[0081] In preferred washing processes, the second detergent composition contains 0.0005 to 8 wt.% active cellulase protein, preferably 0.001 to 4 wt.% active cellulase protein.

[0082] Washing processes in which the aqueous liquor has a cellulase concentration of 1 to 1500 ppb, preferably 1 to 500 ppb and particularly 1 to 50 ppb, following step e) have proven to be particularly advantageous from a technical standpoint.

[0083] Preferably, the second detergent composition contains an enzyme from the esterase group, preferably from the polyesterase group. The use of esterases, in particular polyesterases, has proven advantageous with regard to the textile-conditioning effect of the washing process.

[0084] In a further preferred embodiment, the second detergent composition contains an enzyme from the group of hexosaminidases, preferably from the group of β-hexosaminidases. 2023P00411WG

[0085] 12

[0086] 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.

[0087] Polypeptides with hexosaminidase activity include dispersins such as dispersin B (DspB), which are β-N-acetylglucosamininidases belonging to the glycoside hydrolase 20 family. Dispersins are produced by the periodontal pathogen Aggregatibacter actinomycetemcomitans, a Gram-negative oral bacterium. Dispersin B is a β-hexosaminidase that specifically hydrolyzes β-1,6-glycosidic bonds of acetylglucosamine polymers. The use of hexosaminidases from the β-hexosaminidase group is preferred.

[0088] An enzyme preparation comprises, in addition to the actual enzyme protein, other components such as enzyme stabilizers, carrier materials, or fillers. The enzyme protein typically constitutes only a fraction of the total weight of the enzyme preparation. Preferably, enzyme preparations contain between 0.1 and 40 wt.%, preferably between 0.2 and 30 wt.%, more preferably between 0.4 and 20 wt.%, and most preferably between 0.8 and 10 wt.% of the enzyme protein. In such compositions, an enzyme stabilizer may be present in an amount of 0.05 to 35 wt.%, preferably 0.05 to 10 wt.%, based on the total weight in the enzyme composition.

[0089] Protein concentration can be determined using established methods, such as the BCA method (bicinchoninic acid; 2,2'-bicinolyl-4,4'-dicarboxylic acid) or the biuret method. The determination of the active protein concentration is carried out by titrating the active sites using a suitable irreversible inhibitor (for proteases, for example, phenylmethylsulfonylfluoride (PMSF)) and determining the residual activity.

[0090] The weight fraction of the liquid organic carrier in the total weight of the second detergent composition is preferably 40 to 95 wt.%, particularly preferably 60 to 90 wt.% and particularly 70 to 85 wt.%.

[0091] Preferred liquid organic carriers are selected from the group of monohydric and polyhydric alcohols, preferably from the group containing glycols, glycol ethers, and polyalkylene glycols. The use of liquid organic carriers from the group containing dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, propylene glycol monobutyl ether, butyl diglycol, methoxytriglycol, ethoxytriglycol, ethylene glycol propyl ether, butoxytriglycol, butyl diglycol acetate, propylene carbonate, and 1,2-butylene carbonate is particularly preferred, especially from the dipropylene glycol group.

[0092] The water content of the second detergent composition is preferably less than 50.

[0093] wt.%, particularly preferably less than 30 wt.% and particularly less than 20 wt.%. 2023P00411WG

[0094] 13

[0095] The rapid and even distribution of the second detergent preparation in the aqueous liquor can be accelerated or improved by the addition of solubilizers.

[0096] In a first process variant, the second detergent composition contains at least one solubilizer from the group consisting of 2-ethylhexyl laurate, 2-ethylhexyl myristate, 2-ethylhexyl palmitate, 2-ethylhexyl cocoate, 2-ethylhexyl stearate, 2-ethylhexyl isostearate, hexyl decyl laurate, hexyl decyl stearate, isopropyl myristate, isopropyl palmitate, isopropyl stearate, isooctyl stearate, isononyl isononanoate, isononyl stearate, isotridecyl nonanoate, 2-octyldodecyl palmitate, isocetyl stearate, in particular from the group consisting of isopropyl palmitate and 2-ethylhexyl palmitate.

[0097] Alternatively or in combination with the solubilizers described above, the second detergent composition may contain at least one solubilizer from the group of cumenesulfonates, preferably from the group of sodium cumenesulfonate and potassium cumenesulfonate.

[0098] As previously explained, the first and second detergent compositions differ in their composition and the active ingredients they contain. In this context, it is preferred to limit the amount of surfactants, builders, and polymers contained in the second detergent composition. Accordingly, preferred second detergent compositions contain less than 10% by weight, more preferably less than 5% by weight, and particularly less than 2% by weight of surfactants, builders, and polymers.

[0099] To improve the fragrance of the washed textiles, the second detergent preparation preferably contains 1 to 32 wt.%, more preferably 5 to 32 wt.%, and particularly 8 to 25 wt.% of a fragrance preparation. When using the same absolute amounts of fragrance preparation, its use in the second detergent preparation has proven superior to its use in the first detergent preparation.

[0100] The textile-care effect of the washing process is enhanced by a sufficiently long drying phase of the textiles at moderate temperatures. For this reason, it is preferred to dry the textiles after the washing program at an ambient temperature of 0 to 40°C. Drying preferably takes place over a period of 2 to 48 hours, particularly preferably 12 to 36 hours.

[0101] This registration will provide, among other things, the following items:

[0102] 1. Washing procedure for textiles in a drum washing machine, comprising the steps a) providing a washing machine with a washing program having a duration of t w b) Introducing textiles into the washing machine's laundry treatment chamber; c) Introducing an aqueous solution into the washing machine's laundry treatment chamber; 2023P00411WG

[0103] 14 d) Introduction of an initial detergent composition comprising at least one surfactant into the laundry treatment chamber of the washing machine at a time between 1 and 50% t w ; e) Introducing a second detergent composition comprising, based on its total weight, i) at least 0.0005 wt.% active cellulase protein ii) at least 40 wt.% of a liquid organic carrier into the aqueous bath at a time between 50% and 99% tw.

[0104] 2. Washing method according to point 1, wherein the drum washing machine comprises a tub, a washing drum located inside the tub as a laundry treatment chamber, and a pumping device designed to pump aqueous liquor out of the tub.

[0105] 3. Washing method according to one of the preceding points, wherein the washing program includes a main wash cycle, at least one rinse cycle and at least one spin cycle.

[0106] 4. Washing method according to one of the preceding points, wherein the washing program includes at least one pre-wash cycle, one main wash cycle, at least one rinse cycle and at least one spin cycle.

[0107] 5. Washing method according to one of the preceding points, wherein the washing program includes a main wash cycle, at least two rinse cycles and at least one spin cycle.

[0108] 6. Washing method according to one of the preceding points, wherein the duration tw of the washing program is 15 to 400 minutes, preferably 30 to 240 minutes and particularly 60 to 180 minutes.

[0109] 7. Washing method according to one of the previous points, wherein the washing program includes a main wash cycle and the first detergent composition is introduced into the aqueous liquor during the main wash cycle.

[0110] 8. Washing method according to one of the previous points, wherein the washing program includes a rinse cycle and the second detergent composition is introduced into the aqueous liquor during the rinse cycle.

[0111] 9. Washing method according to one of the preceding points, wherein the washing program includes two or more rinse cycles and the second detergent composition is introduced into the aqueous liquor during the second rinse cycle.

[0112] 10. Washing method according to any of the preceding points, wherein the washing program comprises two or more rinse cycles and the second detergent composition is introduced into the aqueous liquor during the last rinse cycle. Washing method according to any of the preceding points, wherein the textiles introduced into the laundry treatment chamber in step b) consist at least partially of cotton or polyester. Washing method according to any of the preceding points, wherein the aqueous liquor in step c) has a volume of 3 to 40 l, preferably 6 to 30 l, and particularly 8 to 20 l. Washing method according to any of the preceding points, wherein the weight ratio of aqueous liquor to textiles in step c) is greater than 1:1, preferably greater than 2:1, and particularly greater than 5:2. Washing method according to any of the preceding points, wherein the aqueous liquor is introduced into the laundry treatment chamber of the washing machine before the first detergent composition.Washing method according to any of the preceding points, wherein the aqueous liquor is introduced into the washing machine's treatment chamber simultaneously with the first detergent composition. Washing method according to any of the preceding points, wherein the aqueous liquor is introduced into the washing machine's treatment chamber after the first detergent composition. Washing method according to any of the preceding points, wherein the first detergent composition is introduced into the washing machine's treatment chamber at a concentration of 1 to 35% tw, preferably 1 to 20% tw. Washing method according to any of the preceding points, wherein the first detergent composition contains an anionic surfactant from the group of calcium ether alkylbenzenesulfonic acids. Washing method according to any of the preceding points, wherein the first detergent composition contains an anionic surfactant from the group of alkyl ethersulfonic acids.Washing method according to one of the preceding points, wherein the first detergent composition contains a non-ionic surfactant from the group of ethoxylated primary C6-18 alcohols, preferably ethoxylated primary C6-18 alcohols with a degree of alkoxylation > 2, particularly preferably C12-14 alcohols with 4 EO or 7 EO, C9-11 alcohols with 7 EO, C13-15 alcohols with 5 EO, 7 EO or 8 EO, C13-15 oxo alcohols with 7 EO, C12-18 alcohols with 5 EO or 7 EO, in particular C12-18 fatty alcohols with 7 EO or C13-15 oxo alcohols with 7 EO 2023P00411WG.

[0113] 16

[0114] 21. Washing process according to any of the preceding points, wherein the first detergent composition contains at least one enzyme preparation, preferably at least two enzyme preparations of enzymes from the group lipase, amylase, protease and mannanase.

[0115] 22. Washing method according to any of the preceding points, wherein the first detergent composition comprises a builder from the group of hydroxyalkane and / or aminoalkane phosphonates, preferably from the group of aminoalkane phosphonates and in particular from the group of ethylenediaminetetramethylenephosphonate (EDTMP) and diethylenetriaminepentamethylenephosphonate (DTPMP), in particular from the group of diethylenetriaminepentamethylenephosphonate (DTPMP).

[0116] 23. Washing method according to any of the preceding points, wherein the first detergent composition comprises a structural component from the group consisting of aminocarboxylic acids and their salts, particularly preferably from the group consisting of methylglycine diacetic acid (MGDA) and its salts, glutamic diacetic acid (GLDA) and its salts, ethylenediamine diacetic acid (EDDS) and its salts, iminodisuccinic acid (IDS) and its salts, and iminodiacetic acid (IDA) and its salts.

[0117] 24. Washing process according to any of the preceding points, wherein the first washing composition comprises polyalkoxylated amine having a weight-average molecular weight Mw in the range of 600 g / mol to 10000 g / mol, obtainable by reacting ammonia or primary alkyl or hydroxyalkyl amines having a molecular weight below 200 g / mol with alkylene oxides.

[0118] 25. Washing process according to any of the preceding points, wherein the first detergent composition contains polyalkoxylated polyalkylenemine obtainable by reacting polyalkylenemines with alkylene oxides.

[0119] 26. Washing procedure according to one of the preceding points, wherein the total quantity of the first detergent composition is introduced in portions into the laundry treatment chamber of the washing machine.

[0120] 27. Washing method according to any of the preceding points, wherein the second detergent composition contains 0.0005 to 8 wt.% active cellulase protein, preferably 0.001 to 4 wt.% active cellulase protein.

[0121] 28. Washing process according to any of the preceding points, wherein the aqueous liquor following step e) has a cellulase concentration of 1 to 1500 ppb, preferably 1 to 500 ppb and particularly 1 to 50 ppb.

[0122] 29. Washing method according to any of the preceding points, wherein the second detergent composition contains an enzyme from the group of esterases, preferably from the group of polyesterases. 2023P00411WG

[0123] 17

[0124] 30. Washing method according to one of the preceding points, wherein the second detergent composition contains an enzyme from the group of hexosaminidases, preferably from the group of β-hexosaminidases.

[0125] 31. Washing process according to any of the preceding points, wherein the second detergent composition contains 40 to 95 wt.% wt.%, preferably 60 to 90 wt.% and particularly 70 to 85 wt.% of a liquid organic carrier.

[0126] 32. Washing method according to one of the preceding points, wherein the second washing composition contains a liquid organic carrier from the group of monohydric and polyhydric alcohols, preferably from the group of glycols, glycol ethers and polyalkylene glycols.

[0127] 33. Washing method according to one of the previous points, wherein the second

[0128] Detergent composition includes a liquid organic carrier from the group

[0129] Dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, propylene glycol monobutyl ether, butyl diglycol, methoxytriglycol, ethoxytriglycol, ethylene glycol propyl ether, butoxytriglycol, butyl diglycol acetate, propylene carbonate, 1,2-butylene carbonate, preferably from the group containing dipropylene glycol.

[0130] 34. Washing method according to one of the previous points, wherein the second

[0131] Detergent composition: at least one solubilizer from the group 2- ethylhexyl laurate, 2-ethylhexyl myristate, 2- ethylhexyl palmitate, 2- ethylhexyl cocoate, 2-

[0132] Ethylhexyl stearate, 2-ethylhexyl isostearate, hexyldecyl laurate, hexyldecyl stearate, isopropyl myristate, isopropyl palmitate, isopropyl stearate, isooctyl stearate, isononyl isononanoate, isononyl stearate,

[0133] Contains isotridecyl nonanoate, 2-octyldodecyl palmitate, isocetyl stearate, in particular from the group isopropyl palmitate and 2-ethylhexyl palmitate.

[0134] 35. Washing process according to any of the preceding points, wherein the second washing composition contains at least one solubilizer from the group of cumenesulfonates, preferably from the group of sodium cumenesulfonate and potassium cumenesulfonate.

[0135] 36. Washing method according to any of the preceding points, wherein the second detergent composition contains less than 50 wt.%, preferably less than 30 wt.% and particularly less than 20 wt.% water.

[0136] 37. Washing process according to any of the preceding points, wherein the second detergent composition contains less than 10 wt.%, preferably less than 5 wt.%, and particularly less than 2 wt.%, washing-active substances from the group consisting of surfactants, builders, and polymers. 2023P00411WG

[0137] 18

[0138] Washing method according to one of the preceding points, wherein the second detergent composition further comprises 1 to 32 wt.%, preferably 5 to 32 wt.% and particularly 8 to 25 wt.% of a fragrance preparation.

[0139] 38. Washing method according to one of the preceding points, wherein the first detergent composition in step d) is dosed from one or more containers integrated into the washing machine, which is / are filled with several times the amount of the first detergent composition necessary to carry out a washing program.

[0140] 39. Washing method according to one of the preceding points, wherein the second detergent composition is dosed in step e) from a container integrated into the washing machine, which is filled with several times the amount of the second detergent composition necessary to carry out a washing program.

[0141] 40. Washing procedure according to one of the previous points, wherein the textiles are dried at an ambient temperature of 0 to 40°C following the washing program.

[0142] 41. Washing method according to one of the preceding points, wherein the textiles are dried for a period of 2 to 48 hours, preferably 12 to 36 hours, following the washing program.

[0143] 2023P00411WG

[0144] 19

[0145] Examples

[0146] Washing tests were carried out in a Bosch WAW324DE / 07 8 ​​kg household washing machine using the 30°C cotton wash program. The program is divided into a main wash of approximately 100 minutes, two rinse cycles of approximately 14 minutes each, and a final rinse cycle of 11 minutes followed by an 11-minute spin cycle.

[0147] The 5kg load of laundry had the following composition:

[0148] 1 piece hoodie, light blue Bershka 63% BW 37% PES

[0149] 1 piece hoodie, light blue Pull & Bear 50% BW 50% PES

[0150] 1 piece sweat shirt, dark blue Russel 50% BW 50% PES

[0151] 1 pc. Undershirt, black Götzburg 75% cotton 25% polyester

[0152] 1 pc. undershirt, black ESGE

[0153] 2 T-shirts Mey Software, white Mey 48.5% PA 48.5% Modal 3% EL

[0154] 1 pair of training pants, black, Decathlon, 50% cotton, 47% polyester, 3% elastane

[0155] 2 pcs. T-shirt, white Xpres Sublio 100% PES

[0156] 1 piece Kipsta training pants, black Decathlon 100% PES

[0157] 5 pcs. WfK pillow 30A, white WfK 100% PES

[0158] Stain monitors were added to the laundry line.

[0159] In the main wash cycle of each trial, 31.3 g of a first detergent preparation was manually dosed at the beginning of the cycle. The composition of this first detergent preparation can be found in the following table: In the washing process E1 according to the invention, 1.7 g of a second detergent preparation is dosed with the water inlet at the beginning of the rinse phase of the final rinse cycle. The composition of this first detergent preparation can be found in the following table:

[0160] As a reference to the inventive experiment E1, two further experiments are carried out.

[0161] V1 = Reference detergent preparation in the main wash cycle without any further additives

[0162] V2 = Reference detergent preparation and 1.7g of the second detergent preparation in the main wash cycle

[0163] Each test series comprises 25 identical washing cycles with identical dosages in terms of quantity and timing. After each cycle, the laundry is air-dried on a clothesline for 18 hours. After 5 and 25 cycles, a visual inspection of the dry laundry was carried out by 10 test subjects under standard lighting conditions (daylight white), examining a selection of textiles and the monitors. The test subjects were asked to decide which of the textiles washed under conditions E1, V1, and V2 gave the best impression of cleaning and care. The results of the test subjects' evaluation are presented in the following tables (entry of the comparison winner):

[0164] Evaluation of 5 washes Evaluation of 25 washes

[0165] The results of the two evaluations are summarized in the following table:

Claims

2023P00411WG 22 Patent claims 1. Washing method for textiles in a drum washing machine, comprising the steps a) providing a washing machine with a washing program having a duration t w b) Introducing textiles into the washing machine's treatment chamber; c) Introducing an aqueous solution into the washing machine's treatment chamber; d) Introducing a first detergent composition comprising at least one surfactant into the washing machine's treatment chamber at a time between 1 and 50% t w ; e) Introducing a second detergent composition comprising, based on its total weight, i) at least 0.0005 wt.% active cellulase protein ii) at least 40 wt.% of a liquid organic carrier into the aqueous bath at a time between 50% and 99% tw.

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

3. Washing method according to one of the preceding claims, wherein the washing program comprises a main washing cycle and the first detergent composition is introduced into the aqueous liquor during the main washing cycle.

4. Washing method according to one of the preceding claims, wherein the washing program includes a rinse cycle and the second detergent composition is introduced into the aqueous liquor during the rinse cycle.

5. Washing method according to one of the preceding claims, wherein the washing program comprises two or more rinse cycles and the second detergent composition is introduced into the aqueous liquor during the last rinse cycle.

6. Washing method according to one of the preceding claims, wherein the textiles introduced into the laundry treatment room in step b) consist at least partially of cotton or polyester.

7. Washing method according to one of the preceding claims, wherein the second detergent composition further comprises an enzyme from the group of esterases, preferably from the group of polyesterases.

8. Washing method according to one of the preceding claims, wherein the second detergent composition further comprises an enzyme from the group of hexosaminidases, preferably from the β-hexosaminidases.

9. Washing method according to one of the preceding claims, wherein the second detergent composition contains 40 to 95 wt.% wt.%, preferably 60 to 90 wt.% and particularly 70 to 85 wt.% of a liquid organic carrier.

10. Washing method according to one of the preceding claims, wherein the second detergent composition further comprises 1 to 32 wt.%, preferably 5 to 32 wt.% and particularly 8 to 25 wt.% of a fragrance preparation.

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