Dispersin- and cellulase-containing detergent with improved storage stability

By separating dispersant and cellulase into distinct detergent compositions, the stability of both enzymes is enhanced, maintaining activity and enabling effective cleaning performance.

DE102023212843B4Active Publication Date: 2025-10-30HENKEL KGAA
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Patent Information

Application Number
DE102023212843
Authority / Receiving Office
DE · DE
Patent Type
Patents
Current Assignee / Owner
Filing Date
2023-12-18
Publication Date
2025-10-30
Estimated Expiration
2043-12-18

AI Technical Summary

Technical Problem

Enzymes in detergents, particularly cellulases and dispersants, suffer from limited storage stability due to interactions with other ingredients, especially in liquid formulations, leading to a loss of activity.

Method used

The detergent is divided into two spatially separate compositions, one containing dispersant and the other cellulase, preventing interaction and maintaining enzyme stability during storage.

Benefits of technology

The spatial separation maintains the stability of dispersants, ensuring they retain activity for up to eight weeks at 30°C, allowing for effective cleaning performance when combined during use.

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Abstract

Detergent comprising at least a first and a second detergent composition, characterized in that the first detergent composition comprises a dispersin, the second detergent composition comprises a cellulase, and the first and second detergent compositions are spatially separated from each other.
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Description

field of technology

[0001] The invention relates to a detergent containing dispersin and cellulase with improved storage stability with respect to dispersin activity. The invention also relates to a packaging unit containing the detergent. Current state of the art

[0002] Modern detergents typically contain enzymes to improve cleaning performance. Enzymes are able, for example, to break down soils of biological origin that are difficult to remove with conventional surfactants, thus significantly improving the cleaning power of detergents. Due to their high effectiveness even at low washing temperatures, enzymes also help to reduce energy consumption during washing.

[0003] Typical soils that can be removed by enzymes include proteins, starch and other complex carbohydrates, as well as fats. Different enzymes are used depending on the expected type of soiling. For example, protases break down protein-containing soils, amylases break down starch, mannanases break down carbohydrates from the mannan group, pectin lyases break down carbohydrates from the pectin group, lipases break down fats, dispersins (hexosaminidases) break down biofilms, and cellulases break down cellulose. Detergents usually contain a mixture of these enzymes.

[0004] Cellulases are particularly important in textile washing. They can break down the cellulose fibers protruding from the fabric, thus removing the fuzz on cotton fabrics. This makes dark fabrics appear darker. On lighter fabrics, less dust gets trapped in the fuzz, resulting in less graying and a lighter appearance. These effects are also known as "anti-greying" and "anti-pilling," respectively.

[0005] Another important class of enzymes for textile washing are the dispersins. Dispersins belong to the group of hexosaminidases. They catalyze the hydrolytic cleavage of β-1,6-glycosidic bonds of N-acetylglucosamines. This enables them to break down bacterial deposits (biofilms) and thus increase the cleaning power of detergents against bacterial soiling. Detergents containing dispersins are therefore particularly effective in preventing the formation of unpleasant and persistent odors in textiles.

[0006] One problem with using enzymes in detergents is their limited storage stability. Enzymes are complex macromolecules whose activity depends significantly on their three-dimensional structure. Interactions can occur between the enzymes and other detergent ingredients, leading to a loss of their native three-dimensional structure and thus a loss of enzyme activity. This limited storage stability is particularly pronounced in liquid detergents. Technical task

[0007] The object of the present invention is to provide a detergent containing cellulase and dispersin with improved storage stability with respect to the stability of the enzymes. In particular, the detergent should be suitable for textile washing. Specifically, it should be a storage-stable liquid detergent. Description of the invention

[0008] Surprisingly, it was found that the storage stability of dispersin in detergent compositions is impaired by the presence of cellulase. The invention therefore provides for dividing the detergent into a first and a second detergent composition, wherein the first detergent composition contains dispersin and the second detergent composition contains cellulase, and wherein the first and second detergent compositions are spatially separated from each other so that no interaction occurs between the dispersin and the cellulase during storage.

[0009] One aspect of the invention therefore relates to a detergent comprising at least a first and a second detergent composition, characterized in that the first detergent composition includes a dispersin the second detergent composition includes a cellulase and the first and second detergent compositions are spatially separated from each other.

[0010] Preferably, the dispersin has an amino acid sequence with 60% or more identity to the amino acid sequence according to SEQ ID NO: 1.

[0011] Preferably, the first and / or the second detergent composition each comprise 35% to 70% by weight surfactants, 5 wt.% to 40 wt.% polyols, 0.1 wt.% to 5 wt.% complexing agents, and 20% by weight or less water, based on the total mass of the respective detergent composition.

[0012] Preferably, the first and / or the second detergent composition each comprise an alkylbenzenesulfonic acid, a fatty acid and an alkoxylated fatty alcohol.

[0013] Preferably, the first and / or the second detergent composition each comprise 15% by weight or less water, based on the total mass of the respective detergent composition.

[0014] Preferably, the first and / or the second detergent composition each comprise 2 to 20 wt.% polymers selected from the group of polyethyleneimines, alkoxylated polyethyleneimines, vinylimidazole / vinylpyrrolidone copolymers and propylene glycol terephthalates, based on the total mass of the respective detergent composition.

[0015] Preferably, the first and / or the second detergent composition has a pH value in the range of 7.5 to 9.

[0016] Preferably, the second detergent composition comprises at least one cellulase with a carbohydrate-binding domain.

[0017] Another aspect of the invention relates to a packaging unit with the detergent according to the invention having several separate chambers, wherein a first chamber contains the first detergent composition and a second chamber contains the second detergent composition.

[0018] Preferably, the chambers of the packaging unit are formed from a water-soluble film that encloses the respective detergent composition, in particular a water-soluble film based on a polyvinyl alcohol, an acetalized polyvinyl alcohol or a polyvinyl alcohol copolymer. Advantageous effects of the invention

[0019] The detergent according to the invention exhibits improved storage stability with regard to the stability of the dispersin it contains. The spatial separation of the dispersin in the first detergent composition and the cellulase in the second prevents interaction between the two enzymes during storage. This results in increased stability of the dispersin. Even after storage at temperatures up to 30 °C for a period of up to eight weeks, the dispersin retains sufficient enzymatic activity. This level of activity cannot be achieved when the dispersin and cellulase are stored together in a detergent composition.

[0020] The improved stability of the dispersin also makes it possible, in particular, to provide liquid detergents that are stable over long periods of time and are otherwise difficult to stabilize.

[0021] At the same time, the detergent according to the invention exhibits excellent cleaning performance, since the first and second detergent compositions can be combined immediately before or during the washing process. In this way, the advantages of the dispersin and the cellulase can be utilized together. Due to the dispersin, the detergent has exceptionally good cleaning performance with regard to bacterial contamination, and due to the cellulase, it can refresh the color and reduce the graying of textiles during washing. Description of the embodiments

[0022] The following section describes in detail embodiments of the present invention. However, the present invention is not limited to the following embodiments.

[0023] One aspect of the invention relates to a detergent. The detergent is used for cleaning items. Within the scope of the invention, "items" include, for example, hard surfaces such as stone floors, metal surfaces, glass surfaces, or wooden surfaces, dishes, or products made of fibrous material. In a broader sense, "items" can also include body surfaces, such as hands. The detergent can be, for example, a floor cleaner, a toilet cleaner, a dishwashing liquid, a textile detergent, or a handwashing liquid.

[0024] In one embodiment, the detergent serves as a dishwashing detergent for cleaning all types of dishes and cutlery made of stainless steel, porcelain, glass or plastic.

[0025] In an alternative embodiment, the detergent is used to clean all types of woven, knitted, or crocheted textiles, as well as furs. In particular, the detergent can be used to clean items made of natural and / or synthetic fibers, such as cotton, wool, linen, polyamide, polyester, polyacrylonitrile, or blends thereof. For example, the detergent can be used as a textile detergent to clean laundry, such as clothing, towels, bed linen, blankets, and curtains. In a preferred embodiment, the detergent is a textile detergent.

[0026] Cleaning refers to the removal of soiling from the items being washed. This soiling can include, in particular, solid pigmented dirt such as dust, soot, and metal abrasion; greasy and oily dirt such as skin oil, cooking grease, and lubricating oil; colored dirt such as fruit or plant juice and blood; and water-soluble dirt such as urea, sugar, and salt.

[0027] The detergent is particularly suitable for being diluted with water to create a wash bath, which can be brought into contact with the items to be cleaned in order to loosen and wash away dirt.

[0028] This detergent can be used for both hand and machine washing. It is particularly suitable as a general-purpose detergent for all washing methods and temperatures. It can also be used as a washing aid in conjunction with another general-purpose detergent to enhance its effectiveness. Furthermore, it can be used before or after treatment with another detergent, for example, to loosen soils before a main wash or to impart additional desirable properties to laundry after a main wash, such as shine, a pleasant scent, a soft feel, wrinkle resistance, or reduced static cling.

[0029] A key feature of the detergent according to the invention is that the detergent comprises two spatially separated detergent compositions, which are referred to within the scope of the invention as the first and second detergent compositions, wherein the first detergent composition comprises a dispersin and the second detergent composition comprises a cellulase.

[0030] The dispersin and cellulase used can each be wild-type enzymes or genetically modified versions of wild-type enzymes. Compared to wild-type enzymes, genetically modified versions may exhibit, for example, point mutations, deletions, or insertions. These may include, in particular, truncated versions of wild-type enzymes or fusion proteins consisting of a known enzyme or a fragment thereof and other polypeptides. The first and second detergent compositions may each also contain mixtures of different dispersins or cellulases.

[0031] Within the scope of this invention, a dispersin is defined as an enzyme capable of cleaving terminal N-acetylhexosamines of N-acetyl-β-hexosaminides, in particular N-acetylglucosides and N-acetylgalactosides. Dispersins thus belong to the group of hexosaminidases of class EC 3.2.1.52. In particular, a dispersin within the scope of this invention is defined as an enzyme capable of cleaving the β-1,6-glycosidic bonds of N-acetylglucosamines. Dispersins are able to dissolve bacterial deposits (biofilms) and thus increase the cleaning performance of detergents against bacterial soiling.

[0032] Suitable dispersins include, in particular, the glycosidases of family 20 (Henrissat classification of glycosidases) from Aggregatibacter actinomycetemcomitans, Terribacillus goriensis, or Terribacillus saccharophilus, or genetically modified variants derived from these. Particularly suitable dispersins are described, for example, in WO 2017 / 186936 A1, WO 2017 / 186943 A1, and WO 2020 / 207944 A1.

[0033] In a preferred embodiment, a dispersin is used whose amino acid sequence has an identity of 60% or more, preferably 70% or more, further preferably 80% or more, further preferably 85% or more, further preferably 90% or more, most preferably 95% or more to the amino acid sequence according to SEQ ID NO: 1.

[0034] The dispersin is preferably present in the first detergent composition in an amount of at least 0.0001 wt.%, more preferably at least 0.001 wt.%, and further preferably at least 0.01 wt.%, based on the mass of active dispersin and the total mass of the first detergent composition. In some embodiments, the amount of dispersin in the first detergent composition is preferably 0.0001 wt.% to 5 wt.%, more preferably 0.001 wt.% to 2.5 wt.%, particularly preferably 0.005 wt.% to 1 wt.%, and most preferably 0.01 wt.% to 0.5 wt.%, in each case based on the total mass of active dispersin and the total mass of the first detergent composition.

[0035] To ensure the stability of the dispersin, the first detergent composition does not contain cellulase.

[0036] Within the scope of the invention, cellulase is defined as an enzyme capable of cleaving the glycosidic bonds of cellulose. Cellulases include, in particular, endoglucanases of class EC 3.2.1.4, exoglucanases of classes EC 3.2.1.176 and EC 3.2.1.91, and β-1,4-glucosidases of class EC 3.2.1.21. Preferably, the cellulase is an endoglucanase of class EC 3.2.1.4.

[0037] The second detergent composition can comprise one or more cellulases. In a particularly preferred embodiment, a mixture of an endoglucanase of class EC 3.2.1.4 and at least one other cellulase is used.

[0038] Cellulases comprise at least one catalytic domain (CD) exhibiting hydrolytic activity. Additionally, certain cellulases comprise one or more carbohydrate-binding domains (CBDs), also known as carbohydrate-binding modules (CBMs). In this case, they can also be fusion proteins in which the catalytic domain and the carbohydrate-binding domain are derived from different wild-type proteins. Preferably, the second detergent composition comprises at least one cellulase with a carbohydrate-binding domain, preferably an endoglucanase with a carbohydrate-binding domain.

[0039] A suitable cellulase is, for example, the Cel45A cellulase from Melanocarpus albomyces (GenBank No. QCO31627.1) or a genetically modified variant derived therefrom. Most preferably, the cellulase has an amino acid sequence that is 60% or more, preferably 70% or more, further preferably 80% or more, further preferably 85% or more, further preferably 90% or more, and most preferably 95% or more identical to the amino acid sequence according to GenBank No. QC031627.1, in particular to the subsequence from position 24 to position 220 of the aforementioned amino acid sequence.

[0040] The second detergent composition preferably contains at least 0.0001 wt.%, more preferably at least 0.001 wt.%, and more preferably at least 0.01 wt.% cellulase, based on the mass of active cellulase and the total mass of the second detergent composition. In some embodiments, the amount of cellulase in the second detergent composition is preferably 0.0001 wt.% to 5 wt.%, more preferably 0.001 wt.% to 2.5 wt.%, particularly preferably 0.005 wt.% to 1 wt.%, and most preferably 0.01 wt.% to 0.5 wt.%, in each case based on the total mass of active cellulase and the total mass of the second detergent composition.

[0041] The second detergent composition preferably does not contain dispersin. This not only prevents a dispersin in the second detergent composition from unnecessarily losing its activity, but it has also been found that the presence of dispersin negatively affects the activity of certain cellulases. Therefore, separating dispersin and cellulases also prevents a loss of cellulase activity.

[0042] Within the scope of the invention, the identity between two amino acid sequences is determined by pairwise alignment according to the Needleman-Wunsch algorithm. An exemplary implementation of this algorithm is provided by the European Bioinformatics Institute (EMBL-EBI) (Madeira F, Pearce M, Tivey ARN, et al. “Search and sequence analysis tools services from EMBL-EBI in 2022”, Nucleic Acids Research, 2022). The alignment is calculated using the BLOSUM62 substitution matrix, a gap-open cost of 10, and a gap-extension cost of 0.5. As a measure of identity, the percentage ratio of identical amino acids in the alignment to the total number of opposing amino acids in the alignment is calculated according to the following formula: (Number of identical amino acids in the alignment) / (Total length of the alignment - Number of gaps in the alignment).

[0043] In addition to the enzymes described above, the first and second detergent compositions may contain further components, such as surfactants, solvents, polymers, complexing agents, and other additives. These further components are described in more detail below, whereby the descriptions, unless otherwise stated, refer to both the first and second detergent compositions. Therefore, unless otherwise stated, the term "detergent composition" refers to both the first and second detergent compositions. Unless otherwise stated, the quantities given refer to the total mass of the respective detergent composition. The first and second detergent compositions may have an identical composition—apart from the enzymes described above—or a different composition.Preferably, the first and second detergent compositions have the same composition with respect to the surfactants, complexing agents and solvents.

[0044] In a preferred embodiment, the preferred embodiments described below refer to the first detergent composition because the stability of the dispersin can be ensured, in particular, under the conditions described below.

[0045] The detergent composition preferably comprises at least one surfactant as the surface-active agent. The surfactant enables the effective removal of soils from the items to be cleaned. The surfactant can be selected, in particular, from the group of anionic, nonionic, cationic, and amphoteric surfactants. The detergent composition can comprise a single surfactant or a mixture of different surfactants.

[0046] Preferably, the detergent composition comprises at least one anionic or nonionic surfactant. Particularly preferably, the detergent composition comprises both at least one anionic and at least one nonionic surfactant.

[0047] The total amount of surfactants in the detergent composition is preferably 35 wt.% to 70 wt.%, particularly preferably 38 wt.% to 68 wt.%, most preferably 40 wt.% to 65 wt.%, in each case based on the total mass of the detergent composition.

[0048] Anionic surfactants include, in particular, soaps, alkylbenzenesulfonates, alkanesulfonates, α-olefin sulfonates, α-sulfofatitic acid esters, alkyl sulfates, alkenyl sulfates, alkyl ether sulfates, ether carboxylic acids and carboxylated alkyl polyglycosides.

[0049] The total amount of anionic surfactants is preferably 10 wt.% to 70 wt.%, particularly preferably 15 wt.% to 60 wt.%, most preferably 20 wt.% to 40 wt.%, in each case based on the total mass of the detergent composition.

[0050] Soap is the salt of a fatty acid. The fatty acid can be linear or branched, saturated or unsaturated. Preferably, a linear saturated or unsaturated fatty acid is used. Particularly preferably, it is a linear saturated fatty acid.

[0051] The fatty acid preferably comprises at least 6 carbon atoms, particularly preferably at least 8 carbon atoms, and most preferably at least 10 carbon atoms. Particularly preferably, the fatty acid comprises 6 to 32 carbon atoms, particularly preferably 8 to 28 carbon atoms, further preferably 10 to 18 carbon atoms, and most preferably 12 to 18 carbon atoms. Preferred fatty acids are selected from the group consisting of caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, and mixtures thereof. Lauric acid, myristic acid, palmitic acid, and stearic acid are particularly suitable.

[0052] Soaps exhibit particularly good properties in detergent composition. Therefore, the detergent composition preferably includes soaps in an amount of 1 wt.% to 20 wt.%, particularly preferably 3 wt.% to 15 wt.%, most preferably 5 wt.% to 10 wt.%, in each case based on the total mass of the detergent composition.

[0053] Preferably, the alkyl or alkenyl sulfates used are the sulfuric acid half-esters of saturated or unsaturated fatty alcohols with 12 to 18 carbon atoms. Preferably, alkyl or alkenyl sulfates with 12 to 16 carbon atoms are used.

[0054] The alkyl ether sulfates preferably used are the sulfuric acid half-esters of alkoxylated fatty alcohols. These are preferably ethoxylated or propoxylated fatty alcohols. The fatty alcohols preferably comprise 6 to 22 carbon atoms, particularly preferably 10 to 20 carbon atoms, and most preferably 12 to 18 carbon atoms. The fatty alcohols are preferably alkoxylated with 1 to 20, particularly preferably 1 to 10, and most preferably 2 to 8 repeating units. The alkyl ether sulfates most preferably have the following structural formula. R1-O-(R2-O) n -SO3 - X + , where R1 represents a linear or branched, saturated or unsaturated alkyl group with 6 to 22 carbon atoms, particularly preferably 10 to 20 carbon atoms, most preferably 12 to 18 carbon atoms; R2 represents an alkenyl group with 2 to 4 carbon atoms, particularly preferably 2 or 3 carbon atoms; n represents a number from 1 to 20, particularly preferably 1 to 10, most preferably 2 to 8; and X + for a cation, preferably an alkali metal cation, particularly preferably for K + or Na + stands.

[0055] The detergent composition comprises alkyl ether sulfates preferably in an amount of 1 wt.% to 30 wt.%, particularly preferably 5 wt.% to 25 wt.%, most preferably 10 wt.% to 20 wt.%, in each case based on the total mass of the detergent composition.

[0056] Alkylbenzenesulfonates are preferably compounds with the following structural formula: R1-Ph-SO3 - X + , where R1 represents a linear or branched, saturated or unsaturated alkyl group having 6 to 22 carbon atoms, particularly preferably 10 to 20 carbon atoms, most preferably 12 to 18 carbon atoms; Ph represents a phenyl group; and X + for a cation, preferably an alkali metal cation, particularly preferably for K + or Na + stands.

[0057] A particularly preferred class of alkylbenzenesulfonates has the following structural formula: R2R3CH-Ph-SO3 - X + , where R2 represents a linear or branched, saturated or unsaturated alkyl group with 6 to 22 carbon atoms, particularly preferably 8 to 20 carbon atoms, most preferably 12 to 18 carbon atoms; R3 represents a linear or branched, saturated or unsaturated alkyl group with 1 to 10 carbon atoms, particularly preferably 1 to 5 carbon atoms, most preferably 1 to 3 carbon atoms; Ph represents a phenyl group; and X + for a cation, preferably H + or an alkali metal cation, particularly preferably for K + or Na + Preferably, in this embodiment, the residues R2 and R3 comprise a total of no more than 21 carbon atoms. Particularly preferably, R2 and R3 are linear alkyl residues.

[0058] Alkylbenzenesulfonates exhibit particularly good properties in detergent compositions. The detergent composition therefore preferably includes alkylbenzenesulfonates in an amount of 10 wt.% to 40 wt.%, particularly preferably 15 wt.% to 30 wt.%, most preferably 20 wt.% to 28 wt.%, in each case based on the total mass of the detergent composition.

[0059] Non-ionic surfactants include, in particular, alkoxylated fatty alcohols, such as fatty alcohol ethoxylates or propoxylates, alkoxylated fatty amines, alkoxylated alkanolamines, fatty acid amides, alkoxylated fatty acid amides, polyhydroxy fatty acid amides, alkylphenol polyglycol ethers, amine oxides, alkyl glucosides, alkyl polyglucosides and alkoxylated alkylphenols.

[0060] The total amount of non-ionic surfactants is preferably 10 wt.% to 70 wt.%, particularly preferably 15 wt.% to 60 wt.%, most preferably 20 wt.% to 40 wt.%, in each case based on the total mass of the detergent composition.

[0061] The alkoxylated fatty alcohols preferably used are compounds with the following structural formula: R1-O-(R2-O)nH, wherein R1 represents a linear or branched, saturated or unsaturated alkyl group having 6 to 22 carbon atoms, particularly preferably 10 to 20 carbon atoms, most preferably 12 to 18 carbon atoms; R2 represents an alkenyl group having 2 to 4 carbon atoms, particularly preferably 2 or 3 carbon atoms; and n represents a number from 1 to 20, particularly preferably 3 to 15, most preferably 5 to 10.

[0062] Alkoxylated fatty alcohols exhibit particularly good properties in detergent composition. The detergent composition therefore preferably includes alkoxylated fatty alcohols in an amount of 5% to 40% by weight, particularly preferably 10% to 35% by weight, and most preferably 15% to 30% by weight, in each case based on the total mass of the detergent composition.

[0063] The alkoxylated alkanolamines preferably used are compounds with the following structural formula: (HO-R 1 -O-(R 2 -O) n -R 3 )3-N where the remainders R 1 , R 2 , R 3 Each represents an alkenyl group with 2 to 4 carbon atoms, and n represents a number from 5 to 30, particularly preferably 10 to 25, most preferably 15 to 20. A particularly preferred alkoxylated amine is propoxylated and ethoxylated triethanolamine.

[0064] Alkoxylated alkanolamines exhibit particularly good properties in detergent composition. The detergent composition therefore preferably includes alkoxylated alkanolamines in an amount of 1 wt.% to 20 wt.%, particularly preferably 2 wt.% to 15 wt.%, most preferably 3 wt.% to 10 wt.%, in each case based on the total mass of the detergent composition.

[0065] In a preferred embodiment, the detergent composition comprises 35 wt.% to 70 wt.%, preferably 38 wt.% to 68 wt.%, most preferably 40 wt.% to 65 wt.% anionic and non-ionic surfactants, in each case based on the total mass of the detergent composition.

[0066] In a preferred embodiment, the detergent composition comprises an alkylbenzenesulfonic acid, a fatty acid and an alkoxylated fatty alcohol.

[0067] Amphoteric surfactants include, in particular, betaines, sulfobetaines and imidazoline derivatives, such as cocoamphodiacetate.

[0068] The total amount of amphoteric surfactants in the detergent composition is preferably 0.1 wt.% to 20 wt.%, particularly preferably 1 wt.% to 15 wt.%, further preferably 2 wt.% to 10 wt.%, most preferably 3 wt.% to 7 wt.%, in each case based on the total mass of the detergent composition.

[0069] In one embodiment, the detergent composition does not include amphoteric surfactants.

[0070] Cationic surfactants are, in particular, fatty amine salts and quaternary ammonium compounds.

[0071] Preferably, the detergent composition contains no or only a limited amount of cationic surfactants. Accordingly, the detergent composition preferably contains no more than 10% by weight, particularly preferably no more than 1% by weight, and most preferably no more than 0.1% by weight of cationic surfactants, in each case based on the total mass of the detergent composition.

[0072] In a particularly preferred embodiment, the detergent composition does not include any cationic surfactants.

[0073] The detergent composition may also include at least one complexing agent. Complexing agents are compounds that bind metal ions, especially alkaline earth metal ions such as magnesium or calcium ions.

[0074] The total amount of complexing agents in the detergent composition is preferably 0.1 wt.% to 5 wt.%, preferably 0.25 wt.% to 3 wt.%, most preferably 0.5 wt.% to 2 wt.%, in each case based on the total mass of the detergent composition.

[0075] Complexing agents include, in particular, phosphates, such as diphosphate and triphosphate salts; phosphonic acids, such as 1-hydroxyethene-1,1-diphosphonic acid, amino-tri(methylenephosphonic acid) and diethylenetriaminepentakis(methylenephosphonic acid) (DTPMP); carboxylic acids, especially di- or polycarboxylic acids, such as citric acid, nitrilotriacetic acid (NTA), N-(2-hydroxyethyl)iminodiacetic acid, ethylenediaminetetraacetic acid (EDTA), 1,2,3,4-cyclopentanetetracarboxylic acid, L-glutamic acid-N,N-diacetic acid (GLDA) and methylglycinediacetic acid (MGDA); and ion exchangers, such as polyacrylic acid, poly-(α-hydroxyacrylic acid), poly-[(3-hydroxymethyl)-hexamethylene-1,3,5-tricarboxylic acid]; Poly-[(4-methoxy)-tetramethylene-1,2-dicarboxylic acid], poly-(tetramethylene-1,2-dicarboxylic acid), and silicates.

[0076] In a preferred embodiment, the detergent composition comprises complexing agents selected from the group of phosphonic acids in an amount of 0.1 wt.% to 5 wt.%, preferably 0.25 wt.% to 3 wt.%, most preferably 0.5 wt.% to 2 wt.%, in each case based on the total mass of the detergent composition.

[0077] In a further embodiment, the amount of phosphonates in the detergent composition is limited to 2% by weight or less, preferably 1% by weight or less, and particularly preferably 0.1% by weight or less. In a particularly preferred embodiment, the detergent composition does not include any phosphonates.

[0078] In a particularly preferred embodiment, the detergent composition comprises complexing agents selected from the group consisting of 1-hydroxyethene-1,1-diphosphonic acid, amino-tri(methylenephosphonic acid) and diethylenetriaminepentakis(methylenephosphonic acid) (DTPMP) in an amount of 0.1 wt.% to 5 wt.%, preferably 0.25 wt.% to 3 wt.%, most preferably 0.5 wt.% to 2 wt.%, in each case based on the total mass of the detergent composition.

[0079] In a preferred embodiment, the detergent composition comprises at least one di- or polycarboxylic acid as a complexing agent. In a particularly preferred embodiment, the detergent composition comprises citric acid, 1,2,3,4-cyclopentane tetracarboxylic acid, L-glutamic acid-N,N-diacetic acid (GLDA), methylglycine diacetic acid (MGDA), or mixtures thereof as complexing agents.

[0080] In one embodiment, the detergent composition comprises complexing agents selected from the group consisting of di- or polycarboxylic acids in an amount of preferably 0.1 wt.% to 5 wt.%, preferably 0.25 wt.% to 3 wt.%, most preferably 0.5 wt.% to 2 wt.%, in each case based on the total mass of the detergent composition.

[0081] In one embodiment, the detergent composition comprises complexing agents selected from the group consisting of citric acid, 1,2,3,4-cyclopentane tetracarboxylic acid, L-glutamic acid-N,N-diacetic acid (GLDA), methylglycine diacetic acid (MGDA), or mixtures thereof in an amount of preferably 0.1 wt.% to 5 wt.%, preferably 0.25 wt.% to 3 wt.%, most preferably 0.5 wt.% to 2 wt.%, in each case based on the total mass of the detergent composition.

[0082] The detergent composition also comprises water in a preferred amount of 20 wt.% or less, based on the total mass of the detergent composition. Preferably, the detergent composition comprises 18 wt.% or less water, most preferably 15 wt.% or less water, in each case based on the total mass of the detergent composition.

[0083] The detergent composition may also include at least one other solvent besides water. Other solvents include, in particular, monohydric or polyhydric alcohols, alkanolamines, and glycol ethers.

[0084] The amount of the additional solvent is preferably 5 wt.% to 40 wt.%, preferably 8 wt.% to 30 wt.%, most preferably 10 wt.% to 20 wt.%, in each case based on the total mass of the detergent composition.

[0085] The first and second detergent compositions are preferably liquid. The total amount of water and other solvents is therefore preferably 5% by weight or more, particularly preferably 10% by weight or more, most preferably 15% by weight or more, in each case based on the total mass of the individual detergent compositions.

[0086] In a preferred embodiment, the detergent composition comprises at least one polyhydric alcohol (polyol). Suitable polyols are, in particular, alcohols with two or more OH groups and 2 to 8 carbon atoms. Polyols with 2 or 3 OH groups and 3 to 6 carbon atoms are especially suitable. Particularly suitable polyols include propanediol, especially 1,2-propanediol; butanediol, especially 1,2-butanediol, 1,3-butanediol, and 1,4-butanediol; glycerol; or mixtures thereof.

[0087] The total amount of polyols is preferably 5 wt.% to 40 wt.%, preferably 8 wt.% to 30 wt.%, most preferably 10 wt.% to 20 wt.%, in each case based on the total mass of the detergent composition.

[0088] The total amount of polyols with two or more OH groups and 2 to 8 carbon atoms is preferably 5 wt.% to 40 wt.%, more preferably 8 wt.% to 30 wt.%, most preferably 10 wt.% to 20 wt.%, in each case based on the total mass of the detergent composition.

[0089] In a preferred embodiment, the detergent composition comprises propanediol in an amount of 1 wt.% to 20 wt.%, preferably 2 wt.% to 8 wt.%, and glycerol in an amount of 1 wt.% to 20 wt.%, preferably 5 wt.% to 15 wt.%, each based on the total mass of the detergent composition.

[0090] The detergent composition may also include one or more auxiliary substances. These include, in particular, bleaching agents such as hypochlorite bleach, perborates, percarbonates, perphosphates and percarbamides; whitening agents; enzyme stabilizers, foam inhibitors, corrosion inhibitors, dyes, fragrances and preservatives.

[0091] The excipients include in particular polymers that are used as performance enhancers, such as polyethyleneimines, alkoxylated polyethyleneimines, vinylimidazole / vinylpyrrolidone copolymers and propylene glycol terephthalates.

[0092] Preferably, the detergent composition contains 2 to 20 wt.%, preferably 5 to 15 wt.%, most preferably 6 to 10 wt.% polymers selected from the group consisting of polyethyleneimines, alkoxylated polyethyleneimines, vinylimidazole / vinylpyrrolidone copolymers and propylene glycol terephthalates, each based on the total mass of the detergent composition.

[0093] The detergent composition may also contain enzymes other than the cellulase and dispersin described above. For example, the detergent composition may contain proteases, amylases, lipases, tannases, mannanases, and polyesterases. Preferably, however, at least the first detergent composition does not contain any other enzymes. The other enzymes are preferably included, if at all, in the second detergent composition. Preferably, neither the first nor the second detergent composition contains a protease in order to avoid proteolytic degradation of the dispersin and cellulase.

[0094] The detergent composition preferably has a pH value of 7 to 12, particularly preferably 7.5 to 9, and most preferably 7.5 to 8.5. The pH value is determined at 20 °C. If the detergent composition has too low a water content to reliably determine the pH value, the composition is diluted with water for measurement. The pH value is preferably adjusted by adding a suitable base. Preferably, the detergent composition comprises a base selected from the group consisting of amines, alkali carbonate, and alkali hydroxide, and particularly preferably selected from monoethanolamine, sodium carbonate, and sodium hydroxide.

[0095] Conventional detergents typically contain boric acid or borates to stabilize enzymes. However, according to the present invention, the use of boric acid or borates for enzyme stabilization is not essential. Rather, the invention allows for the elimination of boric acid or borates. In one embodiment, the amount of boric acid and borates in the detergent composition is therefore limited to no more than 1% by weight, preferably no more than 0.5% by weight, more preferably no more than 0.1% by weight, and most preferably no more than 0.01% by weight, in each case based on the total mass of the detergent composition. In a particularly preferred embodiment, the detergent composition does not include boric acid or borates.

[0096] The detergent may comprise, in addition to the first and second detergent compositions, further detergent compositions, each spatially separated from the others. These may have the same composition with regard to surfactants, complexing agents, solvents, and pH value as the detergent compositions described above. Furthermore, the further detergent compositions may contain the excipients described above. In particular, the further detergent compositions may contain additional enzymes not present in the first two detergent compositions, such as proteases, amylases, or mannanases.

[0097] Another essential feature of the invention is that the first and second detergent compositions are spatially separated from each other. This is preferably achieved by the detergent comprising packaging having several chambers, wherein the first and second detergent compositions are contained in spatially separated chambers.

[0098] Another aspect of the invention is therefore a packaging unit with several spatially separated chambers, wherein a first chamber contains the first detergent composition and a second chamber contains the second detergent composition.

[0099] In a preferred embodiment, the chambers of the packaging unit are formed from a water-soluble film that encloses the respective detergent composition. The water-soluble film is thus in direct contact with the detergent composition. When used in a washing process, the water-soluble film dissolves, allowing the individual detergent compositions to be released and mixed during the wash cycle.

[0100] The water-soluble film can comprise one or more structurally different water-soluble polymers. Particularly suitable water-soluble polymers are polymers from the group of (optionally acetalized) polyvinyl alcohols (PVALs) and their copolymers. Preferably, the water-soluble film is based on a polyvinyl alcohol, an acetalized polyvinyl alcohol, or a polyvinyl alcohol copolymer.

[0101] The water-soluble film is preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer with a molecular weight in the range of 10,000 to 1,000,000 g / mol, preferably from 20,000 to 500,000 g / mol, particularly preferably from 30,000 to 100,000 g / mol and particularly from 40,000 to 80,000 g / mol.

[0102] Polyvinyl alcohol or polyvinyl alcohol copolymer is generally produced by hydrolysis of polyvinyl acetate. Preferred polyvinyl alcohols and polyvinyl alcohol copolymers have a degree of hydrolysis of 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol%, and especially 82 to 88 mol%.

[0103] Preferred polyvinyl alcohol copolymers comprise, in addition to vinyl alcohol, an ethylene-unsaturated carboxylic acid, its salt, or its ester. Particularly preferably, such polyvinyl alcohol copolymers contain, in addition to vinyl alcohol, sulfonic acids such as 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS), acrylic acid, methacrylic acid, acrylic acid esters, methacrylic acid esters, or mixtures thereof; among the esters are C 1-4 -Alkyl esters or -hydroxyalkyl esters are preferred. Other suitable monomers include ethylene-unsaturated dicarboxylic acids, such as itaconic acid, maleic acid, fumaric acid, and mixtures thereof.

[0104] Suitable water-soluble films for use are distributed by companies such as MonoSol LLC, for example under the designations M8720, M8310, C8400, or M8900 from Kuraray. Films such as Solublon® PT, Solublon® GA, Solublon® KC, or Solublon® KL from Aicello Chemical Europe GmbH are also suitable.

[0105] The water-soluble films may contain additional active ingredients or fillers, as well as plasticizers and / or solvents, especially water.

[0106] Other active ingredients include, for example, materials that protect the ingredients of the preparation, enclosed by the film material, from degradation or deactivation by light exposure. Antioxidants, UV absorbers, and fluorescent dyes have proven particularly suitable for this purpose.

[0107] Examples of plasticizers that can be used include glycerin, ethylene glycol, diethylene glycol, propanediol, 2-methyl-1,3-propanediol, sorbitol or mixtures thereof.

[0108] To reduce its coefficient of friction, the surface of the water-soluble film of the detergent portion unit can optionally be dusted with fine powder. Sodium aluminosilicate, silicon dioxide, talc, and amylose are examples of suitable powders.

[0109] Preferred water-soluble films are suitable for processing in a thermoforming apparatus.

[0110] The total volume of the packaging unit, including all chambers, is preferably from 12 ml to 30 ml, preferably from 12 ml to 20 ml.

[0111] Preferably, the packaging unit has more than two chambers for holding additional detergent compositions.

[0112] Preferably, at least one of the chambers of the packaging unit is transparent.

[0113] Another aspect of the invention relates to a method for cleaning laundry by bringing the laundry into contact with the detergent described above, wherein the first and second detergent compositions are mixed together during contact. This is preferably a method for textile cleaning.

[0114] In a particularly preferred embodiment, the detergent described above is introduced into the wash liquor of a textile washing machine. In preferred process variants, the detergent is dosed directly into the drum or into the detergent dispenser drawer, if a designated compartment is provided, of the textile washing machine. Particularly preferably, a packaging unit containing the detergent as described above is introduced into the wash liquor.

[0115] The machine washing process preferably takes place at temperatures of 20°C to 60°C, preferably from 30°C to 45°C. Preferred textile washing processes are used for cleaning cotton or wool fabrics. Examples

[0116] The present invention is described in more detail below with reference to examples. However, the present invention is not limited to the following examples.

[0117] Various detergents, each containing one or two detergent compositions, were produced and their storage stability was investigated. Each detergent composition was prepared using the base composition specified in Table 1, with cellulase and / or dispersin added in the amounts shown in Table 2. Table 1: Basic composition of detergents (amounts in wt.%) Alkylbenzenesulfonic acid 27 Ethoxylated fatty alcohol C12-C18 7EO 24 fatty acid 9 Glycerol 11 Propylene glycol 6 Ethoxylated polyethyleneimine, homopolymer, 20EO 7 CP 1-vinylimidazole-1-vinylpyrrolidone 0,5 Polypropylene terephthalate 2 Sodium DTPMP 0,5 Fragrances, dyes, preservatives <2 Enzymes See Table 2 Water rest Table 2: Enzyme component of the individual detergent compositions (amounts in wt.%) detergent 1 2 3 4 Detergent composition 1 2 3 4 5 6 7 Antipilling-Cellulase 1 0,2 0,2 0,2 0,2 Antigraying-Cellulase 2 0,4 0,4 0,4 0,4 Dispersin 0,8 0,8 0,8 0,8 1 “Anti-pilling” cellulase, for example, is available from BASF. 2 “Antigraying” cellulase, for example, is available from Novozymes.

[0118] Detergent 1 is a detergent according to the invention in which dispersin and cellulase are provided in separate detergent compositions. Detergents 2 and 4 are each comparative detergents with two separate detergent compositions, in which the dispersin is combined with one of the two cellulases. Detergent 3 consists of a single detergent composition in which the dispersin is combined with both cellulases.

[0119] To investigate storage stability, the detergent compositions according to Table 2 were stored at room temperature or at 30°C for up to eight weeks, and the dispersin and cellulase activity in the individual compositions was determined immediately after preparation of the composition, after four weeks, and after eight weeks.

[0120] The dispersin activity was determined by photometric measurement of the hydrolysis of a sample substrate. 4-Nitrophenol-N-acetyl-β-D-glucosaminide (pNP-NAG) was used as the sample substrate, the hydrolysis of which can be determined by measuring the absorbance at 405 nm. A sample of each detergent composition was first diluted with water (2 g detergent composition / 40 ml water) and then with reaction solution (2.5 mg / ml pNP-NAG in 45 mM citrate, 0.01% Brij-L23, pH 5.3). Simultaneously, samples with different concentrations of a reference enzyme were prepared. The samples were incubated for 90 minutes at 40 °C with shaking at 300 rpm. After incubation, the reaction was stopped by adding a stop solution (0.6 M sodium carbonate, pH 10.3). Subsequently, the absorbance at 405 nm was determined.The relative enzymatic activity of the detergent samples was determined from the extinction measured at the endpoint in relation to the activity of the enzyme immediately after the detergent composition was prepared.

[0121] Cellulase activity was determined by detecting the cleavage of carboxymethylcellulose (CMC) using standard methods (M. Lever, Anal. Biochem., vol. 47, pp. 273-279, 1972). One sample of each detergent composition was incubated with carboxymethylcellulose solution. The glucose released was reacted with p-hydroxybenzoic acid hydrazide (PAHBAH) to form a stable, yellow complex, which can be detected photometrically at 410 nm. The relative enzymatic activity of the detergent samples was determined based on the absorbance at 410 nm, compared to the enzyme activity immediately after preparation of the detergent composition.

[0122] The measured relative enzyme activities are shown in the following tables. Table 3: Dispersin at room temperature detergent composition 0 weeks 4 weeks 8 weeks 1 1 2 100,0% 87,4% 63,6% 2 3 4 100,0% 68,3% 42,5% 3 5 100,0% 69,4% 53,4% 4 6 7 100,0% 74,6% 58,2% Table 4: Cellulase at room temperature detergent composition 0 weeks 4 weeks 8 weeks 1 1 100,0% 100,0% 100,0% 2 2 3 100,0% 100,0% 100,0% 4 100,0% 100,0% 100,0% 3 5 100,0% 96,1% 97,9% 4 6 100,0% 100,0% 100,0% 7 100,0% 79,9% 87,4% Table 5: Dispersin at 30°C detergent composition 0 weeks 4 weeks 8 weeks 1 1 2 100,0% 66,7% 24,6% 2 3 4 100,0% 52,1% 22,5% 3 5 100,0% 56,4% 22,0% 4 6 7 100,0% 60,0% 19,7% Table 6: Cellulase at 30°C detergent composition 0 weeks 4 weeks 8 weeks 1 1 100,0% 93,6% 94,3% 2 2 3 100,0% 65,7% 90,5% 4 100,0% 93,9% 98,0% 3 5 100,0% 96,8% 91,2% 4 6 100,0% 100,0% 100,0% 7 100,0% 60,5% 46,3%

[0123] The detergent 1 according to the invention, in which the dispersin and the cellulase are used in separate detergent compositions, exhibits the best storage stability in these tests. After both four and eight weeks of storage at room temperature, the dispersin shows a higher residual activity than the comparison detergents 2 to 4, in which the dispersin is used together with one or two cellulases in a detergent composition. This effect is independent of the type of cellulase, since each of the two cellulases has a negative effect on the activity of the dispersin (see detergents 2 and 4). The improved storage stability of the dispersin is also observed at a storage temperature of 30 °C.

[0124] Furthermore, the experiments show that the antipilling cellulase loses activity when used together with dispersin in a composition (detergent composition 7). This effect is less pronounced with the antigraying cellulase (detergent composition 4). Therefore, with the detergent according to the invention, the cellulase activity can also be better preserved in dispersin-sensitive cellulases, and a broader spectrum of cellulases can be used.

Claims

[1] Washing preparation comprising at least a first and a second washing preparation composition, characterized by that the first detergent composition includes a dispersin, the second detergent composition includes a cellulase, and the first and second detergent compositions are spatially separated from each other. [2] Detergent according to claim 1, wherein the dispersin has an amino acid sequence with an identity of 60% or more to the amino acid sequence according to SEQ ID NO:

1. [3] Detergent according to claim 1 or 2, wherein the first and / or the second detergent composition is respectively 35% to 70% by weight surfactants, 5 wt.% to 40 wt.% polyols, 0.1 wt.% to 5 wt.% complexing agents, and comprise 20% by weight or less water, based on the total mass of the respective detergent composition. [4] Detergent according to any one of claims 1 to 3, wherein the first and / or the second detergent composition each comprise an alkylbenzenesulfonic acid, a fatty acid and an alkoxylated fatty alcohol. [5] Detergent according to any one of claims 1 to 4, wherein the first and / or the second detergent composition each comprise 15% by weight or less water, based on the total mass of the respective detergent composition. [6] Detergent according to any one of claims 1 to 5, wherein the first and / or the second detergent composition each comprise 2 to 20 wt.% polymers selected from the group consisting of polyethyleneimines, alkoxylated polyethyleneimines, vinylimidazole / vinylpyrrolidone copolymers and propylene glycol terephthalates, based on the total mass of the respective detergent composition. [7] Detergent according to any one of claims 1 to 6, wherein the first and / or the second detergent composition has a pH value in the range of 7.5 to 9. [8] Detergent according to any one of claims 1 to 7, wherein the second detergent composition comprises at least one cellulase with a carbohydrate-binding domain. [9] Packaging unit with the detergent according to any one of claims 1 to 8 having several separate chambers, wherein a first chamber contains the first detergent composition and a second chamber contains the second detergent composition. [10] Packaging unit according to claim 9, wherein the chambers of the packaging unit are formed from a water-soluble film enclosing the respective detergent composition, in particular a water-soluble film based on a polyvinyl alcohol, an acetalized polyvinyl alcohol or a polyvinyl alcohol copolymer.

Citation Information

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