Detergent containing dispersin and cellulase and improved storage stability
By separating dispersin and cellulase in different compartments of the detergent, the stability of both enzymes is improved, ensuring effective cleaning performance over time.
Patent Information
- Application Number
- EP2024212162
- Authority / Receiving Office
- EP · EP
- Patent Type
- Applications
- Current Assignee / Owner
- Priority Date
- 2023-12-18
- Filing Date
- 2024-11-11
- Publication Date
- 2025-06-25
AI Technical Summary
Enzymes in detergents, particularly cellulase and dispersin, suffer from limited storage stability due to interactions with other ingredients, especially in liquid formulations, leading to a loss of enzymatic activity.
The detergent is divided into two spatially separated compositions, with dispersin in one and cellulase in the other, preventing interaction and maintaining enzyme stability.
The separation method enhances the storage stability of dispersin, allowing it to maintain enzymatic activity for up to eight weeks at temperatures up to 30°C, while preserving the cleaning effectiveness of both enzymes when combined during use.
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Abstract
Description
field of technology
[0001] The invention relates to a dispersin- and cellulase-containing detergent 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, for example, are capable of breaking down biologically derived soils that are difficult to remove with conventional detergents, and can thus significantly improve the cleaning performance of detergents. Due to their high effectiveness even at low washing temperatures, enzymes also help 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 soiling. For example, protases are used to break down protein-containing soils, amylases to break down starch, mannanases to break down carbohydrates from the mannan group, pectate lyases to break down carbohydrates from the pectin group, lipases to break down fats, dispersins (hexosaminidases) to break down biofilms, and cellulases to 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 eliminating the fuzz on cotton fabrics. This makes dark textiles appear darker. In light-colored textiles, less dust remains in the fuzz, causing the fabrics to gray less and appear brighter. These effects are also known as "anti-greying" or "anti-pilling."
[0005] Another important class of enzymes for textile washing are dispersins. Dispersins belong to the group of hexosaminidases. They catalyze the hydrolytic cleavage of β-1,6-glycosidic bonds of N-acetylglucosamines. They are thus able to dissolve bacterial deposits (biofilms) and thus increase the cleaning performance of detergents against bacterial soils. Dispersin-containing detergents can therefore effectively prevent the formation of unpleasant and persistent odors in textiles.
[0006] One problem with the use of enzymes in detergents is their limited storage stability. Enzymes are complex macromolecules whose activity depends largely on their three-dimensional structure. Interactions between the enzymes and the other ingredients in detergents can occur, leading to a loss of the 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 cellulase- and dispersin-containing detergent with improved storage stability with respect to the stability of the enzymes. In particular, the detergent should be suitable for textile washing. In particular, 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
[0009] Detergent composition containing cellulase and wherein the first and second detergent compositions are spatially separated from one another so that there is no interaction between the dispersin and the cellulase during storage.
[0010] 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 comprises a dispersin, the second detergent composition comprises a cellulase, and the first and second detergent compositions are spatially separated from one another.
[0011] Preferably, 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.
[0012] Preferably, the first and / or the second
[0013] Detergent composition 35 wt% to 70 wt% surfactants, 5 wt% to 40 wt% polyols, 0.1 wt% to 5 wt% complexing agents, and 20 wt% or less water, based on the total mass of the respective detergent composition.
[0014] Preferably, the first and / or the second
[0015] Detergent composition each containing an alkylbenzenesulfonic acid, a fatty acid and an alkoxylated fatty alcohol.
[0016] Preferably, the first and / or the second
[0017] Detergent composition in each case 15 wt% or less of water, based on the total mass of the respective detergent composition.
[0018] Preferably, the first and / or the second
[0019] Detergent composition in each case 2 to 20 wt.% of 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.
[0020] Preferably, the first and / or second detergent composition has a pH in the range of 7.5 to 9.
[0021] Preferably, the second detergent composition comprises at least one cellulase having a carbohydrate binding domain.
[0022] A further aspect of the invention relates to a packaging unit with the detergent according to the invention with a plurality of separate chambers, wherein a first chamber contains the first detergent composition and a second chamber contains the second detergent composition.
[0023] Preferably, 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. Advantageous effects of the invention
[0024] The detergent according to the invention has improved storage stability with regard to the stability of the dispersin it contains. The spatial separation of dispersin in the first detergent composition and cellulase in the second detergent composition prevents interaction between the two enzymes during storage. This leads to increased stability of the dispersin. The dispersin still exhibits sufficient enzymatic activity even after storage at temperatures of up to 30°C for a period of up to eight weeks. This activity cannot be achieved if dispersin and cellulase are stored together in a detergent composition.
[0025] The improved stability of the dispersin also makes it possible to provide storage-stable liquid detergents that would otherwise be difficult to stabilize.
[0026] 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 cellulase can be utilized jointly. Due to the dispersin, the detergent exhibits exceptionally good cleaning performance with respect to bacterial contamination, and due to the cellulase, it can refresh the color and reduce graying of textiles during textile washing. Description of the embodiments
[0027] Embodiments of the present invention will be described in detail below. However, the present invention is not limited to the following embodiments.
[0028] One aspect of the invention relates to a detergent. The detergent serves to clean laundry. For the purposes of the invention, laundry includes, for example, hard surfaces such as stone floors, metal surfaces, glass or wooden surfaces, dishes, or products made of fiber material. In the broadest sense, the laundry can also be body surfaces, such as the hands. The detergent can be, for example, a floor cleaner, a toilet cleaner, a dishwashing detergent, a fabric detergent, or a handwashing detergent.
[0029] 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.
[0030] In an alternative embodiment, the detergent is used to clean all types of woven, knitted, or warp-knitted textiles, as well as furs. In particular, the detergent can be used to clean laundry made of natural and / or synthetic fibers, for example, cotton, wool, linen, polyamide, polyester, polyacrylonitrile, or blends thereof. For example, the detergent is used as a textile detergent for cleaning laundry, such as clothing, towels, bed linen, blankets, and curtains. In a preferred embodiment, the detergent is a textile detergent.
[0031] Cleaning refers to the removal of soiling from the laundry. This soiling can include, in particular, solid pigmented soiling, such as dust, soot, and metal abrasion; greasy and oily soiling, such as skin grease, cooking fat, and lubricating oil; colored soiling, such as fruit or plant juice and blood; and water-soluble soiling, such as urea, sugar, and salt.
[0032] The detergent is particularly suitable for being diluted with water to form a wash bath, which can be brought into contact with the laundry to be cleaned in order to loosen and wash away soiling.
[0033] The detergent can be used for both manual and machine washing. The detergent is particularly suitable as a general-purpose detergent for all washing methods and temperatures. It can also be used as a washing aid together with another general-purpose detergent to extend and / or enhance its effect. It can also be used before or after treatment with another detergent, for example, to remove soiling before a main wash cycle or to impart further desirable properties to the laundry after a main wash cycle, such as shine, pleasant smell, pleasant feel, crease resistance, or low static charge.
[0034] An essential feature of the detergent according to the invention is that the detergent comprises two spatially separated detergent compositions, which are referred to in the invention as first and second detergent compositions, wherein the first detergent composition comprises a dispersin and the second detergent composition comprises a cellulase.
[0035] The dispersin and cellulase used can each be wild-type enzymes or genetically modified variants of wild-type enzymes. Genetically modified variants can, for example, contain point mutations, deletions, or insertions compared to wild-type enzymes. These can, in particular, be shortened (truncated) variants of wild-type enzymes or fusion proteins composed of a known enzyme or a fragment thereof and other polypeptides. The first and second detergent compositions can each also contain mixtures of different dispersins or cellulases.
[0036] For the purposes of this invention, dispersin refers to an enzyme capable of cleaving terminal N-acetylhexosamines of N-acetyl-β-hexosaminides, particularly N-acetylglucosides and N-acetylgalactosides. Dispersins thus belong to the group of hexosaminidases of class EC 3.2.1.52. For the purposes of this invention, dispersin refers in particular to an enzyme capable of cleaving the β-1,6-glycosidic bonds of N-acetylglucosamines. Dispersins are capable of dissolving bacterial deposits (biofilms) and thus increasing the cleaning performance of detergents against bacterial soils.
[0037] Suitable dispersins are in particular the glycosidases of family 20 (classification of glycosidases according to Henrissat) from Aggregatibacter actinomycetemcomitans, Terribacillus goriensis or Terribacillus saccharophilusor genetically modified variants derived therefrom. Particularly suitable dispersins are described, for example, in WO 2017 / 186936 A1, WO 2017 / 186943 A1, and WO 2020 / 207944 A1.
[0038] In a preferred embodiment, a dispersin is used whose amino acid sequence has an identity of 60% or more, preferably 70% or more, more preferably 80% or more, more preferably 85% or more, more preferably 90% or more, most preferably 95% or more to the amino acid sequence according to SEQ ID NO: 1.
[0039] The dispersin is preferably present in the first detergent composition in an amount of at least 0.0001 wt.%, preferably at least 0.001 wt.%, more 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.%, preferably 0.001 wt.% to 2.5 wt.%, more preferably 0.005 wt.% to 1 wt.%, 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.
[0040] To ensure the stability of the dispersin, the first detergent composition does not contain cellulase.
[0041] For the purposes of the invention, cellulase refers to 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. The cellulase is preferably an endoglucanase of class EC 3.2.1.4.
[0042] The second detergent composition may 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.
[0043] Cellulases comprise at least one catalytic domain (CD) exhibiting hydrolytic activity. In addition, certain cellulases comprise one or more carbohydrate-binding domains (CBD), also referred to as carbohydrate-binding modules (CBM). In this case, they can also be fusion proteins in which the catalytic domain and the carbohydrate-binding domain are each 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.
[0044] A suitable cellulase is, for example, Cel45A cellulase from Melanocarpus albomyces(GenBank No. QCO31627.1) or a genetically modified variant derived therefrom. It is most preferably a cellulase 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 GenBank No. QCO31627.1, in particular to the partial sequence from position 24 to position 220 of said amino acid sequence.
[0045] The second detergent composition preferably contains at least 0.0001 wt.%, preferably at least 0.001 wt.%, more preferably at least 0.01 wt.% of 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.%, preferably 0.001 wt.% to 2.5 wt.%, more preferably 0.005 wt.% to 1 wt.%, 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.
[0046] The second detergent composition preferably does not contain dispersin.
[0047] This not only prevents a dispersin in the second detergent composition from unnecessarily losing its activity. It has also been found that the presence of dispersin negatively affects the activity of certain cellulases. Thus, separating dispersin from cellulases can also prevent a loss of cellulase activity.
[0048] In the context of the invention, the identity between two amino acid sequences is determined by pairwise alignment using 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).
[0049] In addition to the enzymes described above, the first and second detergent compositions may comprise further components, for example surfactants, solvents, polymers, complexing agents, and other auxiliaries. These further components are described in more detail below, whereby, unless otherwise stated, the statements refer to both the first and second detergent compositions. Unless otherwise stated, the term "detergent composition" hereinafter refers to both the first and second detergent compositions. Unless otherwise stated, the quantities 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 surfactants, complexing agents and solvents.
[0050] In a preferred embodiment, the preferred embodiments described below relate to the first detergent composition because the stability of the dispersin can be ensured in particular under the conditions described below.
[0051] The detergent composition preferably comprises at least one surfactant as a detergent-active substance. The surfactant allows for effective removal of soils from the laundry 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.
[0052] The detergent composition preferably comprises at least one anionic or nonionic surfactant. More preferably, the detergent composition comprises both at least one anionic and at least one nonionic surfactant.
[0053] The total amount of surfactants in the detergent composition is preferably 35 wt% to 70 wt%, more 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.
[0054] Anionic surfactants include, in particular, soaps, alkylbenzenesulfonates, alkanesulfonates, α-olefinsulfonates, α-sulfofatty acid esters, alkyl sulfates, alkenyl sulfates, alkyl ether sulfates, ether carboxylic acids and carboxylated alkylpolyglycosides.
[0055] The total amount of anionic surfactants is preferably 10 wt% to 70 wt%, more 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.
[0056] 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. A linear saturated fatty acid is particularly preferred.
[0057] The fatty acid preferably comprises at least 6 carbon atoms, more preferably at least 8 carbon atoms, most preferably at least 10 carbon atoms. The fatty acid particularly preferably comprises 6 to 32 carbon atoms, particularly preferably 8 to 28 carbon atoms, further preferably 10 to 18 carbon atoms, 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.
[0058] Soaps exhibit particularly good properties in detergent compositions. The detergent composition therefore preferably comprises soaps in an amount of 1 wt.% to 20 wt.%, particularly preferably 3 wt.% to 15 wt.%, and most preferably 5 wt.% to 10 wt.%, based in each case on the total mass of the detergent composition.
[0059] Sulfuric acid semiesters of saturated or unsaturated fatty alcohols with 12 to 18 carbon atoms are preferably used as alkyl or alkenyl sulfates. Alkyl or alkenyl sulfates with 12 to 16 carbon atoms are preferred.
[0060] The alkyl ether sulfates used are preferably 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, most preferably 12 to 18 carbon atoms. The fatty alcohols are preferably alkoxylated with 1 to 20, particularly preferably 1 to 10, most preferably 2 to 8 repeating units.The alkyl ether sulfates particularly preferably have the following structural formula R 1 -O-(R 2 -O) n -SO 3- X +< , where R 1 is a linear or branched, saturated or unsaturated alkyl radical having 6 to 22 carbon atoms, particularly preferably 10 to 20 carbon atoms, most preferably 12 to 18 carbon atoms; R 2 is an alkenyl radical having 2 to 4 carbon atoms, particularly preferably 2 or 3 carbon atoms; n is a number from 1 to 20, particularly preferably 1 to 10, most preferably 2 to 8; and X +< is a cation, preferably an alkali metal cation, particularly preferably K +< or Na +<.
[0061] The detergent composition preferably comprises alkyl ether sulfates in an amount of 1 wt% to 30 wt%, more 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.
[0062] As alkylbenzenesulfonates, compounds having the following structural formula are preferably used: R 1 -Ph-SO 3- X +< , where R 1 stands for a linear or branched, saturated or unsaturated alkyl radical having 6 to 22 carbon atoms, particularly preferably 10 to 20 carbon atoms, most preferably 12 to 18 carbon atoms; Ph stands for a phenyl radical; and X +< stands for a cation, preferably an alkali metal cation, particularly preferably K +< or Na +<.
[0063] A particularly preferred class of alkylbenzenesulfonates has the following structural formula: R 2 R 3 CH-Ph-SO 3 -< X +< , where R 2 represents a linear or branched, saturated or unsaturated alkyl radical having 6 to 22 carbon atoms, more preferably 8 to 20 carbon atoms, most preferably 12 to 18 carbon atoms; R 3 represents a linear or branched, saturated or unsaturated alkyl radical having 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, most preferably 1 to 3 carbon atoms; Ph represents a phenyl radical; and X +< represents a cation, preferably H +< or an alkali metal cation, more preferably K +< or Na +<. Preferably, the radicals R 2 and R 3 in this embodiment comprise a total of no more than 21 carbon atoms. R 2 and R 3 are particularly preferably linear alkyl radicals.
[0064] Alkylbenzenesulfonates exhibit particularly good properties in detergent compositions. The detergent composition therefore preferably comprises alkylbenzenesulfonates in an amount of 10 wt.% to 40 wt.%, particularly preferably 15 wt.% to 30 wt.%, and most preferably 20 wt.% to 28 wt.%, based in each case on the total mass of the detergent composition.
[0065] Non-ionic surfactants are 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.
[0066] The total amount of nonionic surfactants is preferably 10 wt% to 70 wt%, more 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.
[0067] As alkoxylated fatty alcohols, preference is given to using compounds having the following structural formula: R 1 -O-(R 2 -O) n -H, where R 1 is a linear or branched, saturated or unsaturated alkyl radical having 6 to 22 carbon atoms, particularly preferably 10 to 20 carbon atoms, most preferably 12 to 18 carbon atoms; R 2 is an alkenyl radical having 2 to 4 carbon atoms, particularly preferably 2 or 3 carbon atoms; and n is a number from 1 to 20, particularly preferably 3 to 15, most preferably 5 to 10.
[0068] Alkoxylated fatty alcohols exhibit particularly good properties in detergent compositions. The detergent composition therefore preferably comprises alkoxylated fatty alcohols in an amount of 5 wt.% to 40 wt.%, particularly preferably 10 wt.% to 35 wt.%, and most preferably 15 wt.% to 30 wt.%, based in each case on the total mass of the detergent composition.
[0069] Alkoxylated alkanolamines which are preferably used are compounds having the following structural formula: (HO-R 1< -O-(R 2< -O) n -R 3< ) 3 -N where the radicals R 1< , R 2< , R 3< each independently of one another represent alkenyl radicals having 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.
[0070] Alkoxylated alkanolamines exhibit particularly good properties in detergent compositions. The detergent composition therefore preferably comprises alkoxylated alkanolamines in an amount of 1 wt.% to 20 wt.%, particularly preferably 2 wt.% to 15 wt.%, and most preferably 3 wt.% to 10 wt.%, based in each case on the total mass of the detergent composition.
[0071] 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% of anionic and nonionic surfactants, in each case based on the total mass of the detergent composition.
[0072] In a preferred embodiment, the detergent composition comprises an alkylbenzenesulfonic acid, a fatty acid and an alkoxylated fatty alcohol.
[0073] Amphoteric surfactants include, in particular, betaines, sulfobetaines and imidazoline derivatives such as cocoamphodiacetate.
[0074] 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.
[0075] In one embodiment, the detergent composition does not comprise amphoteric surfactants.
[0076] Cationic surfactants are in particular fatty amine salts and quaternary ammonium compounds.
[0077] However, the detergent composition preferably comprises no or only a limited amount of cationic surfactants. Accordingly, the detergent composition preferably comprises 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.
[0078] In a particularly preferred embodiment, the detergent composition does not comprise any cationic surfactants.
[0079] The detergent composition may further comprise at least one complexing agent. Complexing agents are compounds that bind metal ions, particularly alkaline earth metal ions such as magnesium or calcium ions.
[0080] 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.
[0081] Complexing agents are 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, in particular 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.
[0082] 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.
[0083] 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, more preferably 0.1% by weight or less. In a particularly preferred embodiment, the detergent composition does not comprise any phosphonates.
[0084] 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.
[0085] 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-cyclopentanetetracarboxylic acid, L-glutamic acid-N,N-diacetic acid (GLDA), methylglycinediacetic acid (MGDA), or mixtures thereof as a complexing agent.
[0086] 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.
[0087] In one embodiment, the detergent composition comprises complexing agents selected from the group consisting of citric acid, 1,2,3,4-cyclopentanetetracarboxylic acid, L-glutamic acid-N,N-diacetic acid (GLDA), methylglycinediacetic acid (MGDA), or mixtures thereof in an amount of preferably 0.1 wt% to 5 wt%, more 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.
[0088] The detergent composition further comprises water in a preferred amount of 20% by weight or less, based on the total mass of the detergent composition. Preferably, the detergent composition comprises 18% by weight or less of water, most preferably 15% by weight or less of water, each based on the total mass of the detergent composition.
[0089] The detergent composition may further comprise at least one other solvent besides water. Other solvents include, in particular, mono- or polyhydric alcohols, alkanolamines, and glycol ethers.
[0090] The amount of the further 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.
[0091] 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, and most preferably 15% by weight or more, based in each case on the total mass of the individual detergent compositions.
[0092] In a preferred embodiment, the detergent composition comprises at least one polyhydric alcohol (polyol). Suitable polyols are, in particular, those alcohols having two or more OH groups and 2 to 8 carbon atoms. Polyols having 2 or 3 OH groups and 3 to 6 carbon atoms are particularly suitable. Suitable polyols include, in particular, propanediol, in particular 1,2-propanediol; butanediol, in particular 1,2-butanediol, 1,3-butanediol, and 1,4-butanediol; glycerol, or mixtures thereof.
[0093] 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.
[0094] The total amount of polyols having two or more OH groups and 2 to 8 carbon atoms 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.
[0095] 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.
[0096] The detergent composition may further comprise one or more adjuvants. These include, in particular, bleaching agents, such as hypochlorite bleach, perborates, percarbonates, perphosphates, and percarbamides; whiteners; enzyme stabilizers, foam inhibitors, corrosion inhibitors, dyes, fragrances, and preservatives.
[0097] The excipients include, in particular, polymers that are used as efficacy enhancers, such as polyethyleneimines, alkoxylated polyethyleneimines, vinylimidazole / vinylpyrrolidone copolymers and propylene glycol terephthalates.
[0098] The detergent composition preferably contains 2 to 20% by weight, preferably 5 to 15% by weight, most preferably 6 to 10% by weight of polymers selected from the group of polyethyleneimines, alkoxylated polyethyleneimines, vinylimidazole / vinylpyrrolidone copolymers and propylene glycol terephthalates, in each case based on the total mass of the detergent composition.
[0099] The detergent composition may also contain further enzymes besides 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 contains no further enzymes. The other enzymes are preferably contained, if at all, in the second detergent composition. Preferably, neither the first nor the second detergent composition contains a protease to avoid proteolytic degradation of the dispersin and cellulase.
[0100] The detergent composition preferably has a pH of 7 to 12, more preferably 7.5 to 9, most preferably 7.5 to 8.5. The pH is determined at 20°C. If the detergent composition has too low a water content to reliably determine the pH, the composition is diluted with water for the measurement. The pH is preferably adjusted by adding a suitable base. The detergent composition preferably comprises a base selected from the group consisting of amines, alkali metal carbonate, and alkali metal hydroxide, more preferably selected from monoethanolamine, sodium carbonate, and sodium hydroxide.
[0101] Conventional detergents usually contain boric acid or boric acid salts (borates) to stabilize enzymes. However, according to the present invention, the use of boric acid or borates is not absolutely necessary for enzyme stabilization. Rather, the invention makes it possible to dispense with the addition 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, 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 comprise boric acid or borates.
[0102] In addition to the first and second detergent compositions, the detergent may comprise further detergent compositions, each of which is spatially separated from the remaining detergent compositions. These may have the same composition with regard to surfactants, complexing agents, solvents, and pH as the detergent compositions described above. Furthermore, the further detergent compositions may contain the auxiliaries described above. The further detergent compositions may, in particular, contain further enzymes not present in the first two detergent compositions, for example, proteases, amylases, or mannanases.
[0103] Another essential feature of the invention is that the first and second detergent compositions are spatially separated from one another. This is preferably achieved by the detergent comprising a package having a plurality of compartments, wherein the first and second detergent compositions are contained in spatially separated compartments.
[0104] A further aspect of the invention is thus a packaging unit with a plurality of spatially separated chambers, wherein a first chamber contains the first detergent composition and a second chamber contains the second detergent composition.
[0105] 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. The water-soluble film dissolves upon use in a washing process, thus allowing the individual detergent compositions to be released and mixed during the wash cycle.
[0106] 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 (PVAL) and their copolymers. The water-soluble film is preferably based on a polyvinyl alcohol, an acetalized polyvinyl alcohol, or a polyvinyl alcohol copolymer.
[0107] The water-soluble film is preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer having a molecular weight in the range from 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 in particular from 40,000 to 80,000 g / mol.
[0108] The 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%.
[0109] Preferred polyvinyl alcohol copolymers comprise, in addition to vinyl alcohol, an ethylenically 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, C 1-4 alkyl esters or hydroxyalkyl esters are preferred. Other suitable monomers include ethylenically unsaturated dicarboxylic acids, for example, itaconic acid, maleic acid, fumaric acid, and mixtures thereof.
[0110] Suitable water-soluble films for use are marketed by MonoSol LLC, for example, under the designation M8720, M8310, C8400, or M8900 from Kuraray. Also suitable are films with the designation Solublon ®< PT, Solublon ®< GA, Solublon ®< KC, or Solublon ®< KL from Aicello Chemical Europe GmbH.
[0111] The water-soluble films may contain additional active ingredients or fillers as well as plasticizers and / or solvents, especially water.
[0112] The group of other active ingredients includes, for example, materials that protect the ingredients of the preparation enclosed in the film material from decomposition or deactivation by light exposure. Antioxidants, UV absorbers, and fluorescent dyes have proven particularly suitable in this regard.
[0113] Plasticizers that can be used include, for example, glycerin, ethylene glycol, diethylene glycol, propanediol, 2-methyl-1,3-propanediol, sorbitol or mixtures thereof.
[0114] To reduce its friction coefficient, the surface of the water-soluble film of the detergent dispenser can optionally be dusted with a fine powder. Sodium aluminosilicate, silicon dioxide, talc, and amylose are examples of suitable dusting agents.
[0115] Preferred water-soluble films are suitable for processing in a thermoforming apparatus.
[0116] The total volume of the packaging unit including all chambers is preferably from 12 ml to 30 ml, preferably 12 ml to 20 ml.
[0117] Preferably, the packaging unit has more than two chambers for accommodating further detergent compositions.
[0118] Preferably, at least one of the chambers of the packaging unit is transparent.
[0119] Another aspect of the invention relates to a method for cleaning laundry by contacting the laundry with the detergent described above, wherein the first and second detergent compositions are mixed with one another during the contacting. This is preferably a method for textile cleaning.
[0120] In a particularly preferred embodiment, the detergent described above is added to the wash liquor of a textile washing machine. In preferred process variants, the detergent is dosed directly into the drum or into the dispenser drawer, if a compartment provided for this purpose, of the textile washing machine. Particularly preferably, a packaging unit containing the detergent as described above is added to the wash liquor.
[0121] The machine textile washing process preferably takes place at temperatures of 20°C to 60°C, preferably 30°C to 45°C. Preferred textile washing processes are used for cleaning cotton or wool fabrics. Examples
[0122] The present invention will now be described in more detail with reference to examples. However, the present invention is not limited to the following examples.
[0123] Various detergents, each with one or two detergent compositions, were prepared and tested for their storage stability. Each detergent composition was prepared using the base composition shown in Table 1, with cellulase and / or dispersin added in the amounts shown in Table 2. Table 1: Basic detergent composition (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 (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< "Antipilling" Cellulase, e.g., available from BASF 2< "Antigraying" Cellulase, e.g., available from Novozymes
[0124] 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 each of 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.
[0125] To investigate the storage stability, the detergent compositions according to Table 2 were each 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 and after eight weeks.
[0126] 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 the respective 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). In parallel, samples with different concentrations of a reference enzyme were prepared. The samples were incubated at 40 °C for 90 minutes while shaking at 300 rpm. After incubation, the reaction was stopped by adding stop solution (0.6 M sodium carbonate, pH 10.3). The absorbance at 405 nm was then determined.From the absorbance measured at the end point, the relative enzymatic activity of the detergent samples was determined in relation to the activity of the enzyme immediately after preparation of the detergent composition.
[0127] Cellulase activity was determined by detecting the cleavage of carboxymethylcellulose (CMC) in a standard manner (M. Lever, Anal. Biochem., vol. 47, pp. 273-279, 1972). A sample of each detergent composition was incubated with carboxymethylcellulose solution. The resulting glucose was reacted with p-hydroxybenzoic acid hydrazide (PAHBAH) to form a stable, yellow complex, which can be detected photometrically at 410 nm. Based on the absorbance at 410 nm, the relative enzymatic activity of the detergent samples was determined in relation to the activity of the enzyme immediately after preparation of the detergent composition.
[0128] 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%
[0129] Detergent 1 according to the invention, in which the dispersin and cellulase are used in separate detergent compositions, demonstrates the best storage stability in these tests. After both four and eight weeks of storage at room temperature, the dispersin exhibits higher residual activity than comparative detergents 2 to 4, in which the dispersin is used together with one or two cellulases in one 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.
[0130] Furthermore, the experiments show that the anti-pilling cellulase loses activity when used together with dispersin in a composition (detergent composition 7). This effect is less pronounced with the anti-graying cellulase (detergent composition 4). Thus, with the detergent according to the invention, cellulase activity can be better preserved even with dispersin-sensitive cellulases, and a broader spectrum of cellulases can be used.
Claims
1. A 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 one another.
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 one of claims 1 or 2, wherein the first and / or the second detergent composition each comprise 35% by weight to 70% by weight of surfactants, 5% by weight to 40% by weight of polyols, 0.1% by weight to 5% by weight of complexing agents, and 20% by weight or less of water, based on the total mass of the respective detergent composition.
4. Detergent according to any one of claims 1 to 5, wherein the first and / or second detergent composition each comprise an alkylbenzenesulfonic acid, a fatty acid and an alkoxylated fatty alcohol.
5. Detergent according to one of claims 1 to 6, wherein the first and / or the second detergent composition each comprise 15% by weight or less of water, based on the total mass of the respective detergent composition.
6. Detergent according to one of claims 1 to 6, wherein the first and / or the second detergent composition each comprise 2 to 20 wt.% of 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.
7. Detergent according to one of claims 1 to 6, wherein the first and / or the second detergent composition has a pH 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 having a carbohydrate binding domain.
9. Packaging unit with the detergent according to one of claims 1 to 8 with a plurality of 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.
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