Cellulase and amylase-containing detergent composition with improved storage stability

Abstract

The invention relates to a detergent composition which can be produced using a first and a second enzyme preparation, wherein the first enzyme preparation comprises a cellulase, and the second enzyme preparation comprises an amylase, characterized in that the first and second enzyme preparations at least 0.5% by weight of the respective enzyme, based on the total mass of active enzyme, at least 45% by weight water and 5% to 45% polyol by weight, based on the total mass of the enzyme preparation. The detergent composition is characterized by improved storage stability.

Description

Field of TechnologyThe invention relates to cellulase- and amylase-containing detergent compositions having improved storage stability, and to the use of cellulase- and amylase-containing enzyme preparations as a constituent of a detergent composition for improving storage stability.Prior ArtModern detergents usually contain enzymes to improve the cleaning performance. Enzymes are, for example, capable of degrading contaminants of biological origin which are difficult to remove with conventional washing-active substances. Because of their high effectiveness even at low wash temperatures, enzymes also contribute to reducing the energy requirement during washing.Typical soils that can be removed by enzymes include proteins, starch and other complex carbohydrates, as well as fats. Depending on the expected contamination, different enzymes are used. Protases serve, for example, for the degradation of protein-containing soils, amylases for the degradation of starch, mannanases for the degradation of carbohydrates from the group of mannans, pectate lyases for the degradation of carbohydrates from the group of pectins, lipases for the degradation of fats, disperseins (hexosaminidases) for the degradation of biofilms, and cellulases for the degradation of cellulose. As a rule, detergents contain a mixture of these enzymes.Cellulases are of particular importance in textile washing. These can break down the cellulose fibers protruding from the textile and thus remove the fluff on cotton materials. As a result, they make a dark textile appear darker.In light textiles, less dust remains caught in the fluff, as a result of which the textiles look less gray and lighter. Amylases are also preferably used in textile washing in order to remove stains from food residues. The combination of cellulases and amylases is thus of particular interest, in particular in textile detergents.One problem with the use of enzymes in detergents is their limited storage stability. Enzymes are complex macromolecules whose activity depends substantially on their three-dimensional structure. Interactions can occur between the enzymes and the other ingredients of detergents, leading to a loss of the native three-dimensional structure and thus to a loss of activity of the enzymes. In addition, enzymes are degraded by proteases optionally contained in the laundry detergent. Often, these processes are accompanied by precipitation of the denatured enzymes, which leads to undesired turbidity of the washing agent.Technical TaskThe object of the present invention is to provide a cellulase- and amylase-containing detergent having improved storage stability with respect to the stability of the enzymes. It is a further object of the invention to provide a laundry detergent with improved cleaning performance in textile washing. In particular, the cleaning performance with respect to blood spots or juice spots is to be improved.DESCRIPTION OF THE INVENTIONSurprisingly, it has been found that the constituents of the amylase- and cellulase-containing enzyme preparations used for producing detergents have an influence on the enzyme stability in the detergents and thus on the storage stability of the detergents. In particular, it has been found that enzyme preparations with a low proportion of polyols are more stable than those with a high proportion of polyol, in particular those with a high proportion of glycerol. Moreover, it has been found that the enzyme preparations mentioned also improve the cleaning performance of the washing agent, in particular with regard to blood stains and juice stains on textiles. This improvement in cleaning performance is particularly pronounced in a laundry detergent additionally comprising a dispersein.One aspect of the invention therefore relates to a laundry detergent composition which can be produced using a first and a second enzyme preparation, wherethe first enzyme preparation comprises a cellulase; andthe second enzyme preparation comprises an amylase, characterized in thatthe first and the second enzyme preparation, respectivelyat least 0.5% by weight of the respective enzyme, based on the total mass of active enzyme,at least 45% by weight of water and5 Weight % to 45 weight % polyolThese are based in each case on the total mass of the enzyme preparation.Preferably, the first and the second enzyme preparation each contain not more than 10% by weight glycerol, in each case based on the total mass of the enzyme preparation.The first and the second enzyme preparation preferably each comprise 5% by weight to 45% by weight of 1,2-propanediol, in each case based on the total mass of the enzyme preparation.The detergent composition preferably comprises the first and the second enzyme preparation in each case in an amount of from 0.01 wt % to 3 wt %, in each case based on the total mass of the enzyme preparation and the total mass of the detergent composition.Preferably, the detergent composition comprises10 From 70% to 70% by weight of surfactants,5 From 50% to 50% by weight of polyols,0,1 % by weight to 5% by weight complexing agent, and50 Weight % or less of water.Preferably, the detergent composition comprises an alkylbenzenesulfonic acid, a fatty acid, an alkoxylated fatty alcohol, and an alkoxylated alkanolamine.Preferably, the detergent composition comprises 15 wt% or less of water.Preferably, the detergent composition comprises a dispersant.A further aspect of the invention relates to the use of a first and a second enzyme preparation as constituents of a laundry detergent composition for improving the storage stability of the laundry detergent composition, wherethe first enzyme preparation comprises a cellulase; andthe second enzyme preparation comprises an amylase, characterized in thatthe first and the second enzyme preparation, respectivelyat least 0.5% by weight of the respective enzyme, based on the total mass of active enzyme,at least 45% by weight of water and5 Weight % to 45 weight % polyolThese are based in each case on the total mass of the enzyme preparation.Preferably, the use serves to improve the cleaning performance of the detergent composition in textile washing with respect to blood and / or juice stains.Advantageous Effects of the InventionThe detergent composition of the present invention has improved storage stability with respect to the stability of the enzymes contained. In particular, little turbidity occurs in the detergent composition of the present invention.Moreover, the detergent composition has improved cleaning performance with respect to soiled fabrics. The detergent composition cleanses blood and juice stains particularly well.DESCRIPTION OF THE EMBODIMENTSHereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.One aspect of the invention relates to a detergent composition. The detergent composition is used for cleaning laundry. Laundry articles referred to in the context of the invention are, for example, hard surfaces, such as stone floors, metal surfaces, glass surfaces or wood 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 composition may be, for example, a floor cleaner, a toilet cleaner, a dishwasher detergent, a textile detergent or a hand detergent.In one embodiment, the detergent composition serves as a dishwashing detergent for cleaning all types of stainless steel, porcelain, glass or plastic tableware.In an alternative embodiment, the detergent composition is for cleaning all types of woven, knitted or knitted fabrics, as well as floats. In particular, the laundry detergent composition can be used for cleaning laundry from natural and / or synthetic fibers, for example from cotton, wool, linen, polyamide, polyester, polyacrylonitrile or mixed fabrics thereof. For example, the detergent composition serves as a textile detergent for cleaning laundry, for example clothes, towel, bed clothes, ceilings and curtain clothes. In a preferred embodiment, the detergent composition is a textile detergent.Cleaning refers to the removal of soiling from the laundry. The soils can be, in particular, solid pigment soils such as dust, carbon black and metal debris, greasy and oily soils such as skin fat, edible fat and lubricating oil, colored soils such as fruit or vegetable juice and blood, and water soluble soils such as urea, sugar and salt.The detergent composition is particularly suitable for dilution with water to a wash bath which can be brought into contact with the laundry to be cleaned in order to remove dirt and to wash it away.The detergent composition can be used in both manual and machine washing. The detergent composition can be used in particular as a heavy-duty detergent for all washing processes and wash temperatures. It can also be used as a washing aid together with another heavy-duty laundry detergent in order to expand and / or enhance its effect. It can also be used before or after treatment with another washing agent, for example in order to dissolve soiling before a main wash cycle or to impart further desirable properties to the laundry after a main wash cycle, such as gloss, pleasant odour, pleasant feel, freedom from wrinkling or low static charge.An essential feature of the detergent composition is that it can be prepared using a first enzyme preparation comprising a cellulase and a second enzyme preparation comprising an amylase. Accordingly, it is a cellulase- and amylase-containing detergent composition.In the context of the invention, enzyme preparations are compositions which comprise the respective enzyme, water and polyol. These are storable and transportable preparations of the respective enzymes.It has been found that detergent compositions prepared using enzyme preparations containing the indicated amounts of enzyme, water and polyol have better storage stability and cleaning performance than compositions prepared using different enzyme preparations. In particular, it has been found that enzyme preparations having a lower water content and a higher content of polyols impair the storage stability and the cleaning performance of the finished detergent composition. This effect may possibly be attributed to the fact that the preparation of the cellulase and the amylase in the presence of a low water content and a high polyol content impairs the stability of the respective enzyme in such a way that this also has effects on the properties of the enzyme in the finished detergent composition.The first and second enzyme preparations are used such that they are added to a detergent matrix to form the detergent composition of the present invention. A detergent matrix is a composition which already contains some or all of the remaining constituents of the finished detergent composition. If the detergent matrix does not yet contain all the remaining constituents of the finished composition, the remaining constituents can be added simultaneously with the first and / or second enzyme preparation or subsequently thereto.The cellulase and amylase used can each be wild-type enzymes or genetically modified variants of wild-type enzymes. Genetically modified variants can have, for example, point mutations, deletions or insertions compared to wild-type enzymes. These can be, in particular, shortened (truncated) variants of wild-type enzymes or fusion proteins of a known enzyme or a fragment thereof and further polypeptides. The first and second enzyme preparations may in each case also comprise mixtures of different cellulases or amylases.Cellulase in the context of the invention is an enzyme which is capable of cleaving the glycosidic bonds of cellulose. Cellulases include, in particular, endoglucanases of the class EC 3.2.1.4, exoglucanases of the classes EC 3.2.1.176 and EC 3.2.1.91 and β-1,4-glucosidases of the classes EC 3.2.1.21. The cellulase is particularly preferably an endoglucanase of the class EC 3.2.1.4.A suitable cellulase is Cel45A cellulase from Melanocarpus albomyces(GenBank No. QCO31627.1) or an genetically modified variant derived therefrom. Very particular preference is given to a cellulase 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 GenBank No. QCO1627.1, in particular with respect to the subsequence from position 24 to position 220 of the amino acid sequence mentioned.In the context of the invention, amylase is an enzyme which can cleave the glycosidic bonds of starch. The amylases include, in particular, α-amylases of the class EC 3.2.1.1, β-amylases of the class EC 3.2.1.2, γ-amylases of the class EC 3.2.1.3 and isoamylases of the class EC 3.2.1.68.A suitable amylase is the alpha-amylase from Cytophaga sp. (GenBank No. AAF00567.1) or an genetically modified variant derived therefrom. Very particular preference is given to an amylase 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 GenBank No. AAF00567.1, in particular with respect to the subsequence from position 37 to position 517 of the amino acid sequence mentioned.In the context 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 Bioinformatic Institute (EMBL-EBI) (Madeira F, Pearlce M, Tidy 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, gap open cost of 10, and gap extension cost of 0.5. As a measure of identity, the percent 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).The first enzyme preparation contains at least 0.5 wt % cellulase, based on the total mass of active cellulase and the total mass of the first enzyme preparation. The first enzyme preparation preferably contains 0.5% by weight to 5% by weight, preferably 0.6% by weight to 2% by weight, most preferably 0.8% by weight to 1.5% by weight cellulase, based on the total mass of active cellulase and the total mass of the first enzyme preparation. Preferably, the first enzyme preparation contains no other enzyme other than cellulase.The second enzyme preparation comprises at least 0.5% by weight amylase, based on the total mass of active amylase and the total mass of the first enzyme preparation. The first enzyme preparation preferably comprises 0.5% by weight to 5% by weight, preferably 0.6% by weight to 2% by weight, most preferably 0.8% by weight to 1.5% by weight of amylase, based on the total mass of active amylase and the total mass of the first enzyme preparation. Preferably, the second enzyme preparation contains no further enzyme other than the amylase.The first and the second enzyme preparation also contain at least 45 wt %, preferably at least 50 wt %, most preferably at least 55 wt % water, based in each case on the total mass of the enzyme preparation.The first and the second enzyme preparation also contain 5% by weight to 45% by weight, preferably 10% by weight to 40% by weight, most preferably 15% by weight to 30% by weight, of polyhydric alcohol (polyol), in each case based on the total mass of the enzyme preparation. As the polyol, a specific polyol or a mixture of polyols may be used. Suitable polyols are, in particular, those alcohols having two or more OH groups and 2 to 8 carbon atoms.Particularly suitable polyols are those having 2 or 3 OH groups and 3 to 6 carbon atoms. Polyols which can be used are, 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.1,2-propanediol has been found to improve the properties of the respective enzymes. The first and the second enzyme preparation therefore preferably comprise 5% by weight to 45% by weight, preferably 10% by weight to 40% by weight, most preferably 15% by weight to 30% by weight, of 1,2-propanediol, in each case based on the total mass of the enzyme preparation.It has also been found that glycerol deteriorates the properties of the respective enzymes. The first and the second enzyme preparation therefore preferably contain not more than 10% by weight, preferably not more than 5% by weight, most preferably not more than 1% by weight, of glycerol, in each case based on the total mass of the enzyme preparation.In a preferred embodiment, the first and the second enzyme preparation comprise 1,2-propanediol in the stated amount. Very particular preference is given here to enzyme preparations which contain not more than 10% by weight, preferably not more than 5% by weight, most preferably not more than 1% by weight, of glycerol. Enzyme preparations with the stated amount of 1,2-propanediol and without glycerol have proven to be particularly stable on storage compared to enzyme preparations with more than 45 wt % glycerol. Such enzyme preparations also result in improved cleaning performance of the detergent composition.In addition to these constituents, the enzyme preparations may also contain further constituents, in particular inactive enzyme, preservative and pH adjusting agent. In addition, the enzyme preparations can also contain residues of the culture medium which was used for biotechnological production of the respective enzyme.The laundry detergent composition preferably comprises the first enzyme preparation in an amount of from 0.01 wt % to 3 wt %, preferably from 0.05 wt % to 2 wt %, most preferably from 0.1 wt % to 1 wt %, in each case based on the total mass of the enzyme preparation and the total mass of the laundry detergent composition.The laundry detergent composition preferably comprises the second enzyme preparation in an amount of from 0.01 wt % to 3 wt %, preferably from 0.05 wt % to 2 wt %, most preferably from 0.1 wt % to 1 wt %, in each case based on the total mass of the enzyme preparation and the total mass of the laundry detergent composition.In addition to the above-described enzyme preparations, the detergent composition comprises further constituents, for example surfactants, solvents, polymers, complexing agents and further auxiliaries.The detergent composition preferably comprises at least one surfactant as a detergent-active substance. The surfactant permits effective detachment of soiling 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 may comprise a single surfactant or a mixture of different surfactants.Preferably, the detergent composition 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.The total amount of surfactants in the detergent composition is preferably 10% by weight to 70% by weight, particularly preferably 20% by weight to 65% by weight, most preferably 40% by weight to 60% by weight, in each case based on the total mass of the detergent composition.Anionic surfactants are, in particular, soaps, alkylbenzenesulfonates, alkanesulfonates, α-olefinsulfonates, α-sulfofatty acid esters, alkyl sulfates, alkenyl sulfates, alkyl ether sulfates, ether carboxylic acids and carboxylated alkyl polyglycosides.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.Soap is the salt of a fatty acid. The fatty acid may be linear or branched, saturated or unsaturated. Preferably, a linear saturated or unsaturated fatty acid is used. It is particularly preferably a linear saturated fatty acid.The fatty acid preferably comprises at least 6 carbon atoms, more preferably at least 8 carbon atoms, most preferably at least 10 carbon atoms. More preferably, the fatty acid comprises 6 to 32 carbon atoms, more preferably 8 to 28 carbon atoms, more preferably 10 to 18 carbon atoms, most preferably 12 to 18 carbon atoms. Preferred fatty acids are selected from the group 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.Soaps have particularly good properties in the detergent composition. The detergent composition therefore comprises soaps preferably in an amount of 1% by weight to 20% by weight, particularly preferably 3% by weight to 15% by weight, most preferably 5% by weight to 10% by weight, in each case based on the total mass of the detergent composition.The alkyl or alkenyl sulfates used are preferably the sulfuric monoesters of saturated or unsaturated fatty alcohols having 12 to 18 carbon atoms. Alkyl or alkenyl sulfates having 12 to 16 carbon atoms are preferably used.Alkyl ether sulfates used are preferably the sulfuric monoesters of alkoxylated fatty alcohols. Preferably, these are ethoxylated or propoxylated fatty alcohols. The fatty alcohols preferably comprise 6 to 22 carbon atoms, more preferably 10 to 20 carbon atoms, most preferably 12 to 18 carbon atoms. The fatty alcohols are preferably alkoxylated with 1 to 20, more preferably 1 to 10, most preferably 2 to 8 repeat units. More preferably, the alkyl ether sulfates have the following structural formula: R 1- O-(R 2- O) n- SO 3- X +, wherein R 1 is a linear or branched, saturated or unsaturated alkyl radical having 6 to 22 carbon atoms, more 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, more preferably 2 or 3 carbon atoms; n is a number from 1 to 20, more preferably 1 to 10, most preferably 2 to 8; and X + is a cation, preferably an alkali metal cation, particularly preferably K + or Na +.The detergent composition comprises alkyl ether sulfates preferably in an amount of 1% by weight to 30% by weight, particularly preferably 5% by weight to 25% by weight, most preferably 10% by weight to 20% by weight, in each case based on the total mass of the detergent composition.The alkylbenzenesulfonates used are preferably compounds having the following structural formula: R 1- Ph-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; Ph is a phenyl radical; and X + is a cation, preferably an alkali metal cation, particularly preferably K + or Na +.A particularly preferred class of alkylbenzenesulfonates has the following structural formula: R 2 R 3 CH-Ph-SO 3- X +, where R 2 is a linear or branched, saturated or unsaturated alkyl radical having 6 to 22 carbon atoms, particularly preferably 8 to 20 carbon atoms, most preferably 12 to 18 carbon atoms; R 3 is a linear or branched, saturated or unsaturated alkyl radical having 1 to 10 carbon atoms, particularly preferably 1 to 5 carbon atoms, most preferably 1 to 3 carbon atoms; Ph is a phenyl radical; and X + is a cation, preferably H + or an alkali metal cation, particularly preferably K + or Na +. Preferably, R 2 and R 3 in this embodiment comprise no more than 21 total carbon atoms. More preferably, R 2 and R 3 are linear alkyl radicals.Alkylbenzenesulfonates have particularly good properties in the detergent composition. The detergent composition therefore comprises alkylbenzenesulfonates preferably in an amount of 7% by weight to 40% by weight, more preferably 10% by weight to 30% by weight, most preferably 15% by weight to 25% by weight, based in each case on the total mass of the detergent composition.Nonionic surfactants are especially 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 alkyl phenols.The total amount of nonionic 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.The alkoxylated fatty alcohols used are preferably compounds having the following structural formula: R1-O-(R2-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.Alkoxylated fatty alcohols have particularly good properties in the detergent composition. The detergent composition therefore comprises alkoxylated fatty alcohols preferably in an amount of 5% by weight to 40% by weight, particularly preferably 10% by weight to 35% by weight, most preferably 15% by weight to 30% by weight, in each case based on the total mass of the detergent composition.The alkoxylated alkanolamines used are preferably 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, denote alkenyl radicals having 2 to 4 carbon atoms, and n denotes 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.Alkoxylated alkanolamines have particularly good properties in the detergent composition. The detergent composition therefore comprises alkoxylated alkanolamines preferably in an amount of 1% by weight to 20% by weight, particularly preferably 2% by weight to 15% by weight, most preferably 3% by weight to 10% by weight, in each case based on the total mass of the detergent composition.In a preferred embodiment, the detergent composition comprises 10% by weight to 70% by weight, preferably 30% by weight to 65% by weight, most preferably 45% by weight to 60% by weight, of anionic and nonionic surfactants, in each case based on the total mass of the detergent composition.In a preferred embodiment, the detergent composition comprises an alkylbenzenesulfonic acid, a fatty acid, an alkoxylated fatty alcohol, and an alkoxylated alkanolamine.Amphoteric surfactants are, in particular, betaines, sulfobetaines and imidazoline derivatives, such as cocoamphodiacetate, for example.The total amount of amphoteric surfactants in the detergent composition is preferably 0.1% by weight to 20% by weight, particularly preferably 1% by weight to 15% by weight, further preferably 2% by weight to 10% by weight, most preferably 3% by weight to 7% by weight, in each case based on the total mass of the detergent composition.In one embodiment, the detergent composition does not comprise amphoteric surfactants.Cationic surfactants are especially fatty amine salts and quaternary ammonium compounds.Preferably, however, the detergent composition comprises no or only a limited amount of cationic surfactants. The detergent composition accordingly preferably comprises not more than 10% by weight, more preferably not more than 1% by weight, most preferably not more than 0.1% by weight, of cationic surfactants, based in each case on the total mass of the detergent composition.In a particularly preferred embodiment, the detergent composition does not comprise cationic surfactants.The detergent composition may further comprise at least one complexing agent. Complexing agents are compounds which bind metal ions, in particular alkaline earth metal ions such as magnesium or calcium ions.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.Complexing agents are in particular phosphates, such as diphosphate and triphosphate salts, phosphonic acids, such as 1-hydroxyethene-1,1-diphosphonic acid, aminotri(methylene phosphonic acid) and diethylenetriaminepentakis(methylene phosphonic 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 methyl glycinediacetic acid (MGDA), and ion exchangers, such as polyacrylic acid, poly(α-hydroxyacrylic acid), poly[(3-hydroxymethyl)hexamethylene-1,3,5-tricarboxylic acid], for example, Poly[(4-methoxy)tetramethylene-1,2-dicarboxylic acid], poly(tetramethylene-1,2-dicarboxylic acid), and silicates.In a preferred embodiment, the detergent composition comprises complexing agents selected from the group of phosphonic acids in an amount of 0.1% by weight to 5% by weight, preferably 0.25% by weight to 3% by weight, most preferably 0.5% by weight to 2% by weight, in each case based on the total mass of the detergent composition.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, particularly preferably 0.1% by weight or less. In a particularly preferred embodiment, the detergent composition does not comprise phosphonates.In a particularly preferred embodiment, the detergent composition comprises complexing agents selected from the group consisting of 1-hydroxyethene-1,1-diphosphonic acid, aminotri(methylenephosphonic acid) and diethylenetriaminepentakis(methylenephosphonic acid) (DTPMP) in an amount of 0.1% by weight to 5% by weight, preferably 0.25% by weight to 3% by weight, most preferably 0.5% by weight to 2% by weight, in each case based on the total mass of the detergent composition.In a preferred embodiment, the detergent composition comprises at least one di- or polycarboxylic acid as complexing agent. In a particularly preferred embodiment, the detergent composition comprises, as complexing agent, citric acid, 1,2,3,4-cyclopentanetetracarboxylic acid, L-glutamic acid-N,N-diacetic acid (GLDA), methyl glycine diacetic acid (MGDA), or mixtures thereof.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% by weight to 5% by weight, preferably 0.25% by weight to 3% by weight, most preferably 0.5% by weight to 2% by weight, in each case based on the total mass of the detergent composition.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), methyl glycine 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.The detergent composition further comprises water in a preferred amount of 50% by weight or less based on the total mass of the detergent composition. Preferably, the detergent composition comprises 40 wt % or less of water, more preferably 30 wt % or less of water, most preferably 15 wt % or less of water, based in each case on the total mass of the detergent composition.The detergent composition may further comprise at least one other solvent other than water. Further solvents are, in particular, monohydric or polyhydric alcohols, alkanolamines and glycol ethers.The amount of the further solvent is preferably 5% by weight to 50% by weight, preferably 8% by weight to 30% by weight, most preferably 10% by weight to 20% by weight, in each case based on the total mass of the detergent composition.The detergent composition is preferably liquid. The total amount of water and further solvents is therefore preferably 5 wt % or more, particularly preferably 10 wt % or more, most preferably 15 wt % or more.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. Particularly suitable polyols are those having 2 or 3 OH groups and 3 to 6 carbon atoms. Polyols which can be used are, 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.The total amount of polyols is preferably 5 wt % to 50 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.The total amount of polyols having two or more OH groups and 2 to 8 carbon atoms is preferably 5 wt % to 50 wt %, more preferably 8 wt % to 30 wt %, most preferably 10 wt % to 20 wt %, based in each case on the total mass of the detergent composition.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 %, based in each case on the total mass of the detergent composition.The detergent composition may further comprise one or more adjuvants. These include, in particular, bleaches, such as hypochlorite bleach, perborates, percarbonates, perphosphates and percarbamides; whiteners; enzyme stabilizers, foam inhibitors, corrosion inhibitors, dyes, fragrances and preservatives.The auxiliaries also include, in particular, polymers which are used as active improvers, such as, for example, polyethyleneimines and propylene glycol terephthalates.The detergent composition may also contain enzymes other than cellulase and amylase described above. For example, the detergent composition may contain proteases, disperseins, lipases, tannases, mannases and polyesterases.In a preferred embodiment, the detergent composition comprises at least one dispersein. For the purposes of the invention, the term dispersein refers to an enzyme which is capable of cleaving the β-1,6-glycosidic bonds of N-acetylglucosamines. The disperseins include, in particular, hexosaminidases of the class EC 3.2.1.52. Dispersens are capable of dissolving bacterial deposits (biofilms) and thus increasing the cleaning performance of detergents against bacterial soils.It has surprisingly been found that the combination of a cellulase according to the invention, an amylase according to the invention and a dispersein improves the cleaning performance of textile detergents with respect to soiling by blood stains and juice stains.A suitable dispersant is the glycosidase of the family 20 (classification of glycosidases according to Henrissat) from Terribacillus gorinsis(NCBI reference sequence No. WP_17006640) or an genetically modified variant derived therefrom.Very particular preference is given to a dispersein 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 NCBI reference sequence No. WP_17006640, in particular to the subsequence from position 28 to position 328 of the amino acid sequence mentioned.The detergent composition therefore preferably contains at least 0.0001% by weight, preferably at least 0.001% by weight, more preferably at least 0.01% by weight of disperseine, based on the mass of active disperseine and the total mass of the detergent composition. In some embodiments, the amount of dispersant in the detergent composition is preferably from 0.0001% by weight to 5% by weight, preferably from 0.001% by weight to 2.5% by weight, particularly preferably from 0.005% by weight to 1% by weight, very particularly preferably from 0.01% by weight to 0.5% by weight, based in each case on the total mass of active dispersant and the total mass of the detergent composition.The detergent composition preferably has a pH of from 7 to 12, more preferably from 7.5 to 9, most preferably from 7.5 to 8.5. pH is determined at 20° C. If the detergent composition has too little water content to reliably determine the pH, the composition is diluted with water for measurement. The pH is preferably adjusted by addition of a suitable base. Preferably, the detergent composition comprises a base selected from the group of amines, alkali carbonate and alkali hydroxide, more preferably selected from monoethanolamine, sodium carbonate and sodium hydroxide.Conventional detergents usually contain boric acid or the salts of boric acid (borates) for stabilizing enzymes. The use of boric acid or borates is, however, not absolutely necessary according to the present invention for enzyme stabilization. The invention rather 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 not more than 1% by weight, preferably not more than 0.5% by weight, preferably not more than 0.1% by weight, most preferably not more than 0.01% by weight, based in each case on the total mass of the detergent composition. In a particularly preferred embodiment, the detergent composition does not comprise boric acid and borates.A further aspect of the invention relates to the use of the above-described first and second enzyme preparations as constituents of the above-described detergent composition for improving the storage stability of the detergent composition. Preferably, the use serves to reduce turbidity of the detergent composition. In one embodiment, the use is also to improve the cleaning performance of a laundry detergent composition in terms of blood and / or juice stains.ExamplesHereinafter, the present invention will be described in more detail by way of Examples. However, the present invention is not limited to the following examples.Using the enzyme preparation described below, various detergent compositions were prepared and examined for their storage stability and cleaning performance.The enzyme preparations A and B are in each case enzyme preparations according to the invention. Both preparations contain an inventive amount of water and polyol (1,2-propanediol).The enzyme preparations C and D are in each case enzyme preparations not according to the invention. Both preparations each contain less than 45 wt.% water and more than 45 wt.% polyol in the form of glycerol.The enzyme preparations contained in each case between 1% by weight and 3% by weight of active enzyme.The following table shows the proportions of active enzyme, water, glycerol and 1,2-propanediol in the individual preparations. All preparations contain a residue of inactive enzyme, pH adjusting agent and optionally small amounts of further additives.A. ACellulase75020B. BAmylase55020C. CCellulase45500D. DAmylase35600The detergent compositions shown in the following table were prepared with the above enzyme preparations:Alkylbenzene sulfonic acid22222222Fatty Acid C12-C187777Ethoxylated fatty alcohol C12-C18 7EO22222222Alkoxylated alkanolamine44441,2-Propanediol5555Glycerol9999monoethanolamine6666Polyethyleneimine6666DTPMP0,40,40,40,4Propylene glycol terephthalate2222Enzyme Preparation A (Cellulase)0,20,2Enzyme preparation B (amylase)0,40,4Enzyme Preparation C (cellulase)0,10,1Enzyme preparation D (amylase)0,40,4Dispersein0,30,3Other Enzymes3333Other Additives 13,73,73,73,7WaterRemainder: Remainder:Remainder: Remainder:Remainder: Remainder:Remainder: Remainder:1 Bitter substances, bleaches, preservatives, dyes, fragrancesCompositions 3 and 4 are compositions of the invention prepared using enzyme preparations A and B. Composition 3 additionally contains a dispersant. Compositions 1 and 2 were prepared using enzyme preparations C and D and thus do not fall under the invention. Composition 1 additionally contains a dispersant.To examine the storage stability, the detergent compositions were held in a screw-lid glass against light and the turbidity was visually evaluated. Haze was evaluated on a scale from 1 (high haze) to 5 (clear). The results of this test are summarized in the following table.11223444Detergent composition 2 which has neither an enzyme preparation according to the invention nor dispersein exhibited a marked turbidity. This is considered to indicate instability of the enzymes in the detergent composition.The turbidity was further increased by addition of dispersein (detergent composition 1). This is an indication that dispersein is unstable in the presence of the enzyme preparations not according to the invention.Detergent compositions 3 and 4, each containing the enzyme preparations of the present invention, exhibited little turbidity. This is an indication that the enzyme preparations according to the invention stabilize the enzymes in the detergent composition and thus lead to improved storage stability of the detergent composition.To examine the cleaning performance, the following washing experiments were carried out. Textile fabrics made of the materials specified which had been provided with the standardized stains likewise specified were washed at 40° C. with wash liquors comprising in each case 1 g / line of the detergent compositions 1 to 4 and then dried. It was washed at 40° C. in the washing machine type Miele WCI 360 WTL. The duration of the wash program was 119 minutes, 74 minutes of which was due to the main wash cycle. Further parameters for the washing test were a water hardness of 16° dh, a water quantity of 17 L and a total of 5 repetitions / washing cycles. The resulting brightness values (Y values) were determined. Y values are mean values from 5 determinations. The Y values are a measure of the cleanliness of the textile samples. The higher the Y value, the better the cleaning performance of the detergent composition. The Y values of the individual detergent compositions are listed in the following table.1234BloodCO49,7N / A50,650,4Juice (blackcurrant)CO58,858,258,958,7The detergent composition 3 according to the invention comprising a combination of the enzyme preparations according to the invention and a dispersein shows the best cleaning performance of all the compositions tested both in blood spots and in juice spots. The detergent composition 2 which comprises neither a dispersant nor one of the enzyme preparations according to the invention exhibits the weakest cleaning performance. Detergent compositions 1 and 4, comprising either the enzyme preparations of the invention (composition 4) or a dispersant (composition 1), exhibit average cleaning performance with respect to juice stains. With respect to blood spots, the composition 4 of the present invention exhibits better cleaning performance than the two comparative compositions 1 and 2.References included in the specificationThis list of documents cited by the applicant has been produced in an automated manner and is only included for the better information of the reader. The list is not part of the German patent application or utility model application. The DPMA does not take any adhesion for any faults or omissions.Cited Non-Patent LiteratureMadeira F, Pearlce M, Tidy ARN, et al., "Search and sequence analysis tools services from EMBL-EBI in 2022", Nucleic Acids Research, 2022

[0037]

Claims

A detergent composition producible using a first and a second enzyme preparation, wherein the first enzyme preparation comprises a cellulase and the second enzyme preparation comprises an amylase, characterized in that the first and the second enzyme preparation each comprise at least 0.5 wt.% of the respective enzyme, based on the total mass of active enzyme, at least 45 wt.% water and 5 wt.% to 45 wt.% polyol, based in each case on the total mass of the enzyme preparation.The detergent composition according to claim 1, wherein the first and second enzyme preparations each contain not more than 10% by weight glycerol, based in each case on the total mass of the enzyme preparation.The detergent composition according to claim 1 or 2, wherein the first and second enzyme preparations each contain from 5% to 45% by weight of 1,2-propanediol, based in each case on the total mass of the enzyme preparation.The detergent composition according to any one of claims 1 to 3, wherein the detergent composition contains the first and second enzyme preparations in an amount of 0.01 wt% to 3 wt%, respectively, based on the total mass of the enzyme preparation and the total mass of the detergent composition.The detergent composition according to any one of claims 1 to 4, wherein the detergent composition comprises 10 wt% to 70 wt% surfactants, 5 wt% to 50 wt% polyols, 0.1 wt% to 5 wt% chelating agent, and 50 wt% or less water.The detergent composition of any one of claims 1 to 5, wherein the detergent composition comprises an alkylbenzenesulfonic acid, a fatty acid, an alkoxylated fatty alcohol, and an alkoxylated alkanolamine.The detergent composition according to any one of claims 1 to 6, wherein the detergent composition comprises 15 wt% or less of water.The detergent composition of any one of claims 1 to 7, wherein the detergent composition comprises a dispersant.Use of a first and a second enzyme preparation as constituents of a laundry detergent composition for improving the storage stability of the laundry detergent composition, wherein the first enzyme preparation comprises a cellulase and the second enzyme preparation comprises an amylase, characterized in that the first and the second enzyme preparation each comprise at least 0.5% by weight of the respective enzyme, based on the total mass of active enzyme, at least 45% by weight of water and 5% by weight to 45% by weight of polyol, based in each case on the total mass of the enzyme preparation.Use according to claim 9, for improving the cleaning performance of the detergent composition in textile washing with respect to blood and / or juice stains.