DE102023212850A1 - Cellulase and amylase-containing detergent composition with improved storage stability - Google Patents

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 technology

The invention relates to cellulase- and amylase-containing detergent compositions with improved storage stability, as well as the use of cellulase- and amylase-containing enzyme preparations as a component of a detergent composition for improving storage stability.

Current state of the art

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. Due to their high effectiveness even at low washing temperatures, enzymes also help reduce energy consumption during washing.

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.

Cellulases are particularly important in textile washing. They can break down the cellulose fibers protruding from the fabric, thus removing the fuzz on cotton fabrics. This makes dark textiles appear darker.

In light-colored textiles, less dust remains in the fluff, resulting in less graying and a brighter appearance. Amylases are also preferred in textile washing to remove stains from food residue. The combination of cellulases and amylases is therefore of particular interest in textile detergents.

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 of detergents can occur, leading to a loss of the native three-dimensional structure and thus to a loss of enzyme activity. Furthermore, enzymes are degraded by proteases that may be present in the detergent. These processes are often accompanied by precipitation of the denatured enzymes, which leads to undesirable cloudiness of the detergent.

Technical task

The object of the present invention is to provide a cellulase- and amylase-containing detergent with improved storage stability with respect to the stability of the enzymes. Furthermore, the object of the invention is to provide a detergent with improved cleaning performance in textile washing. In particular, the cleaning performance with respect to blood or juice stains is to be improved.

Description of the invention

Surprisingly, it was discovered that the components of the amylase- and cellulase-containing enzyme preparations used in the manufacture of detergents influence the enzyme stability in the detergents and thus the storage stability of the detergents. In particular, it was found that enzyme preparations with a low polyol content are more stable than those with a high polyol content, especially those with a high glycerol content. Furthermore, it was discovered that these enzyme preparations also improve the cleaning performance of the detergent, particularly with regard to blood and juice stains on textiles. This improvement in cleaning performance is particularly pronounced in a detergent that additionally contains a dispersin.

• die erste Enzympräparation eine Cellulase umfasst, und
• die zweite Enzympräparation eine Amylase umfasst, dadurch gekennzeichnet, dass
• die erste und die zweite Enzympräparation jeweils
• mindestens 0,5 Gew.-% des jeweiligen Enzyms, bezogen auf die Gesamtmasse an aktivem Enzym,
• mindestens 45 Gew.-% Wasser und
• 5 Gew.-% bis 45 Gew.-% Polyol

umfassen, jeweils bezogen auf die Gesamtmasse der Enzympräparation.One aspect of the invention therefore relates to a detergent composition which can be prepared 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 wt% to 45 wt% polyol

each based on the total mass of the enzyme preparation.

Preferably, the first and second enzyme preparations each contain no more than 10% by weight of glycerol, based on the total mass of the enzyme preparation.

Preferably, the first and second enzyme preparations each contain 5 wt.% to 45 wt.% 1,2-propanediol, each based on the total mass of the enzyme preparation.

Preferably, the detergent composition contains the first and second enzyme preparations in an amount of 0.01 wt.% to 3 wt.%, each based on the total mass of the enzyme preparation and the total mass of the detergent composition.

• 10 Gew.-% bis 70 Gew.-% Tenside,
• 5 Gew.-% bis 50 Gew-% Polyole,
• 0,1 Gew.-% bis 5 Gew.-% Komplexbildner, und
• 50 Gew.-% oder weniger Wasser.

Preferably, the detergent composition comprises

• 10 wt% to 70 wt% surfactants,
• 5 wt% to 50 wt% polyols,
• 0.1 wt% to 5 wt% complexing agent, and
• 50% by weight or less 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% by weight or less of water.

Preferably, the detergent composition comprises a dispersin.

• die erste Enzympräparation eine Cellulase umfasst, und
• die zweite Enzympräparation eine Amylase umfasst, dadurch gekennzeichnet, dass
• die erste und die zweite Enzympräparation jeweils
• mindestens 0,5 Gew.-% des jeweiligen Enzyms, bezogen auf die Gesamtmasse an aktivem Enzym,
• mindestens 45 Gew.-% Wasser und
• 5 Gew.-% bis 45 Gew.-% Polyol

umfassen, jeweils bezogen auf die Gesamtmasse der Enzympräparation.A further aspect of the invention relates to the use of a first and a second enzyme preparation as components of a detergent composition for improving the storage stability of the detergent composition, 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 wt% to 45 wt% polyol

each based 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 regard to blood and/or juice stains.

Advantageous effects of the invention

The detergent composition according to the invention has improved storage stability with regard to the stability of the enzymes it contains. In particular, only low turbidity occurs in the detergent composition according to the invention.

In addition, the detergent composition offers improved cleaning performance on soiled textiles. The detergent composition cleans blood and juice stains particularly well.

Description of the embodiments

Embodiments of the present invention will be described in detail below. 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. For the purposes of the invention, laundry includes, for example, hard surfaces such as stone floors, metal surfaces, glass surfaces, 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 composition can be, for example, a floor cleaner, a toilet cleaner, a dishwashing detergent, a fabric detergent, or a handwashing detergent.

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

In an alternative embodiment, the detergent composition is used to clean all types of woven, knitted, or warp-knitted textiles, as well as furs. In particular, the detergent composition 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 composition is used as a textile detergent for cleaning laundry, for example, clothing, towels, bed linen, blankets, and curtains. In a preferred embodiment, the detergent composition is a textile detergent.

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.

The detergent composition 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.

The detergent composition can be used for both manual and machine washing. The detergent composition can be used, in particular, as a general-purpose detergent for all washing processes 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 loosen 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.

An essential feature of the detergent composition is that it can be produced using a first enzyme preparation comprising a cellulase and a second enzyme preparation comprising an amylase. It is therefore a cellulase- and amylase-containing detergent composition.

For the purposes of the invention, enzyme preparations refer to compositions containing the respective enzyme, water, and polyol. These are storable and transportable preparations of the respective enzymes.

It has been shown that detergent compositions prepared using enzyme preparations with the specified amounts of enzyme, water, and polyol exhibit better storage stability and cleaning performance than compositions prepared using different enzyme preparations. In particular, enzyme preparations with a lower water content and a higher polyol content have been shown to impair the storage stability and cleaning performance of the finished detergent composition. This effect can possibly be attributed to the fact that the preparation of the cellulase and amylase in the presence of a low water content and a high polyol content impairs the stability of the respective enzyme to such an extent that this also affects the properties of the enzyme in the finished detergent composition.

The first and second enzyme preparations are used by adding them to a detergent matrix to form the detergent composition according to the invention. A detergent matrix is a composition that already contains some or all of the remaining components of the finished detergent composition. If the detergent matrix does not yet contain all of the remaining components of the finished composition, the remaining components can be added simultaneously with or subsequently to the first and/or second enzyme preparation.

The cellulase and amylase 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 enzyme preparations can also contain mixtures of different cellulases or amylases.

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 particularly preferably an endoglucanase of class EC 3.2.1.4.

A suitable cellulase is the Cel45A cellulase from Melanocarpus albomyces (GenBank No. QCO31627.1) or a genetically modified variant derived therefrom. Most preferably, it is 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 to the partial sequence from position 24 to position 220 of said amino acid sequence.

For the purposes of the invention, amylase refers to an enzyme that can cleave the glycosidic bonds of starch. Amylases include, in particular, α-amylases of class EC 3.2.1.1, β-amylases of class EC 3.2.1.2, γ-amylases of class EC 3.2.1.3, and isoamylases of class EC 3.2.1.68.

A suitable amylase is the α-amylase from Cytophaga sp. (GenBank No. AAF00567.1) or a genetically modified variant derived therefrom. It is most preferably 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 to the partial sequence from position 37 to position 517 of said amino acid sequence.

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 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, gap open cost of 10 and gap extension cost of 0.5. The measure of identity is the percentage ratio of identical amino acids in the alignment to the total number of opposing amino acids in the alignment. ment 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. Preferably, the first enzyme preparation contains 0.5 wt.% to 5 wt.%, preferably 0.6 wt.% to 2 wt.%, most preferably 0.8 wt.% to 1.5 wt.% 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 besides the cellulase.

The second enzyme preparation contains at least 0.5 wt.% amylase, based on the total mass of active amylase and the total mass of the first enzyme preparation. Preferably, the first enzyme preparation contains 0.5 wt.% to 5 wt.%, preferably 0.6 wt.% to 2 wt.%, most preferably 0.8 wt.% to 1.5 wt.% 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 other enzyme besides amylase.

The first and second enzyme preparations also contain at least 45% by weight, preferably at least 50% by weight, most preferably at least 55% by weight of water, in each case based on the total mass of the enzyme preparation.

The first and second enzyme preparations also contain 5% to 45% by weight, preferably 10% to 40% by weight, most preferably 15% to 30% by weight, of polyhydric alcohol (polyol), each based on the total mass of the enzyme preparation. A specific polyol or a mixture of polyols can be used as the polyol. Suitable polyols are, in particular, those alcohols with two or more OH groups and 2 to 8 carbon atoms.

Polyols with 2 or 3 OH groups and 3 to 6 carbon atoms are particularly suitable. Suitable polyols include, in particular, propanediol, especially 1,2-propanediol; butanediol, especially 1,2-butanediol, 1,3-butanediol, and 1,4-butanediol; glycerol, or mixtures thereof.

It has been shown that 1,2-propanediol improves the properties of the respective enzymes. The first and second enzyme preparations therefore preferably contain 5 wt.% to 45 wt.%, preferably 10 wt.% to 40 wt.%, and most preferably 15 wt.% to 30 wt.% of 1,2-propanediol, based in each case on the total mass of the enzyme preparation.

It has also been shown that glycerol impairs the properties of the respective enzymes. Therefore, the first and second enzyme preparations preferably contain no more than 10 wt.%, preferably no more than 5 wt.%, and most preferably no more than 1 wt.% of glycerol, based on the total mass of the enzyme preparation.

In a preferred embodiment, the first and second enzyme preparations contain 1,2-propanediol in the stated amount. Very particular preference is given to enzyme preparations containing no more than 10% by weight, preferably no more than 5% by weight, and most preferably no more than 1% by weight of glycerol. Enzyme preparations containing the stated amount of 1,2-propanediol and no glycerol have proven to be particularly storage-stable compared to enzyme preparations containing more than 45% by weight of glycerol. Such enzyme preparations also lead to improved cleaning performance of the detergent composition.

In addition to these components, the enzyme preparations may contain other ingredients, in particular inactive enzymes, preservatives, and pH adjusters. Furthermore, the enzyme preparations may also contain residues of the culture medium used for the biotechnological production of the respective enzyme.

The detergent composition preferably contains the first enzyme preparation in an amount of 0.01 wt.% to 3 wt.%, preferably 0.05 wt.% to 2 wt.%, most preferably 0.1 wt.% to 1 wt.%, in each case based on the total mass of the enzyme preparation and the total mass of the detergent composition.

The detergent composition preferably contains the second enzyme preparation in an amount of 0.01 wt% to 3 wt%, preferably 0.05 wt% to 2 wt%, most preferably 0.1 wt% to 1 wt%, in each case based on the total mass of the enzyme preparation and the total mass of the detergent composition.

In addition to the enzyme preparations described above, the detergent composition includes other components, such as surfactants, solvents, polymers, complexing agents and other auxiliaries.

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.

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.

The total amount of surfactants in the detergent composition is preferably 10 wt% to 70 wt%, more preferably 20 wt% to 65 wt%, most preferably 40 wt% to 60 wt%, in each case based on the total mass of the detergent composition.

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.

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.

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.

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.

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.

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.

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 represents 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 represents an alkenyl radical having 2 to 4 carbon atoms, particularly preferably 2 or 3 carbon atoms; n represents a number from 1 to 20, particularly preferably 1 to 10, most preferably 2 to 8; and X ⁺ represents a cation, preferably an alkali metal cation, particularly preferably K ⁺ or Na ⁺ .

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

Compounds with the following structural formula are preferably used as alkylbenzenesulfonates: R ₁ -Ph-SO ₃ ^- X ⁺ , where R ₁ represents 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 represents a phenyl radical; and X ⁺ represents 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 represents 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 represents 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 represents a phenyl radical; and X ⁺ represents a cation, preferably H ⁺ or an alkali metal cation, particularly preferably K ⁺ or Na ⁺ . In this embodiment, the radicals R ₂ and R ₃ preferably comprise a total of no more than 21 carbon atoms. R ₂ and R ₃ are particularly preferably linear alkyl radicals.

Alkylbenzenesulfonates exhibit particularly good properties in detergent compositions. The detergent composition therefore preferably comprises alkylbenzenesulfonates in an amount of 7 wt.% to 40 wt.%, particularly preferably 10 wt.% to 30 wt.%, and most preferably 15 wt.% to 25 wt.%, based in each case on the total mass of the detergent composition.

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.

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.

Compounds with the following structural formula are preferably used as alkoxylated fatty alcohols: R1-O-(R2-O)nH, where R ₁ represents 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 represents an alkenyl radical having 2 to 4 carbon atoms, particularly preferably 2 or 3 carbon atoms; and n represents a number from 1 to 20, particularly preferably 3 to 15, most preferably 5 to 10.

Alkoxylated fatty alcohols have particularly good properties in detergent compositions. Therefore, the detergent composition preferably comprises alkoxylated fatty alcohols in a Amount of 5 wt% to 40 wt%, particularly preferably 10 wt% to 35 wt%, most preferably 15 wt% to 30 wt%, in each case based on the total mass of the detergent composition.

As alkoxylated alkanolamines, compounds with the following structural formula are preferably used: (HO-R ¹ -O-(R ² -O)nR ³ ) ₃ -N where the radicals R ¹ , R ² , R ³ each independently 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.

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.

In a preferred embodiment, the detergent composition comprises 10 wt% to 70 wt%, preferably 30 wt% to 65 wt%, most preferably 45 wt% to 60 wt% 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 include, in particular, betaines, sulfobetaines and imidazoline derivatives such as cocoamphodiacetate.

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.

In one embodiment, the detergent composition does not comprise amphoteric surfactants.

Cationic surfactants are in particular fatty amine salts and quaternary ammonium compounds.

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.

In a particularly preferred embodiment, the detergent composition does not comprise any cationic surfactants.

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.

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, 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-hydroxy-acrylic 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.

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.

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.

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 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.

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.

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.

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.

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% by weight or less of water, more preferably 30% 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.

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.

The amount of the further solvent 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 detergent composition is preferably liquid. The total amount of water and other solvents is therefore preferably 5% by weight or more, more preferably 10% by weight or more, most preferably 15% by weight 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. Polyols having 2 or 3 OH groups and 3 to 6 carbon atoms are particularly suitable. Suitable polyols include, in particular, propanediol, especially 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%, 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.

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.

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.

The excipients include, in particular, polymers that are used as effect enhancers, such as polyethyleneimines and propylene glycol terephthalates.

The detergent composition may also contain other enzymes besides the cellulase and amylase described above. For example, the detergent composition may contain proteases, dispersins, lipases, tannases, mannases, and polyesterases.

In a preferred embodiment, the detergent composition comprises at least one dispersin. For the purposes of the invention, dispersin refers to an enzyme capable of cleaving the β-1,6-glycosidic bonds of N-acetylglucosamines. Dispersins include, in particular, hexosaminidases of class EC 3.2.1.52. Dispersins 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 dispersin improves the cleaning performance of textile detergents with regard to soiling caused by blood and juice stains.

A suitable dispersin is the glycosidase of family 20 (classification of glycosidases according to Henrissat) from Terribacillus goriensis (NCBI reference sequence no. WP_170061640) or a genetically modified variant derived from it.

Most preferably, it is a dispersin 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 NCBI Reference Sequence No. WP_170061640, in particular to the partial sequence from position 28 to position 328 of said amino acid sequence.

The detergent composition therefore preferably contains at least 0.0001 wt.%, preferably at least 0.001 wt.%, more preferably at least 0.01 wt.% of dispersin, based on the mass of active dispersin and the total mass of the detergent composition. In some embodiments, the amount of dispersin in the 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 detergent composition.

The detergent composition preferably has a pH of 7 to 12, particularly 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, To 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, particularly preferably selected from monoethanolamine, sodium carbonate, and sodium hydroxide.

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.

A further aspect of the invention relates to the use of the above-described first and second enzyme preparations as components 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 also serves to improve the cleaning performance of a detergent composition for textile washing with respect to blood and/or juice stains.

Examples

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.

Using the enzyme preparation described below, various detergent compositions were prepared and tested for their storage stability and cleaning performance.

Enzyme preparations A and B are each enzyme preparations according to the invention. Both preparations contain an amount of water and polyol (1,2-propanediol) according to the invention.

Enzyme preparations C and D are each enzyme preparations not according to the invention. Both preparations contain less than 45 wt.% water and more than 45 wt.% polyol in the form of glycerol.

The enzyme preparations each contained between 1 wt% and 3 wt% 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 adjuster, and possibly small amounts of other additives. enzyme Water (wt%) Glycerol (wt%) 1,2-Propanediol (wt%) A Cellulase 75 0 20 B Amylase 55 0 20 C Cellulase 45 50 0 D Amylase 35 60 0

The detergent compositions shown in the following table were prepared using the above-mentioned enzyme preparations: 1 2 3 4 Alkylbenzenesulfonic acid 22 22 22 22 Fatty acid C12-C18 7 7 7 7 Ethoxylated fatty alcohol C12-C18 7EO 22 22 22 22 Alkoxylated alkanolamine 4 4 4 4 1,2-Propanediol 5 5 5 5 Glycerol 9 9 9 9 Monoethanolamine 6 6 6 6 Polyethylenimine 6 6 6 6 DTPMP 0.4 0.4 0.4 0.4 Propylene glycol terephthalate 2 2 2 2 Enzyme preparation A (cellulase) 0.2 0.2 Enzyme preparation B (amylase) 0.4 0.4 Enzyme preparation C (cellulase) 0.1 0.1 Enzyme preparation D (amylase) 0.4 0.4 Dispersin 0.3 0.3 Other enzymes 3 3 3 3 Other additives ¹ 3.7 3.7 3.7 3.7 Water rest rest rest rest ¹ Bitter substances, bleaching agents, preservatives, dyes, fragrances

Compositions 3 and 4 are compositions according to the invention that were prepared using enzyme preparations A and B. Composition 3 additionally contains a dispersin. Compositions 1 and 2 were prepared using enzyme preparations C and D and therefore do not fall within the scope of the invention. Composition 1 additionally contains a dispersin.

To test storage stability, the detergent compositions were held in a screw-cap jar against light, and the turbidity was visually assessed. Turbidity was rated on a scale of 1 (very turbid) to 5 (clear). The results of this test are summarized in the following table. Detergent composition turbidity 1 1 2 2 3 4 4 4

Detergent composition 2, which contains neither an enzyme preparation according to the invention nor dispersin, exhibited significant turbidity. This is considered an indication of enzyme instability in the detergent composition.

The addition of Dispersin further increased the turbidity (detergent composition 1). This indicates that Dispersin is unstable in the presence of the non-inventive enzyme preparations.

Detergent compositions 3 and 4, each containing the enzyme preparations according to the invention, exhibited only slight turbidity. This indicates 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.

The following washing tests were carried out to investigate the cleaning performance. Textile fabrics made of the specified materials, which were washed with the standardized The textiles that had been soiled were washed at 40°C using wash liquors containing 1g/l of detergent compositions 1 to 4 and then dried. The washing was carried out in a Miele WCI 360 WTL washing machine at 40°C. The washing program lasted 119 minutes, 74 minutes of which were for the main wash cycle. Other parameters for the washing test were a water hardness of 16°dh, a water volume of 17 L and a total of 5 repetitions/wash cycles. The resulting brightness values (Y values) were determined. The Y values are the average values of 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. pollution Textile Compositions 1 2 3 4 blood CO 49.7 N/A 50.6 50.4 Juice (Blackcurrant) CO 58.8 58.2 58.9 58.7

Detergent composition 3 according to the invention, comprising a combination of the enzyme preparations according to the invention and a dispersin, exhibits the best cleaning performance of all tested compositions on both blood and juice stains. Detergent composition 2, which comprises neither a dispersin nor one of the enzyme preparations according to the invention, exhibits the weakest cleaning performance. Detergent compositions 1 and 4, which comprise either the enzyme preparations according to the invention (composition 4) or a dispersin (composition 1), exhibit average cleaning performance with respect to juice stains. With respect to blood stains, composition 4 according to the invention exhibits better cleaning performance than the two comparative compositions 1 and 2.

QUOTES CONTAINED IN THE DESCRIPTION

This list of documents submitted by the applicant was generated automatically and is included solely for the convenience of the reader. This list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited non-patent literature

• Madeira F, Pearce M, Tivey ARN, et al. “Search and sequence analysis tools services from EMBL-EBI in 2022”, Nucleic Acids Research, 2022 [0037]

Claims (10)

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% 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, in each case based on the total mass of the enzyme preparation. Detergent composition according to Claim 1 , wherein the first and the second enzyme preparation each contain not more than 10 wt.% glycerol, in each case based on the total mass of the enzyme preparation. Detergent composition according to Claim 1 or 2 , wherein the first and the second enzyme preparation each contain 5 wt.% to 45 wt.% 1,2-propanediol, in each case based on the total mass of the enzyme preparation. Detergent composition according to one of the Claims 1 until 3 , wherein the detergent composition contains the first and the second enzyme preparation each in an amount of 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. Detergent composition according to one of the Claims 1 until 4 wherein the detergent composition comprises 10 wt% to 70 wt% surfactants, 5 wt% to 50 wt% polyols, 0.1 wt% to 5 wt% complexing agents, and 50 wt% or less water. Detergent composition according to one of the Claims 1 until 5 wherein the detergent composition comprises an alkylbenzenesulfonic acid, a fatty acid, an alkoxylated fatty alcohol and an alkoxylated alkanolamine. Detergent composition according to one of the Claims 1 until 6 wherein the detergent composition comprises 15% by weight or less of water. Detergent composition according to one of the Claims 1 until 7 wherein the detergent composition comprises a dispersin. Use of a first and a second enzyme preparation as components of a detergent composition for improving the storage stability of the 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, in each case based on the total mass of the enzyme preparation. Use according to Claim 9 , to improve the cleaning performance of the detergent composition in textile washing with regard to blood and/or juice stains.