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WO2025131851A1 - Composition détergente contenant de la cellulase et de l'amylase et présentant une stabilité au stockage améliorée - Google Patents

Composition détergente contenant de la cellulase et de l'amylase et présentant une stabilité au stockage améliorée Download PDF

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Publication number
WO2025131851A1
WO2025131851A1 PCT/EP2024/085380 EP2024085380W WO2025131851A1 WO 2025131851 A1 WO2025131851 A1 WO 2025131851A1 EP 2024085380 W EP2024085380 W EP 2024085380W WO 2025131851 A1 WO2025131851 A1 WO 2025131851A1
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Prior art keywords
detergent composition
enzyme
enzyme preparation
total mass
acid
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German (de)
English (en)
Inventor
Inga Kerstin Vockenroth
Zoe Weidner
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Publication of WO2025131851A1 publication Critical patent/WO2025131851A1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38618—Protease or amylase in liquid compositions only
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/04—Carboxylic acids or salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/42—Amino alcohols or amino ethers
    • C11D1/44—Ethers of polyoxyalkylenes with amino alcohols; Condensation products of epoxyalkanes with amines
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2003—Alcohols; Phenols
    • C11D3/2041—Dihydric alcohols
    • C11D3/2048—Dihydric alcohols branched
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2003—Alcohols; Phenols
    • C11D3/2065—Polyhydric alcohols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38645—Preparations containing enzymes, e.g. protease or amylase containing cellulase
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38663—Stabilised liquid enzyme compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/12—Soft surfaces, e.g. textile

Definitions

  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • enzyme preparations with a low polyol content are more stable than those with a high polyol content, especially those with a high glycerol content.
  • the aforementioned Enzyme preparations also improve the cleaning performance of the detergent, especially with regard to blood and juice stains on textiles. This improvement in cleaning performance is particularly pronounced in a detergent that also contains a dispersant.
  • One aspect of the invention therefore 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 the second enzyme preparation each contain 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
  • 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.
  • 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.
  • 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.
  • the detergent composition comprises
  • the detergent composition comprises an alkylbenzenesulfonic acid, a fatty acid, an alkoxylated fatty alcohol and an alkoxylated alkanolamine.
  • the detergent composition comprises 15% by weight or less of water.
  • the detergent composition comprises a dispersin.
  • 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 the second enzyme preparation each contain at least 0.5 wt.% of the respective enzyme, based on the total mass of active enzyme, at least 45 wt.% water and
  • the use serves to improve the cleaning performance of the detergent composition in textile washing with regard to blood and/or juice stains.
  • 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.
  • the detergent composition is used for cleaning laundry.
  • laundry includes, for example, hard surfaces such as stone floors, metal surfaces, glass surfaces, or wooden surfaces, dishes, or products made of fiber material.
  • 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.
  • the detergent composition serves as a dishwashing detergent for cleaning all types of dishes and cutlery made of stainless steel, porcelain, glass or plastic.
  • the detergent composition is used to clean all types of woven, knitted, or warp-knitted textiles, as well as furs.
  • 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.
  • the detergent composition is used as a textile detergent for cleaning laundry, for example, clothing, towels, bed linen, blankets, and curtains.
  • 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.
  • 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
  • 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.
  • 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.
  • 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 refers to 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.
  • 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 ß-1,4-glucosidases of classes 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, further preferably 80% or more, further preferably 85% or more, further preferably 90% or more, most preferably 95% or more to the amino acid sequence according to GenBank No. QCO31627.1, in particular to the partial sequence from position 24 to position 220 of said amino acid sequence.
  • amylase refers to an enzyme that can cleave the glycosidic bonds of starch.
  • Amylases include, in particular, ⁇ -amylases of class EC 3.2.1.1, ⁇ -amylases of class EC 3.2.1.2, ⁇ -amylases of class EC 3.2.1.3, and isoamylases of class EC 3.2.1.68.
  • a suitable amylase is the ⁇ -amylase from Cytophaga sp. (GenBank No. AAF00567.1) or a genetically modified variant derived therefrom. Most preferably, it is an amylase whose amino acid sequence has an identity of 60% or more, preferably 70% or more, further preferably 80% or more, further preferably 85% or more, further preferably 90% or more, most preferably 95% or more to the amino acid sequence according to GenBank No. AAF00567.1, in particular to the partial sequence from position 37 to position 517 of said amino acid sequence.
  • 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, TiveyARN, et al. “Search and sequence analysis tools services from EMBL-EBI in 2022”, Nucleic Acids Research, 2022).
  • the alignment is calculated using the BLOSUM62 substitution matrix, a gap open cost of 10, and a gap extension cost of 0.5.
  • the percentage ratio of identical amino acids in the alignment to the total number of opposing amino acids in the alignment is calculated according to the following formula: (number of identical amino acids in the alignment) / (total length of the alignment - number of gaps in the alignment).
  • the first enzyme preparation contains at least 0.5% by weight of cellulase, based on the total mass of active cellulase and the total mass of the first enzyme preparation.
  • the first enzyme preparation contains 0.5% to 5% by weight, preferably 0.6% to 2% by weight, most preferably 0.8% to 1.5% by weight of cellulase, based on the total mass of active cellulase and the total mass of the first enzyme preparation.
  • 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.
  • 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.
  • 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.
  • polyol polyhydric alcohol
  • 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.
  • the first and second enzyme preparations therefore preferably contain 5 wt.% to 45 wt.%, preferably 10 wt.% to 40 wt.%, most preferably 15 wt.% to 30 wt.% of 1,2-propanediol, in each case based on the total mass of the enzyme preparation.
  • 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.
  • 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.
  • 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.
  • 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, a-olefinsulfonates, a-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.
  • 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.
  • 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:
  • Ri is a linear or branched, saturated or unsaturated alkyl radical having 6 to 22 carbon atoms, particularly preferably 10 to 20 carbon atoms, most preferably 12 to 18 carbon atoms;
  • R 2 is an alkenyl radical having 2 to 4 carbon atoms, particularly preferably 2 or 3 carbon atoms;
  • n is a number from 1 to 20, particularly preferably 1 to 10, most preferably 2 to 8;
  • X + is 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.
  • Ri-Ph-SO 3 - X + where Ri stands for a linear or branched, saturated or unsaturated alkyl radical having 6 to 22 carbon atoms, particularly preferably 10 to 20 carbon atoms, most preferably 12 to 18 carbon atoms; Ph stands for a phenyl radical; and X + stands for a cation, preferably an alkali metal cation, particularly preferably K + or Na + .
  • 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 + .
  • 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.
  • alkoxylated fatty alcohols such as fatty alcohol ethoxylates or propoxylates
  • alkoxylated fatty amines 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
  • 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.
  • Ri 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;
  • F 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 exhibit particularly good properties in detergent compositions.
  • the detergent composition therefore preferably comprises alkoxylated fatty alcohols in an amount of 5 wt.% to 40 wt.%, particularly preferably 10 wt.% to 35 wt.%, and most preferably 15 wt.% to 30 wt.%, based in each case on the total mass of the detergent composition.
  • alkoxylated alkanolamines compounds with the following structural formula are preferably used:
  • 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.
  • 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.
  • 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.
  • the detergent composition does not comprise amphoteric surfactants.
  • Cationic surfactants are in particular fatty amine salts and quaternary ammonium compounds.
  • 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.
  • 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-( ⁇ -hydroxyacrylic acid), poly-[(3-hydroxymethyl)-hexamethylene-1,3,5-tricarboxylic acid], Poly-[
  • 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.
  • 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.
  • 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.
  • 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.
  • DTPMP diethylenetriaminepentaki
  • the detergent composition comprises at least one di- or polycarboxylic acid as a complexing agent.
  • 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.
  • 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.
  • 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.
  • 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
  • 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.
  • 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.
  • the detergent composition comprises at least one polyhydric alcohol (polyol).
  • polyols are, in particular, those alcohols having two or more OH groups and 2 to 8 carbon atoms. Polyols having 2 or 3 OH groups and 3 to 6 carbon atoms are particularly suitable.
  • Suitable polyols include, in particular, propanediol, in particular 1,2-propanediol; butanediol, in particular 1,2-butanediol, 1,3-butanediol, and 1,4-butanediol; glycerol, or mixtures thereof.
  • 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.
  • 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.
  • adjuvants 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.
  • the detergent composition may contain proteases, dispersins, lipases, tannases, mannases, and polyesterases.
  • the detergent composition comprises at least one dispersin.
  • a dispersin refers to an enzyme capable of cleaving the ß-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.
  • a suitable dispersin is the glycosidase of family 20 (classification of glycosidases according to Henrissat) from Terribacillus goriensis (NCBI reference sequence no. WP_1 70061640) 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.
  • 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, more preferably 7.5 to 9, most preferably 7.5 to 8.5.
  • the pH is determined at 20°C. If the detergent composition has too low a water content to reliably determine the pH, the composition is diluted with water for the measurement.
  • the pH is preferably adjusted by adding a suitable base.
  • the detergent composition preferably comprises a base selected from the group consisting of amines, alkali metal carbonate, and alkali metal hydroxide, more preferably selected from monoethanolamine, sodium carbonate, and sodium hydroxide.
  • the detergent composition usually contain boric acid or boric acid salts (borates) to stabilize enzymes.
  • boric acid or borates is not mandatory according to the present invention for enzyme stabilization. Rather, the invention allows the addition of boric acid or borates to be dispensed with.
  • the amount of Boric acid and borates in the detergent composition are therefore limited to no more than 1 wt.%, preferably no more than 0.5 wt.%, more preferably no more than 0.1 wt.%, most preferably no more than 0.01 wt.%, in each case based on the total mass of the detergent composition.
  • 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 components of the above-described detergent composition for improving the storage stability of the detergent composition.
  • the use serves to reduce turbidity of the detergent composition.
  • the use also serves to improve the cleaning performance of a detergent composition for textile washing with respect to blood and/or juice stains.
  • 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.
  • 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.
  • 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.
  • 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.
  • Detergent composition 3 according to the invention containing 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 contains neither a dispersin nor one of the enzyme preparations according to the invention, exhibits the weakest cleaning performance.
  • Detergent compositions 1 and 4 which contain either the enzyme preparations according to the invention (composition 4) or a dispersin (composition 1), exhibit average cleaning performance on juice stains. With regard to blood stains, composition 4 according to the invention exhibits better cleaning performance than the two comparative compositions 1 and 2.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
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Abstract

L'invention concerne une composition détergente qui peut être produite à l'aide d'une première et d'une seconde préparation enzymatique, la première préparation enzymatique comprenant une cellulase et la seconde préparation enzymatique comprenant une amylase, caractérisée en ce que la première et la seconde préparation enzymatique comprennent chacune au moins 0,5 % en poids de l'enzyme correspondante, sur la base de la masse totale d'enzyme active, au moins 45 % en poids d'eau, et de 5 % en poids à 45 % en poids de polyol, dans chaque cas sur la base de la masse totale de la préparation enzymatique. La composition détergente est caractérisée par une stabilité au stockage améliorée.
PCT/EP2024/085380 2023-12-18 2024-12-10 Composition détergente contenant de la cellulase et de l'amylase et présentant une stabilité au stockage améliorée Pending WO2025131851A1 (fr)

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DE102023212850.0A DE102023212850A1 (de) 2023-12-18 2023-12-18 Cellulase- und Amylase-haltige Waschmittelzusammensetzung mit verbesserter Lagerstabilität

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US20120270267A1 (en) 2010-01-04 2012-10-25 Novozymes A/S Alpha-Amylases
WO2017106633A1 (fr) 2015-12-18 2017-06-22 Basf Enzymes Llc Formulation liquide d'alpha-amylase
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