WO2017144623A1 - Stabilisation de protéase dans des produits de nettoyage contenant de l'alkylbenzène sulfonate - Google Patents

Stabilisation de protéase dans des produits de nettoyage contenant de l'alkylbenzène sulfonate Download PDF

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Publication number
WO2017144623A1
WO2017144623A1 PCT/EP2017/054251 EP2017054251W WO2017144623A1 WO 2017144623 A1 WO2017144623 A1 WO 2017144623A1 EP 2017054251 W EP2017054251 W EP 2017054251W WO 2017144623 A1 WO2017144623 A1 WO 2017144623A1
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Prior art keywords
cleaning agent
protease
detergent
formula
dishwashing detergent
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PCT/EP2017/054251
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German (de)
English (en)
Inventor
Detlef Buisker
Timothy O'connell
Daniela HERBST
Marianne Schmeling
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Henkel Ag & Co. Kgaa
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Publication of WO2017144623A1 publication Critical patent/WO2017144623A1/fr

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    • 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
    • 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
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/143—Sulfonic acid esters
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/042—Acids
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/046—Salts
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/122—Sulfur-containing, e.g. sulfates, sulfites or gypsum
    • 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
    • C11D3/166—Organic compounds containing borium
    • 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
    • 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
    • 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
    • C11D2111/14—Hard surfaces

Definitions

  • the present invention relates to the use of sodium formate, sodium sulfate, lower aliphatic alcohols or boric acid and their esters or salts for stabilizing a protease in a cleaning agent containing at least one compound from the class of compounds of the formula R-SO 3 " Y + (I), as
  • the present invention also relates to a cleaning agent containing at least one compound of the formula (I) as defined herein, at least one protease and at least one of the aforementioned compounds which act as a protease stabilizer.
  • enzymes in detergents have been established in the art for decades. They serve to extend the range of services of the funds concerned according to their specific activities. These include in particular hydrolytic enzymes such as proteases, amylases, lipases and cellulases. The first three hydrolyze proteins, starches and fats and thus contribute directly to soil removal. Cellulases are used in particular because of their tissue effect.
  • Another group of detergent and cleaning agent enzymes are oxidative enzymes, in particular oxidases, which, where appropriate, in combination with other components, are preferably used to bleach soiling or to produce the bleaching agents in situ.
  • enzymes which are subjected to constant optimization, further enzymes are constantly being made available for use in detergents and cleaners in order to be able to optimally address particular soiling, such as pectinases, ⁇ -glucanases, mannanases or other hemicellulases (glycosidases) Hydrolysis in particular of special vegetable polymers.
  • soiling such as pectinases, ⁇ -glucanases, mannanases or other hemicellulases (glycosidases) Hydrolysis in particular of special vegetable polymers.
  • proteases and in particular serine proteases. They serve the degradation of protein-containing stains on the cleaning material.
  • proteases are very unstable, whereby at high alkylbenzenesulfonate levels the cleaning power of the cleaning agent as a whole is reduced.
  • an improvement in the protease stability can generally be achieved with high surfactant contents, such high surfactant contents (> 24% by weight) can not be achieved with alkylbenzenesulfonates.
  • the object of the present invention was therefore to identify compounds by means of which use proteases in cleaning agents, in particular hand dishwashing detergents, with a high content of anionic surfactants of the formula (I), as defined herein, can be stabilized.
  • cleaning agents containing at least one compound of the formula (I) as defined herein, in particular at least one linear alkylbenzenesulfonate, and at least one protease, for stabilizing the protease sodium formate, sodium sulfate, a lower one aliphatic alcohol and / or boric acid, an ester and / or salts thereof is added.
  • the present invention is directed to the use of a compound selected from the group consisting of sodium formate, sodium sulfate, lower aliphatic alcohols and boric acid and their esters and salts and combinations thereof for stabilizing a protease in a detergent, preferably dishwashing detergent, especially preferred hand dishwashing detergent, containing at least one compound of the formula wherein
  • R is a linear or branched unsubstituted alkylaryl radical
  • Y is a monovalent cation or the nth part of an n-valent cation, preferably selected from the group consisting of Na + , K + , NH 4 + , Mg 2+ , Y 2 Ca 2+ 2 Mn 2+ and mixtures thereof.
  • the present invention is directed to a cleaning agent, preferably dishwashing detergent, more preferably hand dishwashing detergent containing
  • R is a linear or branched unsubstituted alkylaryl radical
  • Y consisting of a monovalent cation or the n-th part of an n-valent cation, in particular selected from the group consisting of Na +, K +, NH 4 +,% Zn 2+, 1/2 Mg 2+, 1/2 Ca 2+ 1/2 Mn 2+ and mixtures thereof, is;
  • the present invention is further directed to the use of a detergent as herein described, preferably dishwashing detergent, more preferably hand dishwashing detergent, for cleaning solid surfaces, and to a process for cleaning hard surfaces, characterized in that in at least one process step a detergent as described herein, preferably dishwashing detergent, more preferably hand dishwashing detergent, is used.
  • At least one includes, but is not limited to, 1, 2, 3, 4, 5, 6 and more.
  • fatty acids or fatty alcohols or their derivatives - unless otherwise stated - representative of branched or unbranched carboxylic acids or alcohols or their derivatives having preferably 6 to 22 carbon atoms.
  • the oxo alcohols or their derivatives which are obtainable, for example, by the RoELEN's oxo synthesis, can also be used correspondingly.
  • alkaline earth metals are referred to below as counterions for monovalent anions, this means that the alkaline earth metal is present only in half - as sufficient to charge balance - amount of substance as the anion.
  • a cleaning agent is to be understood as meaning all agents which are suitable for cleaning solid surfaces, for example dishwashing agents, in particular hand dishwashing detergents.
  • dishwashing agents in particular hand dishwashing detergents.
  • Other suitable ingredients will be described in detail below.
  • a protease is to be understood as meaning all enzymes which are capable of hydrolyzing acid amide linkages of proteins. Suitable proteases are also described in more detail below.
  • the cleaning agent according to the invention contains at least one protease and at least one compound containing the at least one protease in the presence of a compound from the class of anionic surfactants of the formula
  • R represents a linear or branched unsubstituted alkylaryl group.
  • Y stands for a monovalent cation or the n-th part of an n-valent cation, the alkali metal ions being preferred, and Na + or K + being preferred, Na + being extremely preferred.
  • Other cations Y + may be selected from NhV, Mn 2+ , and mixtures thereof.
  • Alkylaryl refers to organic radicals consisting of an alkyl radical and an aromatic radical Typical examples of such radicals include but are not limited to alkylbenzene radicals such as benzyl, butylbenzene radicals, nonylbenzene radicals, decylbenzene radicals, undecylbenzene radicals. Dodecylbenzene radicals, tridecylbenzene radicals and the like.
  • such surfactants are selected from linear or branched alkylbenzenesulfonates of the formula A-1
  • R ' and R " together contain from 9 to 19, preferably from 1 to 15, and in particular from 1 to 13, carbon atoms
  • a particularly preferred representative can be described by the formula A-1a:
  • the compound of formula (I) is preferably the sodium salt of a linear alkyl benzene sulfonate.
  • the at least one compound from the class of anionic surfactants of the formula (I) is present in an amount of 1 to 30% by weight, preferably 6 to 24% by weight in the washing or cleaning agent, in each case based on the total weight of the detergent.
  • the cleaning agent may contain at least one other surfactant in addition to the at least one compound from the class of anionic surfactants of the formula R-SO3 " Y + (I)."
  • Further surfactants are, in particular, other anionic surfactants, nonionic surfactants and mixtures thereof also cationic, zwitterionic and amphoteric surfactants in question.
  • the cleaning agents according to the invention preferably contain at least one further anionic surfactant, in particular an anionic surfactant of the formula
  • R is a linear or branched, substituted or unsubstituted alkyl, aryl or alkylaryl radical, preferably a linear, unsubstituted alkyl radical, more preferably a fatty alcohol radical.
  • Preferred radicals R are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl radicals and mixtures thereof, where the representatives with even number of carbon atoms are preferred.
  • radicals R are derived from C 12 -C 18 -fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or C 10 -C 20 oxo alcohols.
  • AO represents an ethylene oxide (EO) or propylene oxide (PO) moiety, preferably an ethylene oxide moiety.
  • the index n stands for an integer from 1 to 50, preferably from 1 to 20 and in particular from 2 to 10. Most preferably, n stands for the numbers 2, 3, 4, 5, 6, 7 or 8.
  • X is a monovalent cation or the nth part of an n-valent cation, the alkali metal ions are preferred, and Na + or K + are preferred, Na + being extremely preferred.
  • Other cations X + can be selected from NhV, Mn 2+ , and mixtures thereof.
  • detergents in various embodiments thus contain at least one further anionic surfactant selected from fatty alcohol ether sulfates of the formula
  • the cleaning agent contains the at least one additional anionic surfactant of the formula (II) in an amount of 2-10% by weight, preferably 3-8% by weight, based on the total weight of the cleaning agent.
  • anionic surfactants are the alkyl sulfates of the formula
  • R 2 is a linear or branched, substituted or unsubstituted alkyl radical, preferably a linear, unsubstituted alkyl radical, more preferably a fatty alcohol radical.
  • Preferred radicals R 2 are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl radicals and mixtures thereof, where the representatives with even number of carbon atoms Atoms are preferred.
  • Particularly preferred radicals R 2 are derived from Ci2-CI8 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or of Cio-C2o-oxo alcohols.
  • Y stands for a monovalent cation or the n-th part of an n-valent cation, the alkali metal ions being preferred, and Na + or K + being preferred, Na + being extremely preferred.
  • Other cations Y + may be selected from NhV, Mn 2+ , and mixtures thereof.
  • these surfactants are selected from fatty alcohol sulfates of formula A-3 ⁇ L ⁇ SO, Na
  • the agents comprise at least one nonionic surfactant, in particular at least one fatty alcohol alkoxylate. In various embodiments, the cleaning agents therefore contain at least one nonionic surfactant of the formula
  • R 3 is a linear or branched, substituted or unsubstituted alkyl radical
  • AO for an ethylene oxide (EO) or propylene oxide (PO) grouping
  • n stands for integers from 1 to 50.
  • R 3 is a linear or branched, substituted or unsubstituted alkyl radical, preferably a linear, unsubstituted alkyl radical, particularly preferably a fatty alcohol radical.
  • Preferred radicals R 2 are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl radicals and mixtures thereof, where the representatives with even number of carbon atoms Atoms are preferred.
  • radicals R 3 are derived from C 12-18 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or from C 10 -C 20 oxo alcohols.
  • AO represents an ethylene oxide (EO) or propylene oxide (PO) moiety, preferably an ethylene oxide moiety.
  • EO ethylene oxide
  • PO propylene oxide
  • m is an integer from 1 to 50, preferably from 1 to 20 and especially from 2 to 10. Most preferably, m is the numbers 2, 3, 4, 5, 6, 7 or 8.
  • nonionic surfactants which may be included in the described compositions within the meaning of the present invention include, but are not limited to, alkyl glycosides, alkoxylated fatty acid alkyl esters, amine oxides, fatty acid alkanolamides, hydroxy mixed ethers, sorbitan fatty acid esters, polyhydroxy fatty acid amides, and alkoxylated alcohols.
  • Suitable amphoteric surfactants are, for example, betaines of the formula (R 1, XR 1, XR 3) N + C 1 COO-, in which R i is an alkyl radical optionally interrupted by hetero atoms or heteroatom groups having 8 to 25, preferably 10 to 21 carbon atoms and R iv and R v are identical or different alkyl radicals having 1 to 3 carbon atoms, in particular Cio-Cis-alkyl dimethylcarboxymethylbetain and Cn-Ci7-alkylamidopropyl-dimethylcarboxymethylbetain.
  • Suitable cationic surfactants include the quaternary ammonium compounds of the formula (R vi ) (R vii ) (R viii ) (R ix ) N + X " , in which R vi to R ix for four identical or different, in particular two long and two short chain, alkyl radicals and X "are an anion, in particular a halide ion, for example, didecyldimethylammonium chloride, Alkylbenzyldidecylammoniumchlorid and mixtures thereof.
  • quaternary surface-active compounds in particular having a sulfonium, phosphonium, iodonium or arsonium group, which are also known as antimicrobial agents.
  • the agent can be designed with an antimicrobial effect or its possibly existing antimicrobial effect due to other ingredients can be improved.
  • the total amount of the surfactants based on the weight of the composition is 2 to 30 wt .-%, preferably 5 to 26 wt .-%.
  • the enzyme stabilizer according to the invention is a compound selected from the group consisting of sodium formate, sodium sulfate, lower aliphatic alcohols and boric acid and their esters and salts. Of course, two or more of these compounds may be used in combination.
  • the salts of the compounds mentioned can also be used in the form of hydrates, such as, for example, sodium sulfate decahydrate.
  • lower aliphatic alcohols as used herein includes monoalcohols, diols, and higher alcohols having up to 6 carbon atoms.
  • polyols for example, glycerol, (mono) ethylene glycol, (Mono) Propylene glycol or sorbitol, without the invention being limited to these.
  • the at least one enzyme stabilizer is glycerin, monopropylene glycol, or a combination thereof.
  • an agent of the invention may also contain at least one further stabilizer.
  • Such stabilizers are known in the art.
  • Reversible protease inhibitors protect the enzymes contained in a detergent or cleanser from proteolytic degradation by reversibly inhibiting the enzymatic activity of the proteases contained in the agent.
  • reversible protease inhibitors benzamidine hydrochloride, boronic acids or their salts or esters are frequently used, including in particular derivatives with aromatic groups, such as ortho-, meta- or para-substituted phenylboronic acids, in particular 4-formylphenyl-boronic acid, or the salts or esters of mentioned compounds.
  • peptide aldehydes that is oligopeptides with a reduced C-terminus, especially those of 2 to 50 monomers are used for this purpose.
  • peptidic reversible protease inhibitors include ovomucoid and leupeptin.
  • specific, reversible peptide inhibitors for the protease subtilisin and fusion proteins from proteases and specific peptide inhibitors are suitable.
  • enzyme stabilizers are amino alcohols such as mono-, di-, triethanol- and -propanolamine and mixtures thereof, aliphatic carboxylic acids up to C12, such as succinic acid, other dicarboxylic acids or salts of said acids. End-capped fatty acid amide alkoxylates are also suitable for this purpose. Some organic acids used as builders can additionally stabilize an enzyme. Also calcium and / or magnesium salts are used for this purpose, such as calcium acetate.
  • Polyamide oligomers or polymeric compounds such as lignin, water-soluble vinyl copolymers or cellulose ethers, acrylic polymers and / or polyamides stabilize the enzyme preparation, inter alia, against physical influences or pH fluctuations.
  • Polyamine N-oxide containing polymers act simultaneously as enzyme stabilizers and as dye transfer inhibitors.
  • Other polymeric stabilizers are linear Cs-ds polyoxyalkylenes.
  • alkylpolyglycosides can stabilize the enzymatic components of the agent according to the invention and, preferably, are capable of additionally increasing their performance.
  • Crosslinked N-containing compounds preferably perform a dual function as soil release agents and as enzyme stabilizers.
  • Hydrophobic, nonionic polymer stabilizes in particular an optionally contained cellulase. Reducing agents and antioxidants increase the stability of the enzymes to oxidative degradation; For example, sulfur-containing reducing agents are familiar, for example sodium sulfite and reducing sugars.
  • the protease is present in an amount of 0.01-0.5% by weight, preferably 0.05-0.4% by weight, and the enzyme stabilizer in an amount of 0.01 to 3 wt .-%, preferably 0.5 to 2 wt .-%, based on the total weight of the cleaning agent in this.
  • the enzyme and the enzyme stabilizer may be pre-formulated in an enzyme composition.
  • the enzyme protein forms only a fraction of the total weight of conventional enzyme preparations.
  • Preferably used protease preparations contain between 0, 1 and 40 wt .-%, preferably between 0.2 and 30 wt .-%, particularly preferably between 0.4 and 20 wt .-% and in particular between 0.8 and 10 wt .-% of the enzyme protein.
  • the enzyme stabilizer may be contained in the enzyme composition in an amount of 0.05-35% by weight, preferably 0.05-10% by weight, based on the total weight. This enzyme composition can then be used in cleaning agents according to the invention in amounts which lead to the above-mentioned final concentrations in the cleaning agent.
  • the protein concentration can be determined by known methods, for example the BCA method (bicinchoninic acid, 2,2'-biquinolyl-4,4'-dicarboxylic acid) or the biuret method.
  • BCA method bicinchoninic acid, 2,2'-biquinolyl-4,4'-dicarboxylic acid
  • the determination of the active protein concentration takes place via a titration of the active sites using a suitable irreversible inhibitor (for proteases, for example phenylmethylsulfonyl fluoride (PMSF)) and determination of the residual activity (compare M. Bender et al., J. Am. Chem. Soc , 24 (1966), pp. 5890-5913).
  • PMSF phenylmethylsulfonyl fluoride
  • the proteases used are preferably alkaline serine proteases. They act as nonspecific endopeptidases, that is, they hydrolyze any acid amide linkages that are internal to peptides or proteins, thereby causing degradation of proteinaceous soils on the articles to be cleaned. Their pH optimum is usually in the clearly alkaline range.
  • the protease stabilized according to the invention is therefore preferably a serine protease, in particular a subtilase, more preferably a subtilisin.
  • the subtilisin may be a wild-type enzyme or a subtilisin variant, wherein the wild-type enzyme or the starting enzyme of the variant is preferably selected from one of the following:
  • alkaline protease from Bacillus amyloliquefaciens ⁇ '
  • alkaline protease from Bacillus licheniformis subtilisin Carlsberg
  • alkaline protease from Bacillus lentus, preferably from Bacillus lentus (DSM 5483),
  • alkaline protease from Bacillus sp. (DSM 14390) or an at least 98.5% identical alkaline protease, and
  • alkaline protease from Bacillus sp. (DSM 14392) or an at least 98, 1% identical alkaline protease.
  • subtilisin 309 examples of the proteases used in the agents described herein are subtilisin 309 or functional fragments / variants thereof and variants of the Bacillus lentus alkaline protease or variants thereof.
  • Subtilisin 309 is sold under the trade name Savinase® by Novozymes A / S, Bagsvaerd, Denmark.
  • subtilisin 309 from Bacillus lentus optimized enzyme variants are available under the trade names Blaze® and Ovozyme® from Novozymes, which represent a preferred embodiment of the invention.
  • alkaline protease from Bacillus lentus DSM 5483 for example, derived under the name BLAP® protease variants are derived, preferred here are the available under the trade name PUR® by the company Novozymes enzymes, and those under the name Thor® from the company Thor Specialties (UK) Ltd. available enzymes.
  • the enzymes to be used may also be formulated together with accompanying substances, for example from the fermentation.
  • the enzymes are preferably used as enzyme liquid formulation (s).
  • the proteases are generally not provided in the form of the pure protein, but rather in the form of stabilized, storable and transportable preparations.
  • Such prefabricated preparations include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, especially in the case of liquid or gel-form detergents, solutions of the enzymes, advantageously as concentrated as possible, low in water and / or added with stabilizers or further auxiliaries.
  • the enzymes may be encapsulated for both the solid and liquid dosage forms, for example by spray-drying or extruding the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are entrapped as in a solidified gel or in those of the core-shell type, in which an enzyme-containing core with a water, air and / or chemical impermeable protective layer is coated.
  • a preferably natural polymer or in the form of capsules for example those in which the enzymes are entrapped as in a solidified gel or in those of the core-shell type, in which an enzyme-containing core with a water, air and / or chemical impermeable protective layer is coated.
  • further active ingredients for example stabilizers, emulsifiers, pigments, bleaches or dyes, may additionally be applied.
  • Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes.
  • such granules for example by applying
  • Detergents according to the invention may contain, in addition to the at least one protease, one or more further enzymes, in particular from the following group: amylases, hemicellulases, cellulases, lipases and oxidoreductases.
  • the amylase (s) is preferably an ⁇ -amylase.
  • the hemicellulase is preferably a ⁇ -glucanase, a pectinase, a pullulanase and / or a mannanase.
  • the cellulase is preferably a cellulase mixture or a one-component cellulase, preferably or predominantly an endoglucanase and / or a cellobiohydrolase.
  • the oxidoreductase is preferably an oxidase, in particular a choline oxidase, or a perhydrolase.
  • the cleaning agents according to the present invention are liquid and contain water as the main solvent, i. they are aqueous cleaning agents.
  • the water content of the aqueous composition according to the invention is usually from 15 to 90% by weight, preferably from 20 to 75% by weight, particularly preferably from 25 to 60% by weight. In various embodiments, the water content is more than 5 wt .-%, preferably more than 15 wt .-% and particularly preferably more than 25 wt .-%, each based on the total amount of detergent.
  • non-aqueous solvents may be added to the detergent.
  • Suitable non-aqueous solvents include mono- or polyhydric alcohols, alkanolamines or glycol ethers, provided that they are miscible with water in the specified concentration range.
  • the solvents are preferably selected from ethanol, n-propanol, i-propanol, butanols, glycol, propanediol, butanediol, methylpropanediol, glycerol, diglycol, propyldiglycol, butyldiglycol, hexyleneglycol, ethylene glycol methyl ether, ethylene glycol ethyl ether,
  • Ethylene glycol propyl ether ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl ether, propylene glycol ethyl ether,
  • Propylene glycol propyl ether dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, methoxytriglycol, ethoxytriglycol, butoxytriglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-ol methoxybutanol, propylene glycol t-butyl ether, di-n-octyl ether and mixtures of these solvents.
  • the one or more non-aqueous solvents is usually contained in an amount of 0.1 to 10% by weight, preferably 1 to 8% by weight, based on the total composition.
  • the cleaning agents according to the invention may contain further ingredients which further improve the performance and / or aesthetic properties of the cleaning agent.
  • these include, for example, additives for improving the drainage and drying behavior, for adjusting the viscosity and / or for stabilization, and other cleaning agents and additives customary in detergents, such as UV stabilizers, perfume, pearlescing agents, dyes, corrosion inhibitors, preservatives, bittering agents, organic Salts, disinfectants, structuring polymers, defoamers, encapsulated ingredients (eg encapsulated perfume), pH adjusters and skin feel-improving or nourishing additives.
  • additives for improving the drainage and drying behavior for adjusting the viscosity and / or for stabilization
  • other cleaning agents and additives customary in detergents such as UV stabilizers, perfume, pearlescing agents, dyes, corrosion inhibitors, preservatives, bittering agents, organic Salts, disinfectants, structuring polymers, defoamers, encapsulated ingredients (eg encapsulated perfume), pH adjust
  • the agent according to the invention may contain one or more additives from the group of surfactants, polymers and builders (builders), usually in an amount of 0.001 to 5% by weight, preferably 0, 01 to 4 wt .-%, in particular 0, 1 to 3 wt .-%, particularly preferably 0.2 to 2 wt .-%, most preferably 0.5 to 1, 5 wt .-%, for example 1 part by weight. %.
  • one or more additives from the group of surfactants, polymers and builders (builders) usually in an amount of 0.001 to 5% by weight, preferably 0, 01 to 4 wt .-%, in particular 0, 1 to 3 wt .-%, particularly preferably 0.2 to 2 wt .-%, most preferably 0.5 to 1, 5 wt .-%, for example 1 part by weight. %.
  • polymeric thickeners are the polycarboxylates which have a thickening effect as polyelectrolytes, preferably homopolymers and copolymers of acrylic acid, in particular acrylic acid copolymers such as acrylic acid-methacrylic acid copolymers, and the polysaccharides, in particular heteropolysaccharides, and other customary thickening polymers.
  • Suitable polysaccharides or heteropolysaccharides are the polysaccharide gums, for example gum arabic, agar, alginates, carrageenans and their salts, guar, guar gum, tragacanth, gellan, Ramzan, dextran or xanthan and their derivatives, for example propoxylated guar, and also their mixtures.
  • polysaccharide thickeners such as starches or cellulose derivatives
  • starches or cellulose derivatives may alternatively or preferably be used in addition to a polysaccharide gum, for example starches of various origins and starch derivatives, for example hydroxyethyl starch, starch phosphate esters or starch acetates, or carboxymethylcellulose or its sodium salt, methyl, ethyl, hydroxyethyl, Hydroxypropyl, hydroxypropyl methyl or hydroxyethyl methyl cellulose or cellulose acetate.
  • starches of various origins and starch derivatives for example hydroxyethyl starch, starch phosphate esters or starch acetates, or carboxymethylcellulose or its sodium salt, methyl, ethyl, hydroxyethyl, Hydroxypropyl, hydroxypropyl methyl or hydroxyethyl methyl cellulose or cellulose acetate.
  • Acrylic acid polymers suitable as polymeric thickeners are, for example, high molecular weight homopolymers of acrylic acid crosslinked with a polyalkenyl polyether, in particular an allyl ether of sucrose, pentaerythritol or propylene (INCI Carbomer), which are also referred to as carboxyvinyl polymers.
  • a polyalkenyl polyether in particular an allyl ether of sucrose, pentaerythritol or propylene (INCI Carbomer), which are also referred to as carboxyvinyl polymers.
  • acrylic acid copolymers are the following acrylic acid copolymers: (i) Copolymers of two or more monomers from the group of acrylic acid, methacrylic acid and their simple ester, preferably formed with C 1-4 alkanols (INCI acrylates copolymer), to which approx the copolymers of methacrylic acid, butyl acrylate and methyl methacrylate (CAS 25035-69-2) or of butyl acrylate and methyl methacrylate (CAS 25852-37-3); (ii) crosslinked high molecular weight acrylic acid copolymers, such as those crosslinked with an allyl ether of sucrose or pentaerythritol copolymers of Cio-30-alkyl acrylates with one or more monomers from the group of acrylic acid, methacrylic acid and their simple, preferably with Ci-4-alkanols formed esters (INCI acrylates / C 10-30 alkyl acrylate crosspolymer).
  • the content of polymeric thickener is usually not more than 8 wt .-%, preferably between 0, 1 and 7 wt .-%, particularly preferably between 0.5 and 6 wt .-%, in particular between 1 and 5 wt .-% and most preferably between 1, 5 and 4 wt .-%, for example between 2 and 2.5 wt .-%, based on the total weight of the cleaning agent.
  • one or more dicarboxylic acids and / or salts thereof may be added, in particular a composition of Na salts of adipic, succinic and glutaric acid, for example as available under the trade name Sokalan ® DSC is.
  • the use is advantageously carried out in amounts of 0.1 to 8 wt .-%, preferably 0.5 to 7 wt .-%, in particular 1, 3 to 6 wt .-% and particularly preferably 2 to 4 wt .-%, based on the total weight of the cleaning agent.
  • the agent according to the invention is preferably free from dicarboxylic acid (salts).
  • one or more further can - especially in hand dishwashing detergents and cleaning agents for hard surfaces - conventional auxiliaries and additives, in particular UV stabilizers, perfumes, pearlescent agents (INCI opacifying agents, for example glycol distearate, for example Cutina ® AGS from Cognis, respectively. this containing mixtures, for example the Euperlane ® Fa.
  • conventional auxiliaries and additives in particular UV stabilizers, perfumes, pearlescent agents (INCI opacifying agents, for example glycol distearate, for example Cutina ® AGS from Cognis, respectively. this containing mixtures, for example the Euperlane ® Fa.
  • the pH of the agent according to the invention can be adjusted by means of customary pH regulators, for example acids such as mineral acids or citric acid and / or alkalis such as sodium or potassium hydroxide, wherein - in particular with the desired hand tolerance - a range from 4 to 9, preferably 5 to 8, in particular 5.5 to 7.5, is preferred.
  • acids such as mineral acids or citric acid
  • alkalis such as sodium or potassium hydroxide
  • the agent according to the invention may contain one or more buffer substances (INCI Buffering Agents), usually in amounts of 0.001 to 5 wt .-%, preferably 0.005 to 3 wt .-%, in particular 0 , 01 to 2 wt .-%, particularly preferably 0.05 to 1 wt .-%, most preferably 0.1 to 0.5 wt .-%, for example, 0.2 wt .-%.
  • buffer substances which are at the same time complexing agents or even chelating agents (INCI chelating agents).
  • Particularly preferred buffer substances are the citric acid or the citrates, in particular the sodium and potassium conduction rates, for example trisodium citrate-2H2O and tripotassium citrate H20.
  • composition according to the invention can be used for cleaning hard surfaces, in particular for manual cleaning of dishes.
  • the subject matter of the present invention is also a process for the cleaning of hard surfaces, which is characterized in that in at least one process step a composition described herein is used.
  • Another object of the invention is the use of a hard surface cleaning agent described herein.
  • a still further subject of the invention is the use of the compounds described herein for stabilizing a protease in a detergent containing at least one compound from the class of compounds of formula (I) as described herein.
  • Example 2 formulation according to the invention
  • AW initial value
  • 2W 2 weeks
  • 4 weeks 4 weeks
  • 8 weeks 8 weeks
  • RA residual activity

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Abstract

La présente invention concerne l'utilisation de formiate de sodium, de sulfate de sodium, d'alcools aliphatiques à bas poids moléculaire ou d'acide borique ainsi que leur esters et sels pour stabiliser une protéase dans un produit de nettoyage contenant au moins un composé issu de la catégorie des composés de formule R-SO3 _Y+ (I) telle que définie selon l'invention. L'invention concerne par ailleurs un produit de nettoyage contenant au moins un composé de formule (I) telle que définie selon l'invention, au moins une protéase et au moins l'un des composés précités qui agissent comme stabilisateur de protéase.
PCT/EP2017/054251 2016-02-24 2017-02-23 Stabilisation de protéase dans des produits de nettoyage contenant de l'alkylbenzène sulfonate WO2017144623A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102016202815.4A DE102016202815A1 (de) 2016-02-24 2016-02-24 Stabilisierung von Protease in Alkylbenzolsulfonat-haltigen Reinigungsmitteln
DE102016202815.4 2016-02-24

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992006154A1 (fr) * 1990-09-28 1992-04-16 The Procter & Gamble Company Tensioactifs d'amides de l'acide gras de polyhydroxy destines a ameliorer l'efficacite des enzymes
WO1995029223A1 (fr) * 1994-04-26 1995-11-02 Novo Nordisk A/S Acides naphtaline-boroniques
WO2004009752A1 (fr) * 2002-07-20 2004-01-29 Cj Corporation Composition detergente liquide alcaline
US20140228274A1 (en) * 2011-07-01 2014-08-14 Novozymes A/S Liquid Detergent Composition

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992006154A1 (fr) * 1990-09-28 1992-04-16 The Procter & Gamble Company Tensioactifs d'amides de l'acide gras de polyhydroxy destines a ameliorer l'efficacite des enzymes
WO1995029223A1 (fr) * 1994-04-26 1995-11-02 Novo Nordisk A/S Acides naphtaline-boroniques
WO2004009752A1 (fr) * 2002-07-20 2004-01-29 Cj Corporation Composition detergente liquide alcaline
US20140228274A1 (en) * 2011-07-01 2014-08-14 Novozymes A/S Liquid Detergent Composition

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
M. BENDER ET AL., J. AM. CHEM. SOC., vol. 88, no. 24, 1966, pages 5890 - 5913

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