EP4504884A1 - Élimination des poils au moyen d?un détergent/d?additifs pour détergent contenant des enzymes - Google Patents

Élimination des poils au moyen d?un détergent/d?additifs pour détergent contenant des enzymes

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Publication number
EP4504884A1
EP4504884A1 EP23709408.1A EP23709408A EP4504884A1 EP 4504884 A1 EP4504884 A1 EP 4504884A1 EP 23709408 A EP23709408 A EP 23709408A EP 4504884 A1 EP4504884 A1 EP 4504884A1
Authority
EP
European Patent Office
Prior art keywords
oil
weight
acid
agent
bleach
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP23709408.1A
Other languages
German (de)
English (en)
Inventor
Shohana ISLAM
Susanne Wieland
Margret VAN LIER
Rainer Sorg
Lea BERG
Walter Heberlein
Sylvia Aust
Ramona Jasny
Christina Roeleke
Karin Kania
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP4504884A1 publication Critical patent/EP4504884A1/fr
Pending legal-status Critical Current

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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
    • C11D3/38609—Protease or amylase in solid 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
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • 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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • C11D3/3917—Nitrogen-containing 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3947—Liquid compositions
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12Y—ENZYMES
    • C12Y304/00—Hydrolases acting on peptide bonds, i.e. peptidases (3.4)
    • C12Y304/24—Metalloendopeptidases (3.4.24)
    • C12Y304/24011—Neprilysin (3.4.24.11), i.e. enkephalinase or neutral endopeptidase 24.11
    • 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 present invention relates to a method for removing hair from textiles, wherein a detergent and/or detergent additive containing at least one protease, at least one bleach and at least one bleach activator is used in at least one method step. Furthermore, the present invention is directed to the use of a detergent and/or detergent additive for removing hair from textiles, the detergent and/or detergent additive containing at least one protease, at least one bleach and at least one bleach activator. The invention further relates to the use of a protease for removing hair from textiles.
  • Pet owners have the problem that a significant amount of pet hair usually remains on clothing and pet blankets. When washing such dirty textile items, hair can get caught in the machine and/or become attached to items.
  • bleaching agents e.g. sodium percarbonate, sodium carbonate
  • bleach activators e.g. tetraacetylethylenediamine (TAED, nonanoyloxybenzenesulfonate (NOBS), dodecanoyloxybenzenesulfonate (LOBS), decanoyloxybenzoic acid (DOBA), Tinocat ® TRS KB2 (BASF)
  • TAED tetraacetylethylenediamine
  • NOBS nonanoyloxybenzenesulfonate
  • LOBS dodecanoyloxybenzenesulfonate
  • DOBA decanoyloxybenzoic acid
  • BASF Tinocat ® TRS KB2
  • a textile detergent and/or care agent and/or a textile detergent additive is used in at least one process step, the agent and/or additive comprising at least one protease, at least one bleaching agent and at least one bleach activator .
  • a first subject of the present invention is therefore a method for removing hair from textiles and/or the interior of a washing machine, wherein in at least one process step a textile detergent and/or care product and/or a textile detergent additive containing at least one protease and at least one bleaching agent and at least one bleach activator is used.
  • the invention also relates to the use of a textile detergent and/or care product and/or a textile detergent additive for removing hair from textiles and/or the interior of a washing machine, wherein the agent contains at least one protease, at least one bleach and at least one bleach activator.
  • the invention also relates to the use of a protease for removing hair from textiles and/or the interior of a washing machine, the protease being used in combination with at least one bleaching agent and at least one bleach activator.
  • the subject matter of the invention includes all conceivable solid and liquid detergent types as well as combination products thereof, both concentrates and undiluted agents, for use on a commercial scale, in the washing machine or for hand washing.
  • the agents within the scope of the invention also include washing aids which are added to the actual detergent when washing textiles manually or by machine in order to achieve a further effect.
  • detergents within the scope of the invention also include textile pre- and post-treatment agents, i.e. those agents with which the item of laundry is brought into contact before the actual laundry, for example to dissolve stubborn dirt, and also those agents that are used in a step following the actual textile washing give the laundry other desirable conditioning properties such as a pleasant feel, crease resistance or low static charge.
  • At least one includes, but is not limited to, 1, 2, 3, 4, 5, 6 and more.
  • the information refers to the type of ingredient and not to the absolute number of molecules.
  • At least one surfactant therefore means, for example, at least one type of surfactant, i.e. it can mean one type of surfactant or a mixture of several different surfactants.
  • the information refers to all compounds of the specified type that are contained in the composition/mixture, i.e. that the composition does not contain any other compounds of this type beyond the specified amount of the corresponding compounds.
  • the number-average molar mass M n When reference is made herein to molar masses, this information always refers to the number-average molar mass M n , unless explicitly stated otherwise.
  • the number average molecular weight can be determined, for example, using gel permeation chromatography (GPC) according to DIN 55672-1:2007-08 with THF Eluent can be determined.
  • the weight-average molecular weight Mw can also be determined using GPC, as described for M n .
  • alkaline earth metals are mentioned below as counterions for monovalent anions, this means that the alkaline earth metal is of course only present in half the amount of substance as the anion - which is sufficient to balance the charge.
  • Liquid as used in the context of the present invention means all flowable compositions (at 20°C, 1013 bar), including gels and paste-like compositions, as well as non-Newtonian liquids that have a yield point.
  • Solid as used herein in the context of the present invention means a powder, granular, extrudate or compact composition.
  • a substance for example a composition or an agent, is solid according to the definition of the invention if it is in the solid state at 25 ° C and 1013 mbar.
  • a substance e.g. a composition or an agent, is liquid according to the definition of the invention if it is in the liquid state at 25 ° C and 1013 mbar. Liquid also includes gel form.
  • Phosphate-free and “phosphonate-free”, as used herein, means that the composition in question is essentially free of phosphates or phosphonates, i.e. in particular phosphates or phosphonates in amounts less than 0.1% by weight, preferably less than 0 .01% by weight, based on the respective composition.
  • An agent according to the invention can be a single-component agent or a multi-component agent.
  • the term “single-component agent” refers to an agent which consists of only a single component.
  • spatially separated in relation to the components of the agent, as used herein means that the individual components cannot come into contact with one another prior to use of the agent.
  • the means for this purpose is provided in a multi-chamber packaging, such as a bottle, tube or a pouch, in particular a two-chamber bottle or a two-chamber pouch, with a respective individual component being located in a separate chamber, separate from the other component(s).
  • component refers to a part of the product that can be distinguished from a possibly further component of the product based on one or more characteristics, e.g. type and/or quantity of its ingredients, physical properties, external appearance, etc.
  • Individual components of the agent can be present in liquid form, as defined herein, or in solid form, as defined herein, and advantageously spatially separated from one another.
  • detergent and/or cleaning agent refers to a composition for cleaning textiles and/or hard surfaces, especially tableware, as explained in the description.
  • the term "textile” as used herein means any textile material, including yarns, yarn precursors, fibers, nonwovens, natural materials, synthetic materials and all other textile materials, fabrics made from these materials and products made from fabrics (e.g. garments and other articles ).
  • the textile or fabric can be in the form of knitted fabrics, woven fabrics, denims, nonwovens, felts, yarns and terry cloth.
  • the textile can be based on cellulose, such as natural cellulose fibers such as cotton, flax/linen, jute, ramie, sisal or coconut fibers, or artificially produced cellulose fibers (e.g. from cellulose) such as viscose/rayon, cellulose acetate fibers (Tricell), lyocell or mixtures thereof.
  • the textile or fabric can also consist of non-cellulosic fibers, for example natural polyamides such as wool, camel, cashmere, mohair, rabbit and silk or synthetic polymers such as nylon, aramid, polyester, acrylic, polypropylene and spandex/elastane or mixtures thereof as well from mixtures of cellulose fibers and non-cellulose fibers.
  • non-cellulosic fibers for example natural polyamides such as wool, camel, cashmere, mohair, rabbit and silk or synthetic polymers such as nylon, aramid, polyester, acrylic, polypropylene and spandex/elastane or mixtures thereof as well from mixtures of cellulose fibers and non-cellulose fibers.
  • mixtures are mixtures of cotton and/or rayon/viscose with one or more accompanying materials such as wool, synthetic fibers (e.g. polyamide fibers, acrylic fibers, polyester fibers, polyvinyl chloride fibers, polyurethane fibers, polyurea fibers, aramid fibers) and
  • the fabric can be conventional washable laundry, e.g. soiled household laundry.
  • fabric or “garment” is used, it is intended to include the broader term “textiles”.
  • Figure 1 shows scanning electron micrographs, which were used to evaluate the structure of animal hair after treatment with different detergent formulations in the course of a simulated washing process (according to Example 4).
  • An agent to be used according to the invention comprises at least one protease, at least one bleaching agent and at least one bleach activator.
  • Proteases which are suitable in the context of the present invention include all proteases suitable for use in textile detergents and/or care products.
  • proteases are the subtilisins BPN' from Bacillus amyloliquefaciens and Carlsberg from Bacillus licheniformis, the protease PB92, the subtilisins 147 and 309, the protease from Bacillus lentus, subtilisin DY and the enzymes that can be assigned to the subtilases, but no longer to the subtilisins in the narrower sense thermitase, proteinase K and the proteases TW3 and TW7.
  • Subtilisin Carlsberg is available in a further developed form under the trade name Alcalase® from the company Novozymes.
  • subtilisins 147 and 309 are sold by the company Novozymes under the trade names Esperase® and Savinase®, respectively.
  • the protease variants known as BLAP® are derived from the protease from Bacillus lentus DSM 5483.
  • proteases are, for example, those under the trade names Durazym®, Relase®, Everlase®, Nafizym®, Natalase®, Kannase® and Ovozyme® from the company Novozymes, which under the trade names Purafect®, Purafect® OxP, Purafect® Prime, Excellase® and Properase® from the company Danisco/Genencor, which sells under the trade name Protosol® from the company Advanced Biochemicals Ltd., which sells under the trade name Wuxi® from the company Wuxi Snyder Bioproducts Ltd., which trades under the trade names Proleather® and Protease P ® from Amano Pharmaceuticals Ltd., and the enzyme available under the name Proteinase K-16 from Kao Corp.
  • proteases from Bacillus gibsonii and Bacillus pumilus, which are disclosed in the international patent applications WO 2008/086916 and WO 2007/131656.
  • Further proteases that can be used advantageously are disclosed in the patent applications WO 91/02792, WO 2008/007319, WO 93/18140, WO 01/44452, GB 1243784, WO 96/34946, WO 2002/029024 and WO 2003/057246.
  • proteases that can be used are those that are naturally present in the microorganisms Stenotrophomonas maltophilia, in particular Stenotrophomonas maltophilia K279a, Bacillus intermedius and Bacillus sphaericus.
  • BLAP Bacillus lentus DSM 5483 protease
  • Such particularly suitable proteases are described, for example, in WO 2016/096714.
  • proteases which have keratolytic activity are particularly suitable.
  • the term “having keratolytic activity” means that a corresponding enzyme is able to cleave peptide bonds (-NH-CO-) of the keratin substrate.
  • Non-limiting examples of commercially available proteases that exhibit keratolytic activity include ALCALASE®, SAVINASE®, SAVINASE® ULTRA, SAVINASE® EVITY®, SAVINASE® EVERIS®, ESPERASE® (Novozymes); BLAPTM and BLAPTM variants (Henkel), Valkerase® (BRI Enzymes), KerA (Creative Enzymes).
  • the at least one protease is a protease with keratolytic activity.
  • the at least one protease is a keratinase.
  • keratinases are proteolytic enzymes that catalyze the cleavage of peptide bonds in proteins. Keratinases fall under the Enzyme Commission Number (EC number) 3.4.21/24/99 and are serine or metalloproteases or proteases with an unknown mechanism of action.
  • the at least one protease is correspondingly selected from the group consisting of proteases with keratolytic activity, preferably from the group consisting of keratinases.
  • Keratinases suitable in the context of the present invention can come from various organisms. Suitable microorganisms are selected from the group consisting of the genera of Escherichia, Klebsiella, Bacillus, Staphylococcus, Corynebacterium, Arthrobacter, Streptomyces, Stenotrophomonas and Pseudomonas, preferably Bacillus, more preferably Bacillus subtilis or Bacillus cereus. Suitable strains such as Bacillus subtilis BF11 or Bacillus cereus BF21 are described, for example, in Lakshmi et al. (“Efficient Degradation of Feather by Keratinase Producing Bacillus sp.” In International Journal of Microbiology, Volume 2013, Article ID 608321, pages 1-7).
  • the keratinase used in the detergent according to the invention is a keratinase commercially available under the trade name “KERATOCLEAN® HYDRA PB” Micro-granules.
  • proteases used here which can be keratinases, can be naturally occurring enzymes or enzymes that have been modified on the basis of naturally occurring enzymes by one or more mutations in order to positively influence desired properties, such as catalytic activity or stability.
  • a genetically modified enzyme may have at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98% or 100% sequence identity with a naturally occurring parent enzyme over the entire length of the Have starting protein.
  • the catalytic activity of a genetically modified enzyme may be at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98%, or 100% of the catalytic activity of the parent enzyme.
  • sequence comparison The identity of nucleic acid or amino acid sequences is determined by sequence comparison. This sequence comparison is based on the BLAST algorithm established and commonly used in the prior art (cf. e.g. Altschul et al., Basic local alignment search tool, J. Mol. Biol., 1990, 215: 403-410, and Altschul et al ., Gapped BLAST and PSI-BLAST: a new generation of protein database search programs, Nucleic Acids Res., 1997, 25: 3389-3402) and is basically done by similar sequences of nucleotides or amino acids in the nucleic acid or amino acid sequences be assigned. A tabular assignment of the relevant positions is called alignment. Another algorithm available in the art is the FASTA algorithm.
  • Sequence comparisons are created using computer programs.
  • the Clustal series see e.g. Chenna et al., Multiple sequence alignment with the Clustal series of programs, Nucleic Acid Res., 2003, 31: 3497-3500
  • T-Coffee see ZB Notredame et al., T-Coffee: A novel method for multiple sequence alignments, J. Mol. Biol., 2000, 302: 205-217
  • programs based on these programs or algorithms are examples of these programs.
  • Sequence comparisons are also possible using the computer program Vector NTI® Suite 10.3 (Invitrogen Corporation, 1600 Faraday Avenue, Carlsbad, California, USA) with the specified standard parameters, whose AlignX module for sequence comparisons is based on ClustalW, or Clone Manager 10 (Use of the BLOSUM 62 scoring matrix for sequence alignment at the amino acid level). Unless otherwise stated, sequence identity reported herein is determined using the BLAST algorithm. Such a comparison also allows a statement to be made about the similarity of the compared sequences to one another. It is usually given in percent identity, i.e. the proportion of identical nucleotides or amino acid residues in the same positions or in positions corresponding to one another in an alignment.
  • the broader concept of homology includes conserved amino acid exchanges in amino acid sequences, i.e. amino acids with similar chemical activity, since these usually exert similar chemical activities within the protein. Therefore, the similarity of the compared sequences can also be indicated as percent homology or percent similarity.
  • Identity and/or homology statements can be made about entire polypeptides or genes or just about individual regions. Homologous or identical regions of different nucleic acid or amino acid sequences are therefore defined by similarities in the sequences. Such areas often have identical functions. They can be small and contain only a few nucleotides or amino acids. Such small areas often perform essential functions for the overall activity of the protein. It can therefore make sense to relate sequence matches only to individual, possibly small areas. Unless otherwise stated, identity or homology information in the present application refers to the total length of the nucleic acid or amino acid sequence specified in each case.
  • Enzymes usable in the context of the present invention may also have amino acid changes, particularly amino acid substitutions, insertions or deletions, compared to naturally occurring enzymes.
  • Such proteases with keratolytic activity which can be keratinases, are further developed, for example, through targeted genetic modification, i.e. through mutagenesis processes, and optimized for specific purposes or with regard to specific properties (e.g. with regard to their catalytic activity, stability, etc.).
  • nucleic acids that encode the enzymes used can be introduced into recombination approaches and thus used to generate completely new enzymes or other polypeptides.
  • the aim is to introduce targeted mutations such as substitutions, insertions or deletions into the known molecules in order, for example, to improve the cleaning performance of enzymes according to the invention.
  • the surface charges and/or the isoelectric point of the molecules and thereby their interactions with the substrate can be changed.
  • the net charge of the enzymes can be changed in order to influence substrate binding, especially for use in detergents.
  • one or more corresponding mutations can further increase the stability of the enzyme and thereby improve its cleaning performance.
  • Advantageous properties of individual mutations e.g. individual substitutions, can complement each other.
  • An enzyme that has already been optimized with regard to certain properties, for example with regard to its activity, can therefore be further developed further within the scope of the invention.
  • the agent contains at least one protease as described and defined above, which is characterized in that it is obtainable from a protease as described above as a starting molecule by single or multiple conservative amino acid substitution.
  • conservative amino acid substitution means the exchange (substitution) of one amino acid residue for another amino acid residue, this Exchange does not result in a change in polarity or charge at the position of the exchanged amino acid, e.g. the exchange of a non-polar amino acid residue for another non-polar amino acid residue.
  • the protease is characterized in that it can be obtained from a protease described above as a starting molecule by fragmentation, deletion, insertion or substitution mutagenesis.
  • fragmentation, deletion, insertion or substitution mutagenesis can also, for example, reduce the allergenicity of the enzymes in question and thus improve their overall usability.
  • the enzymes retain their catalytic activity even after mutagenesis, i.e. their catalytic activity corresponds at least to that of the starting enzyme, i.e. in a preferred embodiment the catalytic activity is at least 80%, preferably at least 90%, of the activity of the starting enzyme.
  • Other substitutions can also have beneficial effects. Both single and several contiguous amino acids can be exchanged for other amino acids.
  • DNA and/or amino acid sequences to produce the corresponding nucleic acids, including complete genes, using methods that are generally known today, such as chemical synthesis or the polymerase chain reaction (PCR) in conjunction with standard molecular biology and/or protein chemistry methods to produce.
  • PCR polymerase chain reaction
  • Such methods are, for example, from Sambrook, J., Fritsch, E.F. and Maniatis, T. 2001. Molecular cloning: a laboratory manual, 3rd Edition Cold Spring Laboratory Press. Known.
  • the protease is as described above in an amount of 1.5 to 20% by weight, preferably 2.0 to 15% by weight, more preferably 2.5 to 12% by weight more preferably 3.0 to 10% by weight of active protein in the agent according to the invention, based on the total weight of the agent.
  • This is preferably a protease that is essentially free of other proteins and/or other cellular contaminants (e.g. lipids, DNA, RNA, etc.).
  • the protein concentration can be determined using known methods, for example the BCA method (bicinchoninic acid; 2,2'-biquinolyl-4,4'-dicarboxylic acid) or the biuret method (Gornall et al., 1948, J. Biol. Chem., 177: 751-766).
  • the active protein concentration can be determined by titrating the active centers using a suitable irreversible inhibitor and determining the residual activity (Bender et al., 1966, J. Am. Chem. Soc. 88(24): 5890-5913).
  • protease can be formulated in forms known for other enzymes used in textile detergents and/or care products, for example in encapsulated form. Corresponding options are known to those skilled in the art.
  • the agent according to the invention can contain, in addition to the protease or alternatively, a protease-producing microorganism, particularly a microorganism of the genus Bacillus, more preferably Bacillus subtilis or Bacillus cereus, most preferably one or both of the strains described by Lakshmi et al. (supra) were described.
  • this microorganism is contained in an amount of 2.0 to 20% by weight, preferably 2.5 to 15% by weight, based on the total weight of the agent according to the invention.
  • one or more further enzymes are included in addition to the at least one protease as described above, these are selected from all enzymes suitable for use in textile detergents and/or care products, that is to say one or more further enzymes are in particular selected from the group consisting of lipases, amylases, cellulases, hemicellulases, mannanases, tannases, xylanases, xanthanases, xyloglucanases, ß-glucosidases, pectinases, carrageenases, perhydrolases, oxidases, and oxidoreductases, as well as mixtures thereof.
  • the amount of further enzyme is advantageously 1 x IO 8 to 5% by weight, based on active protein, in particular from 1 x 10 -7 to 3% by weight, from 0.00001 to 1% by weight, from 0 .00005 to 0.5% by weight, from 0.0001 to 0.1% by weight and particularly preferably from 0.0001 to 0.05% by weight, in each case based on the total weight of the agent and based on active Protein.
  • an agent as described herein may additionally comprise further proteases.
  • the at least one protease with keratolytic activity and/or keratinase is contained in the amounts defined above, ie in amounts of 1.5 to 20% by weight, preferably 2.0 to 15% by weight, more preferably 2. 5 to 12% by weight, more preferably 3.0 to 10% by weight, of active protein, based on the total weight of the agent, and is the at least one further protease, ie a protease which has no keratolytic activity, in the usual amounts contained, ie, for example, in amounts of 1 x 10 -8 to 1% by weight, each based on the total weight of the agent and based on active protein.
  • the enzymes used particularly preferably show synergistic cleaning performance against certain dirt or stains, i.e. the enzymes contained in the agent composition support each other in their cleaning performance.
  • a synergism is very particularly preferably between a protease and a further enzyme of an agent according to the invention, including in particular between a protease and an amylase and/or a lipase and/or a mannanase and/or a cellulase and/or a pectinase.
  • Synergistic effects can occur not only between different enzymes, but also between one or more enzymes and other ingredients of the agent according to the invention.
  • the enzymes to be used additionally in the context of the present invention can, for example, originally come from microorganisms, for example of the genera Bacillus, Streptomyces, Humicola or Pseudomonas, and/or can be produced by suitable microorganisms using known biotechnological processes, for example by transgenic expression hosts, e.g. of the genera Escherichia, Bacillus or by filamentous fungi.
  • these can in particular also be technical enzyme preparations of the respective enzyme, ie that accompanying substances can be present. Therefore the enzymes can be prepared and used together with accompanying substances, for example from fermentation or with other stabilizers.
  • the enzymes are generally not provided in the form of pure protein, but rather in the form of stabilized, storable and transportable preparations.
  • These prefabricated preparations include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, in particular in the case of liquid or gel-like agents, solutions of the enzymes, advantageously as concentrated as possible, with little water and/or mixed with stabilizers or other auxiliaries.
  • the enzymes can be encapsulated for both the solid and liquid dosage forms, for example by spray drying or extrusion of the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are enclosed as in a solidified gel or in those of the core-shell type, in which an enzyme-containing core is covered with a water-, air- and/or chemical-impermeable protective layer.
  • Additional active ingredients such as stabilizers, emulsifiers, pigments, bleaches or dyes, can also be applied in superimposed layers.
  • Such capsules are applied using methods known per se, for example by shaking or rolling granulation or in fluid bed processes. Such granules are advantageously low-dust, for example by applying polymeric film formers, and are storage-stable due to the coating.
  • An enzyme-containing formulation usually contains the at least one enzyme in an amount of 0.1 to 50% by weight, preferably 0.1 to 20% by weight, based on the total weight of the formulation.
  • the enzymes are preferably used as enzyme liquid formulation(s).
  • a liquid enzyme-containing formulation contains at least one organic solvent, preferably selected from alcohols, particularly preferably polyhydric polyhydric alcohols that are liquid under standard conditions (20 ° C, 1013 mbar), in particular glycerol, 1,2-propanediol and sorbitol, as well as mixtures thereof . If these are included, the amount is preferably from 0.1 to 99.9% by weight, more preferably 10 to 90% by weight, based on the total weight of the enzyme-containing formulation.
  • Bleaching agents suitable in the context of the present invention i.e. those which are suitable for use in textile washing and/or care processes and correspondingly suitable agents or are usually used in such, are known in the prior art.
  • Suitable bleaching agents generally include hypochlorites, hydrogen peroxide or hydrogen peroxide-providing substances.
  • the at least one bleaching agent is not a chlorine-containing bleaching agent. In various embodiments, this is at least one bleaching agent in an amount of 5 to 70% by weight, preferably in an amount of up to 50% by weight, in particular up to 40% by weight and particularly preferably from 7 to 30% by weight .-%, based on the total weight of the agent.
  • the at least one bleaching agent is a peroxygen-based bleaching agent.
  • Peroxygen-based bleaching agents are advantageously contained in amounts in the range from 5 to 70% by weight, in particular from 5 to 30% by weight, based on the total weight of the agent.
  • the bleaching agents in question are preferably the peroxygen compounds generally used in detergents, such as percarboxylic acids, for example dodecanediperic acid or phthaloylamine peroxycaproic acid, hydrogen peroxide, alkali metal perborate, which can be present as a tetra- or monohydrate, percarbonate, perpyrophosphate and persilicate, which are generally used as alkali metal salts, in particular as sodium salts.
  • Photobleaching such as tetrabenzotetraazoporphyrins or similar, is also suitable.
  • Such bleaching agents are preferably in amounts of up to 70% by weight, for example in amounts of approximately 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16 , 17, 18, 19, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65 or 70% by weight, in particular up to 50% by weight, more preferably up to 40% by weight , and particularly preferably from 7% by weight to 30% by weight, based on the total weight of the respective agent, in particular percarbonate is used.
  • solid peroxygen compounds are to be used, they can be used in the form of powders or granules, which can also be coated in a manner known in principle.
  • the addition of small amounts of known bleach stabilizers such as phosphonates, borates or metaborates and metasilicates as well as magnesium salts such as magnesium sulfate can be useful.
  • the amount of bleach activator is preferably up to 17% by weight, in particular 0.3% by weight to 15% by weight, based on the total weight of the agent.
  • Bleach activators suitable in the context of the present invention include all known and commonly used bleach activator compounds.
  • bleach activator compound which produces peroxocarboxylic acid under perhydrolysis conditions it is possible in particular to use compounds which, under perhydrolysis conditions, produce optionally substituted perbenzoic acid and/or aliphatic peroxocarboxylic acids with 1 to 12 carbon atoms, in particular 2 to 4 carbon atoms, alone or in mixtures.
  • Bleach activators which carry O- and/or N-acyl groups, in particular with the above-mentioned number of carbon atoms, and/or optionally substituted benzoyl groups are suitable.
  • multiply acylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), N- Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates or carboxylates or the sulfonic or carboxylic acids of these, in particular nonanoyl or isononanoyl or lauroyloxybenzenesulfonate (NOBS or iso-NOBS or LOBS) or decanoyloxybenzoate (DOBA), their formal carbonic acid ester derivatives such as 4-(2- Decanoyloxyethoxycarbonyloxy)
  • bleach activator compounds such as nitriles, from which perimide acids form under perhydrolysis conditions
  • nitriles include, in particular, aminoacetonitrile derivatives with a quaternized nitrogen atom according to the formula (I) in which R 11 represents -H, -CH3, a C2-24-alkyl or -alkenyl radical, a substituted Ci-24-alkyl or C2-24-alkenyl radical with at least one substituent from the group -CI, -Br, - OH, -NH2, -CN and -N (+) -CH2-CN, an alkyl or alkenylaryl radical with a Ci-24-alkyl group, or for a substituted alkyl or alkenylaryl radical with at least one, preferably two, optionally substituted Ci -24-alkyl group(s) and optionally further substituents on the aromatic
  • the amount of such bleach activators i.e. the bleach activator compounds that produce peroxocarboxylic acid under perhydrolysis conditions and the bleach activator compounds that produce perimide acids under perhydrolysis conditions, is preferably 0.3 to 14% by weight, preferably up to 12% by weight, in particular from 1 to 12% by weight, for example 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12% by weight, based on the total weight of the respective agent.
  • the bleach activators can be coated or granulated in a known manner with coating substances, granulated with the aid of carboxymethyl cellulose
  • Tetraacetylethylenediamine with average grain sizes of 0.01 to 0.8 mm, granulated 1,5-diacetyl-2,4- dioxohexahydro-1,3,5-triazine, and/or trialkylammonium acetonitrile prepared in particle form is particularly preferred.
  • bleach-activating transition metal complexes can also be used as bleach activators. These are preferably selected from cobalt, iron, copper, titanium, vanadium, manganese and ruthenium complexes.
  • Both inorganic and organic compounds come into consideration as ligands in such transition metal complexes, including, in addition to carboxylates, in particular compounds with primary, secondary and/or tertiary amine and/or alcohol functions, such as pyridine, pyridazine, pyrimidine, pyrazine, imidazole, pyrazole , triazole, 2,2'-bispyridylamine, tris-(2-pyridylmethyl)amine, 1,4,7-triazacyclononane and its substituted derivatives such as 1,4,7-trimethyl-1,4,7-triazacyclononane, 1,5 ,9-triazacyclododecane and its substituted derivatives such as 1,5,9-trimethyl-1,5,9-triazacyclododecane 1,4,8,11-tetraazacyclotetradecane and its substituted derivatives such as 5,5,7,12,12,14- Hexamethyl-1,4,8,11-tetraazacyclote
  • the inorganic neutral ligands include, in particular, ammonia and water. If not all coordination sites of the transition metal central atom are occupied by neutral ligands, the complex contains further, preferably anionic and among these in particular monodentate or bidentate ligands. These include in particular the halides such as fluoride, chloride, bromide and iodide, and the (NO2) group, i.e. a nitro ligand or a nitrito ligand.
  • the (NO2) group can also be bonded to a transition metal in a chelating manner or it can bridge two transition metal atoms asymmetrically or r] 1 -O-bridged.
  • the transition metal complexes can also carry other, generally simpler ligands, in particular monovalent or polyvalent anion ligands.
  • suitable substances include nitrate, acetate, trifluoroacetate, formate, carbonate, citrate, oxalate, perchlorate and complex anions such as hexafluorophosphate.
  • the anion ligands are intended to ensure charge balance between the transition metal central atom and the ligand system.
  • the presence of oxo ligands, peroxo ligands and imino ligands is also possible. In particular, such ligands can also have a bridging effect, so that polynuclear complexes are formed.
  • both metal atoms in the complex do not have to be the same.
  • the use of dinuclear complexes in which the two transition metal central atoms have different oxidation numbers is also possible. If anion ligands are missing or the presence of anion ligands does not lead to charge balancing in the complex, anionic counterions are present in the transition metal complex compounds to be used according to the invention, which neutralize the cationic transition metal complex.
  • anionic counterions include, in particular, nitrate, hydroxide, hexafluorophosphate, sulfate, chlorate, perchlorate, the halides such as chloride or the anions of Carboxylic acids such as formate, acetate, oxalate, benzoate or citrate.
  • transition metal complex compounds that can be used are Mn(IV)2(pO)3(1,4,7-trimethyl-1,4,7-triazacyclononane)dihexafluorophosphate, [N,N'-bis[(2-hydroxy-5- vinylphenyl)methylene]-1,2-diaminocyclohexane]manganese(III) chloride, [N,N'-bis[(2-hydroxy-5-nitrophenyl)methylene]-1,2-diaminocyclohexane]manganese(III)acetate, [ N,N'-bis[(2-hydroxyphenyl)methylene]-1,2-phenylenediamine]manganese(III)acetate, [N,N'-bis[(2-hydroxyphenyl)methylene]-1,2-diaminocyclohexane]manganese (III) chloride, [N,N'-Bis[(2-hydroxyphenyl)methylene]-1,2-diamin
  • bleach-activating transition metal complexes e.g. (hydrazinylmethylmorpholinium chloride, Mn-salen complex
  • bleach-activating transition metal complexes are preferably in amounts of up to 0.5% by weight, in particular from 0.0005 to 0.2% by weight, in each case based on entire product included.
  • R 2 is preferably hydrogen.
  • R 1 and/or R 3 is preferably an alkyl, phenyl or naphthyl group substituted with an electron-withdrawing group.
  • R 4 is preferably hydrogen.
  • the preferred electron-withdrawing group is an ammonium group which may carry alkyl or hydroxyalkyl groups or, including the N atom carrying an alkyl group, is formed as a heterocyloalkyl group which may carry further heteroatoms.
  • Preferred embodiments of the compounds according to general formula (II) include those of general formula (III), in which R 1 represents a Ci-4-alkyl group which has a substituent selected from carries, in which R 10 is hydrogen or a Ci-28-alkyl, C2-28-alkenyl, C2-22-alkynyl, C3-12-cycloalkyl, C3-12-cycloalkenyl, C -g-aralkyl -, C3-2o-heteroalkyl, C3-12-cycloheteroalkyl, C5-16-heteroaralkyl group and A- represents the anion of an organic or inorganic acid, R 2 and R 4 have the meaning given for formula (II) and R 5 , R 6 , R 7 and R 8 independently of one another for R 1 , hydrogen, halogen, a hydroxy, amino, an optionally substituted N-mono or di-Ci-4-alkyl or C2-4-hydroxyalkyl amino-, N-phenyl-
  • the anion A- is preferably carboxylate such as lactate, citrate, tartrate or succinate, perchlorate, tetrafluoroborate, hexafluorophosphate, alkyl sulfonate, arylsulfonate such as p-toluenesulfonate, alkyl sulfate such as methosulfate, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, phosphate, isocyanate, Rhodanide, nitrate, fluoride, chloride, bromide, hydrogen carbonate or carbonate, whereby in the case of polyvalent anions the charge balance can be achieved through the presence of additional cations such as sodium or ammonium ions.
  • carboxylate such as lactate, citrate, tartrate or succinate, perchlorate, tetrafluoroborate, hexafluorophosphate, alkyl sulfonate, arylsul
  • acylhydrazone of the formula (IV) is particularly preferred.
  • Acylhydrazones of the general formulas (II), (III) or (IV) are preferably used in amounts of 0.001 to 5% by weight, in particular 0.05 to 0.15% by weight, in the agents described here.
  • At least one bleach activator is used.
  • the at least one bleach activator is selected from the group consisting of bleach activator compounds that yield peroxocarboxylic acid under perhydrolysis conditions; bleach activator compounds which form perimidic acid under perhydrolysis conditions; Bleach activating transition metal complexes and acylhydrazones.
  • the different bleach activators preferably from the above-described groups of bleach activator compounds which produce peroxocarboxylic acid under perhydrolysis conditions, bleach activator compounds which form perimidic acid under perhydrolysis conditions, transition metal complexes which activate bleach and acylhydrazones to be chosen.
  • the total amount of bleach activators is preferably up to 17% by weight, in particular 0.3 to 15% by weight, more preferably up to 13% by weight, in particular from 1 to 12% by weight, for example 1, 2, 3 , 4, 5, 6, 7, 8, 9, 10, 11 or 12% by weight, each based on the total weight of the respective agent.
  • the weight ratio of bleach to bleach activator is approximately 5:1 to 15:1, preferably approximately 8:1 to 12:1, e.g., approximately 10:1.
  • An agent as described herein may be a liquid or a solid product. Since the agents described here can also be multi-component agents, combination products are also possible, i.e. products containing both liquid and solid components or formulations.
  • a textile detergent and/or care product or textile detergent and/or care product additive as described herein is in the form of a concentrate.
  • Concentrates are known in the art and expressly fall within the scope of the present invention.
  • Suitable concentrates can in particular be in the form of a gel-like or pasty, preferably low-water or essentially water-free formulation.
  • a textile detergent and/or care product or textile detergent and/or care product additive as described herein is present in the form of a solid agent, in particular in powder form.
  • the agents can contain further ingredients, for example at least one further component, preferably at least two further components, which further improve the application-related and/or aesthetic properties of the agent.
  • these include, for example, fragrances, surfactants, builders, as well as additives for adjusting the viscosity and/or stabilization, as well as other auxiliaries and additives common in detergents, such as UV stabilizers, dyes, pearlescent agents, preservatives, bitter substances, organic salts, disinfectants , (structuring) polymers, defoamers and pH adjusters.
  • the amount of correspondingly suitable components in compositions according to the invention depends on the respective intended use of the composition and the trained specialist is generally familiar with suitable dosages of these components or is able to find appropriate quantities in the literature.
  • an agent as described herein further comprises at least one fragrance.
  • fragrances or fragrances or perfume oils can be used as fragrances or fragrances or perfume oils.
  • perfume oils for the purposes of this invention, the terms “fragrance(s)”, “fragrances” and “perfume oil(s)” are used synonymously. This refers in particular to all those substances or their mixtures that are perceived by humans and animals as an odor, in particular by humans as a pleasant smell.
  • perfume oils or perfume oil components can be used as fragrance components.
  • perfume oils or fragrances can contain individual fragrance compounds, e.g. B.
  • the synthetic products can be of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type.
  • Fragrance compounds of the aldehyde type are, for example, Adoxal (2,6,10-trimethyl-9-undecenal), anisaldehyde (4-methoxybenzaldehyde), Cymal (3-(4-isopropylphenyl)-2-methylpropanal), ethyl vanillin, florhydral (3- (3-isopropylphenyl)butanal), Helional (3-(3,4-methylenedioxyphenyl)-2-methylpropanal), Heliotropin, Hydroxycitronellal, Lauraldehyde, Lyral (3-and 4-(4-Hydroxy-4-methylpentyl)-3- cyclohexene-1-carboxaldehyde), methylnonylacetaldehyde, Lilial (3-(4-tert-butylphenyl)-2-methylpropanal), phenylacetaldehyde, undecylenaldehyde, vanillin, 2,6,
  • Fragrance compounds of the ketone type are, for example, methyl-ß-naphthyl ketone, musk indanone (1,2,3,5,6,7-hexahydro-1,1,2,3,3-pentamethyl-4H-inden-4-one), Tonalide (6-acetyl-1,1, 2, 4,4,7-hexamethyltetralin), a-damascone, ß-damascone, ⁇ -damascone, iso-damascone, damascenone, methyldihydrojasmonate, menthone, carvone, camphor, coavone (3 ,4,5,6,6-Pentamethylhept-3-en-2-one), fenchone, a-lonone, ß-lonone, y-methyl-ionone, fleuramone (2-heptylcyclopentanone), dihydrojasmone, cis-jasmone, iso -E-Super
  • Fragrance compounds of the alcohol type are, for example, 10-undecen-1-ol, 2,6-dimethylheptan-2-ol, 2-methylbutanol, 2-methylpentanol, 2-phenoxyethanol, 2-phenylpropanol, 2-tert-butycyclohexanol, 3.5 ,5-trimethylcyclohexanol, 3-hexanol, 3-methyl-5-phenylpentanol, 3-octanol, 3-phenylpropanol, 4-heptenol, 4-isopropylcyclohexanol, 4-tert-butycyclohexanol, 6,8-dimethyl-2-nona-nol , 6-nonen-1-ol, 9-decen-1-ol, a-methylbenzyl alcohol, a-terpineol, amyl salicylate, benzyl alcohol, benzyl salicylate, ß-terpineol, buty
  • Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethyl benzyl carbinyl acetate (DMBCA), phenyl ethyl acetate, benzyl acetate, ethyl methyl phenyl glycinate, allyl cyclohexyl propionate, styrallyl propionate, benzyl salicylate, cyclohexyl salicylate, floramate, melusate and yes smacyclate.
  • DMBCA dimethyl benzyl carbinyl acetate
  • benzyl ethyl acetate benzyl acetate
  • ethyl methyl phenyl glycinate allyl cyclohexyl propionate
  • the ethers include, for example, benzyl ethyl ether and ambroxan.
  • the hydrocarbons mainly include terpenes such as limonene and pinene.
  • fragrances are preferably used, which together produce an appealing scent.
  • a mixture of fragrances can also be referred to as perfume or perfume oil.
  • perfume oils can also contain natural fragrance mixtures such as those available from plant sources.
  • the fragrances of plant origin include essential oils such as angelica root oil, anise oil, arnica flower oil, basil oil, bay oil, champaca flower oil, citrus oil, precious fir oil, noble fir cone oil, elemi oil, eucalyptus oil, fennel oil, spruce needle oil, galbanum oil, geranium oil, ginger grass oil, guaiac wood oil, gurjun balsam oil, helichrysum oil, ho oil , Ginger oil, iris oil, jasmine oil, kajeput oil, kalus oil, chamomile oil, campaign oil, canaga oil, cardamoma oil, cassia oil, pine needle oil, copaivable oil, coriander oil, wasted oil, caraway oil, cumin oil, labdanum oil, lavender oil, lemon grass oil, lime oil, lime oil, mandarin oil, mandarin oil, mandarin oil, mandarin oil, mandarin oil.
  • a fragrance In order to be perceivable, a fragrance must be volatile; in addition to the nature of the functional groups and the structure of the chemical compound, the molecular weight also plays an important role. Most fragrances have molecular weights of up to around 200 Daltons, while molecular weights of 300 Daltons and above are more of an exception. Due to the different volatility of fragrances, the smell of a perfume or fragrance composed of several fragrances changes during evaporation, with the odor impressions being divided into “top note” and “middle note” or “body”). and “base note” (end note or dry out). Analogous to the description in the international patent publication WO 2016/200761, top, heart and base notes can be determined based on their vapor pressure (determinable using the test methods described in WO 2016/200761). be classified as follows:
  • the adhesive fragrances that can be used in the context of the present invention include, for example, the essential oils such as angelica root oil, anise oil, arnica flower oil, basil oil, bay oil, bergamot oil, champaca flower oil, noble fir oil, noble fir cone oil, elemi oil, eucalyptus oil, fennel oil, spruce needle oil, galbanum oil, geranium oil, Gingergrass oil, Guaiac wood oil, Gurjun balsam oil, Helichrysum oil, Ho oil, Ginger oil, Iris oil, Kajeput oil, Calamus oil, Chamomile oil, Camphor oil, Kanaga oil, Cardamom oil, Cassia oil, Pine needle oil, Copalva balsam oil, Coriander oil, Spearmint oil, Caraway oil, Cumin oil, Lavender oil, Lemongrass oil, Lime oil, Tangerine oil, Melissa oil, musk seed oil, myrrh oil, clove oil, neroli oil, niaoul
  • Higher boiling or solid fragrances of natural or synthetic origin include, for example: ambrettolide, a-amylcinnamaldehyde, anethole, anisaldehyde, anise alcohol, anisole, anthranilic acid methyl ester, acetophenone, benzyl acetone, benzaldehyde, benzoic acid ethyl ester, benzophenone, benzyl alcohol, benzyl acetate, benzyl benzoate, benzyl formate, benzyl valerianate, borneol, Bornyl acetate, a-bromostyrene, n-decylaldehyde, n-dodecylaldehyde, eugenol, eugenol methyl ether, eucalyptol, farnesol, fenchone, fenchyl acetate, geranyl acetate, geranyl
  • the more volatile fragrances include, in particular, the lower-boiling fragrances of natural or synthetic origin, which can be used alone or in mixtures.
  • Examples of more volatile fragrances are alkyl isothiocyanates (alkyl mustard oils), butanedione, limonene, linalool, linayl acetate and propionate, menthol, menthone, methyl-n-heptenone, phellandrene, phenylacetaldehyde, terpinyl acetate, citral, citronellal.
  • Fragrance compounds of the aldehyde type that can preferably be used are Hydroxycitronellal (CAS 107-75-5), Helional (CAS 1205-17-0), Citral (5392-40-5), Bourgeonal (18127-01-0), Triplal (CAS 27939 -60-2), Ligustral (CAS 68039-48-5), Vertocitral (CAS 68039-49-6), Florhydral (CAS 125109-85- 5), Citronellal (CAS 106-23-0), Citronellyloxyacetaldehyde (CAS 7492 -67-3).
  • fragrances described in WO 2016/200761 in particular the fragrances mentioned in Tables 1, 2 and 3, as well as the modulators listed in Tables 4a and 4b can also be used.
  • This publication is incorporated herein by reference in its entirety.
  • a perfume oil can also be contained in the form of a perfume oil preparation and, for example, comprise at least one further active ingredient in oil form.
  • suitable active ingredients in oil form are those which are suitable for washing, cleaning, care and/or finishing purposes, in particular
  • Textile care substances such as preferably silicone oils, and/or
  • Skin care active ingredients are all those active ingredients that provide the skin with a sensory and/or cosmetic benefit.
  • Skin-care active ingredients are preferably selected from the following substances: a) waxes such as carnauba, spermaceti, beeswax, lanolin and/or derivatives thereof and others; b) Hydrophobic plant extracts; c) hydrocarbons such as squalene and/or squalane; d) Higher fatty acids, preferably those with at least 12 carbon atoms, for example lauric acid, stearic acid, behenic acid, myristic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid, isostearic acid and/or polyunsaturated fatty acids and others; e) Higher fatty alcohols, preferably those with at least 12 carbon atoms, for example lauryl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, behenyl alcohol, cholesterol and/or
  • the content of the at least one fragrance which can also be in the form of a perfume oil or as a component of a perfume oil composition, as described above, is preferably between approximately 0.0001 to 5% by weight, in particular between approximately 0.005 and 3.0 % by weight, preferably between approximately 0.01 and 1.5% by weight, more preferably between approximately 0.05 and 1.0% by weight, based on the total weight of a respective agent.
  • a fragrance as defined above, and possibly also other components, such as additional fragrances and skin feeling-improving active ingredients, are incorporated wholly or partially into microcapsules.
  • Microcapsule refers to capsules with micron-scale core-shell morphology that have a capsule shell that completely encloses a core. “Completely enclosing” or “completely surrounding” as used herein in relation to the microcapsules means that the core is completely surrounded by the shell, ie in particular is not embedded in a matrix in such a way that it is exposed at one point. It is further preferred that the capsule shell is designed in such a way that the release of the contents is controlled, ie the contents are not released spontaneously in an uncontrolled manner independent of a release stimulus. For this reason, the capsule shell is preferably substantially impermeable to the encapsulated contents.
  • substantially impermeable means that the contents of the capsule or individual ingredients cannot spontaneously penetrate the shell, but can only be released by opening the capsule or, optionally, over a longer period of time ongoing diffusion process can take place.
  • the core may be solid, liquid and/or gaseous, but is preferably solid and/or liquid.
  • the microcapsules are preferably essentially spherical and have diameters in the range from 0.01 to 1000 pm, in particular 0.1 to 500 pm.
  • the capsule shell and capsule core consist of different materials, in particular the capsule shell is preferably solid under standard conditions (20 ° C, 1013 mbar), the core is preferably solid and / or liquid, in particular liquid.
  • z. B. high molecular compounds of animal or plant origin e.g. B. protein compounds (gelatin, albumin, casein), cellulose derivatives (methyl cellulose, ethyl cellulose, cellulose acetate, cellulose nitrate, carboxymethyl cellulose) and in particular synthetic polymers (e.g. polyamides, polyolefins, polyesters, polyurethanes, epoxy resins, silicone resins and condensation products of carbonyl and NH Group-containing compounds) can be used.
  • synthetic polymers e.g. polyamides, polyolefins, polyesters, polyurethanes, epoxy resins, silicone resins and condensation products of carbonyl and NH Group-containing compounds
  • the shell material can be selected, for example, from polyacrylates, polyethylene, polyamides, polystyrenes, polyisoprenes, polycarbonates, polyesters, polyureas, polyurethanes, polyolefins, polysaccharides, epoxy resins, vinyl polymers, urea crosslinked with formaldehyde or glutaraldehyde, melamine crosslinked with formaldehyde, gelatin polyphosphate Coacervates, optionally crosslinked with glutaraldehyde, gelatin-gum arabic coacervates, silicone resins, polyamines reacted with polyisocyanates, acrylate monomers polymerized by free radical polymerization, silk, wool, gelatin, cellulose, proteins, and mixtures and copolymers of the aforementioned.
  • polyacrylates polyethylene, polyamides, polystyrenes, polyisoprenes, polycarbonates, polyesters, polyureas, polyurethanes, polyolefins, polysacc
  • polyacrylates polyethylene, polyamides, polystyrenes, polyisoprenes, polycarbonates, polyesters, polyureas, polyurethanes, polyolefins, epoxy resins, vinyl polymers and urea and/or melamine crosslinked with formaldehyde or glutaraldehyde.
  • the known microencapsulation processes are suitable for producing suitable microcapsules, in which, for example, the phase to be encapsulated is encapsulated by coating with film-forming polymers (such as those mentioned above), which are deposited on the material to be encapsulated after emulsification and coacervation or interface polymerization.
  • the phase to be encapsulated is a benefit composition, preferably a fragrance composition, usually in the form of a perfume oil.
  • the capsules can release the encapsulated benefits via various mechanisms.
  • capsules that have a mechanically stable capsule shell, but which then becomes permeable to the agents contained due to one or more environmental influences, such as changes in temperature or the ionic strength or the pH of the surrounding medium, can be used become.
  • Stable capsule wall materials are also possible, through which the at least one advantage medium, for example a perfume oil and possibly further advantage medium, can diffuse over time.
  • the capsules can release the at least one beneficial agent contained preferably when the pH value or the ionic strength of the environment changes, when the temperature changes, when exposed to light, by diffusion and / or when subjected to mechanical stress.
  • the capsules are fragile, that is, they can release entrapped agent due to mechanical stress such as friction, pressure or shear stress that breaks the shell of the capsules.
  • the capsule is thermally labile, that is, enclosed substances can be released if the capsules are at a temperature of at least 70 ° C, preferably at least 60 ° C, preferably at least 50 ° C and in particular at least 40 ° C is exposed.
  • the capsule can become permeable to the enclosed beneficial agent(s) after exposure to radiation of a specific wavelength, preferably through exposure to sunlight.
  • the capsules are fragile and at the same time thermally unstable and/or unstable to radiation of a certain wavelength.
  • Suitable microcapsules can be water-soluble and/or water-insoluble, but are preferably water-insoluble capsules.
  • the water-insolubility of the capsules has the advantage that they can survive washing, cleaning or other treatment applications and are therefore able to release the at least one beneficial agent only after the aqueous washing, cleaning or treatment process, such as during drying simply by increasing the temperature or by exposure to sunlight or, in particular, by friction on the surface.
  • Water-insoluble capsules that are broken open by friction are particularly preferred.
  • capsules that can be rubbed” or “capsules that can be broken open by friction” means in particular those capsules which, when they adhere to a surface treated with them (e.g. textile surface), can be opened or broken open by mechanical rubbing or pressure, so that the contents are released only results as a result of mechanical influence, e.g. when you dry your hands with a towel on which such capsules have been deposited.
  • Capsules that can be advantageously used can have average diameters dso of ⁇ 250 pm, preferably in the range from 1 to 100 pm, preferably between 3 and 95 pm, in particular between 4 and 90 pm, for example between 5 and 80 pm, for example between 5 and 40 pm have.
  • the dso value indicates the diameter that results when 50% by weight of the capsules have a smaller diameter and 50% by weight of the capsules have a larger diameter than the determined dso value.
  • the dso value of the particle size distribution of the microcapsules is ⁇ 70 pm, preferably ⁇ 60 pm, particularly preferably ⁇ 50 m.
  • the dso value of the particle size distribution is the value at which 90% of all particles are smaller and 10% of the particles are larger than this value.
  • the shell of the capsules surrounding the core or (filled) cavity preferably has an average thickness in the range between approximately 50 and 500 nm, preferably between around 100 nm and approximately 250 nm. Capsules can be easily rubbed in particular if they are within the previously specified ranges regarding the average diameter and the average thickness.
  • the dso value indicates the diameter that results when 50% by weight of the capsules have a smaller diameter and 50% by weight of the capsules have a larger diameter than the determined dso value. It is further preferred that the dgo value of the particle size distribution of the microcapsules is ⁇ 70 pm, preferably ⁇ 60 pm, particularly preferably ⁇ 50 pm. The dgo value of the particle size distribution is the value at which 90% of all particles are smaller and 10% of the particles are larger than this value.
  • the diameter of the capsules or the particle size of the microcapsules can be determined using conventional methods. It can be determined, for example, with the aid of dynamic light scattering, which can usually be carried out on diluted suspensions containing, for example, 0.01 to 1% by weight of capsules. It can also be done by evaluating light microscopic or electron microscopic images of capsules.
  • a microcapsule according to the invention has an average diameter dso of approximately 1 to 80 pm, preferably approximately 5 to 40 pm, in particular approximately 20 to 35 pm, for example approximately 22 to approximately 33 pm.
  • the wall material of the microcapsules preferably comprises polyurethanes, polyolefins, polyamides, polyesters, polysaccharides, epoxy resins, silicone resins and/or polycondensation products of carbonyl compounds and compounds containing NH groups.
  • melamine-urea-formaldehyde microcapsules or melamine-formaldehyde microcapsules or urea-formaldehyde microcapsules can preferably be used.
  • Microcapsules based on melamine-formaldehyde resins are particularly preferred.
  • microcapsules as such has long been well known to those skilled in the art. Particularly suitable processes for producing microcapsules are in principle described, for example, in US 3516941, in US 3415758 or also in EP 0026914 A1. The latter describes, for example, the production of microcapsules by acid-induced condensation of melamine-formaldehyde precondensates and/or their Ci-C4 alkyl ethers in water in which the hydrophobic material forming the capsule core is dispersed, in the presence of a protective colloid.
  • an agent as described herein particularly comprises at least one surfactant.
  • Suitable surfactants include, in particular, anionic surfactants, nonionic surfactants and mixtures thereof, but also cationic, zwitterionic and amphoteric surfactants.
  • Suitable compounds from the class of anionic surfactants are those of the formula (V)
  • R-SO 3 X + ( V) in which R represents a linear or branched unsubstituted alkylaryl radical and + , with Na + being extremely preferred. Further cations X + can be selected from NHT, % Zn 2+ , % Mg 2+ , % Ca 2+ , % Mn 2+ and mixtures thereof.
  • Alkylaryl refers to organic radicals consisting of an alkyl radical and an aromatic radical. Typical examples of such residues 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 alkylbenzene sulfonates of the formula (V-1):
  • V-1 in which R' and R" together contain 9 to 19, preferably 11 to 15 and in particular 11 to 13 carbon atoms.
  • a very particularly preferred representative can be described by the formula A- 1 a:
  • the compound of formula (V) is preferably the sodium salt of a linear alkyl benzene sulfonate.
  • Preferred anionic surfactants are those of the formula (VI)
  • R 1 represents a linear or branched, substituted or unsubstituted alkyl radical, preferably a linear, unsubstituted alkyl radical, particularly preferably a fatty alcohol radical.
  • Preferred radicals R 1 are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl radicals and mixtures thereof, the representatives having an even number of C Atoms are preferred.
  • Particularly preferred radicals R 1 are derived from C s fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or from Cio-20-oxo alcohols.
  • X stands for a single-quality cation or the n-ten part of an N-quality cation, preferably the alkali metal ions and below Na + or K + , where Na + is extremely preferred. Further cations X + can be selected from NHT, % Zn 2+ , % Mg 2+ , % Ca 2+ , % Mn 2+ and mixtures thereof.
  • AO stands for an ethylene oxide (EO) or propylene oxide (PO) group, preferably an ethylene oxide group.
  • the index n represents an integer from 1 to 50, preferably from 1 to 20 and in particular from 2 to 10. Very particularly preferably n represents the numbers 2, 3, 4, 5, 6, 7 or 8 a monovalent cation or the nth part of an n-valent cation, preference being given to the alkali metal ions and among them Na + or K + , with Na + being extremely preferred.
  • Further cations X+ can be selected from NHT, % Zn 2+ , % Mg 2+ , % Ca 2+ , % Mn 2+ and mixtures thereof.
  • agents in various embodiments can therefore contain at least one anionic surfactant selected from fatty alcohol ether sulfates of the formula (VI-1)
  • anionic surfactants that can be used with preference are the alkyl sulfates of the formula (VII)
  • R 2 represents 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, the representatives having an even number of C Atoms are preferred.
  • Particularly preferred radicals R 2 are derived from Ci2-18 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or from Cio-20-oxo alcohols.
  • X stands for a single-quality cation or the n-ten part of an N-quality cation, preferably the alkali metal ions and below Na + or K + , where Na + is extremely preferred. Further cations X + can be selected from NHT, % Zn 2+ , % Mg 2+ , % Ca 2+ , % Mn 2+ and mixtures thereof.
  • these surfactants are selected from fatty alcohol sulfates of the formula (VI 1-1)
  • anionic surfactants that can be used are the alkyl ester sulfonates, in particular those of the formula (VIII)
  • R 1 represents a linear or branched, substituted or unsubstituted alkyl radical, preferably a linear, unsubstituted alkyl radical.
  • Preferred radicals R 1 are selected from nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl radicals and mixtures thereof, the representatives with an odd number of carbon atoms are preferred.
  • radicals R 1 -CH are derived from C s fatty acids, for example from lauryl, myristyl, cetyl or stearyl acid.
  • R 2 represents a linear or branched, substituted or unsubstituted alkyl radical, preferably a linear, unsubstituted alkyl radical.
  • X stands for a single-quality cation or the n-ten part of an N-quality cation, preferably the alkali metal ions and below Na + or K + , where Na + is extremely preferred. Further cations X + can be selected from NHZ, % Zn 2+ , % Mg 2+ , % Ca 2+ , % Mn 2+ and mixtures thereof.
  • the secondary alkanesulfonates are also suitable as anionic surfactants. These have, for example, the formula (IX)
  • R 1 CH SO 3 Alkyl form, preferably with 10 to 30 carbon atoms, preferably with 10 to 20 carbon atoms and X + is selected from the group Na + , K + , NHZ, % Zn 2+ , % Mg 2+ , % Ca 2+ , % Mn 2 + and mixtures thereof, preferably Na + .
  • the at least one secondary alkane sulfonate has the following formula (IX-1):
  • m and n are independently an integer between 0 and 20.
  • m + n is an integer between 7 and 17, preferably 10 to 14 and X + is selected from the group Na + , K + , NHZ, % Zn 2+ , % Mg 2+ , % Ca 2+ , % Mn 2+ and mixtures thereof, preferably Na + .
  • the at least one secondary alkanesulfonate is secondary C14-17 sodium alkanesulfonate.
  • a secondary C14-17 sodium alkane sulfonate is sold, for example, by the company Clariant under the trade name “Hostapur SAS60”.
  • Fatty alcohol alkoxylates are particularly suitable as nonionic surfactants.
  • the agents therefore contain at least one nonionic surfactant of the formula (X)
  • R 3 represents 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, the representatives having an even number of C Atoms are preferred.
  • Particularly preferred radicals R 3 are derived from Ci2-is fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or from Cio-20-oxo alcohols.
  • AO stands for an ethylene oxide (EO) or propylene oxide (PO) group, preferably an ethylene oxide group.
  • EO ethylene oxide
  • PO propylene oxide
  • the index m stands for an integer from 1 to 50, preferably from 1 to 20 and in particular from 2 to 10. Most preferably m stands for the numbers 2, 3, 4, 5, 6, 7 or 8.
  • fatty alcohol alkoxylates to be preferably used are compounds of the formula (X-1)
  • Amine oxides are also suitable as nonionic surfactants.
  • all amine oxides established in the prior art for these purposes are, that is to say, compounds which have the formula R 1 R 2 R 3 NO, in which each R 1 , R 2 and R 3 independently of the others is optionally substituted, for example hydroxy-substituted , C1-30 hydrocarbon chain can be used.
  • Particularly preferred amine oxides used are those in which R 1 is C12-18 alkyl and R 2 and R 3 are each independently C1-4 alkyl, in particular C12-18 alkyldimethylamine oxides.
  • Suitable amine oxides are N-cocoalkyl-N,N-dimethylamine oxide, N-tallow alkyl-N,N-dihydroxyethylamine oxide, myristyl/cetyldimethylamine oxide or lauryldimethylamine oxide.
  • nonionic surfactants that can be contained in the agents described in the sense of the present invention include, but are not limited to, alkyl glycosides, alkoxylated fatty acid alkyl esters, fatty acid alkanolamides, hydroxy mixed ethers, sorbitan fatty acid esters, polyhydroxy fatty acid amides and alkoxylated alcohols. Such surfactants are known in the art.
  • Suitable alkyl (poly) glycosides are, for example, those of the formula R 2 O-[G] P , in which R 2 is an unbranched or branched alkyl with 12 to 16 carbon atoms, G is a sugar residue with 5 or 6 carbon atoms, in particular glucose, and the index p is 1 to 10.
  • Suitable amphotensides are, for example, betaines of the formula (XI)
  • R'" is an alkyl radical, optionally interrupted by heteroatoms or heteroatom groups, with 8 to 25, preferably 10 to 21 carbon atoms and R iv as well R v represent similar or different alkyl radicals with 1 to 3 carbon atoms, in particular C10-18-alkyldimethylcarboxymethylbetaine and Cn-17-alkylamidopropyldimethylcarboxymethylbetaine.
  • Suitable cation surfactants include the quaternary ammonium compounds of the formula (XII)
  • R vi )(R vii )(R viii ) ( R ix ) N + represent an anion, in particular a halide ion, for example didecyldimethylammonium chloride, alkylbenzyldidecyl ammonium chloride and mixtures thereof.
  • Other suitable cationic surfactants are the quaternary surface-active compounds, in particular with a sulfonium, phosphonium, iodonium or arsonium group, which are also known as antimicrobial active ingredients. Through the use of quaternary surfactants Compounds with an antimicrobial effect can be used to design the agent with an antimicrobial effect or to improve the antimicrobial effect that may already be present due to other ingredients.
  • the total amount of surfactants is 5 to 75% by weight, preferably 5 to 35% by weight, more preferably 10 to 30% by weight.
  • An agent as described herein contains, in some embodiments, at least one water-soluble and/or water-insoluble, organic and/or inorganic builder.
  • the general builders that can be used include, in particular, aminocarboxylic acids and their salts, zeolites, silicates, carbonates, organic (co)builders and - where there are no ecological prejudices against their use - also phosphates.
  • the agents are phosphate-free.
  • crystalline layered silicates of the general formula NaMSi x is 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20.
  • the crystalline layered silicates of the formula NaMSixO2x+i ⁇ y H2O are sold, for example, by the company Clariant GmbH (Germany) under the trade name Na-SKS.
  • silicates Na-SKS-1 (Na2Si22Ü45 ⁇ x H2O, Kenyaite), Na-SKS-2 (Na2Sii4Ü29 ⁇ x H2O, magadiite), Na-SKS-3 (Na2SisOi7 ⁇ x H2O) or Na-SKS-4 (Na2Si4Og ⁇ x H2O, Makatite).
  • Particularly suitable for the purposes of the present invention are crystalline layered silicates of the formula NaMSi x O2x+i ⁇ y H2O, in which x represents 2.
  • both ß- and 5-sodium disilicates are Na2Si2Os ⁇ y H2O and, above all, Na-SKS-5 (a-Na 2 Si 2 O 5 ), Na-SKS-7 (ß-Na 2 Si 2 O 5 , natrosilite ), Na-SKS-9 (NaHSi 2 O 5 ⁇ H2O), Na-SKS-10 (NaHSi2O5 ⁇ 3 H2O, kanemite), Na-SKS-11 (t-Na2Si2Os) and Na-SKS-13 (NaHSi2Os), but in particular Na-SKS-6 (ö-Na2Si2Os) is preferred.
  • Amorphous sodium silicates with a modulus Na2O:SiO2 of 1:2 to 1:3.3, preferably from 1:2 to 1:2.8 and in particular from 1:2 to 1:2.6, which are preferably delayed in dissolution, can also be used and have secondary washing properties.
  • the delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compaction/densification or by overdrying.
  • amorphous is understood to mean that the silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-radiation, which have a width of several degree units of the diffraction angle , cause.
  • the agents can also contain, in particular, phosphonates as a further builder.
  • a hydroxyalkane and/or aminoalkane phosphonate is preferably used as the phosphonate compound.
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • the preferred aminoalkane phosphonates are ethylenediaminetetramethylene phosphonate (EDTMP), diethylenetriaminepentamethylene phosphonate (DTPMP) and their higher homologues.
  • Phosphonates are contained in the detergents preferably in amounts of 0.1 to 10% by weight, in particular in amounts of 0.5 to 8% by weight, based on the total weight of the dishwashing detergent.
  • Alkaline carriers include, for example, alkali metal hydroxides, alkali metal carbonates, alkali metal bicarbonates, alkali metal sesquicarbonates, the alkali metal silicates mentioned, alkali metal silicates, and mixtures of the aforementioned substances, with preference being given to using the alkali metal carbonates, in particular sodium carbonate, sodium bicarbonate or sodium sesquicarbonate, for the purposes of this invention.
  • the optional alkali metal hydroxides are preferably used only in small amounts, preferably in amounts below 10% by weight, preferably below 6% by weight, particularly preferably below 4% by weight .-% and in particular below 2% by weight, based on the total weight of the agent. Particular preference is given to agents which, based on their total weight, contain less than 0.5% by weight and in particular no alkali metal hydroxides.
  • polycarboxylates/polycarboxylic acids polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders and the phosphonates already mentioned above as builders should be mentioned as organic builders.
  • organic builders these substance classes are described below.
  • Useful organic builders include, for example, the polycarboxylic acids that can be used in the form of the free acid and/or their sodium salts, whereby polycarboxylic acids are understood to mean those carboxylic acids that carry more than one acid function.
  • these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, nitrilotriacetic acid (NTA), provided such use is not objectionable for ecological reasons, as well as mixtures of these.
  • NTA nitrilotriacetic acid
  • the free acids typically also have the properties of an acidifying component and thus serve also for setting a lower and milder pH value.
  • citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures of these should be mentioned.
  • aminocarboxylic acids and/or their salts are aminocarboxylic acids and/or their salts. Particularly preferred representatives of this class are methylglycinediacetic acid (MGDA) or its salts and glutamic diacetic acid (GLDA) or its salts or ethylenediaminediacetic acid or its salts (EDDS). Also suitable are iminodisuccinic acid (IDS) and iminodiacetic acid (IDA).
  • the content of these aminocarboxylic acids or their salts can be, for example, between 0.1 and 30% by weight, preferably between 1 and 25% by weight and in particular between 5 and 20% by weight. Aminocarboxylic acids and their salts can be used together with the aforementioned builders.
  • the at least one builder is selected from the group consisting of methyl glycine diacetic acid (MGDA), glutamic diacetic acid (GLDA) and 1-hydroxyethane-1,1-diphosphonate (HEDP).
  • MGDA is preferably used as MGDA trisodium salt (MGDA-Nas)
  • GLDA is preferably used as GLDA tetrasodium salt (GLDA-Na4).
  • agents according to the invention or individual components of an agent according to the invention can contain water as the main solvent, i.e. it is an aqueous agent or an aqueous component.
  • the water content of an aqueous agent or an aqueous component is usually 15 to 70% by weight, preferably 20 to 60% by weight. In various embodiments, the water content is more than 5% by weight, preferably more than 15% by weight and particularly preferably more than 50% by weight, based in each case on the total amount of the aqueous agent or the aqueous component.
  • non-aqueous solvents can be added.
  • Suitable non-aqueous solvents include mono- or polyhydric alcohols, alkanolamines or glycol ethers, provided they are miscible with water in the specified concentration range.
  • the solvents are preferably selected from ethanol, n-propanol, I-Propanol, butanols, glycol, propandiol, buttiol, methylpropandiol, glycerin, Diglykol, propyldiglycol, butyldiglycol, hexylene glycol, ethylene gly olthythy.
  • ethylene glycolpropylether ethylene glycolmono-n- butylether, diethylene glycolmethyl 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-methoxybutanol, propylene glycol t-butyl ether, di-n-octyl ether and mixtures of these Solvent.
  • the one or more non-aqueous solvents are usually in an amount of 0.1 to 60% by weight, preferably 5 to 60% by weight, more preferably 10 to 30% by weight, based on the total weight of the aqueous By means of or the aqueous component.
  • the pH value of the agents according to the invention can be adjusted using conventional pH regulators.
  • the pH value of agents according to the invention is in a range from 6.5 to 12, preferably 7.0 to 11.5, preferably greater than 7, in particular 7.5 to 10.5.
  • Acids and/or alkalis, preferably alkalis serve as pH adjusters.
  • Suitable acids are, in particular, organic acids such as acetic acid, citric acid, glycolic acid, lactic acid, succinic acid, adipic acid, malic acid, tartaric acid and gluconic acid or amidosulfonic acid.
  • the mineral acids hydrochloric acid, sulfuric acid and nitric acid or mixtures thereof can also be used.
  • Suitable bases come from the group of alkali and alkaline earth metal hydroxides and carbonates, in particular alkali metal hydroxides, of which potassium hydroxide is preferred.
  • the alkali source described above is particularly preferably used to adjust the pH value. Even if volatile alkali, for example in the form of ammonia and/or alkanolamines, which can contain up to 9 carbon atoms in the molecule, can be used to adjust the pH, the alkanolamine can be selected from the group consisting of mono -, di-, triethanol- and -propanolamine and mixtures thereof, such volatile alkali sources, in particular ethanolamines, are preferably avoided.
  • the agents according to the invention therefore contain less than 1.75% by weight of alkanolamine, in particular monoethanolamine, and they are very particularly preferably free of it.
  • an agent according to the invention can further contain one or more buffer substances (INCI buffering agents), usually in amounts of 0.001 to 5% by weight. Buffer substances that are also complexing agents or even chelating agents (chelators, INCI chelating agents) are preferred. Particularly preferred buffer substances are citric acid or citrates, in particular sodium and potassium citrates, for example trisodium citrate 2 H2O and tripotassium citrate H2O.
  • Polymers suitable as additives are, in particular, maleic acid-acrylic acid copolymer Na salt (e.g. the commercially available Sokalan® CP 5 from BASF, Ludwigshafen (Germany)), modified polyacrylic acid Na salt (e.g. the commercially available Sokalan® CP 10 from BASF, Ludwigshafen (Germany)), modified polycarboxylate Na salt (e.g. the commercially available Sokalan® HP 25 from BASF, Ludwigshafen (Germany)), polyalkylene oxide, modified heptamethyltrisiloxane (e.g.
  • maleic acid-acrylic acid copolymer Na salt e.g. the commercially available Sokalan® CP 5 from BASF, Ludwigshafen (Germany)
  • modified polyacrylic acid Na salt e.g. the commercially available Sokalan® CP 10 from BASF, Ludwigshafen (Germany)
  • modified polycarboxylate Na salt e.g. the commercially available Sokalan® HP 25 from BASF, Ludwigs
  • the commercially available Silwet® L-77 from the company BASF, Ludwigshafen (Germany)
  • polyalkylene oxide modified heptamethyltrisiloxane
  • modified heptamethyltrisiloxane e.g. the commercially available Silwet® L-7608 from BASF, Ludwigshafen (Germany)
  • polyethersiloxanes copolymers of polymethylsiloxanes with ethylene oxide-Zpropylene oxide segments (polyether blocks)
  • preferably water-soluble linear polyethersiloxanes with terminal polyether blocks such as the commercially available compounds Tegopren® 5840, Tegopren® 5843, Tegopren® 5847, Tegopren® 5851, Tegopren® 5863 or Tegopren® 5878 from Evonik, Essen (Germany).
  • the polymers mentioned are dispensed with.
  • Polymeric thickeners which can also be contained in the agent are the polycarboxylates which have a thickening effect as polyelectrolytes, preferably homo- and copolymers of acrylic acid, in particular acrylic acid copolymers such as acrylic acid-methacrylic acid copolymers, and the polysaccharides, in particular heteropolysaccharides, as well as other common thickeners Polymers.
  • Suitable polysaccharides or heteropolysaccharides are the polysaccharide gums, for example gum arabic, agar, alginates, carrageenans and their salts, guar, guaran, tragacant, gellan, Ramzan, dextran or xanthan gum and their derivatives, e.g. propoxylated guar, as well as their mixtures.
  • polysaccharide thickeners such as starches or cellulose derivatives
  • starches or cellulose derivatives can be used as an alternative, but preferably 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 carboxymethyl cellulose or its sodium salt, methyl, ethyl, hydroxyethyl, Hydroxypropyl, hydroxypropylmethyl or hydroxyethyl methylcellulose or cellulose acetate.
  • starches of various origins and starch derivatives for example hydroxyethyl starch, starch phosphate esters or starch acetates, or carboxymethyl cellulose or its sodium salt, methyl, ethyl, hydroxyethyl, Hydroxypropyl, hydroxypropylmethyl or hydroxyethyl methylcellulose or cellulose acetate.
  • a preferred polymeric thickener is the microbial anionic heteropolysaccharide xanthan gum, which is produced by Xanthomonas campestris and some other species under aerobic conditions with a molecular weight of 2 to 15 x 10 6 and is available, for example, from Kelco under the trade name Keltrol®, e.g. as a cream-colored powder Keltrol® T (Transparent) or as white granules Keltrol® RD (Readily Dispersable).
  • Keltrol® e.g. as a cream-colored powder Keltrol® T (Transparent) or as white granules Keltrol® RD (Readily Dispersable).
  • Acrylic acid polymers suitable as polymeric thickeners are, for example, high molecular weight homopolymers of acrylic acid (INCI: carbomer) crosslinked with a polyalkenyl polyether, in particular an allyl ether of sucrose, pentaerythritol or propylene, which are also referred to as carboxyvinyl polymers.
  • polyalkenyl polyether in particular an allyl ether of sucrose, pentaerythritol or propylene, which are also referred to as carboxyvinyl polymers.
  • Such polyacrylic acids are available, among others, from BFGoodrich under the trade name Carbopol®, e.g. Carbopol® 940 (molecular weight Mw approx. 4000000 g/mol), Carbopol® 941 (molecular weight Mw approx. 1250000 g/mol) or Carbopol® 934 (molecular weight Mw approx. 3000000 g/mol).
  • acrylic acid copolymers are particularly suitable polymeric thickeners:
  • Copolymers of two or more monomers from the group of acrylic acid, methacrylic acid and their simple esters, preferably formed with Ci-4-alkanols (INCI: Acrylates Copolymer), which include the copolymers of methacrylic acid, butyl acrylate and methyl methacrylate (CAS 25035-69-2) or butyl acrylate and methyl methacrylate (CAS 25852-37-3) and which are available, for example, from Rohm & Haas under the trade names Aculyn® and Acusol®, e.g. the anionic non-associative polymers Aculyn® 33 (crosslinked), Acusol® 810 and Acusol® 830 (CAS 25852-37-3);
  • crosslinked high molecular weight acrylic acid copolymers which include, for example, the copolymers of Cio-30-alkyl acrylates crosslinked with an allyl ether of sucrose or pentaerythritol 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) and which are available, for example, from BFGoodrich under the trade name Carbopol®, e.g.
  • Carbopol® ETD2623 and Carbopol® 1382 (INCI: Acrylates/C 10 -30 Alkyl Acrylate Crosspolymer) and Carbopol® AQUA 30 (formerly Carbopol® EX 473).
  • An agent as described herein may contain one or more water-soluble salts to reduce viscosity. These can be inorganic and/or organic salts; in a preferred embodiment, the agent contains at least one inorganic salt.
  • Inorganic salts that can be used according to the invention are preferably selected from the group comprising colorless water-soluble halides, sulfates, sulfites, carbonates, hydrogen carbonates, nitrates, nitrites, phosphates and/or oxides of alkali metals, alkaline earth metals, of aluminum and/or transition metals; Ammonium salts can also be used. Halides and sulfates of alkali metals are particularly preferred; The inorganic salt is therefore preferably selected from the group comprising sodium chloride, potassium chloride, sodium sulfate, potassium sulfate and mixtures thereof. Sodium chloride is particularly preferred.
  • the organic salts that can be used according to the invention are, in particular, colorless water-soluble alkali metal, alkaline earth metal, ammonium, aluminum and/or transition metal salts of carboxylic acids, including dicarboxylic acids.
  • the salts are preferably selected from the group comprising formate, acetate, propionate, citrate, malate, maleate, tartrate, succinate, malonate, oxalate, lactate, fumarate, adipate, succinate, glutarate, methylglycinediacetic acid trisodium salt and mixtures thereof.
  • An optical brightener is preferably made from the substance classes of distyrylbiphenyls, stilbenes, 4,4'-diamino-2,2'-stilbenedisulfonic acids, coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, naphthalamides, benzoxazole systems, the benzisoxazole systems, the benzimidazole systems, the pyrene derivatives substituted by heterocycles and mixtures thereof.
  • optical brighteners include disodium 4,4'-bis(2-morpholino-4-anilino-s-triazine-6-ylamino)stilbene disulfonate (e.g. available as Tinopal® DMS from BASF SE), disodium 2,2' -bis(phenyl-styryl) disulfonate (e.g. available as Tinopal® CBS from BASF SE), 4,4'-bis[(4-anilino-6-[bis(2-hydroxyethyl)amino]-1,3,5- triazin-2-yl)amino]stilbene-2,2'-disulfonic acid (e.g.
  • Tinopal® UNPA available as Tinopal® UNPA from BASF SE
  • hexasodium 2,2'-[vinylenebis[(3-sulphonato-4,1-phenylene)imino [6-(diethylamino)-1,3,5-triazine-4,2-diyl]imino]]bis(benzene-1,4-disulfonate) e.g. available as Tinopal® SFP from BASF SE
  • 2,2' -(2,5-thiophenediyl)bis[5-1,1-dimethylethyl)benzoxazole e.g. available as Tinopal® SFP from BASF SE
  • 2,5-bis(benzoxazol-2-yl)thiophene available as Tinopal® UNPA from BASF SE
  • Suitable dye transfer inhibitors include polymers and copolymers of cyclic amines such as vinylpyrrolidone and/or vinylimidazole.
  • Polymers suitable as a color transfer inhibitor include polyvinylpyrrolidone (PVP), polyvinylimidazole (PVI), copolymers of vinylpyrrolidone and vinylimidazole (PVP/PVI), polyvinylpyridine-N-oxide, poly-N-carboxymethyl-4-vinylpyridium chloride, polyethylene glycol-modified copolymers of vinylpyrrolidone and vinylimidazole and mixtures thereof.
  • Polyvinylpyrrolidone (PVP), polyvinylimidazole (PVI) or copolymers of vinylpyrrolidone and vinylimidazole (PVP/PVI) are particularly preferably used as color transfer inhibitors.
  • the polyvinylpyrrolidones (PVP) used preferably have an average molecular weight of 2,500 to 400,000 and are commercially available from ISP Chemicals as PVP K 15, PVP K 30, PVP K 60 or PVP K 90 or from BASF as Sokalan® HP 50 or Sokalan® HP 53 available.
  • the copolymers of vinylpyrrolidone and vinylimidazole (PVP/PVI) used preferably have a molecular weight in the range from 5,000 to 10,000.
  • a PVP/PVI copolymer is commercially available, for example from BASF under the name Sokalan® HP 56.
  • Another extremely preferably usable color transfer inhibitor are polyethylene glycol-modified copolymers of vinylpyrrolidone and vinylimidazole, which are available, for example, from BASF under the name Sokalan® HP 66 are.
  • the agents described herein are preferably preassembled into dosage units. These metering units preferably comprise the amount of washing and/or care-active substances necessary for a textile cleaning and/or care cycle.
  • suitable dosage units have a weight of between 12 and 30 g, for example.
  • the volume of the aforementioned dosing units and their spatial shape are particularly preferably chosen so that the pre-assembled units can be dosed via the dosing chamber of a washing machine.
  • the volume of the dosing unit is therefore preferably between 10 and 35 ml, preferably between 12 and 30 ml.
  • the detergents in particular the prefabricated dosage units, particularly preferably have a water-soluble coating.
  • an agent as described herein is in the form of a unit dose as described above.
  • such an agent according to the invention is in particular encased in a water-soluble film.
  • the water-soluble covering is preferably formed from a water-soluble film material selected from the group consisting of polymers or polymer mixtures.
  • the wrapping may be formed from one or two or more layers of the water-soluble film material.
  • the water-soluble film material of the first layer and the additional layers, if present, can be the same or different. Films that can be glued and/or sealed to form packaging such as tubes or pillows after they have been filled with an agent are particularly preferred. In various embodiments, the films have the shape of multi-chamber pouches.
  • the water-soluble coating contains polyvinyl alcohol or a polyvinyl alcohol copolymer.
  • Water-soluble coatings that contain polyvinyl alcohol or a polyvinyl alcohol copolymer have good stability with a sufficiently high water solubility, in particular cold water solubility.
  • Suitable water-soluble films for producing the water-soluble coating are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer, the molecular weight of which is in the range from 10,000 to 1,000,000 g/mol, preferably from 20,000 to 500,000 g/mol, particularly preferably from 30,000 to 100,000 g/mol and in particular from 40,000 to 80,000 g/mol.
  • Polyvinyl alcohol is usually produced by hydrolysis of polyvinyl acetate, as the direct synthesis route is not possible. The same applies to polyvinyl alcohol copolymers, which are made from polyvinyl acetate copolymers. It is preferred if at least one layer of the water-soluble coating comprises a polyvinyl alcohol, the degree of hydrolysis of which is 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%.
  • a polyvinyl alcohol-containing film material suitable for producing the water-soluble coating can additionally contain a polymer selected from the group comprising (meth)acrylic acid-containing (co)polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters, polyethers, polylactic acid or mixtures of the above Polymers may be added.
  • a preferred additional polymer is polylactic acids.
  • preferred polyvinyl alcohol copolymers include dicarboxylic acids as further monomers. Suitable dicarboxylic acids are Itaconic acid, malonic acid, succinic acid and mixtures thereof, with itaconic acid being preferred.
  • polyvinyl alcohol copolymers include an ethylenically unsaturated carboxylic acid, its salt or its ester.
  • such polyvinyl alcohol copolymers particularly preferably contain acrylic acid, methacrylic acid, acrylic acid esters, methacrylic acid esters or mixtures thereof.
  • the film material contains further additives.
  • the film material can, for example, contain plasticizers such as dipropylene glycol, ethylene glycol, diethylene glycol, propylene glycol, glycerin, sorbitol, mannitol or mixtures thereof.
  • Other additives include, for example, release aids, fillers, crosslinking agents, surfactants, antioxidants, UV absorbers, anti-blocking agents, anti-adhesive agents or mixtures thereof.
  • Suitable water-soluble films for use in the water-soluble wrappings of the water-soluble packaging according to the invention are films sold by MonoSol LLC, for example under the names M8630, C8400 or M8900.
  • Other suitable films include films called Solublon® PT, Solublon® GA, Solublon® KC or Solublon® KL from Aicello Chemical Europe GmbH or the VF-HP films from Kuraray.
  • the present invention relates to both manual and mechanical processes for washing, caring for or conditioning textiles.
  • the present invention relates to methods for removing hair from textiles and/or the interior of a washing machine, wherein at least one textile detergent and/or care product and/or a textile detergent additive, as described herein, is introduced together with the textiles into a household washing machine or an industrial one Washing machine is given and subjected to a washing program so that the hair to be removed can be broken down and/or removed during the washing and/or care process.
  • active substances according to the invention i.e. enzyme, as defined above, bleach and bleach activator, enables hair to be removed accordingly even at low temperatures.
  • a corresponding method therefore comprises treating the textiles, i.e.
  • washing and/or caring for the textiles with a textile detergent and/or care product and/or a textile detergent additive, as described herein, at temperatures in the range from 0 to 90°C, preferably from 20 to 60°C, in particular from 40 to 60°C, for example 40°C, 45°C, 50°C, 55°C or 60°C.
  • an agent as described here can also be used advantageously in combination with other textile detergents and/or care agents in corresponding processes.
  • the present invention particularly relates to those methods in which, in addition to at least one agent as described herein, a textile conditioning agent is further used.
  • a further subject of the present invention is the use of a textile detergent and/or care product and/or a
  • Textile detergent additive for removing hair from textiles and/or the interior of a Washing machine, wherein the agent contains at least one enzyme, at least one bleach and at least one bleach activator.
  • the present invention relates to uses in which a detergent as described herein is used in the washing machine or in a manual textile washing process.
  • a further subject of the present invention is the use of a protease for removing hair from textiles and/or the interior of a washing machine, the protease being used in combination with at least one bleaching agent and at least one bleach activator.
  • the aforementioned active substances are preferably part of a textile detergent and/or care product and/or a textile detergent additive.
  • Example 1 Detergent and additive recipes
  • Table 2 Composition of detergent additive containing keratolytic protease or
  • Example 2 Determination of animal hair removal on a small scale (qualitative)
  • Reducing agent sodium sulfite 10% stock solution: 10 g in 100 ml ddH2Ü, of which 300 pl into the Eppendorf tube so that a final concentration of 1% sodium sulfite is present (correspondingly in the samples without: add 300 pl ddH2Ü)
  • Enzyme 1x: 0.7% enzyme raw material; 10x: 7% enzyme raw material
  • a tuft of hair was placed in a 5 ml Eppendorf tube (per tube: 20 mg ⁇ 1 mg). Then 3 ml of buffer and the appropriate amount of enzyme were added to the tubes. The tubes were incubated at 40°C with rotation (spinning and shaking) for 18 h. The tubes were then centrifuged for 10 min at 3000 rpm. The supernatant was removed and discarded, and the residue was dried at 70 ° C for 2.5 h. The inspection was carried out visually. Table 3: Results of the qualitative assessment
  • Example 3 Determination of animal hair loss on a small scale (quantitative)
  • Detergent additive 5.9 g/l (according to table 2, but without enzyme)
  • Bleach activator (Tinocat LT® B249): 0.0104 g/l (corresponds to 0.16% by weight based on the total weight of the additive)
  • Enzyme (Savinase 16 L): 0.64 g/l (corresponds to 9.77% by weight based on the total weight of the additive)
  • Detergent additive 5.9 g/l (according to table 2, but without enzyme)
  • Enzyme (Savinase 16 T): 0.64 g/l (corresponds to 9.79% by weight based on the total weight of the additive)
  • the wash liquor was filtered using a filtration cascade in the following stages:
  • a home-made four-stage filter cascade was used to filter the washing liquor.
  • the device is a horizontally stacked stainless steel cascade that provides fractional filtration. This facilitates filtration and enables the particle size distribution to be estimated.
  • the individual stages can be screwed on so that the number of filtration stages can be adapted to individual needs.
  • Each stage contains removable stainless steel filters that can be used flexibly for subsequent analyzes such as microscopy and gravimetric measurements.
  • four stainless steel filters with a diameter of 47 mm were used, with pore size in decreasing order from 60 pm (plain weave) to 25 pm (plain weave), 10 pm (plain weave) and 5 pm filters (twill weave). All filters were manufactured by Rolf Körner GmbH and pre-cleaned in an ultrasonic bath.
  • a total of three silicone sealing rings were used per stainless steel filter.
  • a vacuum pump (PC 3001 VARIO Vacuubrand) was connected to the filter cascade. The vacuum pump worked at 250 mbar. The washing liquor was placed in the upper funnel for filtration. After the washing liquid had been filtered, the cascade was additionally rinsed with distilled water.
  • the filter cake thus obtained was analyzed using scanning electron microscopy.
  • the SEM images (see Fig. 1) in backscattered electron mode (correlated with material contrast) show a normal hair structure with intact scales in hair treated with formulation 1 (benchmark) (a, b, c).
  • Recipe 1 hardly differs from recipe 2 (d-f).
  • the hair treated with formulation 3 (g-i) shows clear differences in structure and an overall damaged surface (g).
  • fractures (h) and angled scales (i) can be seen.
  • the combination of the additive containing bleach and bleach activator with the enzyme Savinase 16 T achieves the best results.

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Abstract

La présente invention concerne un procédé permettant d'éliminer les poils sur des textiles, au moins une étape du procédé consistant à utiliser un détergent et/ou un additif pour détergent contenant au moins une protéase, au moins un agent de blanchiment et au moins un activateur de blanchiment. La présente invention porte également sur l'utilisation d'un détergent et/ou d'un additif pour détergent pour éliminer les poils sur des textiles, le détergent et/ou l'additif pour détergent contenant au moins une protéase, au moins un agent de blanchiment et au moins un activateur de blanchiment. L'invention concerne en outre l'utilisation d'une protéase dans le but d'éliminer les poils de textiles.
EP23709408.1A 2022-04-01 2023-03-06 Élimination des poils au moyen d?un détergent/d?additifs pour détergent contenant des enzymes Pending EP4504884A1 (fr)

Applications Claiming Priority (2)

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DE102022107827.2A DE102022107827A1 (de) 2022-04-01 2022-04-01 Haarentfernung durch Waschmittel/-Additive enthaltend Enzyme
PCT/EP2023/055603 WO2023186459A1 (fr) 2022-04-01 2023-03-06 Élimination des poils au moyen d'un détergent/d'additifs pour détergent contenant des enzymes

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EP4574955A1 (fr) * 2023-12-22 2025-06-25 Henkel AG & Co. KGaA Composition détergente à haute concentration présentant une stabilité au stockage améliorée

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US3415758A (en) 1960-03-09 1968-12-10 Ncr Co Process of forming minute capsules en masse
US3516941A (en) 1966-07-25 1970-06-23 Minnesota Mining & Mfg Microcapsules and process of making
GB1234445A (fr) 1967-10-03 1971-06-03
DE2940786A1 (de) 1979-10-08 1981-04-16 Basf Ag, 6700 Ludwigshafen Verfahren zur herstellung von mikrokapseln
DK0493398T3 (da) 1989-08-25 2000-05-22 Henkel Research Corp Alkalisk, proteolytisk enzym og fremgangsmåde til fremstilling deraf
DK28792D0 (da) 1992-03-04 1992-03-04 Novo Nordisk As Nyt enzym
US5922083A (en) * 1995-04-03 1999-07-13 Procter & Gamble Company Detergent composition comprising a mutant amylase enzyme and oxygen bleaching agent
ATE429490T1 (de) 1995-05-05 2009-05-15 Novozymes As Protease-varianten und verbindungen
EP1244779B1 (fr) 1999-12-15 2014-05-07 Novozymes A/S Variants de subtilase a performance de nettoyage amelioree sur des taches d'oeuf
AU2001291649A1 (en) 2000-10-02 2002-04-15 Novozymes A/S Nucleic acids encoding polypeptides having proteolytic activity
US20050054843A1 (en) 2001-12-31 2005-03-10 Estell David A Proteases producing an altered immunological response and methods of making and using the same
SE0303120D0 (sv) 2003-03-24 2003-11-25 Forskarpatent I Syd Ab Novel alkaline protease
DE102006022224A1 (de) 2006-05-11 2007-11-15 Henkel Kgaa Subtilisin aus Bacillus pumilus und Wasch- und Reinigungsmittel enthaltend dieses neue Subtilisin
JP2009540859A (ja) 2006-07-07 2009-11-26 ザ プロクター アンド ギャンブル カンパニー セルラーゼ及び漂白触媒を含む組成物
DE102007003143A1 (de) 2007-01-16 2008-07-17 Henkel Kgaa Neue Alkalische Protease aus Bacillus gibsonii und Wasch- und Reinigungsmittel enthaltend diese neue Alkalische Protease
BR112015011173A2 (pt) * 2012-12-12 2017-07-11 Unilever Nv composição de limpeza, método de alvejamento de um substrato alvejável e uso da composição de limpeza
EP4530348A3 (fr) 2014-12-15 2025-08-06 Basf Se Composition détergente comprenant des variants de subtilase
EP3103431A1 (fr) 2015-06-12 2016-12-14 The Procter and Gamble Company Compositions de parfums et utilisations associées
GB201701356D0 (en) 2017-01-27 2017-03-15 Cares Laboratory Ltd Hair removal from textiles
CN114214221B (zh) * 2021-08-30 2023-11-17 河南科技学院 一种产角蛋白酶的嗜麦芽窄食单胞菌及其应用

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WO2023186459A1 (fr) 2023-10-05
DE102022107827A1 (de) 2023-10-05

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