Hair removal by means of detergent / detergent additives containing enzymes

Abstract

The present invention relates to a method for removing hair from textiles, wherein in at least one method step a detergent and / or detergent additive containing at least one protease, at least one bleaching agent and at least one bleach activator is used. The present invention also relates to the use of a detergent and / or detergent additive for removing hair from textiles, wherein the detergent and / or detergent additive contains at least one protease, at least one bleaching agent and at least one bleach activator. The invention further relates to the use of a protease for removing hair from textiles.

Description

[0001] HAIR REMOVAL USING DETERGENTS / ADDITIVES CONTAINING ENZYMES

[0002] 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 bleaching agent, 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, wherein the detergent and / or detergent additive contains at least one protease, at least one bleaching agent, and at least one bleach activator. Furthermore, the invention relates to the use of a protease for removing hair from textiles.

[0003] Pet owners often face the problem that a considerable amount of pet hair is left on clothing and pet bedding. When washing such soiled textiles, hair can get caught in the washing machine and / or become stuck to the item.

[0004] Animal hair can be dissolved in the presence of 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)) under highly alkaline conditions and at high temperatures (85 to 95°C) and thus be more easily rinsed off. However, this is not practical or energy-efficient today, as consumers generally no longer wash at 85-95°C or do not want to wash at such high temperatures.

[0005] With the existing market solution such as Vamoosh Pet Hair Dissolver, which has a high alkalinity and also contains bleach and bleach activator, washing must be carried out at 85 to 95°C in order to achieve hair removal during washing.

[0006] There is therefore still a need for products and processes for washing textile articles that enable energy-efficient hair removal.

[0007] This object is achieved by a process in which a textile washing and / or care agent and / or a textile washing agent additive is used in at least one process step, wherein the agent and / or additive comprises at least one protease, at least one bleaching agent and at least one bleach activator.

[0008] 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 method step a textile washing and / or care agent and / or a textile washing agent additive containing at least one protease, at least one bleaching agent and at least one bleach activator is used.

[0009] In a further aspect, the invention also relates to the use of a textile washing and / or care agent and / or a textile washing agent 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 bleaching agent and at least one bleach activator.

[0010] In another aspect, the invention also relates to the use of a protease for removing hair from textiles and / or the interior of a washing machine, wherein the protease is used in combination with at least one bleaching agent and at least one bleach activator.

[0011] These and other aspects, features, and advantages of the invention will become apparent to those skilled in the art upon review of the following detailed description and claims. Any feature of one aspect of the invention may be employed in any other aspect of the invention.

[0012] The subject matter of the invention includes all conceivable solid and liquid detergent types and combination products thereof, both concentrates and undiluted detergents, for use on a commercial scale, in washing machines or for hand washing. The detergents within the scope of the invention also include washing aids that are added to the actual detergent during manual or machine washing to achieve an additional effect. Furthermore, detergents within the scope of the invention also include textile pre- and post-treatment agents, i.e. agents with which the laundry is brought into contact before the actual washing, e.g. to dissolve stubborn soils, and also agents that impart further desirable conditioning properties to the laundry, such as a pleasant feel, resistance to creasing or low static charge, in a step following the actual textile washing.

[0013] “At least one”, as used herein, includes, but is not limited to, 1, 2, 3, 4, 5, 6 and more. When referred to an ingredient, the statement 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., one type of surfactant or a mixture of several different surfactants can be meant. Together with weight information, the statement refers to all compounds of the specified type that are contained in the composition / mixture, i.e., the composition does not contain any further compounds of this type beyond the stated amount of the corresponding compounds.

[0014] All percentages are by weight unless otherwise stated.

[0015] Numerical ranges specified in the format "from x to y" include the specified values. If multiple preferred numerical ranges are specified in this format, it goes without saying that all ranges resulting from the combination of the different endpoints will also be included.

[0016] “Approximately” or “ca.” as used herein in connection with a numerical value refers to the numerical value ±10%, preferably ±5%.

[0017] Whenever reference is made to molar masses, these figures always refer to the number-average molar mass M n , unless explicitly stated otherwise. The number-average molar mass can be determined, for example, by gel permeation chromatography (GPC) according to DIN 55672-1:2007-08 using THF as eluent. The mass-average molar mass Mw can also be determined by GPC, as for M n described.

[0018] Whenever alkaline earth metals are mentioned below as counterions for monovalent anions, this means that the alkaline earth metal is naturally present in only half the amount of the anion - sufficient to balance the charge.

[0019] “Liquid”, as used in the context of the present invention, refers to 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.

[0020] “Solid form”, as used herein, in the context of the present invention refers to a powder, granulate, extrudate or compact composition.

[0021] A substance, e.g. 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.

[0022] A substance, e.g., a composition or agent, is liquid according to the invention's definition if it exists in the liquid state at 25°C and 1013 mbar. Liquid also includes gel.

[0023] “Phosphate-free” and “phosphonate-free” as used herein means that the composition in question is substantially free of phosphates or phosphonates, ie in particular contains phosphates or phosphonates in amounts of less than 0.1% by weight, preferably less than 0.01% by weight, based on the respective composition.

[0024] An agent according to the invention can be a single-component agent or a multi-component agent. In the context of the present invention, the term "single-component agent" refers to an agent consisting of only a single component. The term "multi-component agent," as used herein, refers to an agent composed of at least two components. It is preferred that the individual components of a multi-component agent according to the invention be spatially separated from one another.

[0025] The expression "spatially separated" in relation to the components of the product, as used herein, means that the individual components cannot come into contact with each other before the product is used. Typically, the product is provided in a multi-chamber package, such as a bottle, tube or pouch, in particular a two-chamber bottle or pouch, wherein each individual component is located in a separate chamber from the other component(s). The spatial separation of individual components of the product makes it possible, on the one hand, to separate incompatible ingredients from one another and, on the other hand, to offer several different components of the product in combination, which are used at different times. In this context, the term "component" refers to a part of the product which can be distinguished by one or more features, e.g.The type and / or quantity of its ingredients, physical properties, external appearance, etc., can be distinguished from any other component of the product. Individual components of the product can be in liquid form, as defined herein, or in solid form, as defined herein, and advantageously spatially separated from one another.

[0026] The term "washing and / or cleaning agent", "washing and cleaning agent" or "washing or cleaning agent", as used herein, is synonymous with the term "agent" and refers to a composition for cleaning textiles and / or hard surfaces, in particular dishes, as explained in the description.

[0027] The term "textile," as used herein, refers to 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 may be in the form of knits, wovens, denims, nonwovens, felts, yarns, and terry cloth. The textile may be cellulose-based, such as natural cellulose fibers like cotton, flax / linen, jute, ramie, sisal, or coconut fibers, or man-made cellulose fibers (e.g., from wood pulp) such as viscose / rayon, cellulose acetate fibers (Tricell), lyocell, or mixtures thereof. The textile or fabric may also be made of non-cellulose fibers, e.g.,Made from natural polyamides such as wool, camel, cashmere, mohair, rabbit, and silk, or from synthetic polymers such as nylon, aramid, polyester, acrylic, polypropylene, and spandex / elastane, or blends thereof, as well as blends of cellulosic and non-cellulosic fibers. Examples of blends include blends 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 / or cellulosic fibers (e.g., rayon / viscose, ramie, flax / linen, jute, cellulose acetate fibers, lyocell). The fabric may be conventional washable laundry, e.g., soiled household linen. When the term "fabric" or "garment" is used, it is intended to include the broader term "textiles."

[0028] Figure 1 shows scanning electron micrographs used to evaluate the structure of animal hair after treatment with different detergent formulations during a simulated washing process (according to Example 4).

[0029] 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.

[0030] Proteases suitable in the context of the present invention include all proteases suitable for use in textile washing and / or care compositions.

[0031] Examples of 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 Thermitase, Proteinase K, and the proteases TW3 and TW7, which are classified as subtilases but no longer as subtilisins in the narrower sense. Subtilisin Carlsberg is available in a further developed form under the trade name Alcalase® from Novozymes. Subtilisins 147 and 309 are marketed under the trade names Esperase® and Savinase®, respectively, by Novozymes. The protease variants known as BLAP® are derived from the protease from Bacillus lentus DSM 5483. Other useful proteases include:the enzymes available under the trade names Durazym®, Relase®, Everlase®, Nafizym®, Natalase®, Kannase® and Ovozyme® from Novozymes, the enzymes available under the trade names Purafect®, Purafect® OxP, Purafect® Prime, Excellase® and Properase® from Danisco / Genencor, the enzyme available under the trade name Protosol® from Advanced Biochemicals Ltd., the enzyme available under the trade name Wuxi® from Wuxi Snyder Bioproducts Ltd., the enzyme available 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. Particularly preferred are also the proteases from Bacillus gibsonii and Bacillus pumilus, which are disclosed in the international patent applications WO 2008 / 086916 and WO 2007 / 131656.Further advantageously usable proteases are disclosed in 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. Other usable proteases are those naturally present in the microorganisms Stenotrophomonas maltophilia, particularly Stenotrophomonas maltophilia K279a, Bacillus intermedius, and Bacillus sphaericus. Protease variants based on Bacillus lentus DSM 5483 protease (BLAP), such as those with the R99E substitution, are particularly suitable. Such particularly suitable proteases are described, for example, in WO 2016 / 096714.

[0032] In the context of the present invention, particularly suitable proteases are those which exhibit keratolytic activity. In the context of the present invention, the term “exhibiting keratolytic activity” means that a corresponding enzyme is capable of cleaving peptide bonds (-NH-CO-) of the keratin substrate. Non-limiting examples of commercially available proteases which exhibit keratolytic activity include ALCALASE®, SAVINASE®, SAVINASE® ULTRA, SAVINASE® EVITY®, SAVINASE® EVERIS®, ESPERASE® (Novozymes); BLAP™ and BLAP™ variants (Henkel), Valkerase® (BRI Enzymes), KerA (Creative Enzymes). In various embodiments, the at least one protease is accordingly a protease with keratolytic activity.

[0033] In various embodiments, the at least one protease is a keratinase. For the purposes of the present application, 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.

[0034] In various embodiments, the at least one protease is selected from the group consisting of proteases with keratolytic activity, preferably from the group consisting of keratinases.

[0035] Keratinases suitable in the context of the present invention can originate from various organisms. Suitable microorganisms are selected from the group consisting of the genera 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).

[0036] In various embodiments of the invention, the keratinase used in the detergent according to the invention is a keratinase commercially available under the trade name “KERATOCLEAN® HYDRA PB” Micro-granules.

[0037] The proteases used here, which may be keratinases, may be naturally occurring enzymes or enzymes that have been modified by one or more mutations on the basis of naturally occurring enzymes in order to positively influence desired properties, such as catalytic activity or stability.

[0038] In the present invention, 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 parent protein. In various embodiments, 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.

[0039] The identity of nucleic acid or amino acid sequences is determined by sequence comparison. This sequence comparison is based on the BLAST algorithm, which is established and commonly used in the state of the art (see, for example, 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 essentially performed by matching similar sequences of nucleotides or amino acids in the nucleic acid or amino acid sequences to one another. A tabular assignment of the relevant positions is referred to as an alignment. Another algorithm available in the state of the art is the FASTA algorithm. Sequence comparisons (alignments), especially multiple sequence comparisons, are created using computer programs. Frequently used are, for example, 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 (cf. e.g. Notredame et al., T-Coffee: A novel method for multiple sequence alignments, J. Mol. Biol., 2000, 302: 205-217) or programs based on these programs or algorithms. Furthermore, sequence comparisons (alignments) are possible using the computer program Vector NTI® Suite 10.3 (Invitrogen Corporation, 1600 Faraday Avenue, Carlsbad, California, USA) with the predefined 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, the sequence identity reported herein is determined using the BLAST algorithm. Such a comparison also allows for a statement about the similarity of the compared sequences to each other.It is usually expressed as percent identity, i.e. the proportion of identical nucleotides or amino acid residues at the same positions or corresponding positions in an alignment. The broader term homology in amino acid sequences includes conserved amino acid substitutions, 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 expressed as percent homology or percent similarity. Identity and / or homology statements can be made for entire polypeptides or genes or just for individual regions. Homologous or identical regions of different nucleic acid or amino acid sequences are therefore defined by similarities in the sequences. Such regions often have identical functions. They can be small and contain only a few nucleotides or amino acids.Such small regions often perform essential functions for the overall activity of the protein. It may therefore be useful to refer sequence matches only to individual, possibly small regions. Unless otherwise stated, however, statements of identity or homology in this application refer to the entire length of the respective nucleic acid or amino acid sequence.

[0040] Enzymes usable in the context of the present invention may also exhibit amino acid changes, in particular amino acid substitutions, insertions, or deletions, compared to naturally occurring enzymes. Such proteases with keratolytic activity, which may be keratinases, have been further developed, for example, by targeted genetic modification, i.e., by mutagenesis methods, and optimized for specific applications or with regard to special properties (e.g., with regard to their catalytic activity, stability, etc.). Furthermore, nucleic acids encoding the enzymes used can be introduced into recombination approaches and thus used to generate completely novel 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 purification performance of enzymes according to the invention.For this purpose, in particular, the surface charges and / or the isoelectric point of the molecules and thus their interactions with the substrate can be altered. For example, the net charge of the enzymes can be altered in order to influence substrate binding, particularly for use in detergents. Alternatively or additionally, one or more appropriate mutations can further increase the stability of the enzyme and thus 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 within the scope of the invention.

[0041] In various embodiments, 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 the starting molecule by single or multiple conservative amino acid substitution. The term "conservative amino acid substitution" means the exchange (substitution) of one amino acid residue for another amino acid residue, wherein this exchange does not lead to a change in the polarity or charge at the position of the exchanged amino acid, e.g., the exchange of one non-polar amino acid residue for another non-polar amino acid residue. Conservative amino acid substitutions within the scope of the invention include, for example: G=A=S, I=V=L=M, D=E, N=Q, K=R, Y=F, S=T, G=A=I=V=L=M=Y=F=W=P=S=T.

[0042] Alternatively or additionally, the protease is characterized in that it is obtainable from a protease described above as the starting molecule by fragmentation, deletion, insertion or substitution mutagenesis. For example, it is possible to delete individual amino acids at the termini or in the loops of the enzyme without thereby losing or reducing the catalytic activity. Furthermore, such fragmentation, deletion, insertion or substitution mutagenesis can also, for example, reduce the allergenicity of the enzymes in question and thus improve their overall usability. Advantageously, 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 individual and multiple amino acids can be exchanged for other amino acids.

[0043] Using methods commonly known today, such as chemical synthesis or the polymerase chain reaction (PCR) in conjunction with standard molecular biological and / or protein chemical methods, a person skilled in the art can produce the corresponding nucleic acids, including complete genes, based on known DNA and / or amino acid sequences. Such methods are known, for example, from Sambrook, J., Fritsch, EF, and Maniatis, T. 2001. Molecular cloning: a laboratory manual, 3rd Edition, Cold Spring Laboratory Press.

[0044] In various embodiments of the invention, the protease, as described above, is present in the agent according to the invention in an amount of 1.5 to 20 wt.%, preferably 2.0 to 15 wt.%, more preferably 2.5 to 12 wt.%, even more preferably 3.0 to 10 wt.% of active protein, based on the total weight of the agent. Preferably, this is a protease that is substantially free of other proteins and / or other cellular contaminants (e.g., lipids, DNA, RNA, etc.).

[0045] The protein concentration can be determined using known methods, e.g., 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 sites using a suitable irreversible inhibitor and determining the residual activity (Bender et al., 1966, J. Am. Chem. Soc. 88(24): 5890-5913).

[0046] The protease can be formulated in forms known for other enzymes used in textile washing and / or care products, e.g., in encapsulated form. Such possibilities are known to those skilled in the art.

[0047] In various embodiments of the invention, the agent according to the invention may contain, in addition to the protease or alternatively, a protease-producing microorganism, in particular 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). In various embodiments of the invention, this microorganism is present in an amount of 2.0 to 20 wt.%, preferably 2.5 to 15 wt.%, based on the total weight of the agent according to the invention.

[0048] If, in various embodiments, in addition to the at least one protease, as described above, one or more further enzymes are present, these are selected from all enzymes suitable for use in textile washing and / or care products, ie one or more further enzymes are selected in particular 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 10 8 to 5 wt.%, based on active protein, in particular from 1 x 10 -7to 3 wt.%, from 0.00001 to 1 wt.%, from 0.00005 to 0.5 wt.%, from 0.0001 to 0.1 wt.%, and particularly preferably from 0.0001 to 0.05 wt.%, each based on the total weight of the agent and based on active protein. If the at least one protease is a protease with keratolytic activity and / or a keratinase, an agent as described herein may additionally comprise other proteases. In such embodiments, 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 wt.%, preferably 2.0 to 15 wt.%, more preferably 2.5 to 12 wt.%, even more preferably 3.0 to 10 wt.% active protein, based on the total weight of the agent, and the at least one further protease, ie a protease which has no keratolytic activity, is contained in the usual amounts, ie for example in amounts of 1 x 10 -8up to 1% by weight, each based on the total weight of the agent and based on active protein.

[0049] Particularly preferably, the enzymes used exhibit synergistic cleaning performance against specific soils or stains, i.e., the enzymes contained in the composition support each other in their cleaning performance. Such synergism most preferably exists between a protease and another 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.

[0050] The enzymes which may additionally be used within the scope of the present invention may, for example, originally originate from microorganisms, for example of the genera Bacillus, Streptomyces, Humicola or Pseudomonas, and / or be produced by suitable microorganisms according to known biotechnological processes, for example by transgenic expression hosts, for example of the genera Escherichia, Bacillus or by filamentous fungi.

[0051] It is emphasized that these may also be technical enzyme preparations of the respective enzyme, meaning that accompanying substances may be present. Therefore, the enzymes can be formulated and used together with accompanying substances, such as those from fermentation or other stabilizers.

[0052] 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, solid preparations obtained by granulation, extrusion, or lyophilization or, particularly in the case of liquid or gel-like products, solutions of the enzymes, preferably as concentrated as possible, with little water content, and / or containing stabilizers or other additives.

[0053] Alternatively, the enzymes can be encapsulated for both solid and liquid dosage forms, e.g. by spray-drying or extrusion of the enzyme solution together with a preferably natural polymer, or in the form of capsules, e.g. those in which the enzymes are enclosed as if in a solidified gel, or in those of the core-shell type, in which an enzyme-containing core is coated with a water-, air- and / or chemical-impermeable protective layer. Additional active ingredients, e.g. stabilizers, emulsifiers, pigments, bleaching agents or dyes, can be applied in deposited layers. Such capsules are applied using methods known per se, e.g. by shake or roll granulation or in fluid-bed processes. Advantageously, such granules, e.g. through the application of polymeric film formers, are low in dust and, due to the coating, are stable in storage.

[0054] Furthermore, it is particularly possible to package two or more enzymes together so that a single granulate has several enzyme activities, as explained above.

[0055] An enzyme-containing formulation as described above contains the at least one enzyme usually in an amount of 0.1 to 50 wt.%, preferably 0.1 to 20 wt.%, based on the total weight of the formulation.

[0056] In liquid formulations, the enzymes are preferably used as liquid enzyme formulation(s). In various embodiments, such a liquid enzyme-containing formulation contains at least one organic solvent, preferably selected from alcohols, particularly preferably 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 wt.%, more preferably 10 to 90 wt.%, based on the total weight of the enzyme-containing formulation.

[0057] Bleaching agents suitable in the context of the present invention, i.e., those suitable for use in textile washing and / or care processes and correspondingly suitable agents or those commonly used in such processes, are known in the art. Suitable bleaching agents generally include hypochlorites, hydrogen peroxide, or hydrogen peroxide-providing substances.

[0058] In various embodiments, however, it is preferred that the at least one bleaching agent is not a chlorine-containing bleaching agent. In various embodiments, the at least one bleaching agent is present in an amount of 5 to 70 wt.%, preferably in an amount of up to 50 wt.%, in particular up to 40 wt.%, and particularly preferably 7 to 30 wt.%, in each case based on the total weight of the agent.

[0059] In various embodiments, the at least one bleaching agent is a peroxygen-based bleaching agent. Peroxygen-based bleaching agents are advantageously present in amounts ranging from 5 to 70 wt.%, in particular from 5 to 30 wt.%, based in each case on the total weight of the agent.

[0060] The bleaching agents considered are preferably the peroxygen compounds typically used in detergents, such as percarboxylic acids, e.g., dodecanediperic acid or phthaloylaminoperoxicaproic acid, hydrogen peroxide, alkali metal perborate, which may be present as the tetrahydrate or monohydrate, percarbonate, perpyrophosphate, and persilicate, which are generally present as alkali metal salts, especially as sodium salts. Photobleaching agents, such as tetrabenzotetraazoporphyrins or similar, are also suitable. Such bleaching agents are preferably present 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, in each case based on the total weight of the respective agent, wherein percarbonate is used in particular.If solid peroxygen compounds are to be used, they can be used in powder or granulate form, which can also be coated in a conventional manner. 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.

[0061] 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.

[0062] Bleach activators suitable in the context of the present invention include all known and commonly used bleach activator compounds.

[0063] As bleach activator compounds that yield peroxocarboxylic acid under perhydrolysis conditions, compounds that yield optionally substituted perbenzoic acid and / or aliphatic peroxocarboxylic acids having 1 to 12 carbon atoms, in particular 2 to 4 carbon atoms, under perhydrolysis conditions, can be used, alone or in mixtures. Suitable bleach activators are those that carry O- and / or N-acyl groups, in particular with the stated number of carbon atoms, and / or optionally substituted benzoyl groups. Preferred are 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 phenolsulfonates or carboxylates or the sulfonic or carboxylic acids thereof, in particular nonanoyl or isononanoyl or lauroyloxybenzenesulfonate (NOBS or iso-NOBS orLOBS) or decanoyloxybenzoate (DOBA), their formal carbonic acid ester derivatives such as 4-(2-decanoyloxyethoxycarbonyloxy)-benzenesulfonate (DECOBS), acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran as well as acetylated sorbitol and mannitol and mixtures thereof (SORMAN), acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetylfructose, tetraacetylxylose and octaacetyl lactose, acetylated, optionally N-alkylated glucamine and gluconolactone, and / or N-acylated lactams, e.g. N-benzoylcaprolactam.

[0064] In addition to or as an alternative to the compounds that form peroxocarboxylic acids under perhydrolysis conditions, other bleach activator compounds, such as nitriles, from which perimidic acids are formed under perhydrolysis conditions, may be present. These include, in particular, aminoacetonitrile derivatives with a quaternized nitrogen atom according to formula (I) in the R 11represents -H, -CH3, a C2-24 alkyl or alkenyl radical, a substituted C2-24 alkyl or alkenyl radical having at least one substituent selected from the group consisting of -Cl, -Br, -OH, -NH2, -CN and -N (+) -CH2-CN, an alkyl or alkenylaryl radical having a Ci-24 alkyl group, or a substituted alkyl or alkenylaryl radical having at least one, preferably two, optionally substituted Ci-24 alkyl group(s) and optionally further substituents on the aromatic ring, R 12 and R 13 are independently selected from -CH2-CN, -CH3, -CH2-CH3, -CH2-CH2-CH3, -CH(CH3)-CH3, -CH2-OH, -CH2-CH2-OH, -CH(OH)-CH3, -CH2-CH2-CH2-OH, -CH2-CH(OH)-CH3, -CH(OH)-CH2-CH3, -(CH2CH2-O) n H with n = 1, 2, 3, 4, 5 or 6, R 14 and R 15 independently of each other a preceding for R 11 , R 12 or R 13 have the meaning given, where at least 2 of the radicals mentioned, in particular R 12 and R 13, including the nitrogen atom and optionally further heteroatoms, may be linked to one another in a ring-closing manner, and then preferably form a morpholine ring, and X is a charge-balancing anion, preferably selected from benzenesulfonate, toluenesulfonate, cumenesulfonate, Cg-11-alkylbenzenesulfonates, C1-20 alkyl sulfates, Cs-22 carboxylic acid methyl ester sulfonates, sulfate, hydrogen sulfate, and mixtures thereof. Oxygen-transferring sulfonimines can also be used.

[0065] The amount of such bleach activators, ie the bleach activator compounds which produce peroxocarboxylic acid under perhydrolysis conditions and the bleach activator compounds which form perimidic 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, e.g. 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12% by weight, in each case based on the total weight of the respective agent.

[0066] To avoid interaction with the peroxygen compounds during storage, the bleach activators may be coated or granulated with coating substances in a known manner, whereby granulated

[0067] 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.

[0068] In addition to such bleach activators, or if desired, instead of them, conventional 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 can be considered as ligands in such transition metal complexes, including carboxylates and 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-tetraazacyclotetradecane, 1,5,8,12-tetraazabicyclo[6.6.2]hexadecane and its substituted derivatives such as 5,12-diethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane, (bis((1-methylimidazol-2-yl)-methyl))-(2-pyridylmethyl)amine, N,N'-(bis(1-methylimidazol-2-yl)methyl)ethylenediamine, N-bis(2-benzimidazolylmethyl)aminoethanol, 2,6-bis(bis(2-benzimidazolylmethyl)aminomethyl)-4-methylphenol, N,N,N',N'-tetrakis(2-benzimidazolylmethyl)-2-hydroxy-1,3-diaminopropane, 2,6-bis(bis(2-pyridylmethyl)aminomethyl)-4-methylphenol, 1,3-bis(bis(2-benzimidazolylmethyl)aminomethyl)benzene, sorbitol, mannitol, erythritol, adonitol, inositol, lactose, and possibly substituted salens, porphins and porphyrins. 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 additional, preferably anionic, and among these, especially mono- or bidentate ligands.These include, in particular, 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 chelated to a transition metal, or it can bind two transition metal atoms asymmetrically or r]. 1-O-bridge. In addition to the ligands mentioned, the transition metal complexes can also bear other, generally simpler ligands, particularly monovalent or polyvalent anion ligands. Examples of possible anions 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. Such ligands, in particular, can also have a bridging effect, resulting in polynuclear complexes. In the case of bridged, dinuclear complexes, 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 absent or the presence of anion ligands does not lead to charge balance 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. These anionic counterions include, in particular, nitrate, hydroxide, hexafluorophosphate, sulfate, chlorate, perchlorate, halides such as chloride, or the anions of carboxylic acids such as formate, acetate, oxalate, benzoate, or citrate.Examples of usable transition metal complex compounds 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- diaminoethane]manganese(III) chloride, [N,N'-bis[(2-hydroxy-5-sulfonatophenyl)methylene]-1,2-diaminoethane]manganese(III) chloride, manganese oxalato complexes, nitropentamminecobalt(III) chloride, nitritopentamminecobalt(III) chloride, hexamminecobalt(III) chloride, chloropentamminecobalt(III) chloride and the peroxo complex [(NH3)5Co-0-0-Co(NH3)5]Cl4.

[0069] In washing or cleaning agents, bleach-activating transition metal complexes (e.g. hydrazinylmethylmorpholinium chloride, Mn-salen complex) are preferably contained in amounts of up to 0.5 wt.%, in particular from 0.0005 to 0.2 wt.%, in each case based on the total agent.

[0070] In addition and / or instead of the aforementioned bleach activators, acylhydrazones of the general formula (II), in the R 1 represents a CFs group or a C1-28-alkyl, C2-28-alkenyl, C2-22-alkynyl, C3-12-cycloalkyl, C3-12-cycloalkenyl, phenyl, naphthyl, C1-g-aralkyl, C3-2o-heteroalkyl or C3-12-cycloheteroalkyl group, which may optionally be substituted, R 2 and R 3independently of one another represent hydrogen or an optionally substituted C1-28-alkyl, C2-28-alkenyl, C2-22-alkynyl, C5-12-cycloalkyl, C3-12-cycloalkenyl, C7-9-aralkyl, C5-28-heteroalkyl, C5-12-cycloheteroalkyl, C5-16-heteroaralkyl, phenyl, naphthyl or heteroaryl group or R 2 and R 3 together with the connecting carbon atom represent an optionally substituted 5-, 6-, 7-, 8- or 9-membered ring, which may optionally contain heteroatoms, and R 4 represent hydrogen or a C1-28 alkyl, C2-28 alkenyl, C2-22 alkynyl, C3-12 cycloalkyl, C5-12 cycloalkenyl, C6-8 aralkyl, C5-20 heteroalkyl, C5-12 cycloheteroalkyl, C5-16 heteroaralkyl group or an optionally substituted phenyl, naphthyl, or heteroaryl group. The acylhydrazones can be in the E or Z configuration; if R 2is hydrogen, the compound of general formula (II) can exist in one of its tautomeric forms or as a mixture of these.

[0071] In the compounds of general formula (II), R 2 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 electron-withdrawing group is preferably an ammonium group, which optionally carries alkyl or hydroxyalkyl groups or, including the N atom carrying an alkyl group, is formed as a heterocycloalkyl group optionally carrying further heteroatoms. Preferred embodiments of the compounds according to general formula (II) include those of general formula (III), in the R 1 represents a Ci-4-alkyl group containing a substituent selected from bears, in which R 10represents hydrogen or a C1-28-alkyl, C2-28-alkenyl, C2-22-alkynyl, C3-12-cycloalkyl, C3-12-cycloalkenyl, C1-6-aralkyl, C3-20-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 for R 1, hydrogen, halogen, a hydroxy, amino, an optionally substituted N-mono or di-Ci-4-alkyl or C2-4-hydroxyalkylamino, N-phenyl or N-naphthylamino, C1-28-alkyl, C1-28-alkoxy, phenoxy, C2-28-alkenyl, C2-22-alkynyl, C3-12-cycloalkyl, C3-12-cycloalkenyl, C1-6-aralkyl, C3-20-heteroalkyl, C3-12-cycloheteroalkyl, C5-16-heteroaralkyl, phenyl or naphthyl group, where the substituents are selected from C1-4-alkyl, C1-4-alkoxy, hydroxy, sulfo, sulfato, halogen, cyano, nitro, Carboxy, phenyl, phenoxy, naphthoxy, amino, N-mono or di-Ci-4-alkyl or C2-4-hydroxyalkylamino, N-phenyl or N-naphthylamino groups, or R 5 and R 6 or R 6 and R 7 or R 7 and R 8 with formation of 1, 2 or 3 carbocyclic or O-, NR 10 - or S- heterocyclic, optionally aromatic and / or optionally Ci-6-alkyl-substituted rings.

[0072] The anion A- is preferably carboxylate such as lactate, citrate, tartrate or succinate, perchlorate, tetrafluoroborate, hexafluorophosphate, alkylsulfonate, arylsulfonate such as p-toluenesulfonate, alkyl sulfate such as methosulfate, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, phosphate, isocyanate, thiocyanate, nitrate, fluoride, chloride, bromide, hydrogen carbonate or carbonate, whereby in the case of multivalent anions the charge balance can be achieved by the presence of additional cations such as sodium or ammonium ions.

[0073] Particularly preferred is the acylhydrazone of formula (IV), Acylhydrazones of the general formulas (II), (III) or (IV) are preferably used in amounts of 0.001 to 5 wt.%, in particular 0.05 to 0.15 wt.% in the compositions described herein.

[0074] In various embodiments, at least one bleach activator is used. In various embodiments, 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 that form perimidic acid under perhydrolysis conditions; bleach-activating transition metal complexes and acylhydrazones. In various embodiments, it may be advantageous to use mixtures of different bleach activators, e.g. at least two different bleach activators in combination, wherein the different bleach activators are preferably selected from the above-described groups of bleach activator compounds that yield peroxocarboxylic acid under perhydrolysis conditions, bleach activator compounds that form perimidic acid under perhydrolysis conditions, bleach-activating transition metal complexes and acylhydrazones.

[0075] 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, e.g. 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12% by weight, in each case based on the total weight of the respective agent.

[0076] In various embodiments, the weight ratio of bleaching agent to bleach activator is about 5:1 to 15:1, preferably about 8:1 to 12:1, e.g. about 10:1.

[0077] An agent as described herein can be a liquid or a solid product. Since the agents described herein can also be multi-component agents, combination products are also possible, i.e., products containing both liquid and solid components or formulations.

[0078] In some embodiments, a fabric washing and / or care agent or fabric washing and / or care agent 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 anhydrous formulation.

[0079] In various embodiments, a textile washing and / or care agent or textile washing and / or care agent additive as described herein is in the form of a solid agent, in particular in powder form.

[0080] In addition to the components defined and described above, the agents can contain further ingredients, e.g. 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, in particular fragrances, surfactants, builders, and also additives for adjusting the viscosity and / or for stabilization, as well as other auxiliaries and additives commonly found in detergents, such as UV stabilizers, dyes, pearlescent agents, preservatives, bittering agents, organic salts, disinfectants, (structuring) polymers, defoamers and pH adjusters. The amount of suitable components in compositions according to the invention depends on the respective intended use of the composition, and the trained person skilled in the art is generally familiar with suitable dosages of these components.is able to find appropriate quantities in the literature.

[0081] In various embodiments, an agent as described herein further comprises at least one fragrance.

[0082] All known substances and mixtures can be used as fragrances, odoriferous substances, or perfume oils. For the purposes of this invention, the terms "odoriferous substance(s)," "fragrances," and "perfume oil(s)" are used synonymously. This refers in particular to all substances or mixtures thereof that are perceived as odors by humans and animals, and in particular, as pleasant odors by humans.

[0083] Perfumes, perfume oils, or perfume oil components can be used as fragrance components. According to the invention, perfume oils or fragrances can be individual fragrance compounds, e.g., synthetic products of the ester, ether, aldehyde, ketone, alcohol, and hydrocarbon type.

[0084] Duftstoffverbindungen vom Typ der Aldehyde sind z.B. Adoxal (2,6,10-Trimethyl-9-undecenal), Anisaldehyd (4-Methoxybenzaldehyd), Cymal (3-(4-lsopropylphenyl)-2-methylpropanal), Ethylvanillin, Florhydral (3-(3-isopropylphenyl)butanal), Helional (3-(3,4-Methylendioxyphenyl)-2-methylpropanal), Heliotropin, Hydroxycitronellal, Lauraldehyd, Lyral (3-und 4-(4-Hydroxy-4-methylpentyl)-3-cyclohexen- 1-carboxaldehyd), Methylnonylacetaldehyd, Lilial (3-(4-tert-Butylphenyl)-2-methylpropanal), Phenylacetaldehyd, Undecylenaldehyd, Vanillin, 2,6,10-Trimethyl-9-undecenal, 3-Dodecen-1-al, a-n- Amylzimtaldehyd, Melonal (2,6-Dimethyl-5-heptenal), 2,4-Di-methyl-3-cyclohexen-1-carboxaldehyd (Triplal), 4-Methoxybenzaldehyd, Benzaldehyd, 3-(4-tert-Butylphenyl)propanal, 2-Methyl-3-(para- methoxyphenyljpropanal, 2-Methyl-4-(2,6,6-trimethyl-2(1)-cyclohexen-1-yl)butanal, 3-Phenyl-2- propenal, cis- / trans-3,7-Dimethyl-2,6-octadien-1 -al, 3,7-Dimethyl-6-octen-1 -al, [(3,7-Dimethyl-6- octenyl)oxy]acetaldehyd,4-lsopropylbenzylaldehyd, 1 ,2,3,4,5,6,7,8-Octahydro-8,8-dimethyl-2- naphthaldehyd, 2,4-Dimethyl-3-cyclohexen-1-carboxaldehyd, 2-Methyl-3-(isopropylphenyl)propanal, 1- Decanal, 2,6-Dimethyl-5-heptenal, 4-(Tricyclo[5.2.1 ,0(2,6)]-decyliden-8)-butanal, Octahydro-4,7- methan-1 H-indencarboxaldehyd, 3-Ethoxy-4-hydroxybenzaldehyd, para-Ethyl-a,a- dimethylhydrozimtaldehyd, a-Methyl-3,4-(methylendioxy)hydrozimtaldehyd, 3,4- Methylendioxybenzaldehyd, a-n-Hexylzimtaldehyd, m-Cymen-7-carboxaldehyd, a- Methylphenylacetaldehyd, 7-Hydroxy-3,7-dimethyloctanal, Undecenal, 2,4,6-Trimethyl-3-cyclohexen- 1-carboxaldehyd, 4-(3)(4-Methyl-3-pentenyl)-3-cyclohexencarboxaldehyd, 1-Dodecanal, 2,4- Dimethylcyclohexen-3-carboxaldehyd, 4-(4-Hydroxy-4-methylpentyl)-3-cylohexen-1-carboxaldehyd, 7- Methoxy-3,7-dimethyloctan-1-al, 2-Methyl-undecanal, 2-Methyldecanal, 1-Nonanal, 1-Octanal, 2,6,10- Trimethyl-5,9-undecadienal, 2-Methyl-3-(4-tert-butyl)propanal, Dihydrozimtaldehyd,1-Methyl-4-(4- methyl-3-pentenyl)-3-cyclohexen-1-carboxaldehyd, 5- oder 6-Methoxyhexahydro-4,7-methanindan-1- oder -2-carboxaldehyd, 3,7-Dimethyloctan-1-al, 1 -Undecanal, 10-Undecen-1-al, 4-Hydroxy-3- methoxybenzaldehyd, 1-Methyl-3-(4-methylpentyl)-3-cyclohexencarboxaldehyd, 7-Hydroxy-3J- dimethyloctanal, trans-4-Decenal, 2,6-Nonadienal, para-Tolylacetaldehyd, 4-Methylphenylacetaldehyd,

[0085] 2-Methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal, ortho-Methoxyzimtaldehyd, 3,5,6-Trimethyl-

[0086] 3-cyclohexen-carboxaldehyd, 3J-Dimethyl-2-methylen-6-octenal, Phenoxyacetaldehyd, 5,9-Dimethyl-

[0087] 4.8-decadienal, Päonienaldehyd (6,10-Dimethyl-3-oxa-5,9-undecadien-1-al), Hexahydro-4, 7- methanindan-1-carboxaldehyd, 2-Methyloctanal, a-Methyl-4-(1-methylethyl)benzolacetaldehyd, 6,6- Dimethyl-2-norpinen-2-propionaldehyd, para-Methylphenoxyacetaldehyd, 2-Methyl-3-phenyl-2-propen- 1 -al, 3,5,5-Trimethylhexanal, Hexahydro-8, 8-dimethyl-2-naphthaldehyd, 3-Propyl-bicyclo-[2.2.1]-hept- 5-en-2-carbaldehyd, 9-Decenal, 3-Methyl-5-phenyl-1-pentanal, Methylnonylacetaldehyd, Hexanal und trans-2-Hexenal.

[0088] 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), α-damascone, β-damascone, δ-damascone, iso-damascone, damascenone, methyldihydrojasmonate, menthone, carvone, camphor, coavone (3,4,5,6,6-pentamethylhept-3-en-2-one), fenchone, α-ionone, β-ionone, γ-methyl-ionone, fleuramone (2-heptylcyclopentanone), dihydrojasmone, cis-jasmone, iso-E-Super (1-(1,2,3,4,5,6J,8-octahydro-2,3,8,8-tetramethyl-2-naphthalenyl)-ethan-1-one (and isomers)), methylcedrenyl ketone, acetophenone, methyl acetophenone, para-methoxyacetophenone, methyl beta-naphtyl ketone, benzylacetone, benzophenone, para-hydroxyphenylbutanone, celery ketone (3-methyl-5-propyl-2-cyclohexenone), 6-isopropyldecahydro-2-naphtone, dimethyloctenone, frescomenthe (2-butan-2-yl-cyclohexan-1-one), 4-(1-ethoxyvinyl)-3,3,5,5-tetramethylcyclohexanone, methylheptenone, 2-(2-(4-Methyl-3-cyclohexen-1-yl)propyl)cyclopentanone,1-(p-Menthen-6(2)yl)-1- propanon, 4-(4-Hydroxy-3-methoxyphenyl)-2-butanon, 2-Acetyl-3,3-dimethylnorbornan, 6,7-Dihydro- 1 ,1 ,2,3,3-pentamethyl-4(5H)-indanon, 4-Damascol, Dulcinyl(4-(1 ,3-benzodioxol-5-yl)butan-2-on), Hexalon (1-(2,6,6-trimethyl-2-cyclohexene-1-yl)-1 ,6-heptadien-3-on), lsocyclemonE(2-acetonaphthon-,

[0089] 1 .2.3.4.5.6.7.8-octahydro-2,3,8,8-tetramethyl), Methylnonylketon, Methylcyclocitron, Methyllavendelketon, Orivon (4-tert-Amylcyclohexanon), 4-tert-Butylcyclohexanon, Delphon (2- Pentycyclopentanon), Muscon (CAS 541-91-3), Neobutenon (1-(5,5-Dimethyl-1-cyclohexenyl)pent-4- en-1-on), Plicaton (CAS 41724-19-0), Velouton (2,2,5-Trimethyl-5-pentylcyclopentan-1-on),2,4,4,7- Tetramethyl-oct-6-en-3-on und Tetrameran (6,10- Dimethylundecen-2-on).

[0090] Fragrance compounds of the alcohol type are for example10-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-lsopropylcyclohexanol, 4-tert-Butycyclohexanol, 6,8-Dimethyl-2-nona-nol, 6-Nonen-1-ol, 9- Decen-1-ol, a-Methylbenzylalkohol, a-Terpineol, Amylsalicylat, Benzylalkohol, Benzylsalicylat, ß- Terpineol, Butylsalicylat, Citronellol, Cyclohexylsalicylat, Decanol, Di-hydromyrcenol, Dimethylbenzylcarbinol, Dimethylheptanol, Dimethyloctanol, Ethylsalicylat, Ethylvanilin, Eugenol, Farnesol, Geraniol, Heptanol, Hexylsalicylat, Isoborneol, Isoeugenol, Isopulegol, Linalool, Menthol, Myrtenol, n-Hexanol, Nerol, Nonanol, Octanol, p-Menthan-7-ol, Phenylethylalkohol, Phenol, Phenylsalicylat, Tetrahydrogeraniol, Tetrahydrolinalool, Thymol, trans-2-cis-6-Nonadicnol, trans-2- Nonen-1-ol, trans-2-Octenol, Undecanol, Vanillin, Champiniol, Hexenol und Zimtalkohol.Fragrance compounds of the ester type include benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate (DMBCA), phenylethyl acetate, benzyl acetate, ethyl methylphenylglycinate, allylcyclohexylpropionate, styrallylpropionate, benzyl salicylate, cyclohexyl salicylate, floramat, melusate and jasmacyclate.

[0091] Ethers include benzyl ethyl ether and ambroxan. Hydrocarbons mainly include terpenes such as limonene and pinene.

[0092] Preferably, mixtures of different fragrances are used, which together create an appealing scent. Such a mixture of fragrances can also be referred to as a perfume or perfume oil. Such perfume oils can also contain natural fragrance mixtures, such as those obtainable from plant sources.

[0093] 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, silver fir oil, silver 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, cajeput oil, calamus oil, chamomile oil, camphor oil, kanaga oil, cardamom oil, cassia oil, pine needle oil, copaiba balsam oil, coriander oil, spearmint oil, caraway oil, cumin oil, labdanum oil, lavender oil, lemongrass oil, linden blossom oil, lime oil, mandarin oil, lemon balm oil, mint oil, musk seed oil, clary oil, myrrh oil, clove oil, Neroli oil, niaouli oil, olibanum oil, orange blossom oil, orange peel oil, oregano oil, palmarosa oil, patchouli oil, Peru balsam oil, petitgrain oil, pepper oil, peppermint oil, allspice oil, pine oil, rose oil, rosemary oil, sage oil, sandalwood oil, celery oil, spike oil, star anise oil, turpentine oil, thuja oil, thyme oil, verbena oil, vetiver oil, juniper berry oil,Wormwood oil, wintergreen oil, ylang-ylang oil, hyssop oil, cinnamon oil, cinnamon leaf oil, citronella oil, lemon oil and cypress oil as well as ambrettolide, ambroxan, 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 valerate, borneol, bornyl acetate, boisambrene forte, a-bromostyrene, n-decylaldehyde, n-dodecylaldehyde, eugenol, eugenol methyl ether, eucalyptol, farnesol, fenchone, fenchyl acetate, geranyl acetate, geranyl formate, heliotropin, heptynecarboxylic acid methyl ester, heptaldehyde, hydroquinone dimethyl ether, Hydroxycinnamaldehyde, Hydroxycinnamic Alcohol, Indole, Iron, Isoeugenol, Isoeugenol Methyl Ether, Isosafrol, Jasmone, Camphor, Carvacrol, Carvone, p-Cresol Methyl Ether, Coumarin, p-Methoxyacetophenone, Methyl-n-amyl ketone, Methylanthranilic acid methyl ester, p-Methylacetophenone, Methyl Chavicol, p-Methylquinoline, Methyl-ß-naphthyl ketone,Methyl-n-nonylacetaldehyde, methyl-n-nonyl ketone, muscone, ß-naphthol ethyl ether, ß-naphthol methyl ether, nerol, n-nonylaldehyde, nonyl alcohol, n-octylaldehyde, p-oxyacetophenone, pentadecanolide, ß-phenylethyl alcohol, phenylacetic acid, pulegone, safrole, isoamyl salicylate, methyl salicylate, hexyl salicylate, cyclohexyl salicylate, santalol, sandelice, skatole, terpineol, thymen, thymol, troenan, γ-undelactone, vanillin, veratrum aldehyde, cinnamaldehyde, cinnamyl alcohol, cinnamic acid, ethyl cinnamate, benzyl cinnamate, diphenyl oxide, limonene, linalool, linalyl acetate and propionate, melusate, menthol, menthone, Methyl-n-heptenone, pinene, phenylacetaldehyde, terpinyl acetate, citral, citronellal, and mixtures thereof. Mixtures of the above-mentioned substances may also be used.

[0094] To be perceptible, a fragrance must be volatile, whereby, in addition to the nature of the functional groups and the structure of the chemical compound, the molecular mass also plays an important role. Most fragrances have molecular masses of up to approximately 200 Daltons, while molecular masses of 300 Daltons and above are rather rare. Due to the varying volatility of fragrances, the smell of a perfume or fragrance composed of several fragrances changes during evaporation, with the olfactory impressions being divided into "top note," "middle note" or "body," and "end note" or "dry out." Analogous to the description in the international patent publication WO 2016 / 200761, top, middle, and base notes can be classified based on their vapor pressure (determinable using the test methods described in WO 2016 / 200761) as follows:

[0095] Top note: Vapor pressure at 25°C: >0.0133 kPa

[0096] Heart note: Vapor pressure at 25°C: 0.0133 to 0.000133 kPa

[0097] Base note: Vapor pressure at 25°C: <0.000133 kPa

[0098] 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, silver fir oil, silver 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, cajeput 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, mandarin oil, lemon balm oil, musk seed oil, myrrh oil, clove oil, neroli oil, niaouli oil, olibanum oil, orange oil, oregano oil, palmarosa oil, Patchouli oil, Peru balsam oil, petitgrain oil, pepper oil, peppermint oil, allspice oil, pine oil, rose oil, rosemary oil, sandalwood oil, celery oil, spike oil, star anise oil, turpentine oil, thuja oil, thyme oil, verbena oil, vetiver oil, juniper berry oil, wormwood oil, wintergreen oil, ylang-ylang oil, hyssop oil, cinnamon oil, cinnamon leaf oil, citronella oil, lemon oil and cypress oil.

[0099] 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 valerate, borneol, bornyl acetate, a-bromostyrene, n-decylaldehyde, n-dodecylaldehyde, eugenol, eugenol methyl ether, eucalyptol, farnesol, fenchone, fenchyl acetate, geranyl acetate, geranyl formate, heliotropin, heptynecarboxylic acid methyl ester, heptaldehyde, hydroquinone dimethyl ether, hydroxycinnamaldehyde, hydroxycinnamal alcohol, indole, iron, isoeugenol, isoeugenol methyl ether, isosafrole, Jasmone, camphor, carvacrol, carvone, p-cresol methyl ether, coumarin, p-methoxyacetophenone, methyl n-amyl ketone, methyl anthranilic acid methyl ester, p-methyl acetophenone, methyl chavicol, p-methyl quinoline, methyl ß-naphthyl ketone, methyl n-nonylacetaldehyde, methyl n-nonyl ketone, muscone,ß-Naphthol ethyl ether, ß-Naphthol methyl ether, nerol, nitrobenzene, n-nonylaldehyde, nonyl alcohol, n-octylaldehyde, p-oxyacetophenone, pentadecanolide, ß-phenylethyl alcohol, phenylacetaldehyde dimethyl acetal, phenylacetic acid, pulegone, safrole, isoamyl salicylate, methyl salicylate, hexyl salicylate, cyclohexyl salicylate, santalol, skatole, terpineol, thymen, thymol, γ-undelactone, vanilin, veratrum aldehyde, cinnamaldehyde, cinnamic alcohol, cinnamic acid, ethyl cinnamate, benzyl cinnamate.

[0100] The more volatile fragrances include, in particular, 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, linalyl acetate and propionate, menthol, menthone, methyl-n-heptenone, phellandrene, phenylacetaldehyde, terpinyl acetate, citral, and citronellal.

[0101] Preferred aldehyde-type fragrance compounds 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).

[0102] In addition to or as an alternative to the above-mentioned fragrances, the fragrances described in WO 2016 / 200761, in particular the fragrances listed 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.

[0103] A perfume oil can also be in the form of a perfume oil preparation and, for example, comprise at least one other active ingredient in oil form. Suitable active ingredients in oil form in this context are those which are suitable for washing, cleaning, care and / or finishing purposes, in particular

[0104] (a) textile care products, such as silicone oils, and / or

[0105] (b) Skin care ingredients, such as preferably vitamin E, natural oils and / or cosmetic oils.

[0106] 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, e.g. 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, e.g.Lauryl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, behenyl alcohol, cholesterol and / or 2-hexadecanol and others; f) esters, preferably those such as cetyl octanoates, lauryl lactates, myristyl lactates, cetyl lactates, isopropyl myristates, myristyl myristates, isopropyl palmitates, isopropyl adipates, butyl stearates, decyl oleates, cholesterol isostearates, glycerol monostearates, glycerol distearates, glycerol tristearates, alkyl lactates, alkyl citrates and / or alkyl tartrates and others; g) lipids such as cholesterol, ceramides and / or sucrose esters and others; h) vitamins such as vitamins A, C and E, vitamin alkyl esters, including vitamin C alkyl esters and others; i) sunscreens; j) phospholipids; k) Derivatives of a-hydroxy acids; l) Germicides for cosmetic use, both synthetic such as salicylic acid and / or others and natural such as neem oil and / or others; m) Silicones; n) Natural oils, e.g. almond oil; and mixtures of any of the above components.

[0107] In various embodiments, the content of the at least one fragrance, which may 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, even more preferably between approximately 0.05 and 1.0% by weight, in each case based on the total weight of a respective agent.

[0108] It may be desirable to keep sensitive benefit agents / active ingredients, such as perfumes and fragrances, as described above, spatially separated from other detergent ingredients until use. An elegant method for incorporating such sensitive, chemically or physically incompatible, or volatile ingredients is the use of microcapsules in which these ingredients are encapsulated in a way that is stable during storage and transport. From which they are released mechanically, chemically, thermally, or enzymatically for or during use.

[0109] In a preferred embodiment, a fragrance as defined above and, if appropriate, other components such as additional fragrances and skin-feel-improving active ingredients are incorporated in whole or in part into microcapsules.

[0110] “Microcapsule”, as used herein, refers to capsules with a core-shell morphology on a micrometer scale, which 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, i.e., 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 such that the release of the contents is controlled, i.e., the contents are not spontaneously released 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”, as used in this context, means that the contents of the capsule orindividual ingredients cannot spontaneously penetrate the shell, but release can only occur by opening the capsule or optionally also via a diffusion process taking place over a longer period of time. The core can 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 of 0.01 to 1000 pm, in particular 0.1 to 500 pm. The capsule shell and capsule core are made of different materials, in particular the capsule shell is preferably solid under standard conditions (20°C, 1013 mbar), the core preferably solid and / or liquid, in particular liquid.

[0111] As capsule material for microcapsules suitable in the context of the present invention, it is generally possible to use, for example, high-molecular compounds of animal or plant origin, e.g. protein compounds (gelatin, albumin, casein), cellulose derivatives (methylcellulose, ethylcellulose, cellulose acetate, cellulose nitrate, carboxymethylcellulose) 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). Specifically, the shell material can be, for example,selected 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. Particular preference is given to polyacrylates, polyethylene, polyamides, polystyrenes, polyisoprenes, polycarbonates, polyesters, polyureas, polyurethanes, polyolefins, epoxy resins, vinyl polymers, and urea and / or melamine crosslinked with formaldehyde or glutaraldehyde.

[0112] For the production of suitable microcapsules, known microencapsulation processes are generally suitable, in which, for example, the encapsulation of the phase to be encapsulated is carried out by coating it with film-forming polymers (as mentioned above), which, after emulsification and coacervation or interfacial polymerization, are deposited on the material to be encapsulated. With regard to the present invention, the phase to be encapsulated is a benefit agent composition, preferably a fragrance composition, usually in the form of a perfume oil.

[0113] The capsules can release the encapsulated benefit agents via various mechanisms. In various embodiments of the present invention, for example, capsules can be used which have a mechanically stable capsule shell which then becomes permeable to the contained agents due to one or more environmental influences, such as changes in temperature or ionic strength or pH of the surrounding medium. Stable capsule wall materials through which the at least one benefit agent, e.g. a perfume oil and optionally other benefit agents, can diffuse over time are also possible. The capsules can release the at least one contained benefit agent preferably upon change in the pH or ionic strength of the environment, upon change in temperature, upon exposure to light, by diffusion and / or upon mechanical stress.In a preferred embodiment of the present invention, the capsules are fragile, meaning they can release encapsulated agents due to mechanical stress such as friction, pressure, or shear stress, which ruptures the capsule shell. In another embodiment, the capsule is thermally labile, meaning encapsulated substances can be released when the capsules are exposed to a temperature of at least 70°C, preferably at least 60°C, more preferably at least 50°C, and especially at least 40°C.

[0114] In a further preferred embodiment, the capsule can become permeable to the enclosed benefit agent(s) after exposure to radiation of a certain wavelength, preferably by exposure to sunlight.

[0115] It is also possible that the capsules are fragile and at the same time thermally labile and / or unstable towards radiation of certain wavelengths.

[0116] Suitable microcapsules can be water-soluble and / or water-insoluble, but are preferably water-insoluble. The water-insolubility of the capsules has the advantage that they can survive washing, cleaning, or other treatment applications and are thus able to release the at least one benefit agent only after the aqueous washing, cleaning, or treatment process, such as during drying by simply increasing the temperature or by exposure to sunlight, or particularly when the surface is subjected to friction.

[0117] Particularly preferred are water-insoluble capsules that are broken open by friction.

[0118] The term "friction-breakable" or "friction-breakable" capsules refers in particular to capsules which, when adhering to a surface treated with them (e.g. textile surface), can be opened or broken by mechanical rubbing or pressure, so that the contents are only released as a result of a mechanical action, e.g. when one dries one's hands with a towel on which such capsules have been deposited.

[0119] Advantageously usable, friable capsules can have average diameters d50 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, e.g. between 5 and 80 pm, e.g. between 5 and 40 pm. The d50 value indicates the diameter which 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 d50 value. It is furthermore preferred that the d50 value of the particle size distribution of the microcapsules is < 70 pm, preferably < 60 pm, particularly preferably < 50 pm. The d50 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.

[0120] The shell of the capsules enclosing the core or (filled) cavity preferably has an average thickness in the range between approximately 50 and 500 nm, preferably between approximately 100 nm and approximately 250 nm. Capsules are particularly easy to grind open when they lie within the previously specified ranges regarding the average diameter and the average thickness. The d50 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 d50 value. It is further preferred that the d50 value of the particle size distribution of the microcapsules is <70 pm, preferably <60 pm, particularly preferably <50 pm. The d50 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.

[0121] The diameter of the capsules or the particle size of the microcapsules can be determined using conventional methods. For example, it can be determined using dynamic light scattering, which can usually be performed on diluted suspensions containing, for example, 0.01 to 1 wt.% capsules. It can also be determined by evaluating light microscopic or electron microscopic images of capsules.

[0122] In various embodiments, a microcapsule according to the invention has an average diameter d50 of approximately 1 to 80 pm, preferably approximately 5 to 40 pm, in particular approximately 20 to 35 pm, e.g. approximately 22 to approximately 33 pm.

[0123] 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. This corresponds to a preferred embodiment of the invention. Preferably, for example, melamine-urea-formaldehyde microcapsules or melamine-formaldehyde microcapsules or urea-formaldehyde microcapsules can be used. Microcapsules based on melamine-formaldehyde resins are particularly preferred.

[0124] The general procedure for microcapsule production as such has long been well known to those skilled in the art. Particularly suitable processes for microcapsule production are described in principle, for example, in US Pat. No. 3,516,941, US Pat. No. 3,415,758, or EP 0026914 A1. The latter describes, for example, microcapsule production by acid-induced condensation of melamine-formaldehyde precondensates and / or their C1-C4 alkyl ethers in water in which the hydrophobic material forming the capsule core is dispersed, in the presence of a protective colloid.

[0125] In various embodiments, an agent as described herein comprises, in particular, at least one surfactant. Suitable surfactants include, in particular, anionic surfactants, nonionic surfactants, and mixtures thereof, but also cationic, zwitterionic, and amphoteric surfactants.

[0126] Suitable compounds from the class of anionic surfactants are those of formula (V)

[0127] R-SO3X +(V), in which R is a linear or branched unsubstituted alkylaryl radical and X is a monovalent cation or the n-th part of an n-valent cation, preference being given to the alkali metal ions and among them Na + or K + , where Na + is highly preferred. Other cations X + can be selected from NHT, % Zn 2+ , % Mg 2+ , % Ca 2+ , % Mn 2+ and their mixtures.

[0128] "Alkylaryl," as used herein, refers to organic radicals consisting of an alkyl radical and an aromatic radical. Typical examples of such radicals include, but are not limited to, alkylbenzene radicals such as benzyl, butylbenzene radicals, nonylbenzene radicals, decylbenzene radicals, undecylbenzene radicals, dodecylbenzene radicals, tridecylbenzene radicals, and the like.

[0129] In various embodiments, such surfactants are selected from linear or branched alkylbenzenesulfonates of the formula (V-1):

[0130] (V-1), in which R' and R" together contain 9 to 19, preferably 11 to 15 and in particular 11 to 13 C atoms. A particularly preferred representative can be described by the formula A-1 a:

[0131] In various embodiments, the compound of formula (V) is preferably the sodium salt of a linear alkylbenzenesulfonate.

[0132] Preferred anionic surfactants are those of formula (VI)

[0133] R 1 -O-(AO) n -SO3- X + (VI).

[0134] In formula (VI) R 1represents 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, with the representatives having an even number of carbon atoms being preferred. Particularly preferred radicals R 1 are derived from C s-fatty alcohols, e.g. from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or from C 10-20 oxo alcohols. X stands for a monovalent cation or the nth part of an n-valent cation, preferably the alkali metal ions, including Na + or K + , where Na + is highly preferred. Other 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 for an ethylene oxide group. The index n stands for an integer from 1 to 50, preferably from 1 to 20 and in particular from 2 to 10. Most preferably, n stands for the numbers 2, 3, 4, 5, 6, 7 or 8. X stands for a monovalent cation or the nth part of an n-valent cation, preferred are the alkali metal ions, and among these, Na + or K + , where Na + is highly preferred. Further cations X+ can be selected from NHT, % Zn 2+ , % Mg 2+ , % Ca 2+ , % Mn 2+ and their mixtures.

[0135] In summary, agents in various embodiments can thus contain at least one anionic surfactant selected from fatty alcohol ether sulfates of the formula (VI-1)

[0136] (VI-1) with k = 11 to 19, n = 2, 3, 4, 5, 6, 7 or 8. Particularly preferred representatives are Na-Ci2-14 fatty alcohol ether sulfates with 2 EO (k = 11-13, n = 2 in formula (VI-1)).

[0137] Other preferred anionic surfactants are the alkyl sulfates of formula (VII)

[0138] R 2 -O-SO3X + (VII).

[0139] In 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, with the representatives having an even number of carbon atoms being preferred. Particularly preferred radicals R 2are derived from C12-C18 fatty alcohols, e.g., coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl, or stearyl alcohol, or from C10-C20 oxo alcohols. X represents a monovalent cation or the nth part of an n-valent cation, preferably alkali metal ions, including Na + or K + , where Na + is highly preferred. Other cations X + can be selected from NHT, % Zn 2+ , % Mg 2+ , % Ca 2+ , % Mn 2+ and their mixtures.

[0140] In various embodiments, these surfactants are selected from fatty alcohol sulfates of the formula (VI 1-1)

[0141] N / a

[0142] (VI 1-1) with k = 11 to 19. Particularly preferred representatives are Na-Ci2-14 fatty alcohol sulfates (k = 11-13 in formula (VII-1)).

[0143] Other anionic surfactants that can be used are the alkyl ester sulfonates, especially those of the formula (VIII)

[0144] R 1 -CH(SO3X + )-C(O)-OR 2 (VIII).

[0145] In 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, with the representatives having an odd number of carbon atoms being preferred. Particularly preferred radicals R 1 -CH are derived from C s-fatty acids, e.g. lauric, myristyl, cetyl or stearyl acid. R 2 represents a linear or branched, substituted or unsubstituted alkyl radical, preferably a linear, unsubstituted alkyl radical. Preferred radicals R 2are Ci-e alkyl radicals, especially methyl (= methyl ester sulfonates). X represents a monovalent cation or the n-th part of an n-valent cation, preferably alkali metal ions, including Na + or K + , where Na + is highly preferred. Other cations X + can be selected from NHZ, % Zn 2+ , % Mg 2+ , % Ca 2+ , % Mn 2+ and their mixtures.

[0146] Secondary alkanesulfonates are also suitable as anionic surfactants. These have, for example, the formula (IX)

[0147] R 1 CH(SO3X + ) R 2 (IX), where R 1 and R 2 independently a linear or branched alkyl having 1 to 20 carbon atoms and with the carbon atom to which they are attached form a linear or branched alkyl, preferably having 10 to 30 carbon atoms, preferably having 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 + .

[0148] In various preferred embodiments, the at least one secondary alkanesulfonate has the following formula (IX-1)

[0149] H3C-(CH2)n-CH(SO3-X + )-(CH2)m-CH3 (IX-1), where m and n are independently an integer between 0 and 20. Preferably, m + n is an integer between 7 and 17, more 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 + .

[0150] In a particularly preferred embodiment, the at least one secondary alkanesulfonate is a secondary C14-17 sodium alkanesulfonate. Such a secondary C14-17 sodium alkanesulfonate is marketed, for example, by Clariant under the trade name "Hostapur SAS60."

[0151] Fatty alcohol alkoxylates are particularly suitable as nonionic surfactants. In various embodiments, the agents therefore contain at least one nonionic surfactant of the formula (X)

[0152] R 3 -O-(AO)mH (X).

[0153] In 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 2are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl radicals and mixtures thereof, with the representatives having an even number of carbon atoms being preferred. Particularly preferred radicals R 3 are derived from C12-18 fatty alcohols, e.g., from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl, or stearyl alcohol, or from C10-20 oxo alcohols. AO stands for an ethylene oxide (EO) or propylene oxide (PO) group, preferably an ethylene oxide group. 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. In summary, the fatty alcohol alkoxylates to be used are compounds of the formula (X-1)

[0154] (X-1), with k = 11 to 19, m = 2, 3, 4, 5, 6, 7 or 8. Particularly preferred representatives are C12-18 fatty alcohols with 7 EO (k = 11-17, m = 7 in formula (X-1)).

[0155] Amine oxides, for example, are also suitable as non-ionic surfactants. In principle, all amine oxides established in the state of the art for these purposes, i.e. compounds having the formula R 1 R 2 R 3 NO, wherein each R 1 , R 2 and R 3 independently of the others is an optionally substituted, e.g. hydroxy-substituted, C1-30 hydrocarbon chain. Particularly preferred amine oxides are those in which R 1 C12-18 alkyl and R 2 and R 3are each independently C1-4 alkyl, in particular C12-18 alkyldimethylamine oxides. Examples of suitable amine oxides are N-cocoalkyl-N,N-dimethylamine oxide, N-tallowalkyl-N,N-dihydroxyethylamine oxide, myristyl / cetyldimethylamine oxide, or lauryldimethylamine oxide.

[0156] Other nonionic surfactants that may be present in the described compositions according to 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.

[0157] Suitable alkyl(poly)glycosides are, for example, those of the formula R 2 O-[G] P , in the R 2 a straight-chain or branched alkyl having 12 to 16 carbon atoms, G is a sugar residue having 5 or 6 carbon atoms, in particular glucose, and the index p is 1 to 10.

[0158] Suitable amphoteric surfactants are, for example, betaines of formula (XI)

[0159] (R iii )(R iv )(R v )N + CH2COO- (XI), in which R'" is an alkyl radical having 8 to 25, preferably 10 to 21 carbon atoms, optionally interrupted by heteroatoms or heteroatom groups, and R iv and R v identical or different alkyl radicals having 1 to 3 carbon atoms, in particular C10-18-alkyldimethylcarboxymethylbetaine and Cn-17-alkylamidopropyldimethylcarboxymethylbetaine.

[0160] Suitable cationic surfactants include the quaternary ammonium compounds of formula (XII)

[0161] (R vi )(R vii )(R viii )(R ix )N + X- (XII), in the R vi to R ixrepresents four identical or different, in particular two long- and two short-chain, alkyl radicals, and X- represents an anion, in particular a halide ion, e.g., didecyldimethylammonium chloride, alkylbenzyldidecylammonium chloride, and mixtures thereof. Other suitable cationic surfactants are quaternary surface-active compounds, in particular those containing a sulfonium, phosphonium, iodonium, or arsonium group, which are also known as antimicrobial agents. By using quaternary surface-active compounds with antimicrobial activity, the agent can be given an antimicrobial effect or its existing antimicrobial effect, possibly due to other ingredients, can be improved.

[0162] In various embodiments, the total amount of surfactants, based on the total weight of the agent, is 5 to 75 wt.%, preferably 5 to 35 wt.%, more preferably 10 to 30 wt.%.

[0163] An agent as described herein contains, in some embodiments, at least one water-soluble and / or water-insoluble, organic and / or inorganic builder.

[0164] Generally applicable builders include, in particular, aminocarboxylic acids and their salts, zeolites, silicates, carbonates, organic (co)builders, and—where there are no environmental objections to their use—phosphates. However, in preferred embodiments, the agents are phosphate-free.

[0165] For example, crystalline layered silicates of the general formula NaMSi xO2x+i ■ y H2O, in which M is sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, particularly preferred values ​​for x being 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 marketed, for example, by Clariant GmbH (Germany) under the trade name Na-SKS. Examples of these silicates are Na-SKS-1 (Na2Si2O45 ■ x H2O, kenyaite), Na-SKS-2 (Na2SiO4 ■ x H2O, magadiite), Na-SKS-3 (Na2SiO7 ■ x H2O) or Na-SKS-4 (Na2SiO4 ■ x H2O, makatite). Crystalline layered silicates of the formula NaMSi are particularly suitable for the purposes of the present invention. xO2x+i ■ y H2O, where x is 2. In particular, both β- and β-sodium disilicates Na2Si2Os ■ y H2O and also especially Na-SKS-5 (α-Na2Si2O5), Na-SKS-7 (β-Na2Si2O5, natrosilite), Na-SKS-9 (NaHSi2O5 ■ H2O), Na-SKS-10 (NaHSi2O5 ■ 3 H2O, kanemite), Na-SKS-11 (β-Na2Si2Os) and Na-SKS-13 (NaHSi2Os), but especially Na-SKS-6 (δ-Na2Si2Os) are preferred.

[0166] Also suitable are amorphous sodium silicates with a Na2O:SiO2 modulus of 1:2 to 1:3.3, preferably 1:2 to 1:2.8, and in particular 1:2 to 1:2.6, which preferably exhibit delayed dissolution and secondary washing properties. The delayed dissolution compared to conventional amorphous sodium silicates can be caused in various ways, e.g., by surface treatment, compounding, compaction, or overdrying. In the context of this invention, the term "amorphous" is understood to mean that the silicates do not produce sharp X-ray reflections in X-ray diffraction experiments, as is typical for crystalline substances, but at most produce one or more maxima of the scattered X-ray radiation, which have a width of several degree units of the diffraction angle.

[0167] In the context of the present invention, it is preferred that this silicate(s), preferably alkali silicates, particularly preferably crystalline or amorphous alkali disilicates, are contained in the agents in amounts of 1 to 40 wt.%, preferably 2 to 35 wt.%, in each case based on the weight of the agent.

[0168] The detergents may also contain phosphonates as additional builders. A hydroxyalkane and / or aminoalkanephosphonate is preferably used as the phosphonate compound. Among the hydroxyalkanephosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance. Ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP), and their higher homologues are preferred as aminoalkanephosphonates. Phosphonates are preferably present in the detergents in amounts of 0.1 to 10 wt.%, in particular in amounts of 0.5 to 8 wt.%, based in each case on the total weight of the dishwashing detergent.

[0169] Further builders are the alkali carriers. Examples of alkali carriers include alkali metal hydroxides, alkali metal carbonates, alkali metal bicarbonates, alkali metal sesquicarbonates, the aforementioned alkali silicates, alkali metasilicates, and mixtures of the aforementioned substances, whereby alkali carbonates, in particular sodium carbonate, sodium bicarbonate or sodium sesquicarbonate, can be used with preference for the purposes of this invention. Due to their low chemical compatibility with some other ingredients of detergents compared to other builder substances, the optional alkali metal hydroxides are preferably used only in small amounts, preferably in amounts below 10% by weight, more preferably below 6% by weight, particularly preferably below 4% by weight and in particular below 2% by weight, in each case 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 do not contain alkali metal hydroxides.

[0170] Particular preference is given to using carbonate(s) and / or bicarbonate(s), preferably alkali metal carbonate(s), particularly preferably sodium carbonate, in amounts of 2 to 50% by weight, preferably 5 to 40% by weight, and in particular 7.5 to 30% by weight, based in each case on the weight of the agent. Particular preference is given to agents which, based on the weight of the agent, contain less than 20% by weight, preferably less than 17% by weight, more preferably less than 13% by weight, and in particular less than 9% by weight of carbonate(s) and / or bicarbonate(s), preferably alkali metal carbonate(s), particularly preferably sodium carbonate.

[0171] Organic builders include, in particular, polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders, and the phosphonates already mentioned above. These classes of substances are described below.

[0172] Useful organic builders include polycarboxylic acids, which can be used in the form of the free acid and / or their sodium salts. Polycarboxylic acids are understood to be carboxylic acids that have more than one acid function. Examples include 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 on ecological grounds, and mixtures thereof. In addition to their builder effect, the free acids typically also have the property of an acidifying component and thus also serve to adjust a lower and milder pH value. Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid, and any mixtures thereof are particularly suitable.

[0173] Another important class of phosphate-free builders are aminocarboxylic acids and / or their salts. Particularly preferred representatives of this class are methylglycinediacetic acid (MGDA) or its salts, glutamic 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 wt.%, preferably between 1 and 25 wt.%, and in particular between 5 and 20 wt.%. Aminocarboxylic acids and their salts can be used together with the aforementioned builders.

[0174] In various embodiments, the at least one builder is selected from the group consisting of methylglycinediacetic acid (MGDA), glutamic acid (GLDA), and 1-hydroxyethane-1,1-diphosphonate (HEDP). MGDA is preferably used as MGDA trisodium salt (MGDA-Nas) and GLDA is preferably used as GLDA tetrasodium salt (GLDA-Na4).

[0175] In some embodiments, agents according to the invention or individual components of an agent according to the invention can contain water as the main solvent, i.e., they are an aqueous agent or an aqueous component. The water content of an aqueous agent or an aqueous component is typically 15 to 70 wt.%, preferably 20 to 60 wt.%. In various embodiments, the water content is more than 5 wt.%, preferably more than 15 wt.%, and particularly preferably more than 50 wt.%, in each case based on the total amount of the aqueous agent or the aqueous component.

[0176] Non-aqueous solvents may also be added. Suitable non-aqueous solvents include mono- or polyhydric alcohols, alkanolamines, or glycol ethers, provided they are miscible with water within the specified concentration range. The solvents are preferably selected from ethanol, n-propanol, i-propanol, butanols, glycol, propanediol, butanediol, methylpropanediol, glycerin, diglycol, propyl diglycol, butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, methoxytriglycol, ethoxytriglycol, butoxytriglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol t-butyl ether, di-n-octyl ether and mixtures of these solvents.

[0177] The one or more non-aqueous solvents are usually present in an amount of 0.1 to 60 wt.%, preferably 5 to 60 wt.%, more preferably 10 to 30 wt.%, based on the total weight of the aqueous agent or the aqueous component.

[0178] In general, the pH of the agents according to the invention can be adjusted using conventional pH regulators. In various embodiments, the pH of agents according to the invention is in a range from 6.5 to 12, preferably 7.0 to 11.5, more 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 also amidosulfonic acid. In addition, 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.Even if volatile alkali, e.g. 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, whereby the alkanolamine can be selected from the group consisting of mono-, di-, triethanolamine and -propanolamine and mixtures thereof, such volatile alkali sources, in particular ethanolamines, are preferably avoided. In various embodiments, the agents according to the invention therefore contain less than 1.75% by weight of alkanolamine, in particular monoethanolamine, and most preferably, they are free thereof.

[0179] To adjust and / or stabilize the pH, a composition according to the invention may further contain one or more buffer substances (INCI buffering agents), typically in amounts of 0.001 to 5 wt.%. Buffer substances that are also complexing agents or even chelating agents (INCI chelating agents) are preferred. Particularly preferred buffer substances are citric acid or citrates, especially sodium and potassium citrates, e.g., trisodium citrate 2 H2O and tripotassium citrate H2O.

[0180] 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. the commercially available Silwet® L-77 from BASF, Ludwigshafen (Germany)), polyalkylene oxide, modified heptamethyltrisiloxane (e.g.the commercially available Silwet® L-7608 from BASF, Ludwigshafen (Germany)) and polyether siloxanes (copolymers of polymethylsiloxanes with ethylene oxide-propylene oxide segments (polyether blocks)), preferably water-soluble linear polyether siloxanes 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). In a particular embodiment of the invention, the polymers mentioned are omitted.

[0181] Polymeric thickeners which may also be contained in the agent are polycarboxylates which act as polyelectrolytes to thicken, preferably homo- and copolymers of acrylic acid, in particular acrylic acid copolymers such as acrylic acid-methacrylic acid copolymers, and polysaccharides, in particular heteropolysaccharides, as well as other customary thickening polymers.

[0182] Suitable polysaccharides or heteropolysaccharides are polysaccharide gums, e.g., gum arabic, agar, alginates, carrageenans and their salts, guar, guaran, tragacanth, gellan gum, ramsan, dextran, or xanthan gum and their derivatives, e.g., propoxylated guar gum, as well as their mixtures. Other polysaccharide thickeners, such as starches or cellulose derivatives, can be used alternatively, but preferably in addition, to a polysaccharide gum. e.g., starches of various origins and starch derivatives, e.g., hydroxyethyl starch, starch phosphate esters, or starch acetates, or carboxymethylcellulose or its sodium salt, methyl, ethyl, hydroxyethyl, hydroxypropyl, hydroxypropylmethyl, or hydroxyethylmethylcellulose, or cellulose acetate.

[0183] 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 106 is produced and is available, for example, from Kelco under the trade name Keltrol®, e.g. as cream-colored powder Keltrol® T (Transparent) or as white granules Keltrol® RD (Readily Dispersable).

[0184] Acrylic acid polymers suitable as polymeric thickeners include high-molecular-weight acrylic acid homopolymers (INCI: Carbomer) crosslinked with a polyalkenyl polyether, particularly an allyl ether of sucrose, pentaerythritol, or propylene, which are also known as carboxyvinyl polymers. Such polyacrylic acids are available from BFGoodrich, among others, under the trade name Carbopol®, e.g., Carbopol® 940 (molecular weight Mw approx. 4,000,000 g / mol), Carbopol® 941 (molecular weight Mw approx. 1,250,000 g / mol), or Carbopol® 934 (molecular weight Mw approx. 3,000,000 g / mol).

[0185] However, the following acrylic acid copolymers are particularly suitable polymeric thickeners:

[0186] (i) Copolymers of two or more monomers from the group of acrylic acid, methacrylic acid and their simple esters, preferably formed with C 1-4 alkanols (INCI: Acrylates Copolymer), which include, for example, the copolymers of methacrylic acid, butyl acrylate and methyl methacrylate (CAS 25035-69-2) or of butyl acrylate and methyl methacrylate (CAS 25852-37-3) and which are available, for example, from Rohm & Haas under the trade names Aculyn® and Acusol®, for example the anionic non-associative polymers Aculyn® 33 (crosslinked), Acusol® 810 and Acusol® 830 (CAS 25852-37-3);

[0187] (ii) crosslinked high molecular weight acrylic acid copolymers, which include, for example, copolymers of C 10-30 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 esters, preferably formed with C 10-30 alkanols (INCI Acrylates / C 10-30 Alkyl Acrylate Crosspolymer) and which are available, for example, from BFGoodrich under the trade name Carbopol®, e.g. the hydrophobic Carbopol® ETD2623 and Carbopol® 1382 (INCI: Acrylates / C 10-30 Alkyl Acrylate Crosspolymer) and Carbopol® AQUA 30 (formerly Carbopol® EX 473).

[0188] An agent as described herein may contain one or more water-soluble salts to reduce viscosity. These may be inorganic and / or organic salts; in a preferred embodiment, the agent contains at least one inorganic salt.

[0189] Inorganic salts usable according to the invention are preferably selected from the group comprising colorless, water-soluble halides, sulfates, sulfites, carbonates, bicarbonates, nitrates, nitrites, phosphates, and / or oxides of alkali metals, alkaline earth metals, 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.

[0190] The organic salts usable 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.

[0191] An optical brightener is preferably selected from the substance classes of distyrylbiphenyls, stilbenes, 4,4'-diamino-2,2'-stilbenedisulfonic acids, coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, naphthalimides, benzoxazole systems, benzisoxazole systems, benzimidazole systems, heterocycle-substituted pyrene derivatives and mixtures thereof.

[0192] Particularly preferred optical brighteners include disodium 4,4'-bis(2-morpholino-4-anilino-s-triazin-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. 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) and / or 2,5-bis(benzoxazol-2-yl)thiophene.

[0193] Suitable dye transfer inhibitors include polymers and copolymers of cyclic amines such as vinylpyrrolidone and / or vinylimidazole. Polymers suitable as dye transfer inhibitors 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 preferred as dye transfer inhibitors. The polyvinylpyrrolidones (PVP) used preferably have an average molecular weight of 2500 to 400000 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.The copolymers of vinylpyrrolidone and vinylimidazole (PVP / PVI) used preferably have a molecular weight in the range of 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 used dye transfer inhibitor is polyethylene glycol-modified copolymers of vinylpyrrolidone and vinylimidazole, which are available, for example, from BASF under the name Sokalan® HP 66. In some embodiments, the agents described herein are preferably pre-packaged into dosage units. These dosage units preferably comprise the amount of washing and / or care-active substances required for one textile cleaning and / or care cycle. In some embodiments, suitable dosage units have, for example, a weight between 12 and 30 g.The volume of the aforementioned dosing units and their spatial shape are particularly preferably selected to ensure 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.

[0194] The detergents, especially the pre-prepared dosage units, particularly preferably have a water-soluble coating. In some embodiments, a detergent as described herein is in the form of a unit dose, as described above. In preferred embodiments, such a detergent according to the invention is particularly coated in a water-soluble film.

[0195] The water-soluble wrapping is preferably formed from a water-soluble film material selected from the group consisting of polymers or polymer blends. The wrapping can 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. Particularly preferred are films that can be glued and / or sealed, for example, to form packages such as tubes or pillows after they have been filled with an agent. In various embodiments, the films take the form of multi-chamber pouches.

[0196] It is preferred that the water-soluble coating contains polyvinyl alcohol or a polyvinyl alcohol copolymer. Water-soluble coatings containing polyvinyl alcohol or a polyvinyl alcohol copolymer exhibit good stability with sufficiently high water solubility, particularly 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 whose molecular weight 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, since the direct synthesis route is not possible. The same applies to polyvinyl alcohol copolymers produced from polyvinyl acetate copolymers.It is preferred if at least one layer of the water-soluble casing comprises a polyvinyl alcohol whose degree of hydrolysis is 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol%, and in particular 82 to 88 mol%. A polymer selected from the group comprising (meth)acrylic acid-containing (co)polymers, polyacrylamides, oxazoline polymers, polystyrenesulfonates, polyurethanes, polyesters, polyethers, polylactic acid, or mixtures of the above polymers can additionally be added to a polyvinyl alcohol-containing film material suitable for producing the water-soluble casing. A preferred additional polymer is polylactic acid. Preferred polyvinyl alcohol copolymers comprise, in addition to vinyl alcohol, dicarboxylic acids as further monomers. Suitable dicarboxylic acids are itaconic acid, malonic acid, succinic acid, and mixtures thereof, with itaconic acid being preferred.Likewise preferred polyvinyl alcohol copolymers comprise, in addition to vinyl alcohol, an ethylenically unsaturated carboxylic acid, its salt, or its ester. Particularly preferably, such polyvinyl alcohol copolymers contain, in addition to vinyl alcohol, acrylic acid, methacrylic acid, acrylic acid esters, methacrylic acid esters, or mixtures thereof.

[0197] It may be preferred for the film material to contain further additives. The film material may contain, for example, plasticizers such as dipropylene glycol, ethylene glycol, diethylene glycol, propylene glycol, glycerin, sorbitol, mannitol, or mixtures thereof. Further additives include, for example, release agents, fillers, crosslinking agents, surfactants, antioxidants, UV absorbers, antiblocking agents, anti-adhesive agents, or mixtures thereof.

[0198] Suitable water-soluble films for use in the water-soluble wrappers of the water-soluble packages according to the invention are films sold by MonoSol LLC, for example, under the designation M8630, C8400, or M8900. Other suitable films include films with the designation Solublon® PT, Solublon® GA, Solublon® KC, or Solublon® KL from Aicello Chemical Europe GmbH, or the VF-HP films from Kuraray.

[0199] The present invention relates to both manual and mechanical processes for washing, caring or conditioning textiles.

[0200] In particular, the present invention relates to methods for removing hair from textiles and / or the interior of a washing machine, wherein at least one textile washing and / or care agent and / or a textile washing agent additive, as described herein, is added together with the textiles to a household washing machine or an industrial washing machine and is subjected to a washing program, so that the hair to be removed can be broken down and / or removed in the washing and / or care process. The combination of active substances according to the invention, ie enzyme, as defined above, bleaching agent and bleach activator, enables a corresponding removal of hair even at low temperatures. In various embodiments, a corresponding method therefore comprises treating the textiles, iewashing and / or caring for the textiles with a textile washing and / or care agent and / or a textile washing 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, e.g. 40°C, 45°C, 50°C, 55°C or 60°C.

[0201] An agent as described herein can, in principle, also be advantageously used in combination with other textile washing and / or care agents in corresponding processes. In various embodiments, the present invention relates in particular to such processes in which, in addition to at least one agent as described herein, a textile conditioning agent is also used.

[0202] The above-described agents are intended for use for textile washing and / or care purposes, as defined herein. Accordingly, a further subject of the present invention is the use of a textile washing and / or care agent and / or a

[0203] 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 bleaching agent, and at least one bleach activator. The present invention relates to uses in which a detergent as described herein is used in a washing machine or in a manual textile washing process.

[0204] The present invention further relates to the use of a protease for removing hair from textiles and / or the interior of a washing machine, wherein the protease is used in combination with at least one bleaching agent and at least one bleach activator. The aforementioned active ingredients are preferably components of a textile washing and / or care product and / or a textile detergent additive.

[0205] All facts, objects, and embodiments described for the means are also applicable to the above subject matter of the invention. Therefore, explicit reference is made here to the disclosure at the appropriate point, with the note that this disclosure also applies to the above uses and methods according to the invention.

[0206] Examples

[0207] Example 1: Detergent and additive formulations

[0208] Table 1 : Composition of liquid commercial detergent matrix (pH = 8.2-8.6;

[0209] Dosage: 50 ml) Table 2: Composition of detergent additive containing keratolytic protease or

[0210] Keratinase (pH = 8-12; dosage: 30-100 g)

[0211] Example 2: Determination of animal hair degradation on a small scale (qualitative)

[0212] Hair: German Shepherd grey; approx. 20 mg per application (+ / - 1 mg)

[0213] Buffer: 100 mM Tris / HCl, 0.1% Brij pH 8.6

[0214] Reducing agent sodium sulfite: 10% stock solution: 10 g in 100 ml ddH2Ü, of which 300 μl are added to the Eppendorf tube to obtain a final concentration of 1% sodium sulfite (correspondingly, in the samples without: add 300 μl ddH2Ü)

[0215] Enzyme: 1x: 0.7% enzyme raw material; 10x: 7% enzyme raw material

[0216] Procedure (3 ml preparation in Eppendorf tubes):

[0217] A tuft of hair was placed in each 5 ml Eppendorf tube (20 mg ± 1 mg per tube). 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 (rotating 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 for 2.5 h at 70°C. The samples were inspected visually. Table 3: Results of the qualitative assessment

[0218] Example 3: Determination of animal hair degradation on a small scale (quantitative)

[0219] Detergent matrix: 2.94 g / l (according to Table 1)

[0220] Detergent additive: 5.9 g / l (according to Table 2, but without enzyme)

[0221] Bleach activator (Tinocat LT® B249): 0.0104 g / l (corresponds to 0.16 wt.% based on the total weight of the additive)

[0222] Enzyme (Savinase 16 L): 0.64 g / l (corresponds to 9.77 wt% based on the total weight of the additive)

[0223] Animal hair: Dog (Golden Retriever) and cat hair 20 mg ± 1 mg.

[0224] The procedure was analogous to Example 2.

[0225] Table 4: Results of the quantitative assessment

[0226] Example 4: Electron microscopic examinations

[0227] Gyrowash experiments with 1200 ml cup

[0228] Temperature: 40 °C

[0229] Duration: 1 hour with 25 steel balls

[0230] Wash volume: 500 ml Substrate: 0.1 g Golden Retriever hair (dog)

[0231] Detergent matrix: 2.94 g / l (according to Table 1)

[0232] Detergent additive: 5.9 g / l (according to Table 2, but without enzyme)

[0233] Enzyme (Savinase 16 T): 0.64 g / l (corresponds to 9.79 wt% based on the total weight of the additive)

[0234] Golden Retriever hair was treated with the following washing recipes:

[0235] Table 5: Series of experiments for electron microscopic examination

[0236] The wash liquor was filtered using a filtration cascade in the following stages:

[0237] 60, 25, 10, 5 pm stainless steel filter and vacuum pump

[0238] A self-constructed four-stage filter cascade was used to filter the wash liquor. The device is a horizontally stacked cascade made of stainless steel, enabling fractional filtration. This facilitates filtration and allows for estimation of the particle size distribution. The individual stages can be screwed together, allowing the number of filtration stages to be adjusted to individual requirements. Each stage contains removable stainless steel filters that can be flexibly used for subsequent analyses such as microscopy and gravimetric measurements. Four stainless steel filters with a diameter of 47 mm were used for each filtration process, with the pore size being arranged in descending order from 60 pm (plain weave) to 25 pm (plain weave), 10 pm (plain weave), and 5 pm (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 operated at 250 mbar. The wash liquor was introduced into the upper funnel for filtration. After the wash liquor was filtered, the cascade was additionally rinsed with distilled water.

[0239] The resulting filter cake 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 cuticles in hair treated with Formula 1 (benchmark) (a, b, c). Formula 1 differs little from Formula 2 (df). However, the hair treated with Formula 3 (gi) exhibits significant differences in structure and an overall damaged surface (g). Additionally, breakage (h) and angled cuticles (i) are visible. The combination of the bleaching agent and bleach activator-containing additive with the enzyme Savinase 16 T achieves the best results.

Claims

Patent claims 1. Method for removing hair from textiles and / or the interior of a washing machine, wherein in at least one process step a textile washing and / or care product and / or a textile detergent additive containing at least one protease, at least one bleaching agent and at least one bleach activator is used.

2. The method according to claim 1, characterized in that the at least one protease is selected from the group consisting of proteases with keratolytic activity, preferably from the group consisting of keratinases.

3. The method according to one of claims 1 or 2, characterized in that the at least one protease is contained in the agent in an amount of 1.5 to 20 wt.%, preferably 2.0 to 15 wt.%, in each case based on the total weight of the agent and based on active protein.

4. The method according to one of the preceding claims, characterized in that the at least one bleaching agent is not a chlorine-containing bleaching agent.

5. The method according to one of the preceding claims, characterized in that the at least one bleaching agent is selected from the group consisting of peroxygen compounds, such as percarboxylic acids, e.g. dodecanediperic acid or phthaloylaminoperoxicapronic acid, hydrogen peroxide, alkali perborate, percarbonate, perpyrophosphate and persilicate.

6. The method according to one of the preceding claims, characterized in that the at least one bleaching agent is contained in an amount of 5 to 70 wt.%, preferably in an amount of up to 50 wt.%, in particular up to 40 wt.% and especially preferably 7 to 30 wt.%, in each case based on the total weight of the agent.

7. The method according to one of the preceding claims, characterized in that the at least one bleaching activator is contained in an amount of 0.3 to 15% by weight, in each case based on the total weight of the agent.

8. The method according to one of the preceding claims, characterized in that the at least one bleach activator is selected from the group consisting of bleach activator compounds which yield peroxocarboxylic acid under perhydrolysis conditions; bleach activator compounds which form perimidic acid under perhydrolysis conditions; bleach activating transition metal complexes and acylhydrazones.

9. The method according to one of the preceding claims, characterized in that the at least one bleaching activator is selected from the group consisting of 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-acylides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates or carboxylates or the sulfonic or carboxylic acids thereof, in particular nonanoyl or isononanoyl or lauroyloxybenzenesulfonate (NOBS or iso-NOBS or iso-NOBS, respectively).LOBS) or decanoyloxybenzoate (DOBA), their formal carbonic acid ester derivatives such as 4-(2-decanoyloxyethoxycarbonyloxy)benzenesulfonate (DECOBS), acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran, as well as acetylated sorbitol and mannitol and their mixtures (SORMAN), acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetylfructose, tetraacetylxylose and octaacetyl lactose, acetylated, optionally N-alkylated glucamine and gluconolactone, and / or N-acylated lactams, e.g., N-benzoylcaprolactam.

10. The method according to one of the preceding claims, characterized in that the weight ratio of bleaching agent to bleach activator is approximately 5:1 to 15:1, preferably approximately 8:1 to 12:1, e.g. approximately 10:

1.

11. The method according to one of the preceding claims, characterized in that the agent comprises at least one further ingredient selected from fragrances, surfactants, builders, additives for adjusting viscosity and / or for stabilization, UV stabilizers, dyes, pearlescent agents, preservatives, bittering agents, organic salts, disinfectants, (structural) polymers, defoamers and pH adjusters.

12. The method according to one of the preceding claims, characterized in that the application temperature is in the range of 0 to 90°C, preferably in the range of 20 to 60°C, in particular in the range of 40 to 60°C.

13. Use of a textile washing 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 product contains at least one protease, at least one bleaching agent and at least one bleach activator.

14. Use of a protease for the removal of hair from textiles and / or the interior of a washing machine, wherein the protease is used in combination with at least one bleaching agent and at least one bleach activator.

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