DE102019135537A1 - Textile material comprising highly concentrated enzyme formulation for washing and cleaning purposes - Google Patents

Abstract

The present invention relates to flat textile materials which have at least one highly concentrated enzyme formulation comprising at least one enzyme in an amount of approximately 10 to approximately 70% by weight on at least part of their surface. The invention also relates to the use of such textile materials for washing and cleaning purposes, preferably for washing, caring for or conditioning textiles, and a method for washing, caring for or conditioning textiles using such a textile material.

Description

The present invention relates to flat textile materials which have at least one highly concentrated enzyme formulation comprising at least one enzyme in an amount of approximately 10 to approximately 70% by weight on at least part of their surface. The invention further relates to the use of such textile materials for washing and cleaning purposes, preferably for washing, caring for or conditioning textiles, and a method for washing, caring for or conditioning textiles using such a textile material.

Enzymes are important components of modern washing and cleaning agents that contribute significantly to the overall performance of the products and, in particular, bring about particular performance improvements on selected stains and soiling. However, in the course of their storage in detergents and cleaning agents, enzymes gradually lose their activity, so that the improvement in performance based on them diminishes over time.

In order to counteract this effect, so-called enzyme stabilizers are usually added to enzyme-containing detergents and cleaning agents. Common enzyme stabilizers differ in their mode of action. The use of glutaraldehyde, for example, is known. However, due to the toxicity of the stabilizer, the instability of the crosslinking in acidic media and also due to the relatively complex formulation process, a corresponding use of glutaraldehyde is generally disadvantageous. The use of supramolecular and low molecular weight stabilizing additives, whose mode of action is based on increasing the surface tension of the protein in the solvent, so that denaturation is less favored thermodynamically, is also common. However, large amounts are required and use in organic solvents is only possible to a limited extent due to the already changed surface tensions. Another active principle of enzyme stabilization is based on the formation of covalent bonds between certain polymers and the enzyme. The disadvantage of this process is, on the one hand, a general reduction in enzymatic activity due to the steric shielding by the polymers, and, on the other hand, it causes significant costs, since the covalent modification represents an additional synthesis step that has to be re-optimized and carried out for each enzyme type.

Overall, the use of enzyme stabilizers is therefore rather problematic, and there is still a need for stable, enzyme-containing formulations for washing and cleaning purposes.

In addition, there is a general tendency to reduce the dosage of detergents and cleaning agents, on the one hand for reasons of sustainability and environmental protection, on the other hand for reasons of commerciality and with a view to increasing online marketing and trading. As a result, increasingly concentrated detergent and cleaning agent formulations, preferably in the form of unit doses, are preferred, which, in turn, are preferred, easy and “clean” to use and are visually appealing. An embodiment of such a detergent or cleaning agent unit dose that is increasingly preferred by consumers are washing or cleaning agent wipes, so-called “laundry sheets”.

It has now surprisingly been found that enzymes in the form of highly concentrated enzyme formulations are generally particularly stable in storage, can easily be applied in pasty form to textile carrier materials and generally enable the design of manageable, visually appealing detergent end products in the form of detergent or cleaning agent wipes.

Furthermore, low-water, highly concentrated enzyme formulations, as described herein, which enable enzyme preparations to be applied to water-soluble textile carrier materials, are also advantageous.

Due to the increased concentration of active protein in the highly concentrated enzyme formulations described herein and, associated therewith, due to the general reduction in the entrainment of accompanying substances, for example from fermentation, the active profile of the resulting detergents and cleaning agents in the form of textile materials, as described herein, can be improved overall become. Furthermore, it is possible to assemble unit doses that are as small as possible and still have effective effects.

A first object of the present invention is therefore a flat textile material, characterized in that the textile material has at least one highly concentrated enzyme formulation comprising at least one enzyme on at least part of its surface, the enzyme content in the highly concentrated enzyme formulation is about 10 to about 70 wt .-%, based on the total weight of the enzyme formulation and based on active protein.

In a further aspect, the invention also relates to the use of such a flat textile material for washing and cleaning purposes, preferably for washing, caring for or conditioning textiles.

Finally, the invention also relates to a method for washing, caring for or conditioning textiles, characterized in that a flat textile material, as described herein, is used in at least one method step.

These and other aspects, features and advantages of the invention will become apparent to those skilled in the art from a study of the following detailed description and claims. Each feature from one aspect of the invention can be used in any other aspect of the invention. Furthermore, it goes without saying that the examples contained herein are intended to describe and illustrate the invention, but not to restrict it, and in particular the invention is not limited to these examples.

The term “textile treatment agent”, as used herein, denotes an agent which is used for textile treatment and which leads to a causal change in at least one property of the textile selected from chemical, physical or aesthetic properties after the end of the treatment. In the context of the present invention, the constituents of a textile treatment agent can in principle be selected and adapted so that the agent has the desired treatment properties, for example textile cleaning, care, conditioning and / or color protecting properties.

In the context of the present invention, the term “conditioning” denotes the imparting of a desired property, for example in relation to textiles, a pleasant feel, freedom from creasing or low static charge.

The subject matter of the invention includes all conceivable washing or cleaning processes, on a commercial scale, in the washing machine or in the case of hand washing or cleaning. These include, for example, washing and cleaning processes and applications for cleaning, care and / or conditioning, pre- and / or post-treatment of textiles, carpets or natural fibers, but also of hard surfaces such as metal, glass, porcelain, ceramics and tiles , Stone, painted surfaces, plastics, wood or leather.

"At least one" as used herein includes, but is not limited to, 1, 2, 3, 4, 5, 6, and more. In relation to an ingredient, the specification refers to the type of ingredient and not to the absolute number of molecules. “At least one surfactant” thus means, for example, at least one type of surfactant, i.e. that one type of surfactant or a mixture of several different surfactants can be meant. Together with weight information, the information relates to all compounds of the specified type that are contained in the composition / mixture, i.e. that the composition does not contain any further compounds of this type beyond the specified amount of the corresponding compounds.

Unless otherwise stated, all percentages are percentages by weight. Numeric ranges specified in the format “from x to y” include the stated values. If several preferred numerical ranges are given in this format, it is understood that all ranges resulting from the combination of the various endpoints are also recorded.

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

If reference is made here to molar masses, these details always relate to the number-average molar mass M _n , unless explicitly stated otherwise. The number average molecular weight can be determined, for example, by means of gel permeation chromatography (GPC) according to DIN 55672-1: 2007-08 with THF as the eluent. The weight average molar mass M _w can also be determined by means of GPC, as described for M _n .

Whenever alkaline earth metals are mentioned in the following as counterions for monovalent anions, this means that the alkaline earth metal is of course only present in half the amount of substance - sufficient to balance the charge - as the anion.

“Liquid”, as used in the context of the present invention, denotes all flowable compositions (at 20 ° C., 1.013 bar), including gels and paste-like compositions, and also non-Newtonian liquids that have a flow limit.

“Phosphate-free” and “phosphonate-free”, as used herein, means that the composition in question is essentially free of phosphates or phosphonates, ie in particular phosphates or phosphonates in quantities of less than 0.1% by weight, preferably less than 0 .01% by weight, based on the respective composition.

The textile material according to the invention is generally a textile material which has a flat shape. “Flat”, in the context of the present invention, denotes a flat extension or shape, for example the shape of a cloth or a sheet. A flat textile material according to the invention, in some embodiments, is in the form of a cloth, a fleece, a knitted fabric or a woven fabric, the dimensions of which are preferably selected to be user-friendly, for example so that the textile material is preferably used as a unit dose in washing and cleaning processes can. In some embodiments, the textile material is woven, non-woven, knitted or braided, preferably non-woven, in the form of a cloth.

According to the invention, the flat textile material can be a water-soluble or water-insoluble textile material.

“Water-soluble” refers, in the context of the present invention, to a material which on contact with water, for example on contact with a washing liquor, not only swells insignificantly, dissolves and / or decomposes, its structure disintegrates or its components go at least partially into solution on contact with water, preferably go essentially into solution, most preferably go completely into solution and / or be suspended.

“Insoluble in water” denotes, in the context of the present invention, a material, the constituents of which essentially do not go into solution or are suspended on contact with water, preferably do not go into solution or are suspended.

Preferably the substrate comprises a material that provides free hydroxyl groups on the surface of the substrate.

The substrate can consist of a single material, but it can also comprise mixtures of different materials. If the textile material is a water-insoluble material, it can comprise cellulose and / or synthetic fibers, for example. A mixture of viscose and cellulose fibers can also be used. Mixtures of cellulose fibers and synthetic fibers or cellulose fibers and viscose and synthetic fibers can also be used. Also suitable are substrates which essentially or exclusively consist of cellulose fibers / materials.

Suitable fibers are, for example, but not limited to, cellulosic fibers, i.e. suitable fibers comprise or consist of cellulose or are cellulose fibers. In various embodiments, the textile material comprises fibers of the cellulose type, such as linen, cotton (cotton blends are also possible) or viscose. A specific example is Lyocell. The fibers can be natural fibers or regenerated cellulose-based fibers, such as cotton or viscose, or mixtures of natural fibers and regenerated fibers. Regenerated cellulose fibers such as viscose, modal and lyocell, or combinations thereof, are particularly suitable. In various embodiments, the fibers used are produced from purified cellulose, in particular from cellulose which contains less than 10% by weight of other components such as hemicellulose or lignin. Preferably the cellulose from which the fibers are formed is substantially free of hemicellulose and lignin. It is also preferred that the fibers used in the textile materials described herein are not wood pulp.

Methods for making suitable regenerated cellulosic fibers are known and involve the chemical conversion of purified cellulose, for example from wood pulp or other natural sources, into a soluble compound which is then dissolved and forced through a spinneret to produce chemically bonded filaments, fibers.

Suitable lyocell fibers are marketed, for example, by Lenzing, AT, under the Tencel® brand.

Although the fibers are preferably based on cellulose, it is also possible to use fibers which comprise or consist of cellulose derivatives, such as, for example, cellulose esters, in particular cellulose acetate.

Suitable synthetic fibers include polypropylene, polyethylene, polyamide, polyester and polyolefin fibers.

In various embodiments, the textile material is a cellulose-based fleece, in particular a lyocell substrate, which can comprise further natural fibers, in particular cellulose fibers. The other existing natural fibers can be different from the cellulose fibers.

In various embodiments, the textile material is at least partially produced from fibers of a cellulosic material, but can also be a composite material in that it also comprises non-cellulosic material. Accordingly, the material can comprise a naturally occurring material or a plastic or a mixture thereof.

The water-insoluble textile material is typically selected so that it has sufficient wet strength and sufficient resistance to abrasion resulting from contact with other materials in a bath, such as a wash liquor or rinse water. Therefore, the textile materials of the present application are preferably strong and robust in order to be suitable in principle for all types of washing machines. The tensile strength refers to the resistance of the textile material to tearing and / or tearing. The direction of tensile strength can be differentiated between machine direction (MD) and cross direction (CD). In the manufacture of the textile material, for example in the form of a cloth, the longitudinal direction (production direction) is the machine direction. The direction perpendicular to it is the transverse direction. In addition, the panels should be robust and stable both wet (i.e. immersed in water for 10 seconds) and dry (as obtained from a supplier). The textile material in the wet state preferably has a tensile strength in the machine direction (MD) of 200 N / m to 1500 N / m, preferably from 400 N / m to 1400 N / m, in particular from 600 N / m to 1300 N / m, particularly preferably from 750 N / m to 1200 N / m and / or in the transverse direction (CD) from 50 N / m to 1000 N / m, preferably from 100 N / m to 800 N / m, particularly preferably from 150 N / m up to 500 N / m. In the dry state, it preferably has a tensile strength in the machine direction (MD) of 1200 N / m to 2800 N / m, preferably from 1400 N / m to 2600 N / m, in particular from 1500 N / m to 2400 N / m, particularly preferred from 1600 N / m to 2200 N / m and / or in the transverse direction (CD) from 200 N / m to 1500 N / m, preferably from 250 N / m to 1000 N / m, in particular from 300 N / m to 800 N / m on.

The textile material can additionally comprise a binder such as polyvinyl acetate, although in various embodiments no such binder is included.

In various other embodiments, the textile material according to the invention is a water-soluble textile material. In this context suitable water-soluble materials from which fibers for the production of water-soluble textile materials can be made are known in the art and include materials made from polymers of natural, synthetic and semi-synthetic origin, such as, for example and without limitation, polyvinyl alcohols, polyamides, polylactides, proteins , Starch, alginate, chitosan, galactans, gum arabic and as well as derivatives and copolymers of the aforementioned.

Examples of commercially available, water-soluble non-woven textile materials are the non-woven fabrics of the Norafin Ecoline product line, sold by Norafin Industries (Germany) GmbH.

In principle, any desired diameter or denier of a respective fiber can be used according to the invention. Fibers with approximately 1.0 to approximately 2.0 dtex, preferably approximately 1.2 to approximately 1.5 dtex and / or approximately 30 to approximately 45 mm, preferably approximately 35 to approximately 42 mm, are suitable, without limitation. The material, for example in the form of a cloth, a fleece or the like, can be wet-laid or spun, depending on the length of the fibers. It is preferred that the fibers have a length of approximately 2 mm to 5 mm for wet-laid nonwovens or from 30 mm to 50 mm for spun nonwovens. In any of the embodiments described herein, all of the fibers can be in the form of a yarn.

The thickness of the flat textile material, ie of an individual textile cloth or a single textile, flat material layer, is preferably from 0.62 mm to 1.5 mm, preferably from 1.0 mm to 1.2 mm. Depending on the fiber material and type of fabric, the permeability for the wash liquor and the stability of the product must be weighed up.

The textile material is preferably formed to a density of 40-200 g / m ² , 40-80 g / m ² , 55-75 g / m ² or 60-75 g / m ² , preferably about 65 g / m ² . The values apply to the textile material in its ready-to-use, ie dry form. The density can according to ISO 9073-1 (from 1989).

The dimensions of a textile material according to the invention that has been cut ready for use, in particular in the form of a unit dose, can have dimensions, for example, in the range of approximately 20-30 cm × 10-20 cm, such as approximately 25 cm × 12 cm. It should be noted, however, that in principle any dimension can be selected that appears advantageous for the respective purpose.

The purpose of the textile material is to provide a carrier for the at least one highly concentrated enzyme formulation, as defined and described below, as well as for further active ingredients, as explained below, and also to provide a sufficient area over which the highly concentrated enzyme formulation and preferably further active ingredients for the Liquid in the bath or washing water in which the flat textile material is to be used are accessible. Preferred applications are laundry applications, in particular in automatic washing machines, such as front loaders or top loaders.

The textile material according to the invention is characterized in that it has at least one highly concentrated enzyme formulation comprising at least one enzyme on at least part of its surface.

The term “highly concentrated enzyme formulation”, as used herein, denotes a formulation comprising at least one enzyme, the enzyme content of which is approximately 10 to approximately 70% by weight, for example approximately 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 35, 40, 45, 50, 55, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69 or 70% by weight, based in each case on the total weight of the highly concentrated enzyme formulation and based on active protein. In some embodiments, the content of at least one enzyme in the highly concentrated enzyme formulation is in particular at least about 20% by weight, preferably at least about 25% by weight, preferably at least 30% by weight, even more preferably at least about 35% by weight, each based on the total weight of the highly concentrated enzyme formulation and based on active protein.

In various embodiments, such a highly concentrated enzyme formulation also contains at least one organic solvent, preferably selected from alcohols, particularly preferably polyhydric alcohols liquid under standard conditions (20 ° C., 1013 mbar), in particular glycerol, 1,2-propanediol and sorbitol, and mixtures thereof. If these are included, the amount is preferably from about 0.1 to about 80% by weight, more preferably from 10 to 70% by weight, based in each case on the total weight of the enzyme formulation and based on the active protein.

In various embodiments of the invention, the at least one enzyme is a free enzyme. This means that the enzyme can act directly with all components of an agent. In other embodiments, a highly concentrated enzyme formulation can contain at least one enzyme that forms an interaction complex with other molecules or that has an “envelope”. Such a separating structure can arise from, but is not limited to, vesicles, such as a micelle or a liposome, or micro / nanocapsules, typically with a polymer shell.

In various embodiments, the at least one highly concentrated enzyme formulation, as defined above, is in an amount of from about 0.0001 to about 5% by weight, preferably from about 0.005 to about 2.5% by weight, more preferably from about 0.01 to about 1.5% by weight, based in each case on the total weight of the textile material.

The at least one enzyme, present in the form of the highly concentrated enzyme formulation, as defined above, in various embodiments, is in total in an amount of 0.00001 to 10% by weight, preferably in an amount of 0.0002 to 0.8% by weight .-% before, in each case based on the total weight of the textile material. The above quantities relate in each case to the active protein.

The protein concentration can generally be determined using known methods, for example the BCA method (bicinchoninic acid; 2,2'-bichinolyl-4,4'-dicarboxylic acid) or the biuret method ( AG Gornall, CS Bardawill and MM David, J. Biol. Chem., 177 (1948), pp. 751-766 ) can be determined. In this regard, the active protein concentration can be determined by titrating the active centers using a suitable irreversible inhibitor and determining the residual activity ( see M. Bender et al., J. Am. Chem. Soc. 88, 24 (1966), pp. 5890-5913 ) respectively.

The highly concentrated enzyme formulation can furthermore contain at least one enzyme stabilizer and / or enzyme inhibitor, preferably in an amount of 0.001 to 50% by weight, more preferably 0.01 to 10% by weight, based on the total weight of the enzyme formulation. All compounds known in the prior art for this purpose are suitable as stabilizers / inhibitors.

In various embodiments, the highly concentrated enzyme formulation can contain water, but low-water to anhydrous compositions are also possible. The abovementioned organic solvents are then used in particular in the latter. “Low water” in the context of the present invention generally refers to water contents of up to 20% by weight, preferably up to 15% by weight, even more preferably up to 10% by weight, and “anhydrous” refers to water contents of up to 5% by weight, in particular compositions in which water is not intentionally added, but rather is brought in with other constituents as a maximum. The water content can be determined by means of Karl Fischer titration. If the agents, individual components or constituents of agents according to the invention are partially water-poor to anhydrous, the stated pH value relates in various embodiments to a 1% solution of the respective composition in distilled water at 25 ° C.

In various embodiments, the pH of the highly concentrated enzyme formulation is in the range from 5 to 9.

The highly concentrated enzyme formulation per se is, in some embodiments, in microcrystalline, particulate form. In the context of the present invention, “microcrystalline” particles are particles whose average particle size D _{50 is} preferably approximately 10 to 5000 μm, more preferably approximately 10 to 3000 μm, in particular approximately 50 to 1500 μm. The average particle size Dso denotes the average diameter, based on which 50% of the totality of the particles have a smaller diameter and 50% of the totality of the particles have a larger diameter.

In some embodiments, the highly concentrated enzyme formulation is in the form of a slurry, preferably in the form of a pasty slurry. In the context of the present invention, the term “slurry” denotes a liquid, enzyme-containing suspension, the at least one enzyme contained in this suspension being present in a highly concentrated form, as defined above. One possible embodiment of this type provides that a highly concentrated enzyme formulation in the form of a slurry comprises the at least one enzyme in particulate, granulated form, the particles preferably having an average particle size D _{50 of} about 10 to 5000 μm, more preferably about 10 to 3000 μm, in particular have approximately 50 to 1500 μm and wherein the particles are present in dispersed form in the slurry.

The at least one enzyme, which, in highly concentrated form, as defined above, is part of the highly concentrated enzyme formulation, can be any one that is known in the prior art for use in detergents and cleaning agents, as defined herein, or that will be used in the future Act enzyme.

The enzyme can be a hydrolytic enzyme or another enzyme in a concentration according to the invention which is appropriate for the effectiveness of the agent.

Preference is given to using all enzymes which can develop a catalytic activity in the agent according to the invention, in particular a protease, lipase, amylase, cellulase, hemicellulase, mannanase, tannase, xylanase, xanthanase, xyloglucanase, β-glucosidase, pectinase, carrageenase, perhydrolase, oxidase , or oxidoreductase and mixtures thereof.

The enzymes particularly preferably show synergistic cleaning performance with respect to certain soiling or stains, ie the enzymes contained in the agent composition mutually support one another in their cleaning performance. Such a synergism is very particularly preferably present between a protease and a further enzyme of an agent according to the invention, including in particular between a protease and an amylase and / or a lipase and / or a mannanase and / or a cellulase and / or a pectinase. Synergistic effects can occur not only between different enzymes, but also occur between one or more enzymes and other ingredients of the agent according to the invention.

Textile detergents according to the invention have in particular at least one protease and at least one amylase. In a further embodiment of the invention, laundry detergents have at least one protease and at least one cellulase. In a further preferred embodiment, laundry detergents have at least one protease and at least one lipase. Textile detergents which contain 3 to 10 different enzymes are particularly preferred, textile detergents which contain 3 to 10 different types of enzymes can be particularly preferred with regard to cleaning performance over a very large spectrum of stains.

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 subtilases, but no longer attributable to the subtilisins in the narrower sense Thermitase, Proteinase K and the proteases TW3 and TW7. Subtilisin Carlsberg is available in a further developed form under the trade name Alcalase® from the Novozymes company. The subtilisins 147 and 309 are sold by the Novozymes company under the trade names Esperase® and Savinase®, respectively. The protease variants under the name BLAP® are derived from the protease from Bacillus lentus DSM 5483. Further usable proteases are, for example, those under the trade names Durazym®, Relase®, Everlase®, Nafizym®, Natalase®, Kannase® and Ovozyme® from the company Novozymes, which are sold under the trade names, Purafect®, Purafect® OxP, Purafect® Prime, Excellase® and Properase® by the company Danisco / Genencor, which is sold under the trade name Protosol® by the company Advanced Biochemicals Ltd., which is sold under the trade name Wuxi® by the company Wuxi Snyder Bioproducts Ltd., which is sold under the trade name Proleather® and Protease P ® from Amano Pharmaceuticals Ltd., and under the name Proteinase K-16 from Kao Corp. available enzymes. The proteases from Bacillus gibsonii and Bacillus pumilus, which are disclosed in the international patent applications, are also used with particular preference WO2008086916 and WO2007131656 . Further proteases which can be used advantageously are disclosed in the patent applications WO9102792 , WO2008007319 , WO9318140 , WO0144452 , GB1243784 , WO9634946 , WO2002029024 and WO2003057246 . Further proteases which can be used are those which are naturally present in the microorganisms Stenotrophomonas maltophilia, in particular 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, for example, in WO 2016/096714 described.

Examples of amylases are the α-amylases from Bacillus licheniformis, Bacillus amyloliquefaciens or Bacillus stearothermophilus and, in particular, their improved further developments for use in detergents or cleaning agents. The enzyme from Bacillus licheniformis is available from the Novozymes company under the name Termamyl® and from the Danisco / Genencor company under the name Purastar® ST. Further development products of this α-amylase are available from Novozymes under the trade names Duramyl® and Termamyl® ultra, from Danisco / Genencor under the name Purastar® OxAm and from Daiwa Seiko Inc. as Keistase®. The α-amylase from Bacillus amyloliquefaciens is marketed by the Novozymes company under the name BAN®, and variants derived from the α-amylase from Bacillus stearothermophilus under the names BSG® and Novamyl®, also by the Novozymes company. Furthermore, the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from Bacillus agaradherens (DSM 9948) should be emphasized. The amylolytic enzymes described in the international patent applications can also be used WO2003002711 , WO2003054177 and WO2007079938 are disclosed, to the disclosure of which is therefore expressly referred to or whose disclosure content in this regard is therefore expressly included in the present patent application. Fusion products of all the molecules mentioned can also be used. In addition, the further developments of the α-amylase from Aspergillus niger and A. oryzae available from the Novozymes company under the trade names Fungamyl® are suitable. Further commercial products that can be used advantageously are, for example, Amylase-LT® and Stainzyme® or Stainzyme ultra® or Stainzyme plus® and Amplify ™ 12L or Amplify Prime ™ 100L, the latter also from Novozymes. Variants of these enzymes obtainable by point mutations can also be used according to the invention.

Examples of cellulases (endoglucanases, EG) is the fungal, endoglucanase (EG) -rich cellulase preparation or its further developments, which is offered by the Novozymes company under the trade name Celluzyme®. The products also available from Novozymes Endolase® and Carezyme® are based on the 50 kD EG and the 43 kD EG from Humicola insolens DSM 1800. Other commercial products from this company that can be used are Cellusoft®, Renozyme® and Celluclean®. Cellulases, for example, which are available from the company AB Enzymes under the trade names Ecostone® and Biotouch®, and which are at least partly based on the 20 kD EG from Melanocarpus, can also be used. Other cellulases from AB Enzymes are Econase® and Ecopulp®. Further suitable cellulases are from Bacillus sp. CBS 670.93 and CBS 669.93, the ones from Bacillus sp. CBS 670.93 is available from Danisco / Genencor under the trade name Puradax®. Other commercial products from Danisco / Genencor that can be used are “Genencor detergent cellulase L” and IndiAge®Neutra.

Lipases or cutinases, for example, are preferably used, in particular because of their triglyceride-cleaving activities, but also to generate peracids in situ from suitable precursors. These include, for example, the lipases originally obtained from Humicola lanuginosa (Thermomyces lanuginosus) or further developed therefrom, in particular those with one or more of the following amino acid exchanges starting from the lipase mentioned in positions D96L, T213R and / or N233R, particularly preferably T213R and N233R. Lipases are sold, for example, by the Novozymes company under the trade names Lipolase®, Lipolase® Ultra, LipoPrime®, Lipozyme® and Lipex®. Another lipase that can be used advantageously is available from Novozymes under the trade name Lipoclean®. Furthermore, e.g. the cutinases that were originally isolated from Fusarium solani pisi and Humicola insolens can be used. Lipases which can also be used are available from Amano under the names Lipase CE®, Lipase P®, Lipase B®, or Lipase CES®, Lipase AKG®, Bacillus sp. Lipase®, Lipase AP®, Lipase M-AP® and Lipase AML® available. From the company Danisco / Genencor, for example, lipases or cutinases can be used whose starting enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii. Other important commercial products are the preparations M1 Lipase® and Lipomax® originally sold by the company Gist-Brocades (now Danisco / Genencor) and those from the company Meito Sangyo KK under the names Lipase MY-30®, Lipase OF® and Lipase PL ® should be mentioned as well as the product Lumafast® from Danisco / Genencor.

According to the invention, oxidoreductases, e.g. oxidases, oxygenases, catalases, peroxidases such as halo-, chloro-, bromo-, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) can be used to increase the bleaching effect. Advantageously, preferably organic, particularly preferably aromatic, compounds that interact with the enzymes are added in order to increase the activity of the oxidoreductases in question (enhancers) or to ensure the flow of electrons (mediators) in the event of greatly differing redox potentials between the oxidizing enzymes and the soiling.

The enzymes to be used in the context of the present invention can originate, for example, originally 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 filamentous fungi.

It is emphasized that technical enzyme preparations of the respective enzyme can also be involved, i.e. accompanying substances can be present. The enzymes can therefore be packaged and used together with accompanying substances, for example from fermentation or with other stabilizers.

Furthermore, it is particularly possible to pack two or more enzymes together, so that a single, highly concentrated enzyme formulation, as defined herein, has several enzyme activities, as explained above.

In addition, a textile material according to the invention can have more than one, for example two different highly concentrated enzyme formulations. Each of the several highly concentrated enzyme formulations can each be located at a separate point on the surface of the flat textile material.

Different highly concentrated enzyme formulations of a textile material according to the invention can advantageously comprise enzymes or enzyme classes which are different from one another, it being possible for the enzymes in each case to be selected such that the broadest possible spectrum of activity can be achieved. A broad spectrum of activity can be achieved, for example, by combining different enzymes with one another in such a way that there is an enzymatic effectiveness against a large number of different types of soiling, for example against grass stains, greasy and starchy soiling.

The highly concentrated enzyme formulation can be applied to at least part of the surface of a carrier material as described above using various application methods. Exemplary application techniques include, without limitation, dripping processes, flexographic printing processes, padding processes, stamping processes, spraying processes and printing processes, such as screen printing and rotary printing processes, and combinations of the aforementioned processes. Rotary printing processes are for example in WO 2015/139865 A1 or EP 0879145 A1 disclosed.

The highly concentrated enzyme formulation can be applied to the carrier fabric with the formation of a wide variety of visually appealing patterns. Furthermore, the incorporation of dyes and pigments enables color variations, which can also contribute to an attractive appearance of the end product. In particular, differently formulated, highly concentrated enzyme formulations can be applied in different shades of color, whereby the identification of the particular enzymes used is also possible for the end user, preferably in combination with a corresponding explanatory legend, for example in the form of an instruction leaflet or as an imprint on the packaging.

In various embodiments, the flat textile material comprises at least two flat textile material layers which are positioned flat on top of one another. In such embodiments, the at least one highly concentrated enzyme formulation can be located between these two textile backing layers. In this way, undesired skin contact with the highly concentrated enzyme formulation in the course of using the end product can advantageously be avoided. Due to the preferably high viscosity of the highly concentrated enzyme formulation, as given for example in the case of a paste, the migration of the highly concentrated enzyme formulation through the textile carrier material, ie an exit from the space formed by the two textile layers, can largely, preferably essentially, most preferably approximately be avoided completely or entirely.

In various embodiments, the at least one highly concentrated enzyme formulation is applied directly to the surface or at least part of the surface of at least one of the two textile carrier layers positioned relative to one another as described above.

In alternative embodiments, a further, i.e. additional flat textile material is inserted into the space formed by the textile carrier layers positioned as described above, which is impregnated with the at least one highly concentrated enzyme formulation. In such embodiments, it is advantageous if the viscosity of the highly concentrated enzyme formulation is less high and, moreover, the material of said further textile layer is selected so that impregnation of the same with the enzyme formulation is made possible / facilitated.

If the flat textile material according to the invention comprises more than one flat layer, as described above, it is advantageous to at least partially fasten said two or more layers to one another, on the one hand to at least largely prevent the highly concentrated enzyme formulation from leaking out, and on the other hand to ensure the best possible ( to ensure a product that is stable in storage and that is suitable for handling by the consumer. The fastening can take place in the most varied of ways and can, for example and without restriction, include the use of a type of adhesive or binding agent, but also a sewing of the layers.

The flat textile material as described herein, which has at least one highly concentrated enzyme formulation comprising at least one enzyme on at least part of its surface, is a textile material which is suitable for use in washing and cleaning processes. In various embodiments, the textile material according to the invention is accordingly a washing or cleaning agent, preferably a textile treatment agent, as defined above.

According to the invention, such an agent comprises, in addition to the at least one highly concentrated enzyme formulation, as defined above, at least one further active ingredient, preferably at least two further active ingredients, which further improve the application and / or aesthetic properties of the agent. These include, for example, in particular surfactants, other enzymes, UV stabilizers, fragrances (perfume), dyes, color-catching compounds, color transfer inhibitors, optical brighteners, preservatives, bitter substances, disinfectants, defoamers, encapsulated ingredients (e.g. encapsulated perfume), pH adjusters and skin feel-improving or nourishing additives.

The amount of appropriately suitable further constituents depends on the intended use of the agent and the trained person skilled in the art is generally familiar with suitable dosages of these constituents or is able to find suitable amounts in the literature.

The textile material according to the invention can, in some embodiments, be coated or impregnated with a color-trapping compound. Due to the absorbent properties of the textile material, the dye scavenger is typically absorbed in or onto the textile carrier material, such as, for example, onto the individual fibers. Suitable ink-trapping coatings are mentioned in the prior art, e.g. in PCT / EP2017 / 050080, the contents of which are incorporated herein by reference in their entirety.

In principle, suitable dye-scavenging compounds are, for example, polyamines or GMAC (glycidyltrimethylammonium chloride), or a precursor of GMAC, such as 3-chloro-2-hydroxypropyltrimethylammonium chloride. Specific examples of suitable dye scavenger compounds are GMAC and their precursors.

wobei R⁴, R⁵, R⁶ und Y''^- die gleiche Bedeutung wie R¹, R², R³ und Y'^- obiger Formel (I) haben, wie vorstehend definiert.Other suitable dye scavenger compounds include N-trisubstituted ammonium-2-hydroxy-3-halopropyl compounds of the general formula (I): X'-CH ₂ -CHOH-CH ₂ -N ⁺ (R ¹ R ² R ³ ) Y'- (I)
wherein R ^1, R ^2, R ³ are each independently methyl, ethyl, propyl, butyl, benzyl or a hydroxyl-substituted derivative thereof, X 'is a halogen atom and Y' ^-, sulfate or sulfonate is chloride, bromide, or
an epoxy propylammonium salt of the general formula (II):

where R ⁴ , R ⁵ , R ⁶ and Y " ^{- have} the same meaning as R ¹ , R ² , R ³ and Y ' ^{- of the} above formula (I), as defined above.

In various embodiments, the dye-scavenging compound is a compound of the formula (I) or (II), where R ¹ , R ² , R ³ or R ⁴ , R ⁵ , R ^{6 are} each independently methyl, ethyl, propyl, butyl, benzyl or a hydroxyl substituted derivative thereof, preferably methyl, ethyl, n-propyl or n-butyl, more preferably methyl or ethyl, most preferably methyl. X 'is a halogen atom, preferably selected from Cl or Br.

Y'- and / or Y "- are selected from chloride, bromide, sulfate or sulfonate, preferably chloride. It will be understood that when Y 'or Y "is a sulfate or sulfonate anion, this refers to ½ sulfate / sulfonate ion, i.e. the anion is shared by two positively charged ammonium compounds.

In various embodiments, the dye-scavenging compound is preferably an epoxypropylammonium salt of the general formula (II), preferably a glycidyltrimethylammonium salt, also known as (2,3-epoxypropyl) trimethylammonium salt, more preferably the chloride salt, which is in solid form or as a 72% aqueous composition of Sigma Aldrich is available, wherein R ^4, R ^5, R ⁶ are each methyl and Y '' ^- is chloride.

Alternatively, the compound can be a compound of formula (I) above, for example 3-chloro-2-hydroxypropyltrimethylammonium chloride available from Sigma Aldrich, where R ¹ , R ² , R ^{3 are} each methyl, X 'is chlorine and Y'-chlorine is.

Of course, more than one compound of formula (I) or (II) can be used in combination, or a corresponding compound can be used in combination with another dye scavenging compound of formula (I) or (II).

Methods for applying dye-scavenging compounds are known in the prior art and can accordingly be used in the context of the present invention.

All known nonionic, anionic, cationic, zwitterionic and amphoteric surfactants can be used as surfactants, at least nonionic and / or anionic surfactants being used in various embodiments.

Suitable compounds from the class of anionic surfactants are those of the formula (I) R-SO ₃ ^- X ⁺ (I)

In this formula (I), R stands for a linear or branched unsubstituted alkylaryl radical. X stands for a monovalent cation or the nth part of an n-valent cation, preferred are the alkali metal ions, including Na ⁺ or K ⁺ , Na ^{+ being} extremely preferred. Further cations X ⁺ can be selected from NH4 ⁺ , ½ Zn ²⁺ , ½ Mg ²⁺ , ½ Ca ²⁺ , ½ Mn ²⁺ , and mixtures thereof.

As used herein, “alkylaryl” refers to organic radicals consisting of an alkyl radical and an aromatic radical. Typical examples of such groups include, but are not limited to, alkylbenzene groups such as benzyl, butylbenzene groups, nonylbenzene groups, decylbenzene groups, undecylbenzene groups, dodecylbenzene groups, tridecylbenzene groups, and the like.

in der R' und R'' zusammen 9 bis 19, vorzugsweise 11 bis 15 und insbesondere 11 bis 13 C-Atome enthalten, dargestellt. Ein ganz besonders bevorzugter Vertreter lässt sich durch die Formel A-1a beschreiben:

In various embodiments, such surfactants are selected from linear or branched alkylbenzenesulfonates of the formula A-1:

in which R 'and R''together contain 9 to 19, preferably 11 to 15 and in particular 11 to 13 carbon atoms. A particularly preferred representative can be described by the formula A-1a:

In various embodiments, the compound of the formula (I) is preferably the sodium salt of a linear alkylbenzenesulfonate.

Preferred anionic surfactants are those of the formula (II) R ¹ -O- (AO) _n -SO3 ^- X ⁺ (II).

In this formula (II), R ^{1 represents} a linear or branched, substituted or unsubstituted alkyl radical, preferably a linear, unsubstituted alkyl radical, particularly preferably a fatty alcohol radical. Preferred radicals R ¹ are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl radicals and mixtures thereof, the representatives with an even number of C- Atoms are preferred. Particularly preferred radicals R ¹ are derived from C ₁₂ -C ₁₈ fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or from C ₁₀ -C ₂₀ oxo alcohols. X stands for a monovalent cation or the nth part of an n-valent cation, preferred are the alkali metal ions, including Na ⁺ or K ⁺ , Na ^{+ being} extremely preferred. Further cations X ⁺ can be selected from NH4 ⁺ , ½ Zn ²⁺ , ½ Mg ²⁺ , ½ Ca ²⁺ , ½ Mn ²⁺ , and mixtures thereof.

AO stands for an ethylene oxide (EO) or propylene oxide (PO) group, preferably an ethylene oxide group. The index n stands for an integer from 1 to 50, preferably from 1 to 20 and in particular from 2 to 10. n is very particularly preferably the numbers 2, 3, 4, 5, 6, 7 or 8. X is a monovalent cation or the n-th part of an n-valent cation; Alkali metal ions and including Na ⁺ or K ⁺ , with Na ^{+ being} extremely preferred. Further cations X + can be selected from NH4 ⁺ , ½ Zn ²⁺ , ½ Mg ²⁺ , ½ Ca ²⁺ , ½ Mn ²⁺ , and mixtures thereof.

mit k = 11 bis 19, n = 2, 3, 4, 5, 6, 7 oder 8. Besonders bevorzugte Vertreter sind Na-C_12-14 Fettalkoholethersulfate mit 2 EO (k = 11-13, n = 2 in Formel II-1).In summary, the agents in various embodiments can thus contain at least one anionic surfactant selected from fatty alcohol ether sulfates of the formula II-1

with k = 11 to 19, n = 2, 3, 4, 5, 6, 7 or 8. Particularly preferred representatives are Na-C _12-14 fatty alcohol ether sulfates with 2 EO (k = 11-13, n = 2 in formula II -1).

Further anionic surfactants that can be used with preference are the alkyl sulfates of the formula R ² -O-SO ₃ ^- X ⁺ (III).

In this formula (III), R ^{2 represents} a linear or branched, substituted or unsubstituted alkyl radical, preferably a linear, unsubstituted alkyl radical, particularly preferably a fatty alcohol radical. Preferred radicals R ² are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl radicals and mixtures thereof, the representatives with an even number of C- Atoms are preferred. Particularly preferred radicals R ² are derived from C ₁₂ -C ₁₈ fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or from C ₁₀ -C ₂₀ oxo alcohols. X stands for a monovalent cation or the nth part of an n-valent cation, preferred are the alkali metal ions, including Na ⁺ or K ⁺ , Na ^{+ being} extremely preferred. Further cations X ⁺ can be selected from NH4 ⁺ , ½ Zn ²⁺ , ½ Mg ²⁺ , ½ Ca ²⁺ , ½ Mn ²⁺ , and mixtures thereof.

mit k = 11 bis 19. Ganz besonders bevorzugte Vertreter sind Na-C_12-14 Fettalkoholsulfate (k = 11-13 in Formel III-1).In various embodiments, these surfactants are selected from fatty alcohol sulfates of the formula III-1

with k = 11 to 19. Very particularly preferred representatives are Na-C _12-14 fatty alcohol sulfates (k = 11-13 in formula III-1).

Other anionic surfactants that can be used are the alkyl ester sulfonates, in particular those of the formula IV: R ¹ -CH (SO ₃ ^- X ⁺⁾ -C (O) -O-R ² (IV).

In this formula (IV), R ^{1 represents} a linear or branched, substituted or unsubstituted alkyl radical, preferably a linear, unsubstituted alkyl radical. Preferred radicals R ¹ are selected from nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl radicals and mixtures thereof, the representatives with an odd number of carbon atoms are preferred. Particularly preferred radicals R ¹ —CH are derived from C ₁₂ -C ₁₈ fatty acids, for example from lauric, myristyl, cetyl or stearic acid. R ² represents a linear or branched, substituted or unsubstituted alkyl radical, preferably a linear, unsubstituted alkyl radical. Preferred radicals R ² are C _1-6 alkyl radicals, in particular methyl (= methyl ester sulfonate). X stands for a monovalent cation or the nth part of an n-valent cation, preferred are the alkali metal ions, including Na ⁺ or K ⁺ , Na ^{+ being} extremely preferred. Further cations X ⁺ can be selected from NH4 ⁺ , ½ Zn ²⁺ , ½ Mg ²⁺ , ½ Ca ²⁺ , ½ Mn ²⁺ , and mixtures thereof.

The secondary alkane sulfonates are also suitable as anionic surfactants. These have, for example, the formula (V) R ¹ CH (SO ₃ ^- X ⁺ ) R ² (V) where each R ¹ and R ^{2 is} independently a linear or branched alkyl having 1 to 20 carbon atoms and with the carbon atom to which they are attached to form a linear or branched alkyl, preferably having 10 to 30 carbon atoms, preferably 10 to 20 carbon atoms and X ^{+ is} selected from the group Na ⁺ , K ⁺ , NH4 ⁺ , ½ Zn ²⁺ , ½ Mg ²⁺ , ½ Ca ²⁺ , ½ Mn ²⁺ and mixtures thereof, preferably Na ⁺ .

In various preferred embodiment, the at least one secondary alkanesulfonate has the following formula (V-1) H ₃ C- (CH ₂ ) _n -CH (SO ₃ ^- X ⁺ ) - (CH ₂ ) _m -CH ₃ (V-1) where m and n are independently an integer between 0 and 20. Preferably m + n is an integer between 7 and 17, preferably 10 to 14 and X ⁺ is selected from the group Na ⁺ , K ⁺ , NH4 ⁺ , ½ Zn ²⁺ , ½ Mg ²⁺ , ½ Ca ²⁺ , ½ Mn ²⁺ and mixtures thereof, preferably Na ⁺ . In a particularly preferred embodiment, the at least one secondary alkanesulfonate is secondary C _14-17 sodium alkanesulfonate. Such a secondary C _14-17 sodium alkanesulfonate is sold, for example, by the Clariant company under the trade name “Hostapur SAS60”.

R3

für einen linearen oder verzweigten, substituierten oder unsubstituierten Alkylrest,

AO

für eine Ethylenoxid- (EO) oder Propylenoxid- (PO) Gruppierung,

m

für ganze Zahlen von 1 bis 50 stehen.

Particularly suitable nonionic surfactants are fatty alcohol alkoxylates. In various embodiments, the agents therefore contain at least one nonionic surfactant of the formula R ³ -O- (AO) _m -H (VI), in the

R3

for a linear or branched, substituted or unsubstituted alkyl radical,

AO

for an ethylene oxide (EO) or propylene oxide (PO) group,

m

stand for whole numbers from 1 to 50.

In the above formula (VI), R ^{3 represents} a linear or branched, substituted or unsubstituted alkyl radical, preferably a linear, unsubstituted alkyl radical, particularly preferably a fatty alcohol radical. Preferred radicals R ² are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl radicals and mixtures thereof, the representatives with an even number of C- Atoms are preferred. Particularly preferred radicals R ³ are derived from C ₁₂ -C ₁₈ fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or from C ₁₀ -C ₂₀ oxo alcohols.

AO 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. m is very particularly preferably the numbers 2, 3, 4, 5, 6, 7 or 8.

mit k = 11 bis 19, m = 2, 3, 4, 5, 6, 7 oder 8. Ganz besonders bevorzugte Vertreter sind C_12-18 Fettalkohole mit 7 EO (k = 11-17, m = 7 in Formel (VI-1)).In summary, the fatty alcohol alkoxylates to be used with preference are compounds of the formula

with k = 11 to 19, m = 2, 3, 4, 5, 6, 7 or 8. Very particularly preferred representatives are C _12-18 fatty alcohols with 7 EO (k = 11-17, m = 7 in formula (VI -1)).

Amine oxides, for example, are also suitable as nonionic surfactants. In principle, in this regard, all amine oxides established in the prior art for these purposes, ie compounds which have the formula R ¹ R ² R ³ NO, in which each R ¹ , R ² and R ^3, independently of the others, are optionally one substituted, for example hydroxy-substituted, C ₁ -C ₃₀ hydrocarbon chain can be used. Amine oxides used with particular preference are those in which R ^{1 is} C ₁₂ -C ₁₈ alkyl and R ² and R ^{3 are} each independently C ₁ -C ₄ alkyl, in particular C ₁₂ -C ₁₈ alkyldimethylamine oxides. Exemplary representatives of suitable amine oxides are N-cocoalkyl-N, N-dimethylamine oxide, N-tallowalkyl-N, N-dihydroxyethylamine oxide, myristyl / cetyldimethylamine oxide or lauryldimethylamine oxide.

Further nonionic surfactants which can be contained in the agents described for the purposes of the present invention include, but are not limited to, alkyl glycosides, alkoxylated fatty acid alkyl esters, fatty acid alkanolamides, hydroxy mixed ethers, sorbitan fatty acid esters, polyhydroxy fatty acid amides and alkoxylated alcohols. Such surfactants are known in the prior art.

Suitable alkyl (poly) glycosides are, for example, those of the formula R ² O- [G] _p , in which R ^{2 is} a linear or branched alkyl with 12 to 16 carbon atoms, G is a sugar residue with 5 or 6 carbon atoms, in particular glucose, and the index p is 1 to 10.

Suitable amphoteric surfactants are, for example, betaines of the formula (R ⁱⁱⁱ ) (R ^iv ) (R ^v ) N ⁺ CH ₂ COO-, in which R ^{iii is} an alkyl radical with 8 to 25, preferably 10 to 21 carbon atoms, optionally interrupted by heteroatoms or heteroatom groups, and R. ^iv and R ^v denote identical or different alkyl radicals with 1 to 3 carbon atoms, in particular C ₁₀ -C ₁₈ -alkyl-dimethylcarboxymethylbetaine and C ₁₁ -C ₁₇ -alkylamidopropyl-dimethylcarboxymethylbetaine.

Suitable cationic surfactants include the quaternary ammonium compounds of the formula (R ^vi ) (R ^vii ) (R ^viii ) (R ^ix ) N ⁺ X ^- , in which R ^vi to R ^{ix represent} four identical or different types, in particular two long and two short-chain, alkyl radicals and X- stand for an anion, in particular a halide ion, for example didecyldimethylammonium chloride, alkylbenzyldidecylammonium chloride and mixtures thereof. Further suitable cationic surfactants are the quaternary surface-active compounds, in particular with a sulfonium, phosphonium, iodonium or arsonium group, which are also known as antimicrobial agents. By using quaternary surface-active compounds with an antimicrobial effect, the agent can be designed with an antimicrobial effect or its antimicrobial effect, which may already be present due to other ingredients, can be improved.

The builders that can generally be used include in particular the aminocarboxylic acids and their salts, zeolites, silicates, carbonates, organic (co) builders and - where there are no ecological prejudices against their use - also the phosphates. According to preferred embodiments, however, the agents according to the invention are phosphate-free.

Organic builders suitable according to the invention are, for example, the polycarboxylic acids (polycarboxylates) which can be used in the form of their sodium salts, polycarboxylic acids being understood as meaning those carboxylic acids which have more than one, in particular two to eight acid functions, preferably two to six, in particular two, three, four or five acid functions carry throughout the molecule. Thus, preferred polycarboxylic acids are dicarboxylic acids, tricarboxylic acids, tetracarboxylic acids and pentacarboxylic acids, in particular di-, tri- and tetracarboxylic acids. The polycarboxylic acids can also carry further functional groups, such as hydroxyl or amino groups. For example, these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids (preferably aldaric acids, for example galactaric acid and glucaric acid), aminocarboxylic acids, in particular aminodicarboxylic acids, aminotricarboxylic acids, aminotetraacetic acid (NDAacetic acid), such as, for example, methylcyl acetic acid (NDA acetic triTA) , Glutamine-N, N-diacetic acid (also known as N, N-bis (carboxymethyl) -L-glutamic acid or GLDA), aspartic acid diacetate (ASDA), hydroxyethyliminodiacetate (HEIDA), iminodisuccinate (IDS) and ethylenediamine disuccinate (EDDS), and their Derivatives and mixtures of these. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, MGDA and mixtures of these.

Also suitable as organic builders are polymeric polycarboxylates (organic polymers with a large number of (in particular more than ten) carboxylate functions in the macromolecule), polyaspartates, polyacetals and dextrins.

In addition to their builder effect, the free acids typically also have the property of an acidifying component and can therefore also be used to adjust the pH. Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures of these should be mentioned in particular.

Agents according to the invention can furthermore be used as builders as crystalline layered silicates of the general formula NaMSi _x O _{2x + 1} · y H ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, where particularly preferred values for x are 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20. It is also possible to use amorphous sodium silicates with a Na ₂ O: SiO ₂ module of 1: 2 to 1: 3.3, preferably 1: 2 to 1: 2.8 and in particular 1: 2 to 1: 2.6, which are preferably delayed in dissolution and have secondary washing properties. In preferred cleaning agents according to the invention, in particular dishwashing agents, preferably machine dishwashing agents, the silicate content, based on the total weight of the cleaning agent, is limited to amounts below 10% by weight, preferably below 5% by weight and in particular below 2% by weight . It is particularly preferred that the agents are free from silicates, where “free” in this context means that the amount is limited to less than 0.1% by weight.

In various embodiments, agents according to the invention contain one or more salts of citric acid, that is to say citrates, as one of their essential builders.

The use of carbonate (s) and / or hydrogen carbonate (s), preferably alkali metal carbonate (s), particularly preferably sodium carbonate (soda), is also preferred.

In addition to the aforementioned builders, the agents according to the invention can also contain alkali metal hydroxides as alkali source. These alkali carriers are preferably only used in small amounts, preferably in amounts below 10% by weight, preferably below 6% by weight, preferably below 5% by weight, particularly preferably between 0.1 and 5% by weight. and in particular between 0.5 and 5% by weight, based in each case on the total weight of the agent. However, it is preferred that the agents contain only small amounts of NaOH, preferably they are free from NaOH. In various embodiments, the agent according to the invention contains potassium hydroxide (KOH) as an alkali source instead of NaOH, preferably in the amounts indicated above, in particular up to 3.5% by weight. In particular, the alkali metal hydroxides, especially KOH, are used in such amounts that the desired pH values of the compositions are achieved.

In general, the pH of the agents according to the invention can be adjusted by means of 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, preferably greater than 7, in particular 7.5 to 10.5. Acids and / or alkalis, preferably alkalis, are used as pH adjusting agents. Suitable acids are in particular organic acids such as acetic acid, citric acid, glycolic acid, lactic acid, succinic acid, adipic acid, malic acid, tartaric acid and gluconic acid or amidosulfonic acid. In addition, however, 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 the 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, for example in the form of ammonia and / or alkanolamines, which can contain up to 9 carbon atoms in the molecule, can be used to adjust the pH, the alkanolamine here being selected from the group consisting of mono -, di-, triethanol and propanolamine and mixtures thereof, such volatile alkali sources, in particular ethanolamines, are preferably dispensed with. In various embodiments, the agents according to the invention therefore contain less than 1.75% by weight alkanolamine, in particular monoethanolamine, and very particularly preferably they are free thereof.

To adjust and / or stabilize the pH, an agent according to the invention can furthermore contain one or more buffer substances (INCI buffering agents), usually in amounts of 0.001 to 5% by weight. Preference is given to buffer substances which are at the same time complexing agents or even chelating agents (chelators, INCI chelating agents). Particularly preferred buffer substances are citric acid or the citrates, in particular the sodium and potassium citrates, for example trisodium citrate-2H ₂ O and tripotassium citrate · H ₂ O.

An optical brightener is preferably selected from the substance classes of the distyrylbiphenyls, the stilbenes, the 4,4'-diamino-2,2'-stilbene disulfonic acids, the coumarins, the dihydroquinolinones, the 1,3-diarylpyrazolines, the naphthalic acid imides, the benzoxazole systems, the benzisoxazole systems, the benzimidazole systems, the pyrene derivatives substituted by heterocycles and mixtures thereof.

Particularly preferred suitable optical brighteners include disodium 4,4'-bis (2-morpholino-4-anilino-s-triazin-6-ylamino) stilbene disulfonate (available for example as Tinopal® DMS from BASF SE), disodium-2,2 '-bis- (phenyl-styryl) disulfonate (available for example 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 (available for example as Tinopal® UNPA from BASF SE), hexasodium 2,2 '- [vinylenbis [(3-sulphonato-4,1-phenylene) imino [6- (diethylamino) -1,3,5-triazine-4,2-diyl] imino]] bis (benzene-1 , 4-disulfonate) (available for example as Tinopal® SFP from BASF SE), 2,2 '- (2,5-thiophenediyl) bis [5-1,1-dimethylethyl) benzoxazole (available for example as Tinopal® SFP from BASF SE) and / or 2,5-bis (benzoxazol-2-yl) thiophene.

Suitable dye transfer inhibitors include polymers and copolymers of cyclic amines such as vinyl pyrrolidone and / or vinyl imidazole. Polymers suitable as a color transfer inhibitor include polyvinyl pyrrolidone (PVP), polyvinyl imidazole (PVI), copolymers of vinyl pyrrolidone and vinyl imidazole (PVP / PVI), polyvinyl pyridine-N-oxide, poly-N-carboxymethyl-4-pyridium chloride, polyethylene glycol-modified copolymers of vinyl pyridazidone as well as mixtures thereof. Polyvinylpyrrolidone (PVP), polyvinylimidazole (PVI) or copolymers of vinylpyrrolidone and vinylimidazole (PVP / PVI) are particularly preferably used as color transfer inhibitors. The polyvinylpyrrolidones (PVP) used preferably have an average molecular weight of 2,500 to 400,000 and are commercially available from ISP Chemicals as PVP K 15, PVP K 30, PVP K 60 or PVP K 90 or from BASF as Sokalan® HP 50 or Sokalan® HP 53 available. The copolymers of vinylpyrrolidone and vinylimidazole (PVP / PVI) used preferably have a molecular weight in the range from 5,000 to 100,000. A PVP / PVI copolymer is commercially available, for example from BASF under the name Sokalan® HP 56. Another extremely preferred color transfer inhibitor are polyethylene glycol-modified copolymers of vinylpyrrolidone and vinylimidazole, which are available, for example, from BASF under the name Sokalan® HP 66 are.

All substances and mixtures known for this can be used as fragrances or fragrances or perfume oils. For the purposes of this invention, the terms “fragrance (s)”, “fragrances” and “perfume oil (s)” are used synonymously. This means in particular all those substances or their mixtures which are perceived as odor by humans and animals, in particular are perceived by humans as a fragrance.

Perfumes, perfume oils or perfume oil constituents can be used as fragrance components. According to the invention, perfume oils or fragrances can contain individual fragrance compounds, e.g. B. the synthetic products of the type of esters, ethers, aldehydes, ketones, alcohols and hydrocarbons.

Fragrance compounds of the aldehyde type are for example adoxal (2,6,10-trimethyl-9-undecenal), anisaldehyde (4-methoxybenzaldehyde), cymal (3- (4-isopropyl-phenyl) -2-methylpropanal), ethylvanillin, florhydral ( 3- (3-isopropylphenyl) butanal), helional (3- (3,4-methylenedioxyphenyl) -2-methylpropanal), heliotropin, hydroxycitronellal, lauraldehyde, lyral (3- and 4- (4-hydroxy-4-methylpentyl) - 3- cyclohexene-1-carboxaldehyde), methylnonylacetaldehyde, Lilial (3- (4-tert-butylphenyl) -2-methylpropanal), phenylacetaldehyde, undecylenealdehyde, vanillin, 2,6,10-trimethyl-9-undecenal, 3-dodecen 1-al, alpha-n-amylcinnamaldehyde, melonal (2,6-dimethyl-5-heptenal), 2,4-dimethyl-3-cyclohexene-1-carboxaldehyde (triplal), 4-methoxybenzaldehyde, benzaldehyde, 3- (4-tert-butylphenyl) propanal, 2-methyl-3- (para-methoxyphenyl) propanal, 2-methyl-4- (2,6,6-timethyl-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] acetaldeh yd, 4-isopropylbenzylaldehyde, 1,2,3,4,5,6,7,8-octahydro-8,8-dimethyl-2-naphthaldehyde, 2,4-dimethyl-3-cyclohexene-1-carboxaldehyde, 2- Methyl 3- (isopropylphenyl) propanal, 1-decanal, 2,6-dimethyl-5-heptenal, 4- (tricyclo [5.2.1.0 (2,6)] -decylidene-8) -butanal, octahydro-4,7 -methane-1 H-indenecarboxaldehyde, 3-ethoxy-4-hydroxybenzaldehyde, para-ethyl-alpha, alpha-dimethylhydrocinnamaldehyde, alpha-methyl-3,4- (methylenedioxy) -hydrocinnamaldehyde, 3,4-methylenedioxybenzaldehyde, alpha-n- Hexylcinnamaldehyde, m-cymene-7-carboxaldehyde, alpha-methylphenylacetaldehyde, 7-hydroxy-3,7-dimethyloctanal, undecenal, 2,4,6-trimethyl-3-cyclohexene-1-carboxaldehyde, 4- (3) (4- Methyl-3-pentenyl) -3-cyclohexenecarboxaldehyde, 1-dodecanal, 2,4-dimethylcyclohexene-3-carboxaldehyde, 4- (4-hydroxy-4-methylpentyl) -3-cyclohexene-1-carboxaldehyde, 7-methoxy-3 , 7-dimethyloctan-1-al, 2-methyl-undecanal, 2-methyl-decanal, 1-nonanal, 1-octanal, 2,6,10-trimethyl-5,9-undecadienal, 2-methyl-3- (4- tert-butyl) propanal, dihydrocinnamaldehyde, 1-methyl-4- (4-methyl-3-pe ntenyl) -3-cyclohexene-1-carboxaldehyde, 5- or 6-methoxyhexahydro-4,7-methanindan-1- or -2-carboxaldehyde, 3,7-dimethyloctan-1-al, 1-undecanal, 10-undecene 1-al, 4-hydroxy-3-methoxybenzaldehyde, 1-methyl-3- (4-methylpentyl) -3-cyclohexenecarboxaldehyde, 7-hydroxy-3J-dimethyl-octanal, trans-4-decenal, 2,6-nonadienal, para-tolylacetaldehyde, 4-methylphenylacetaldehyde, 2-methyl-4- (2,6,6-trimethyl-1-cyclohexen-1-yl) -2-butenal, ortho-methoxycinnamaldehyde, 3,5,6-trimethyl-3- cyclohexene-carboxaldehyde, 3J-dimethyl-2-methylene-6-octenal, phenoxyacetaldehyde, 5,9-dimethyl-4,8-decadienal, peony aldehyde (6,10-dimethyl-3-oxa-5,9-undecadiene-1- al), hexahydro-4,7-methanindan-1-carboxaldehyde, 2-methyloctanal, alpha-methyl-4- (1-methylethyl) benzene acetaldehyde, 6,6-dimethyl-2-norpinene-2-propionaldehyde, para-methylphenoxyacetaldehyde, 2-methyl-3-phenyl-2-propen-1-al, 3,5,5-trimethylhexanal, hexahydro-8,8-dimethyl-2-naphthaldehyde, 3-propyl-bicyclo- [2.2.1] -hept- 5-en-2-carbaldehyde, 9-decenal, 3-methyl-5-phenyl-1-pentanal, Methylnonylacetaldehyde, hexanal and trans-2-hexenal.

Fragrance compounds of the ketone type are, for example, methyl beta-naphthyl ketone, musk indanone (1,2,3,5,6,7-hexahydro-1,1,2,3,3-pentamethyl-4H-inden-4-one), Tonalid (6-acetyl-1,1,2,4,4,7-hexamethyltetralin), alpha-damascone, beta-damascone, delta-damascone, iso-damascone, damascenone, methyl dihydrojasmonate, menthone, carvone, camphor, coavone (3 , 4,5,6,6-pentamethylhept-3-en-2-one), fenchone, alpha-ionone, beta-ionone, gamma-methyl-ionone, fleuramone (2-heptylcyclopen-tanone), 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) ), Methyl cedrenyl ketone, acetophenone, methylacetophenone, para-methoxyacetophenone, methyl beta-naphthyl ketone, benzylacetone, benzophenone, para-hydroxyphenylbutanone, celery ketone (3-methyl-5-propyl-2-cyclohexenone), 6-isopropyldecahydro- , Dimethyloctenone, Frescomenthe (2-butan-2-yl-cyclohexan-1-one), 4- (1-ethoxyvinyl) -3,3,5,5-tetramethylcyclohexanone, methylheptenone, 2- (2- (4-methyl- 3-cyclohe xen-1-yl) propyl) cyclopentanone, 1- (p-menthen-6 (2) yl) -1-propanone, 4- (4-hydroxy-3-methoxyphenyl) -2-butanone, 2-acetyl-3, 3-dimethylnorbornane, 6,7-dihydro-1,1,2,3,3-pentamethyl-4 (5H) -indanone, 4-damascol, dulcinyl (4- (1,3-benzodioxol-5-yl) butane 2-one), hexalone (1- (2,6,6-trimethyl-2-cyclohexene-1-yl) -1,6-heptadien-3-one), isocyclemonE (2-acetonaphthon-1,2,3, 4,5,6,7,8-octahydro-2,3,8,8-tetramethyl), methyl nonyl ketone, methylcyclocitron, methyl lavender ketone, orivon (4-tert-amyl-cyclohexanone), 4-tert-butylcyclohexanone, Delphon (2- pentyl-cyclopentanone), Muscon (CAS 541-91-3), neobutenone (1- (5,5-dimethyl-1-cyclohexenyl) pent-4-en-1-one), Plicaton (CAS 41724-19-0) , Velouton (2,2,5-trimethyl-5-pentylcyclopentan-1-one), 2,4,4,7-tetramethyl-oct-6-en-3-one and tetrameran (6,10-dimethylundecen-2- on).

Fragrance compounds of the alcohol type are, for example, 10-undecen-1-ol, 2,6-dimethylheptan-2-ol, 2-methyl-butanol, 2-methylpentanol, 2-phenoxyethanol, 2-phenylpropanol, 2-tert.-butycyclohexanol, 3,5,5-trimethylcyclohexanol, 3-hexanol, 3-methyl-5-phenyl-pentanol, 3-octanol, 3-phenyl-propanol, 4-heptenol, 4-isopropyl-cyclohexanol, 4-tert.-butycyclohexanol, 6 , 8-dimethyl-2-nona-nol, 6-nonen-1-ol, 9-decen-1-ol, α-methylbenzyl alcohol, α-terpineol, amyl salicylate, benzyl alcohol, benzyl salicylate, β-terpineol, butyl salicylate, citronellol, cyclohexyl salicyl , Decanol, dihydromyrcenol, dimethylbenzylcarbinol, dimethylheptanol, dimethyloctanol, ethyl salicylate, ethyl vanilin, eugenol, farnesol, geraniol, heptanol, hexyl salicylate, isoborneol, isoeugenol, isopulegol, non-hexanol, menthol, n-hexanol, n-neranol, n-alcohol, n-hexanol, n-hexanol, menthol, myyranol, n-hexanol, n-neranol, n-hexanol, n-hexanol, n-alcohol, n-hexanol, n-hexanol, n-hexanol, n-neranol, n-hexanol, n-hexanol, -7-ol, phenylethyl alcohol, phenol, phenyl salicylate, tetrahydrogeraniol, tetrahydrolinalool, thymol, trans-2-cis-6-nonadicnol, trans-2-nonen-1-ol, trans-2- Octenol, Undecanol, Vanillin, Champiniol, Hexenol and Cinnamon Alcohol.

Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate (DMBCA), phenylethyl acetate, benzyl acetate, ethylmethylphenylglycinate, allylcyclohexylglycinate, allylcyclohexylpropionate, allylcyclohexylpropionate, allylcyclohexylpropionate, allylcyclohexylpropionate, benzacylate, benzacylpropionate, benzacylate, and jasacylsacylpropionate, jasacylate.

The ethers include, for example, benzyl ethyl ether and ambroxan. The hydrocarbons mainly include terpenes such as limonene and pinene.

Mixtures of different fragrances are preferably used, which together produce an appealing fragrance note. Such a mixture of fragrances can also be referred to as perfume or perfume oil. Such perfume oils can also contain natural fragrance mixtures, such as are available from vegetable sources.

The fragrances of vegetable origin include essential oils such as angelica root oil, anise oil, arnica flower oil, basil oil, bay oil, champaca flower oil, citrus oil, noble fir oil, noble fir cone oil, elemi oil, eucalyptus oil, fennel oil, spruce needle oil, guajun oil, gourd oil, gherkin oil, galbanum oil, gherkin oil, gjajun oil , Ginger oil, iris oil, jasmine oil, kajeput oil, calamus oil, chamomile oil, camphor oil, kanaga oil, cardamom oil, cassia oil, pine needle oil, copaiva balsam oil, coriander oil, spearmint oil, caraway oil, cumin oil, labdanum oil, lavender oil, lemon linden oil, almond blossom oil , Muscatel oil, myrrh oil, clove oil, neroli oil, niaouli oil, olibanum oil, orange blossom oil, orange peel oil, origanum oil, palmarosa oil, patchouli oil, Peru balsam oil, petitgrain oil, pepper oil, peppermint oil, allspice oil, celery oil, sage oil, starch oil, rosemary oil, sandstone oil, rosemary oil , Turpentine oil, thuja oil, thyme oil, verbena oil, vetiver oil, juniper berry oil, W ermut 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, alpha-amylcinnamaldehyde, anethole, anisaldehyde, anisalcohol, anisole, anthranilic acid methyl ester, benzyl acetophenone, methyl ester, benzyl acetophenone. Benzophenone, benzyl alcohol, benzyl acetate, benzyl benzoate, benzyl formate, benzyl valerianate, borneol, bornyl acetate, boisambrene forte, alpha-bromostyrene, n-decyl aldehyde, n-dodecyl aldehyde, eugenol, eugenol methyl ether, eucalyptyl acetate, geranium acid ethyl acetate, geranium acid ethyl acetate, geranium acetyl acetate, fenchone, fencheptanyol , Heptaldehyde, hydroquinone dimethyl ether, hydroxycinnamaldehyde, hydroxycinnamic alcohol, indole, iron, isoeugenol, isoeugenol methyl ether, isosafrole, jasmone, camphor, karvakrol, karvon, p- Cresol methyl ether, coumarin, p-methoxyacetophenone, methyl-n-amyl ketone, methyl anthranilic acid methyl ester, p-methylacetophenone, methylchavikol, p-methylquinoline, methyl-beta-naphthyl ketone, methyl-n-nonylacetaldehyde, methyl-n-nonyl ketone, muscone, beta beta-naphthol methyl ether, nerol, n-nonylaldehyde, nonyl alcohol, n-octylaldehyde, p-oxy-acetophenone, pentadecanolide, beta-phenylethyl alcohol, phenylacetic acid, pulegon, safrol, salicylic acid isoamyl ester, salicylic acid methyl ester, salicylic acid methyl ester, salicylic acid methyl ester, salicloyl hexyl ester, santyl hexyl ester Terpineol, thyme, thymol, troenan, gamma-undelactone, vanillin, veratrumaldehyde, cinnamaldehyde, cinnamon alcohol, cinnamic acid, ethyl cinnamate, benzyl cinnamate, diphenyloxide, limonene, linalool, linalyl acetate, and - propionate, melusate, menthol, menthol, , Phenylacetaldehyde, terpinylacetate, citral, citronellal, and mixtures thereof.

Mixtures of the substances mentioned can also be used.

• Kopfnote: Dampfdruck bei 25°C: >0,0133 kPa
• Herznote: Dampfdruck bei 25°C: 0,0133 bis 0,000133 kPa
• Basisnote: Dampfdruck bei 25°C: <0,000133 kPa

In order to be perceptible, an odoriferous substance must be volatile, with the molecular weight also playing an important role in addition to the nature of the functional groups and the structure of the chemical compound. Most fragrances, for example, have molar masses of up to about 200 Dalton, while molar masses of 300 Dalton and above are an exception. Due to the different volatility of odoriferous substances, the smell of a perfume or fragrance composed of several odoriferous substances changes during evaporation, whereby the olfactory impressions are classified as “top note”, “middle note” or “body”. and “base note” (end note or dry out). Analogous to the description in the international patent publication WO 2016/200761 A2 top, heart and base notes can be determined based on their vapor pressure (using the in the WO 2016/200761 can be determined as follows:

• Top note: vapor pressure at 25 ° C:> 0.0133 kPa
• Heart note: vapor pressure at 25 ° C: 0.0133 to 0.000133 kPa
• Base note: vapor pressure at 25 ° C: <0.000133 kPa

The firmly adhering fragrances that can be used in the context of the present invention include, for example, the essential oils such as angelica root oil, anise oil, arnica flower oil, basil oil, bay oil, bergamot oil, champaca flower oil, noble fir oil, noble fir cone oil, elemi oil, eucalyptus oil, fennel oil, spruce needle oil, Ginger grass oil, guaiac oil, gurjun balsam oil, helichrysum oil, Ho oil, ginger oil, iris oil, kajeput oil, calamus oil, chamomile oil, camphor oil, kanaga oil, cardamom oil, cassia oil, pine needle oil, copalva balsam oil, coriander oil, lime, lavender oil, almond oil, caraway seed oil, lime oil, cumin oil, almond oil Melissa oil, musk seed oil, myrrh oil, clove oil, neroli oil, niaouli oil, olibanum oil, orange oil, origanum oil, palmarosa oil, patchouli oil, Peru balsam oil, petitgrain oil, pepper oil, peppermint oil, allspice oil, pine oil, celery oil, rosemary oil, sandalwood oil, rose oil, rosemary oil, sandalwood oil Thuja oil, thyme oil, verbena oil, vetiver oil, juniper berry oil, wormwood oil, wintergreen oil, Yl ang-ylang oil, hyssop oil, cinnamon oil, cinnamon leaf oil, citronella oil, lemon oil and cypress oil.

High-boiling or solid fragrances of natural or synthetic origin include, for example: ambrettolide, α-amylcinnamaldehyde, anethole, anisaldehyde, aniseed alcohol, anisole, anthranilic acid methyl ester, acetophenone, benzylacetone, benzaldehyde, benzoic acid ethyl ester, benzophenone, benzyl alcohol, benzyl acetate, benzyl valyl benzoate, Bornyl acetate, α-bromostyrene, n-decylaldehyde, n-dodecyl aldehyde, eugenol, eugenol methyl ether, eucalyptol, farnesol, fenchone, fenchyl acetate, geranyl acetate, geranyl formate, heliotropine, methyl heptinic acid, methyl ester, heptaldehyde, hydroxyzimethyl ether, hydroxyzimethylether, hydroxyzimethylether, hydroxyzimethylether Iron, isoeugenol, isoeugenol methyl ether, isosafrol, jasmone, camphor, carvakrole, carvone, p-cresol methyl ether, coumarin, p-methoxyacetophenone, methyl-n-amyl ketone, methyl anthranilic acid methyl ester, p-methylaceto-phenone, methyl chavikol, p-methylquinoline, methyl chavikol, p-methylquinoline β-naphthyl ketone, methyl-n-nonylacetaldehyde, methyl-n-nonyl ketone, muscon, β-N aphthol ethyl ether, β-naphthol methyl ether, nerol, nitrobenzene, n-nonyl aldehyde, nonyla alcohol, n-octyl aldehyde, p-oxy-acetophenone, pentadecanolide, β-phenyl-ethyl alcohol, phenylacetaldehyde-dimethyl acetal, phenylacetic acid, salicyl isoyl ester, salicyl isoethyl ester, pulegyl, saicethyl ester Cyclohexyl salicylate, santalol, skatol, terpineol, thyme, thymol, γ-undelactone, vanilin, veratrumaldehyde, cinnamaldehyde, cinnamic alcohol, cinnamic acid, ethyl cinnamate, benzyl cinnamate

The more volatile fragrances include, in particular, the lower-boiling fragrances of natural or synthetic origin, which can be used alone or in mixtures. Examples of more volatile fragrances are alkyl isothiocyanates (alkyl mustard oils), butanedione, limonene, linalool, linaylacetate and propionate, menthol, menthone, methyl-n-heptenone, phellandrene, phenylacetaldehyde, terpinylacetate, citral, citronellal.

Fragrance compounds of the aldehyde type that can be used with preference 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).

In addition or as an alternative to the aforementioned fragrances, those in the WO 2016/200761 A2 described fragrances, in particular the fragrances mentioned in Tables 1, 2 and 3, as well as the modulators listed in Tables 4a and 4b are used. This publication is incorporated herein by reference in its entirety.

1. (a) Textilpflegestoffe, wie vorzugsweise Silikonöle, und/oder
2. (b) Hautpflegestoffe, wie vorzugsweise Vitamin E, natürliche Öle und/oder kosmetische Öle.

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

1. (a) Textile care materials, such as preferably silicone oils, and / or
2. (b) Skin care substances, such as preferably vitamin E, natural oils and / or cosmetic oils.

1. a) Wachse wie beispielsweise Carnauba, Spermaceti, Bienenwachs, Lanolin und/oder Derivate derselben und andere.
2. b) Hydrophobe Pflanzenextrakte
3. c) Kohlenwasserstoffe wie beispielsweise Squalene und/oder Squalane
4. d) Höhere Fettsäuren, vorzugsweise solche mit wenigstens 12 Kohlenstoffatomen, beispielsweise Laurinsäure, Stearinsäure, Behensäure, Myristinsäure, Palmitinsäure, Ölsäure, Linolsäure, Linolensäure, Isostearinsäure und/oder mehrfach ungesättigte Fettsäuren und andere.
5. e) Höhere Fettalkohole, vorzugsweise solche mit wenigstens 12 Kohlenstoffatomen, beispielsweise Laurylalkohol, Cetylalkohol, Stearylalkohol, Oleylalkohol, Behenylalkohol, Cholesterol und/oder 2-Hexadecanaol und andere.
6. f) Ester, vorzugsweise solche wie Cetyloctanoate, Lauryllactate, Myristyllactate, Cetyllactate, Isopropylmyristate, Myristylmyristate, Isopropylpalmitate, Isopropyladipate, Butylstearate, Decyloleate, Cholesterolisostearate, Glycerolmonostearate, Glyceroldistearate, Glyceroltristearate, Alkyllactate, Alkylcitrate und/oder Alkyltartrate und andere.
7. g) Lipide wie beispielsweise Cholesterol, Ceramide und/oder Saccharoseester und andere.
8. h) Vitamine wie beispielsweise die Vitamine A, C und E, Vitaminalkylester, einschließlich Vitamin-C-Alkylester und andere.
9. i) Sonnenschutzmittel
10. j) Phospholipide
11. k) Derivate von alpha-Hydroxysäuren
12. l) Germizide für den kosmetischen Gebrauch, sowohl synthetische wie beispielsweise Salicylsäure und/oder andere als auch natürliche wie beispielsweise Neemöl und/oder andere.
13. m) Silikone
14. n) Natürliche Öle, z.B. Mandelöl sowie Mischungen jeglicher vorgenannter Komponenten.

Skin care active ingredients are all those active ingredients which give the skin a sensory and / or cosmetic advantage. Skin care active ingredients are preferably selected from the following substances:

1. a) waxes such as carnauba, spermaceti, beeswax, lanolin and / or derivatives thereof and others.
2. b) Hydrophobic plant extracts
3. c) Hydrocarbons such as squalene and / or squalane
4. d) Higher fatty acids, preferably those with at least 12 carbon atoms, for example lauric acid, stearic acid, behenic acid, myristic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid, isostearic acid and / or polyunsaturated fatty acids and others.
5. e) Higher fatty alcohols, preferably those with at least 12 carbon atoms, for example lauryl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, behenyl alcohol, cholesterol and / or 2-hexadecanol and others.
6. f) Esters, preferably those such as cetyloctanoate, lauryl lactate, myristyl lactate, cetyl lactate, isopropyl myristate, myristyl myristate, isopropyl palmitate, isopropyl adipate, butyl stearate, decyl oleate, cholesterol isostearate, glycerol monostearate and / or glycerol monostearate, glycerol tartarate and / or alkyl citrate tr
7. g) lipids such as cholesterol, ceramides and / or sucrose esters and others.
8. h) Vitamins such as vitamins A, C and E, vitamin alkyl esters, including vitamin C alkyl esters and others.
9. i) sunscreens
10. j) phospholipids
11. k) derivatives of alpha-hydroxy acids
12. l) Germicides for cosmetic use, both synthetic, such as salicylic acid and / or others, and natural, such as neem oil and / or others.
13. m) silicones
14. n) Natural oils, such as almond oil and mixtures of any of the aforementioned components.

It may be desirable to keep the active ingredients that have a positive effect on the feeling of the skin or also other sensitive active ingredients, such as perfumes, spatially separated from other constituents of the agent until they are used. An elegant method for incorporating such sensitive, chemically or physically incompatible or volatile ingredients consists in the use of microcapsules in which these ingredients are enclosed in a stable manner for storage and transport and from which they are released mechanically, chemically, thermally or enzymatically for or during use . In a preferred embodiment, therefore, one or more of the active ingredients and / or perfumes and / or fragrances that have a positive effect on the feeling on the skin is fully or partially incorporated into microcapsules.

Microcapsules are finely dispersed liquid or solid phases encased in film-forming polymers, during the production of which the polymers precipitate on the material to be encased (active ingredient) after emulsification and coacervation or interfacial polymerisation. The active ingredient is encased in a shell-like manner by a solid membrane (microcapsule in the narrower sense) or enclosed by a matrix (microsphere or sphere). In the following, the term microcapsule is used in a summarizing sense for both variants. Such capsules are usually microscopic (<50 µm) and are sometimes referred to as nanocapsules or nanospheres; they can be dried like powders. Furthermore, larger capsules or pearls (> 0.5 mm) that are visible to the naked eye and filled with active ingredients can also be produced.

All surfactant-stable capsules and capsule materials or spheres and spherical materials available on the market can be used as microcapsules, such as the commercially available Primasphere® (chitosan and agar or carboxymethyl cellulose) and Primasponge® (alginate, chitosan, agar) from BASF, Hallcrest Microcapsules ® (gelatine, gum arabic) from Hallcrest, Inc. (US), Coletica Thalaspheres® (maritime collagen) from Coletica (FR), Lipotec Millicapseln® (alginic acid, agar-agar) from Lipotec SA (ES), Induchem Unispheres® (lactose, microcrystalline cellulose, hydroxypropylmethyl cellulose) and Unicerin® C30 (lactose, microcrystalline cellulose, hydroxypropylmethyl cellulose) from Induchem AG (CH), Kobo Glycospheres (modified starch, fatty acid esters, phospholipids) and Softspheres® Agar-agar) from Kobo (US) and Kuhs Probiol Nanospheres (phospholipids) from Kuhs (DE) and others. The microcapsules can have any shape in the context of production, but they are preferably egg-shaped or ellipsoidal or in particular approximately spherical. The diameter along its greatest spatial extent can, depending on the active ingredient and application, be on average between 100 nm (visually not recognizable as a capsule) and 10 mm. The preferred mean diameter is in the range between 0.1 mm and 7 mm; microcapsules with a mean diameter between 0.4 mm and 5 mm are particularly preferred. To improve the appearance, dyes, color pigments or pearlescent components can also be added.

The release of the active ingredient from the microcapsules can take place mechanically by rubbing the microcapsules during the cleaning process. Other options are the release of the active ingredient by changing the temperature (adding it to warm washing liquor), by shifting the pH value, changing the electrolyte content, etc.

Dyes suitable in the context of the present invention are divided into anionic, nonionic and cationic dyes.

Anionic dyes are known to those skilled in the art as acid dyes. Corresponding representatives of this class of dyes can be found, for example, in the Color Index (short: C.I.) published by the British Society of Dyers and Colourists and the American Association of Textile Chemists and Colorists. The inventive limiting quantity range of the anionic dyes thus relates at least to all of the acid dyes mentioned in the Color Index as anionic dyes. The commercial products Basacid Blue V20, Sensient Blue, Tartrazine Acid Yellow 23, Sunset Yellow E110, Iragon Blue ABL80, Sanolin Violet E 2 R and Vibracolor violet AVI 43 are listed as examples

Nonionic dyes suitable according to the invention are selected from at least one nonionic azo dye. Exemplary nonionic dyes include, but are not limited to, Liquitint® Violet 200, Liquitint® Violet CT, Liquitint® Blue HP, Liquitint® Cyan 15, and Liquitint® Brillant Orange (both from Milliken).

Preferred cationic dyes are the basic dyes (according to the Color Index: Basic Dyes). Cationic dyes particularly preferred according to the invention are selected from at least one dye from the group formed by cationic azo dye, xanthene dye, phenazine dye, phenoxazine dye, thiazine dye, polymethine dye, diarylcarbenium dye and triarylmethane dye. Examples are the dyes methylene blue, rhodamine B, vibracolor citrus yellow and crystal violet

The dye can also be applied to the textile material according to the invention as a component of the highly concentrated enzyme formulation.

The detergents and cleaning agents described herein in the form of a textile material, as described above, are in some embodiments preferably pre-packaged into metering units. These dosing units preferably include the amount of washing or washing necessary for a cleaning cycle active cleaning substances. In preferred embodiments the textile material is in the form of a unit dose.

In some embodiments, prefabricated dosing units can have a water-soluble coating. In preferred embodiments, the textile material according to the invention is in particular encased by a water-soluble film. The agent described herein is particularly preferably present in a water-soluble film envelope if the textile material itself is water-soluble, as defined above.

The water-soluble envelope is preferably formed from a water-soluble film material which is selected from the group consisting of polymers or polymer mixtures. The envelope can be formed from one or from two or more layers of the water-soluble film material. The water-soluble film material of the first layer and the further layers, if any, can be the same or different.

It is preferred that the water-soluble casing contains polyvinyl alcohol or a polyvinyl alcohol copolymer. Water-soluble casings which contain polyvinyl alcohol or a polyvinyl alcohol copolymer have good stability with sufficiently high water solubility, in particular cold water solubility.

Suitable water-soluble films for producing the water-soluble envelope 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 gmol ^-1 , preferably from 20,000 to 500,000 gmol ^-1 , particularly preferably from 30,000 to 100,000 gmol ^-1 and in particular from 40,000 to 80,000 gmol ^-1 .

The production of polyvinyl alcohol is usually done by hydrolysis of polyvinyl acetate, since the direct synthesis route is not possible. The same applies to polyvinyl alcohol copolymers which are produced from polyvinyl acetate copolymers. It is preferred if at least one layer of the water-soluble coating 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, polystyrene sulfonates, polyurethanes, polyesters, polyethers, polylactic acid or mixtures of the above polymers can also be added to a polyvinyl alcohol-containing film material suitable for producing the water-soluble envelope be. A preferred additional polymer are polylactic acids.

Preferred polyvinyl alcohol copolymers include, 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 include vinyl alcohol as well as an ethylenically unsaturated carboxylic acid, its salt or its ester. Such polyvinyl alcohol copolymers particularly preferably contain acrylic acid, methacrylic acid, acrylic acid esters, methacrylic acid esters or mixtures thereof in addition to vinyl alcohol.

It can be preferred that the film material contains further additives. The film material can for example contain plasticizers such as dipropylene glycol, ethylene glycol, diethylene glycol, propylene glycol, glycerine, sorbitol, mannitol or mixtures thereof. Further additives include, for example, release aids, fillers, crosslinking agents, surfactants, antioxidants, UV absorbers, antiblocking agents, anti-stick agents or mixtures thereof.

Suitable water-soluble films for use in the water-soluble envelopes of the water-soluble packaging according to the invention are films which are 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 films VF-HP from Kuraray.

The use of the flat textile material according to the invention, as described above, for washing and cleaning purposes, preferably for washing, caring for or conditioning textiles, as defined herein, represents a further subject matter of the invention.

Another subject matter of the invention is a method for washing, caring for or conditioning textiles, characterized in that a flat textile material, as described herein, is used in at least one method step. The subject of the present application is therefore in particular a method for washing textiles in an automatic washing machine or for cleaning dishes in a dishwasher, in which the agent according to the invention is used while running a washing or dishwashing program before the start of the main wash cycle or during the main wash cycle in the interior of a washing machine or dishwasher is metered. The metering in or introduction of the agent according to the invention into the interior of the washing machine or dishwasher can take place manually; alternatively, the agent can be metered into the interior of the washing machine or dishwasher by means of the metering chamber.

In general, processes for cleaning textiles are characterized in that various active cleaning substances are applied to the items to be cleaned in several process steps and washed off after the exposure time, or that the items to be cleaned are treated with the agent in some other way. The same applies to processes for cleaning all materials other than textiles, in particular hard surfaces. All conceivable washing or cleaning processes can be enriched in at least one of the process steps by the use of a washing or cleaning agent according to the invention in the form of a flat textile material, as described herein, and then represent embodiments of the present invention textile material according to the invention can in principle also be used advantageously in combination with other washing and cleaning agents in corresponding processes.

The present invention relates to both manual and machine washing and cleaning processes.

All facts, subjects and embodiments that are described for means according to the invention are also applicable to this subject matter of the invention. For this reason, reference is expressly made at this point to the disclosure at the appropriate point with the note that this disclosure also applies to the above methods according to the invention.

Examples

The and show single-layer textile materials according to the invention (embodiment: cloth, each 250 mm × 118 mm), on the surface of which a highly concentrated enzyme formulation, as defined herein, was printed as a colored pattern.

shows a cross-sectional view (sketch) of a two-layer textile material according to the invention, the highly concentrated enzyme formulation, as defined herein, being applied in the form of an enzyme slurry between the two textile layers positioned flat on top of one another.

shows a cross-sectional view (sketch) of a three-layer textile material according to the invention, the middle textile layer being impregnated with the highly concentrated enzyme formulation, as defined herein, in the form of an enzyme slurry and located between the two other textile layers. All three layers are positioned flat on top of each other and form a kind of "sandwich".

QUOTES INCLUDED IN THE DESCRIPTION

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

Patent literature cited

• WO 2008086916 [0062]
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Non-patent literature cited

• ISO 9073-1 [0042]
• A. G. Gornall, C. S. Bardawill and M.M. David, J. Biol. Chem., 177 (1948), pp. 751-766 [0051]
• see M. Bender et al., J. Am. Chem. Soc. 88, 24 (1966), pp. 5890-5913 [0051]

Claims (12)

Flat textile material, characterized in that the textile material has at least one highly concentrated enzyme formulation comprising at least one enzyme on at least part of its surface, the enzyme content in the highly concentrated enzyme formulation being approximately 10 to approximately 70% by weight, based on the total weight of the enzyme formulation and based on active protein. The flat textile material after Claim 1 , characterized in that the highly concentrated enzyme formulation is in liquid, preferably pasty, slurry form. The flat textile material after Claim 2 , characterized in that the slurry comprises the enzyme in particulate, granulated form, the particles preferably having an average particle size D 50 of approximately 10 to 5000 μm and the particles being dispersed in the slurry. The flat textile material according to one of the Claims 1 to 3 , characterized in that the highly concentrated enzyme formulation in an amount of about 0.0001 to about 5 wt .-%, preferably about 0.005 to about 2.5 wt .-%, more preferably about 0.01 to about 1.5 wt .-% %, is present, based in each case on the total weight of the textile material. The flat textile material according to one of the Claims 1 to 4th , characterized in that the flat textile material is in the form of a cloth, the cloth being woven, not woven, knitted or braided. The flat textile material according to one of the Claims 1 to 5 , characterized in that the textile material is water-soluble or water-insoluble. The flat textile material according to one of the Claims 1 to 6th , characterized in that the flat textile material comprises at least two flat textile material layers and the highly concentrated enzyme formulation is located between the at least two flat textile materials positioned one on top of the other. The flat textile material according to one of the Claims 1 to 7th , characterized in that the textile material has at least one further active substance, preferably at least two further active substances, selected from the group consisting of surfactants, further enzymes, UV stabilizers, fragrances (perfume), dyes, color-trapping compounds, color transfer inhibitors, optical brighteners, preservatives, Bitter substances, disinfectants, defoamers, encapsulated ingredients (eg encapsulated perfume), pH adjusters and additives that improve or care for the skin. The flat textile material according to one of the Claims 1 to 8th , characterized in that it is a textile treatment agent. The flat textile material according to one of the Claims 1 to 9 , characterized in that the textile material is in the form of a unit dose, preferably wrapped in a water-soluble film. Use of the flat textile material according to one of the Claims 1 to 10 for washing and cleaning purposes, preferably for washing, caring for or conditioning textiles. A method for washing, caring for or conditioning textiles, characterized in that a flat textile material according to one of the at least one method step Claims 1 to 10 is applied.

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