Washing and cleaning agents comprising environmentally compatible microcapsules

Abstract

The invention relates to washing and cleaning agents comprising: microcapsules comprising a core material, the core material comprising at least one fragrance; and a shell, the shell consisting of at least one first layer and one second layer, the chemical compositions of which differ from one another, and the shell having a biodegradability, measured in accordance with OECD 301 F, of at least 40%. The invention further relates to the use of such agents in methods for conditioning textiles or for cleaning textiles and / or hard surfaces.

Description

AREA OF INVENTION

[0001] The invention relates to comprehensively stable microcapsules for washing and cleaning agents with environmentally friendly wall materials. BACKGROUND OF THE INVENTION

[0002] Microencapsulation is a versatile technology. It offers solutions for numerous innovations – from the paper industry to household products, microencapsulation enhances the functionality of a wide variety of active substances. Encapsulated active ingredients can be used more economically and improve the sustainability and environmental compatibility of many products. However, the polymeric wall materials of the microcapsules themselves vary considerably in their environmental compatibility. Microcapsule walls based on the natural product gelatin, and therefore completely biodegradable, have long been used in carbonless copy paper. A process for gelatin encapsulation, developed as early as the 1950s, is disclosed in US 2,800,457. Since then, a multitude of variations regarding materials and process steps have been described. Furthermore, biodegradable or...Enzymatically degradable microcapsule walls are used to utilize enzymatic degradation as a method for releasing the core material. Such microcapsules are described, for example, in WO 2009 / 126742 A1 or WO 2015 / 014628 A1. KR 20040094930 A discloses a microcapsule containing a washing or cleaning agent, consisting of a core material, e.g., a fragrance, and a capsule wall composed of a polymer inner layer of urethane or urea and a chitosan outer layer. The microcapsules are identified as biodegradable.

[0003] WO 2011 / 110368 A2 discloses microcapsules whose capsule wall is obtainable by reaction with: phloroglucinol / melamine, glutaraldehyde, AMPS / methoxy-molyethylene glycol monoacrylate copolymer, or resorcinol / melamine, glutaraldehyde, AMPS / methoxy-polyethylene glycol monoacrylate copolymer.

[0004] However, such microcapsules are unsuitable for many industrial applications and household products. This is because natural material-based microcapsules do not meet the diffusion tightness, chemical resistance, and temperature resistance required for, for example, detergents and cleaning agents, adhesive systems, paints and dispersions, nor do they meet the required core material loading requirements. In these so-called high-demand areas, conventional organic polymers such as melamine-formaldehyde polymers (see, for example, EP 2 689 835 A1, WO 2018 / 114056 A1, WO 2014 / 016395 A1, WO 2011 / 075425 A1 or WO 2011 / 120772 A1); polyacrylates (see, for example, WO 2014 / 032920 A1, WO 2010 / 79466 A2); polyamides; Polyurethane or polyureas (see, for example, WO 2014 / 036082 A2 or WO 2017 / 143174 A1) are used. Capsules made from such organic polymers possess the required diffusion tightness, stability, and chemical resistance.However, these organic polymers are only enzymatically or biodegradable to a very limited extent.

[0005] Various approaches are described in the prior art in which biopolymers are combined as an additional component with the organic polymers of the microcapsule shell for use in demanding applications. However, the primary goal is not to produce biodegradable microcapsules, but rather to modify the release, stability, or surface properties of the microcapsules. For example, WO 2014 / 044840 A1 describes a process for producing two-layer microcapsules with an inner polyurea layer and an outer gelatin-containing layer. The polyurea layer is produced by polyaddition on the inner surface of the gelatin layer, which is obtained through coacervation.According to the description, the resulting capsules possess the necessary stability and sealing properties for use in detergents and cleaning agents due to the polyurea layer, and additionally, the gelatin provides them with stickiness to adhere to surfaces. Specific stability and resistance values ​​are not mentioned. However, a disadvantage of polyurea capsules is the unavoidable side reaction of the core materials with the diisocyanates used to produce the urea, which must be added to the oil-based core.

[0006] On the other hand, prior art also describes microcapsules based on biopolymers which, by adding a protective layer, achieve improved sealing or stability against environmental influences or a targeted adjustment of delayed release behavior. For example, WO 2010 / 003762 A1 describes particles with a core-shell-shell structure. Inside each particle, the core contains a sparingly water-soluble or water-insoluble organic active ingredient. The shell directly enclosing the core contains a biodegradable polymer, and the outer shell contains at least one metal or semimetal oxide. While this structure does result in a biodegradable shell, the microcapsules are nevertheless used in food, cosmetics, or pharmaceuticals according to WO 2010 / 003762 A1, but are unsuitable for the demanding applications according to the invention due to insufficient sealing. SUMMARY OF THE INVENTION

[0007] The present invention is based, among other things, on the discovery that microcapsules can be produced by means of a multilayer shell structure. These microcapsules are essentially biodegradable yet possess sufficient stability and sealing properties to be used in detergents and cleaning agents. This is achieved by having a first stabilizing and structural layer constitute the main part of the capsule shell. This first layer consists of naturally occurring and readily biodegradable materials such as gelatin or alginate, or of materials ubiquitous in nature. This first layer is combined with a second sealing layer, which can consist of materials known for microencapsulation, such as melamine-formaldehyde or methacrylate. The second layer can be arranged either on the outside or on the inside of the first layer.Preferably, the second layer is arranged on the inside of the first layer. The inventors have succeeded in designing the sealing second layer with a previously unattainable minimal wall thickness while still ensuring sufficient sealing, as shown in Example 5. This keeps its proportion of the total wall very small, so that the microcapsule wall exhibits a biodegradability of at least 40% as measured according to OECD 301 F, as shown in Examples 6 and 7.

[0008] Thus, according to a first aspect, the invention relates comprehensively to washing and cleaning agents: a) Microcapsules comprising a core material, wherein the core material comprises at least one fragrance, and a shell, wherein the shell consists of at least a first and a second layer having different chemical compositions, and wherein the shell has a biodegradability, as measured according to OECD 301 F in accordance with the measurement method in Example 6 of the description, of at least 40% over a period of 28 days; and, optionally, b) at least one further component selected from surfactants, enzymes, builders and lift-enhancing agents, wherein the second layer is a polymer comprising an aldehydic component, an aromatic alcohol and an amine component, wherein the second layer contains an aromatic alcohol selected from the group consisting of resorcinol, phloroglucinol and aminophenol, and the proportion of the aromatic alcohol based on the total weight of the second layer is in the range of 1.0 to 20 wt%, wherein the proportion of the aldehydic component for wall formation based on the total weight of the second shell is in the range of 5 to 50 wt%, and wherein the proportion of the amine component based on the total weight of the second layer is in the range of 20% to 85 wt%.

[0009] Furthermore, in another aspect, the invention relates to the use of washing and cleaning agents according to the first aspect in a method for cleaning textiles and / or hard surfaces. FIGURES

[0010] Fig. 1shows a light microscopic image of the capsules MK 1 used according to the invention at 50x and 500x magnification taken with an Olympus 5 BX 50 microscope. Fig. 2 Figure 1 shows a light microscopic image of the reference microcapsule MK 2 (melamine-formaldehyde) at 50x and 500x magnification taken with an Olympus BX 50 microscope. Fig. 3 Figure 1 shows a light microscopic image of the reference microcapsule MK 3 (gelatin-alginate) at 50x and 500x magnification taken with an Olympus BX 50 microscope. Fig. 4Figure 1 shows a diagram of the course of the biodegradation of the MK 1 microcapsule used according to the invention over 28 days (shown as a solid line). (a) shows the result according to OECD 301F. The degradation of ethylene glycol is shown as a dashed line as a positive control. (b) shows the result according to OECD 302C. The degradation of aniline is shown as a dashed line as a positive control. Fig. 5 Figure 1 shows a comparison of the biodegradation process over 28 days of the microcapsule MK 1 according to the invention, the MF reference microcapsule MK 2, and the gelatin / alginate reference microcapsule MK 3. A measurement according to OECD 301F for the first 10 days of biodegradation is shown. The time window in which the microcapsule MK 1 according to the invention reaches a degradation level of 60% is also indicated. Fig. 6Figure 1 shows a light microscopic image of the capsules MK 4 according to the invention at 50x and 500x magnification taken with an Olympus BX 50 microscope. Fig. 7 Figure 1 shows a diagram of the course of biodegradation according to OECD 301 F over 60 days after washing of the inventive microcapsule MK 1 over time, as well as the MF reference microcapsule MK 2 and the gelatin / alginate reference microcapsule MK 3. The degradation of ethylene glycol is shown as a dashed line, and the degradation of walnut shell flour as a dotted line, both as positive controls. DETAILED DESCRIPTION OF THE INVENTION Definitions

[0011] "Biodegradability" refers to the ability of organic chemicals to be broken down biologically, i.e., by living organisms or their enzymes. Ideally, this chemical metabolism proceeds completely to mineralization, but it can also stop at the level of degradable transformation products. The OECD guidelines for testing chemicals are generally accepted and are also used in the context of chemical registration. The tests of the OECD 301 (AF) test series demonstrate rapid and complete biodegradation under aerobic conditions. Different test methods are available for highly soluble, poorly soluble, and volatile substances. In particular, the manometric respiration test (OECD 301 F) is used during the registration process. Inherent biodegradability can be determined using the OECD 302 standard, for example, the MITI-II test (OECD 302 C).

[0012] For the purposes of this invention, "biodegradable" or "biodegradable" refers to microcapsule walls that exhibit a biodegradability of at least 40% as measured according to OECD 301 F or at least 20% as measured according to OECD 302 C (MITI-II test), and thus possess inherent or basic biodegradability. This corresponds to the limit value for OECD 302 C according to the "Revised Introduction to the OECD Guidelines for testing of Chemicals, section 3, Part 1, dated 23 March 2006". Microcapsule walls with a limit value of at least 60% as measured according to OECD 301 F are also referred to as rapidly biodegradable.

[0013] "Tightness" with respect to a substance, gas, liquid, radiation, or similar, is a property of material structures. According to the invention, the terms "tightness" and "tightness" are used synonymously. Tightness is a relative term and always refers to predefined conditions.

[0014] In this invention, the term "(Meth)Acrylate" refers to both methacrylates and acrylates.

[0015] According to the invention, the term "microcapsules" refers to particles containing an inner space or core filled with a solid, gelled, liquid, or gaseous medium and enclosed (encapsulated) by a continuous shell of film-forming polymers. These particles preferably have small dimensions. The terms "microcapsules," "core-shell capsules," or simply "capsules" are used synonymously.

[0016] Microencapsulation is a manufacturing process in which tiny and minute portions of solid, liquid, or gaseous substances are enclosed in a shell made of polymeric or inorganic wall materials. The resulting microcapsules can have a diameter ranging from a few millimeters to less than 1 µm.

[0017] The microcapsule according to the invention thus has a multilayered shell. The shell enclosing the core material of the microcapsule is regularly also referred to as the "wall" or "shell".

[0018] The microcapsules according to the invention, with a multilayer shell, can also be referred to as multilayer microcapsules or a multilayer microcapsule system, since the individual layers can also be considered as individual shells. "Multilayer" and "multilayer" are thus used synonymously.

[0019] "Wall-forming components" are those that build the microcapsule wall. microcapsules

[0020] The microcapsules used in the washing and cleaning agents according to a first aspect of the invention comprise a core material and a shell, the shell consisting of at least a first and a second layer having different chemical compositions, and the shell exhibiting a biodegradability of at least 40% as measured according to OECD 301 F according to the measurement procedure in Example 6 of the description over a period of 28 days. Measured according to OECD 302 C, the microcapsules according to the invention exhibit a biodegradability of at least 20%.

[0021] As shown in examples 6 and 7, the microcapsule shells are biodegradable according to OECD standards due to the high proportion of natural components.

[0022] According to one embodiment, the first layer of the microcapsules contains one or more biodegradable components as wall formers. This first layer forms the main stabilizing component of the microcapsule shell and thus ensures the high biodegradability of at least 40% according to OECD 301 F. Suitable biodegradable components as wall formers for the first layer include proteins such as gelatin; polysaccharides such as alginate, gum arabic, chitin, or starch; phenolic macromolecules such as lignin; polyglucosamines such as chitosan; polyvinyl esters such as polyvinyl acetate and polyvinyl alcohols, in particular highly saponified and fully saponified polyvinyl alcohols; phosphazenes; and polyesters such as polylactide or polyhydroxyalkanoate. This list of specific components in the individual classes of substances is only exemplary and should not be considered limiting. Suitable natural wall formers are known to those skilled in the art.Furthermore, the various methods for wall formation, such as coacervation or interfacial polymerization, are known to the person skilled in the art.

[0023] These biodegradable components can be selected according to the specific application to form a stable multilayer shell with the material of the second layer. The second layer can be arranged either on the outside or on the inside of the first layer. Preferably, the second layer is arranged on the inside of the first layer. Furthermore, the biodegradable components can be selected to ensure compatibility with the core material when arranged on the inside, or compatibility with the chemical properties of the application area when arranged on the outside. The biodegradable components can be combined as desired to influence the biodegradability, stability, and chemical resistance of the microcapsule.

[0024] In one embodiment of the first aspect, the shell of the microcapsules exhibits a biodegradability of 50% according to OECD 301 F. In another embodiment, the shell of the microcapsule exhibits a biodegradability of at least 60% (OECD 301 F). In a further embodiment, the biodegradability is at least 70% (OECD 301 F). According to OECD 302 C, the microcapsule according to the invention can exhibit a biodegradability of at least 25%. According to one embodiment, the biodegradability is at least 30% (OECD 302 C). According to a further embodiment, the biodegradability is at least 40% (OECD 302 C). The biodegradability is measured in each case over a period of 28 days. In the extended ready biodegradation method, biodegradability is measured over a period of 60 days (see Opinion on an Annex XV dossier proposing restrictions on intentionally-added microplastics of June 11, 2020 ECHA / RAC / RES-O-0000006790-71-01 / F).Preferably, the microcapsules are cleaned of dissolved residues by washing before determining their biodegradability. In one embodiment, the capsule dispersion is washed in water after preparation by centrifugation three times and redispersion. For this purpose, the sample is centrifuged. After filtering off the clear supernatant, the mixture is made up with water, and the sediment is redispersed by shaking. Various reference samples can be used to measure biodegradability, such as the rapidly degradable ethylene glycol or natural walnut shell flour, which exhibits the typical step-like degradation of a complex mixture. The microcapsule according to the invention shows similar, and preferably better, biodegradability over a period of 28 or 60 days than the walnut shell flour.

[0025] The high level of biodegradability achieved according to the invention is attained both through the wall-forming materials used and through the shell's design. Simply using a certain percentage of naturally occurring, potentially biodegradable components does not automatically guarantee a corresponding level of biodegradability. This depends on how the potentially biodegradable components are present within the shell.

[0026] According to a preferred embodiment, the first layer contains gelatin. According to another preferred embodiment, the first layer contains alginate. According to a further preferred embodiment, the first layer contains both gelatin and alginate. As shown in the exemplary embodiment, both gelatin and alginate are suitable for the production of microcapsules according to the invention, which have high biodegradability and high stability. Other suitable combinations of natural components in the first layer are gelatin and Gum arabic.

[0027] According to one embodiment, the first layer contains one or more curing agents. Curing agents according to the invention are aldehydes, such as glutaraldehyde, glyoxal, and formaldehyde, as well as tannins, enzymes such as transglutaminase, and organic anhydrides such as maleic anhydride. Glutaraldehyde is the preferred curing agent due to its very good crosslinking properties. Glyoxal is also preferred due to its good crosslinking properties and, compared to glutaraldehyde, its lower toxicological classification. The use of curing agents results in a higher density of the first layer, which consists of natural wall structures. Furthermore, the curing agents reduce the stickiness of the layer and thus its tendency to agglomerate. However, curing agents lead to reduced biodegradability of the natural polymers.Due to the combination of the first layer with the second layer acting as a diffusion barrier, the amount of curing agent in the first layer can be kept low, which in turn contributes to the layer's easy biodegradability. According to one embodiment, the proportion of curing agent in the first layer is less than 25% by weight.

[0028] Unless explicitly defined otherwise, the proportions of the components of the layers refer to the total weight of the layer, i.e., the total dry weight of the components used in the production, excluding components used in the production that are not incorporated into the layer or are incorporated only to a minor extent, such as surfactants and protective colloids. Above this value, the biodegradability according to the invention as defined in OECD 301 F cannot be guaranteed. Preferably, the proportion of the curing agent in the first layer is in the range of 5–15 wt%. This proportion leads to effective cross-linking of the gelatin and, through a quantitative reaction, results in the formation of as little residual monomer as possible. The range of 9 wt% to 12 wt% is also suitable.-% is particularly preferred, it ensures the required degree of cross-linking and a stable coating of the second shell to buffer the otherwise sensitive diffusion barrier and equip it with further barrier properties, and has very little residual aldehyde, which is broken down in a subsequent alkaline adjustment of the slurry via an aldol reaction.

[0029] In one embodiment, the first layer contains gelatin and glutaraldehyde. In another embodiment, the first layer contains gelatin, alginate, and glutaraldehyde. In a further embodiment, the first layer contains gelatin and glyoxal. In yet another embodiment, the first layer contains gelatin, alginate, and glyoxal. The precise chemical composition of the first layer is not crucial. It merely needs to ensure sufficient stability of the microcapsule wall and the release behavior required for the respective application. It is essential that it contains only small amounts, or preferably no, unnatural persistent components. Consequently, the first layer can also contain one or more inorganic components as wall formers, either as an alternative or in addition to the biodegradable components. Inorganic components as wall formers can be, in particular, calcium carbonates or polysilicates.These are particularly suitable because, as ubiquitous components, they are environmentally friendly. Since there is no need to degrade these inorganic components, they are considered fully biodegradable according to the invention, even though the criteria according to OECD 301 or OECD 302 are not applicable to these components.

[0030] According to the invention, the second layer is also referred to as a sealing layer or diffusion barrier. Despite the small wall thickness of the second layer, the microcapsules exhibit a high degree of sealing. As shown in Example 5, this sealing is sufficient for use in demanding environments. In one embodiment, the second layer has an average thickness in the range of 0.01 µm to 1 µm. A layer thickness greater than 1 µm would excessively increase the proportion of the components of the second layer in the total capsule wall and thus no longer guarantee sufficient biodegradability. With a layer thickness of less than 0.01 µm, the second layer would no longer provide a sufficient diffusion barrier. Therefore, the microcapsules would be unsuitable for demanding environments. With a layer thickness of 0.02 µm or more, the second layer exhibits sufficient sealing for most applications.For easy biodegradability of the microcapsule, the wall thickness of the second layer should be no more than 0.5 µm. A wall thickness of 0.05 µm to 0.30 µm is particularly preferred. Within this range, optimal density is achieved while maintaining easy biodegradability.

[0031] The second layer is a polymer comprising an aldehydic component, an aromatic alcohol, and an amine component. Manufacturing processes for producing microcapsules with these wall materials are known to those skilled in the art. For the production of the second layer, a polymer selected from a polycondensation product of an aldehydic component with one or more aromatic alcohols and amine components can be used.

[0032] As shown in embodiments 1 and 4, the low wall thickness of the second layer according to the invention can be achieved in particular with a melamine-formaldehyde layer containing aromatic alcohols or m-aminophenol.

[0033] The use of amine-aldehyde compounds in the second layer, particularly melamine-formaldehyde, has the advantage that these compounds form a hydrophilic surface with a high proportion of hydroxy functionality, thus exhibiting excellent compatibility with the hydrogen-bonding components of the first layer, such as biodegradable proteins, polysaccharides, chitosan, lignins, and phosphazenes, as well as inorganic wall materials like CaCO₃ and polysiloxanes. Similarly, polyacrylates, particularly those consisting of styrene, vinyl compounds, methyl methacrylate, and 1,4-butanediol acrylate (methacrylic acid), can be produced as a microcapsule wall by initiation, for example, with tert-butyl hydroperoxide in a radical-induced polymerization (polyacrylates). These form a hydrophilic surface with a high proportion of hydroxy functionality and are therefore equally compatible with the components of the first layer according to the invention.

[0034] Thus, a wall-forming component of the second layer is an aldehydic component. According to one embodiment, the aldehydic component of the second layer is selected from the group consisting of formaldehyde, glutaraldehyde, succinaldehyde, furfural, and glyoxal. Microcapsules have already been successfully produced with these aldehydes (see WO 2013 037 575 A1), so it can be assumed that similarly dense capsules can be obtained as with formaldehyde.

[0035] Based on the investigations of the present invention, the proportion of the aldehydic component for wall formation, relative to the total weight of the second shell, should be in the range of 5 to 50 wt.%. It is assumed that a sufficiently stable and dense, thin layer cannot be obtained outside these limits. Preferably, the concentration of the aldehydic component in the second layer is in the range of 10 to 30 wt.%. Particularly preferably, the concentration of the aldehydic component in the second layer is in the range of 15 to 20 wt.%.

[0036] Suitable amine components for the second layer include melamine, melamine derivatives, and urea, or combinations thereof. Etherified melamine derivatives and methylolated melamine derivatives are particularly appropriate. Melamine in its methylolated form is preferred. The amine components can be used, for example, in the form of alkylated mono- and polymethylol-urea precondensation products or partially methylolated mono- and polymethylol-1,3,5-triamono-2,4,6-triazine precondensation products such as Luracoll SD® (from BASF). In one embodiment, the amine component is melamine. In an alternative embodiment, the amine component is a combination of melamine and urea.

[0037] The aldehyde component and the amine component can be present in a molar ratio ranging from 1:5 to 3:1. For example, the molar ratio can be 1:5, 1:4.5, 1:4, 1:3.5, 1:3, 1:2.5, 1:2, 1:1.8, 1:1.6, 1:1.4, 1:1.3, 1:1.2, 1:1, 1.5:1, 2:1, 2.5:1, or 3:1. Preferably, the molar ratio is in the range of 1:3 to 2:1. Particularly preferably, the molar ratio of the aldehyde component and the amine component can be in the range of 1:2 to 1:1. The aldehyde component and the amine component are generally used in a ratio of approximately 1:1.3. This molar ratio allows for a complete reaction of the two reactants and results in a high density of the capsules. For example, aldehyde-amine capsule walls with a molar ratio of 1:2 are also known. These capsules have the advantage that the proportion of the highly cross-linking aldehyde, especially formaldehyde, is very low.However, these capsules have a lower density than capsules with a ratio of 1:1.3. Capsules with a ratio of 2:1 have an increased density, but have the disadvantage that the aldehyde component is partially unreacted in the capsule wall and the slurry.

[0038] The proportion of the amine components (e.g., melamine and / or urea) in the second layer, based on the total weight of the second layer, is in the range of 20 wt.% to 85 wt.%. For example, the proportion of the amine component can be 20 wt.%, 25 wt.%, 30 wt.%, 35 wt.%, 40 wt.%, 45 wt.%, 50 wt.%, 55 wt.%, 60 wt.%, 65 wt.%, 70 wt.%, 75 wt.%, 80 wt.%, or 85 wt.%. In a preferred embodiment, the proportion of the amine component in the second layer, based on the total weight of the second layer, is in the range of 40 wt.% to 80 wt.%. Particularly preferred is the proportion of the amine component in the range of 55 wt.% to 70 wt.%.

[0039] The aromatic alcohol makes it possible to significantly reduce the wall thickness of the second layer, which is composed of the amine and aldehyde components, while still obtaining a layer that possesses the necessary density and is sufficiently stable, at least in combination with the first layer. The aromatic alcohols impart increased density to the wall because their highly hydrophobic aromatic structure hinders the diffusion of low-molecular-weight substances. The second layer contains an aromatic alcohol selected from the group consisting of resorcinol, phloroglucinol, and aminophenol. In combination with the amine and aldehyde components, the aromatic alcohol is used in a molar ratio to the aldehyde component ranging from (alcohol:aldehyde) 1:1 to 1:20, preferably from 1:2 to 1:10.

[0040] The proportion of aromatic alcohol in the second layer, based on the total weight of the second layer, ranges from 1.0 wt% to 20 wt%. For example, the proportion of aromatic alcohol can be 1.5 wt%, 2.0 wt%, 2.5 wt%, 3.0 wt%, 4.0 wt%, 5.0 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, 15 wt%, 16 wt%, 17 wt%, 18 wt%, 19 wt%, or 20 wt%. Due to their aromatic structure, aromatic alcohols impart a color to the capsule wall, which increases with the proportion of aromatic alcohol. Such coloration is undesirable in many applications. Furthermore, aromatic alcohols are susceptible to oxidation, which leads to a change in color over time. This makes it difficult to counteract the unwanted coloration of the microcapsules with a dye. Therefore, aromatic alcohols should not be used above 20.0% by weight.Below 1.0 wt.%, no effect on density is detectable. In a preferred embodiment, the proportion of aromatic alcohol in the second layer, based on the total weight of the second layer, is in the range of 5.0 to 15.0 wt.%. Up to a percentage of 15.0 wt.%, the coloration is tolerable in most applications. In a particularly preferred embodiment, the proportion of aromatic alcohol in the second layer, based on the total weight of the second layer, is in the range of 7.0 to 13.0 wt.%. In particular, the proportion of aromatic alcohol in the second layer is in the range of 9.0 wt.% to 13.0 wt.%.

[0041] In one embodiment, the second layer of the microcapsules contains melamine, formaldehyde, and resorcinol. In another embodiment, the second layer of the microcapsules contains melamine, urea, formaldehyde, and resorcinol. In a preferred embodiment, the second layer of the microcapsules contains melamine in the range of 25 to 40 wt.%, formaldehyde in the range of 15 to 20 wt.%, and resorcinol in the range of 0.1 to 12 wt.%, and optionally urea in the range of 15 to 20 wt.%. These proportions refer to the amounts used for wall formation of the layer and are based on the total weight of the second layer without the protective colloid.

[0042] To produce the second layer, which consists of an aldehydic component, an amine component, and an aromatic alcohol, a protective colloid can also be used. A suitable protective colloid is 2-acrylamido-2-methylpropanesulfonic acid (AMPS, commercially available as Lupasol® < PA 140, BASF) or its salts. The proportion of the protective colloid in the components used to produce the second layer can range from 10 to 30 wt% based on the total dry weight of the components used. According to one embodiment, the proportion of the protective colloid in the components used to produce the second layer is in the range of 15 to 25 wt%. The protective colloid can also be present in the finished microcapsule shell to a certain low percentage. Determining the proportion of the protective colloid in the second layer is technically difficult. Moreover, the proportion is only small.Consequently, the other proportions of the other components are represented as if the protective colloid were not included.

[0043] Preferred (meth)acrylate polymers are homo- or copolymers, preferably copolymers, of 2-acrylamido-2-methylpropanesulfonic acid or its salts (AMPS). Copolymers of 2-acrylamido-2-methylpropanesulfonic acid or its salts are preferred, e.g., copolymers with one or more comonomers from the group consisting of (meth)acrylates, vinyl compounds such as vinyl esters or styrenes, unsaturated di- or polycarboxylic acids such as maleic acid esters, or salts of amyl or allyl compounds.

[0044] In contrast to known biodegradable microcapsules, the microcapsules according to the invention exhibit a high degree of tightness. According to one embodiment, the microcapsules have a tightness that ensures a maximum leakage of 80% by weight of the core material used after storage for a period of 12 weeks at a temperature of 0 to 40 °C.

[0045] In addition to the shell material, the tightness also depends on the type of core material. The tightness of the microcapsules according to the invention was determined for the fragrance oil Weiroclean from Kitzing GmbH, since this fragrance oil is representative of microencapsulated fragrance oils in its chemical properties. Weiroclean has the following components (with proportions based on total weight): 1-(1,2,3,4,5,6,7,8-octahydro-2,3,8,8-tetramethyl-2-naphthalenyl)ethanone 25-50 % 2-Hydroxy-benzoic acid 2-hexyl ester 10 - 25 % Phenylmethylbenzoic acid 5 - 10 % 3-Methyl-4-(2,6,6-trimethyl-2-cyclohexenyl)-3-buten-2-one 1 - 5 % 3,7-Dimethyl-6-octen-1-ol 1 - 5 % 3-Methyl-5-phenylpentanol 1 - 5 % 2,6-Dimethyloct-7-en-2-ol 1 - 5 % 4-(2,6,6-Trimethylcyclohex-1-eneyl)-but-3-ene-2-one 1 - 5 % 3a,4,5,6,7,7a-Hexahydro-4,7-methano-1H-indene-6-yl-propanoic acid 1 - 5 % 2-tert-Butylcyclohexylacetic acid 1 - 5 % 2-Heptylcyclopentanone 1 - 5 % Pentadecane-15-olide 1 - 5 % 2H-1-Benzopyran-2-one 0.1 - 1 % 2,6-Di-tert-butyl-p-cresol 0.1 - 1 % 4-Methyl-3-decen-5-ol 0.1 - 1 % 2,4-Dimethyl-3-cyclohexene-1-carboxaldehyde 0.1 - 1 % [(2E)-3,7-dimethylocta-2,6-dienyl]acetate 0.1 - 1 % Allyl hexanoate 0.1 - 1 % 2-Methylundecanal 0.1 - 1 % 10-Undecenal 0.1 - 1 % cis-3,7-dimethyl-2,6-octadienyl ethanoate 0.1 - 1 % 3,7,11-Trimethyldodeca-1,6,10-trien-3-ol 0.1 - 1 % Undecan-2-on 0.1 - 1 %.

[0046] At least one fragrance is used as the core material. Fragrance or perfume oils optimized for microencapsulation in the detergent and cleaning agent sector are particularly preferred, such as the Weiroclean fragrance formulation (Kurt Kitzing GmbH). The fragrances can be used in solid or liquid form, but liquid form is especially common.

[0047] Fragrances that can be used as core materials are not subject to any special restrictions. Individual fragrance compounds of natural or synthetic origin, such as esters, ethers, aldehydes, ketones, alcohols, and hydrocarbons, can be used. Examples of ester-type fragrance compounds are benzyl acetate and phenoxyethyl isobutyrate. p-tert-Butyl cyclohexyl acetate, linalyl acetate, dimethyl benzyl carbinyl acetate (DMBCA), phenyl ethyl acetate, benzyl acetate, ethyl methyl phenyl glycinate, allyl cyclohexyl propionate, styrallyl propionate, benzyl salicylate, cyclohexyl salicylate, floramate, melusate and jasmacyclate. Examples of ethers include benzyl ethyl ether and ambroxane; aldehydes include those mentioned above, such as the linear alkanals with 8 to 18 carbon atoms, citral, citronellal, citronellyl oxyacetaldehyde, cyclamenaldehyde (3-(4-propan-2-ylphenyl)butanal), lilial, and bourgeonal; ketones include, for example, ionones, [alpha]-isomethyl ionone, and methylcedryl ketone; alcohols include anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol, and terpineol; and hydrocarbons mainly include terpenes such as limonene and pinene. However, mixtures of various fragrances are preferred, as they combine to create an appealing scent.

[0048] Geeignete Duftstoffaldehyde können ausgewählt werden aus Adoxal (2,6,10-Trimethyl-9-undecenal), Anisaldehyd (4-Methoxybenzaldehyd), Cymal oder Cyclamenaldehyd (3-(4-Isopropylphenyl)-2-methylpropanal), Nympheal (3-(4-Isobutyl-2-methylphenyl)propanal), Ethylvanillin, Florhydral (3-(3-Isopropylphenyl)butanal]), Trifernal (3-Phenylbutyraldehyd), Helional (3-(3,4-Methylendioxyphenyl)-2-methylpropanal), Heliotropin, Hydroxycitronellal, Lauraldehyd, Lyral (3- und 4-(4-Hydroxy-4-methylpentyl)-3-cyclohexen-1-carboxaldehyd), Methylnonylacetaldehyd, Lilial (3-(4-tert-Butylphenyl)-2-methylpropanal), Phenylacetaldehyd, Undecylenaldehyd, Vanillin, 2,6,10-Trimethyl-9-undecenal, 3-Dodecen-1-al, alpha-n-Amylzimtaldehyd, Melonal (2,6-Dimethyl-5-heptenal), Triplal (2,4-Dimethyl-3-cyclohexen-1-carboxaldehyd), 4-Methoxybenzaldehyd, Benzaldehyd, 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]acetaldehyd, 4-Isopropylbenzylaldehyd, 1,2,3,4,5,6,7,8-Octahydro-8,8-dimethyl-2-naphthaldehyd, 2,4-Dimethyl-3-cyclohexen-1-carboxaldehyd, 2-Methyl-3-(isopropylphenyl)propanal, 1-Decanal, 2,6-Dimethyl-5-heptenal, 4-(Tricyclo[5.2.1.0(2,6)]-decyliden-8)-butanal, Octahydro-4,7-methan-1H-indencarboxaldehyd, 3-Ethoxy-4-hydroxybenzaldehyd, para-Ethyl-alpha,alpha-dimethylhydrozimtaldehyd, alpha-Methyl-3,4-(methylendioxy)-hydrozimtaldehyd, 3,4-Methylendioxybenzaldehyd, alpha-n-Hexylzimtaldehyd, m-Cymen-7-carboxaldehyd, alpha-Methylphenylacetaldehyd, Tetrahydrocitral (3,7-Dimethyloctanal), Undecenal, 2,4,6-Trimethyl-3-cyclohexen-1-carboxaldehyd, 4-(3)(4-Methyl-3-pentenyl)-3-cyclohexencarboxaldehyd, 1-Dodecanal, 2,4-Dimethylcyclohexen-3-carboxaldehyd, 4-(4-Hydroxy-4-methylpentyl)-3-cylohexen-1-carboxaldehyd, 7-Methoxy-3,7-dimethyloctan-1-al, 2-Methyldecanal, 1-Nonanal, 1-Octanal, 2,6,10-Trimethyl-5,9-undecadienal, 2-Methyl-3-(4-tert-butyl)propanal, Dihydrozimtaldehyd, 1-Methyl-4-(4-methyl-3-pentenyl)-3-cyclohexen-1-carboxaldehyd, 5- oder 6-Methoxyhexahydro-4,7-methanindan-1-oder -2-carboxaldehyd, 3,7-Dimethyloctan-1-al, 1-Undecanal, 10-Undecen-1-al, 4-Hydroxy-3-methoxybenzaldehyd, 1-Methyl-3-(4-methylpentyl)-3-cyclohexencarboxaldehyd, 7-Hydroxy-3,7-dimethyl-octanal, trans-4-Decenal, 2,6-Nonadienal, para-Tolylacetaldehyd, 4-Methylphenylacetaldehyd, 2-Methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal, ortho-Methoxyzimtaldehyd, 3,5,6-Trimethyl-3-cyclohexencarboxaldehyd, 3,7-Dimethyl-2-methylen-6-octenal, Phenoxyacetaldehyd, 5,9-Dimethyl-4,8-decadienal, Päonienaldehyd (6,10-Dimethyl-3-oxa-5,9-undecadien-1-al), Hexahydro-4,7-methanindan-1-carboxaldehyd, 2-Methyloctanal, alpha-Methyl-4-(1-methylethyl)benzolacetaldehyd, 6,6-Dimethyl-2-norpinen-2-propionaldehyd, para-Methylphenoxyacetaldehyd, 2-Methyl-3-phenyl-2-propen-1-al, 3,5,5-Trimethylhexanal, Hexahydro-8,8-Dimethyl-2-naphthaldehyde, 3-Propylbicyclo[2.2.1]-hept-5-ene-2-carbaldehyde, 9-Decenal, 3-Methyl-5-phenyl-1-pentanal, Floral (4,8-Dimethyl-4,9-decadienal), Aldehyde C12MNA (2-Methylundecanal), Liminal (beta-4-Dimethylcyclohex-3-ene-1-propan-1-al), Methylnonylacetaldehyde, Hexanal, trans-2-Hexenal and mixtures thereof.

[0049] Suitable fragrance ketones include, but are not limited to, methyl beta-naphthyl ketone, musk indanone (1,2,3,5,6,7-hexahydro-1,1,2,3,3-pentamethyl-4H-inden-4-one), calone (methylbenzodioxepinone), tonalid (6-acetyl-1,1,2,4,4,7-hexamethyltetralin), alpha-damascone, beta-damascone, delta-damascone, iso-damascone, damascenone, methyl dihydrojasmonate (hedione), menthone, carvone, camphor, koavone (3,4,5,6,6-pentamethylhept-3-en-2-one), fenchone, alpha-ionone, beta-ionone, dihydro-beta-ionone, gamma-methyl-ionone, and fleuramone. (2-heptylcyclopentanone), frambinone methyl ether (4-(4-methoxyphenyl)butan-2-one), dihydrojasmone, cis-jasmone, 1-(1,2,3,4,5,6,7,8-octahydro-2,3,8,8-tetramethyl-2-naphthalenyl)-ethan-1-one and isomers thereof, methylcedrenyl ketone, Acetophenone, methyl acetophenone, para-methoxyacetophenone, methyl betanaphtyl ketone, benzylacetone, benzophenone, para-hydroxyphenylbutanone, celery ketone (3-methyl-5-propyl-2-cyclohexenone), 6-isopropyldeca-hydro-2-naphtone, dimethyl octenone,Frescomenthe (2-Butan-2-ylcyclohexan-1-on), 4-(1-Ethoxyvinyl)-3,3,5,5-tetramethylcyclohexanon, Methylheptenon, 2-(2-(4-Methyl-3-cyclohexen-1-yl)propyl)cyclopentanon, 1-(p-Menthen-6(2)yl)-1-propanon, 4-(4-Hydroxy-3-methoxyphenyl)-2-butanon, 2-Acetyl-3,3-dimethylnorbornan, 6,7-Dihydro-1,1,2,3,3-pentamethyl-4(5H)in-danon, 4-Damascol, Dulcinyl (4-(1,3-Benzodioxol-5-yl)butan-2-on), Hexalon (1-(2,6,6-Trimethyl-2-cyclohexen-1-yl)-1,6-heptadien-3-on), Isocyclemon E (2-Acetonaphthon-1 ,2,3,4,5,6,7,8-octahydro-2,3,8,8-tetramethyl), Methylnonylketon, Methylcyclocitron, Methyllavendelketon, Orivon (4-tert-Amylcyclohexanon), 4-tert-Butylcyclohexanon, Delphon (2-Pentylcyclopentanon), Muscon (CAS 541 -91 -3), Neobutenon (1-(5,5-dimethyl-1-cyclo-hexenyl)pent-4-en-1-on), Plicaton (CAS 41724-19-0), Velouton (2,2,5-trimethyl-5-pentylcyclopentan-1-on), 2,4,4,7-Tetramethyl-oct-6-en-3-on, Tetrameran (6,10-dimethylundecen-2-on) und Mischungen davon.,

[0050] The core materials may also contain natural fragrance mixtures derived from plant sources, such as pine, citrus, jasmine, patchouli, rose, or ylang-ylang oil. Clary sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, frankincense oil, galbanum oil, and labdanum oil, as well as orange blossom oil, neroli oil, orange peel oil, and sandalwood oil are also suitable. Other conventional fragrances that may be included in the compositions according to the present invention are, for example, essential oils such as angelica root oil, anise oil, arnica flower oil, basil oil, bay oil, champaca flower oil, silver fir oil, silver fir cone oil, elemi oil, eucalyptus oil, fennel oil, spruce needle oil, galbanum oil, geranium oil, ginger grass oil, guaiac wood oil, gurjun balsam oil, helichrysum oil, ho oil, ginger oil, iris oil, cajeput oil, calamus oil, chamomile oil, camphor oil, kanaga oil, cardamom oil, cassia oil, and pine needle oil.Copaiba balsam oil, coriander oil, spearmint oil, caraway oil, cumin oil, lavender oil, lemongrass oil, lime oil, mandarin oil, lemon balm oil, musk seed oil, myrrh oil, clove oil, neroli oil, niaouli oil, frankincense oil, oregano oil, palmarosa oil, patchouli oil, Peruvian balsam oil, petitgrain oil, pepper oil, peppermint oil, pimento oil, pine oil, rose oil, rosemary oil, sandalwood oil, celery oil, spike oil, star anise oil, turpentine oil, thuja oil, thyme oil, verbena oil, vetiver oil, juniper berry oil, wormwood oil, wintergreen oil, ylang-ylang oil, hyssop oil, cinnamon oil, cinnamon leaf oil, citronella oil, lemon oil, cypress oil, ambrettolide, ambroxan, α-amylcinnamaldehyde, anethole, anisaldehyde Anise alcohol, anisole, anthranilic acid methyl ester, acetophenone, benzylacetone, benzaldehyde, benzoic acid ethyl ester, benzophenone, benzyl alcohol, benzyl acetate, benzyl benzoate, benzyl formate, benzyl valerianate, borneol, bornyl acetate, Boisambrene forte, α-bromostyrene, n-decylaldehyde, n-dodecylaldehyde, Eugenol, eugenol methyl ether, eucalyptol, farnesol, fenchone, fenchyl acetate,Geranyl acetate, geranyl formate, heliotropin, heptyne carboxylic acid methyl ester, heptaldehyde, hydroquinone dimethyl ether, hydroxycinnamaldehyde, hydroxycinnamaldehyde alcohol, indole, ira, isoeugenol, isoeugenol methyl ether, isosafrole, jasmon, camphor, carvacrol, carvone, p-cresol methyl ether, coumarin, p-methoxyacetophenone, methyl n-amyl ketone, methyl anthranilic acid methyl ester, p-methylacetophenone, methyl chavicol, p-methylquinoline, methyl β-naphthyl ketone, methyl n-nonylacetaldehyde, methyl n-nonyl ketone, muscone, β-naphthol ethyl ether, β-naphthol methyl ether, nerol, n-nonylaldehyde, nonyl alcohol, n-octylaldehyde, p-oxyacetophenone Pentadecanolide, β-Phenylethyl alcohol, Phenylacetic acid, Pulegone, Safrole, Isoamyl salicylate, Methyl salicylate, Hexyl salicylate, Cyclohexyl salicylate, Santalol, Sandelice, Skatole, Terpineol, Thymene, Thymol, Troenane, γ-Undelactone, Vanillin, Veratraldehyde, Cinnamaldehyde, Cinnamyl alcohol, Cinnamic acid, Ethyl cinnamic acid, Benzyl cinnamic acid, Diphenyl oxide, LimoneneLinalool, linalyl acetate and propionate, melusate, menthol, menthone, methyl-n-heptenone, pinene, phenylacetaldehyde, terpinyl acetate, citral, citronellal and mixtures thereof.

[0051] The tightness of the capsule wall can be influenced by the choice of shell components. According to one embodiment, the microcapsules exhibit a tightness that ensures a maximum leakage of 75 wt.%, 70 wt.%, 65 wt.%, 60 wt.%, 55 wt.%, 50 wt.%, 45 wt.%, and 40 wt.% of the core material used when stored for a period of 12 weeks at a temperature of 0 to 40 °C. The microcapsules are stored in a model formulation appropriate to the target application. Furthermore, the microcapsules are also stable in the product in which they are used, for example, in detergents, cleaning agents, dishwashing liquids, fabric softeners, and textile care products. The standard formulations of these products are known to those skilled in the art. Typically, the pH value in the environment of the microcapsules during storage is in the range of 2 to 11.

[0052] The second layer can be arranged on the inside or outside of the first layer. According to one embodiment, the second layer is arranged on the inside of the first layer. Such an arrangement has the advantage that the sealing layer can additionally serve as a chemical protective layer between the biodegradable first layer and the core material. This is particularly important in cases where the core material can chemically attack the biodegradable material of the first layer. With this design, the problem arises that the very thin second layer must first be formed as a template during encapsulation. This has been solved in this case by selecting suitable wall layers and additives.One advantage of the template strategy, i.e., manufacturing the capsule starting with the construction of the very thin second layer as a template, is that the components used as wall formers can be placed in the continuous aqueous phase, thus ensuring minimal contact with the core material during shell construction. The components of the additional first layer can then be deposited as the first layer without interaction with the core material.

[0053] The microcapsule shells according to the invention have at least two layers, i.e., they can be, for example, two-layered, three-layered, four-layered, or five-layered. Preferably, the microcapsules are two- or three-layered.

[0054] In one embodiment, the microcapsule has a third layer arranged on the outside of the first layer. In another embodiment, the third layer is arranged on the outside of the second layer. Preferably, in this embodiment, the second layer is located on the outside of the first layer. This third layer can be used to adapt the surface properties of the microcapsule for a specific application. Examples include improving the adhesion of the microcapsules to various surfaces and reducing agglomeration. The third layer also binds residual aldehyde, thereby reducing the content of free aldehydes in the capsule dispersion. Furthermore, it can provide additional (mechanical) stability or further increase the sealing capacity.Depending on the application, the third layer can contain a component selected from amines, organic salts, inorganic salts, alcohols, ethers, polyphosphazenes, and precious metals.

[0055] Precious metals increase the capsule's density and can impart additional catalytic properties to the microcapsule surface, or the antibacterial effect of a silver layer. Organic salts, particularly ammonium salts, lead to cationization of the microcapsule surface, resulting in improved adhesion to, for example, textiles. Alcohols, when incorporated via free hydroxyl groups, also lead to the formation of hydrogen bonds, which likewise improve adhesion to substrates. An additional polyphosphazene layer or coating with inorganic salts, such as silicates, further increases density without affecting biodegradability. According to a preferred embodiment, the third layer contains activated melamine.On the one hand, the melamine traps any free aldehyde components of the second layer, increases the density and stability of the capsule, and can also influence the surface properties of the microcapsules and thus the adhesion and agglomeration behavior.

[0056] Due to the thin wall thicknesses, the proportion of the second layer in the shell, based on the total weight of the shell, is at most 30%. For high biodegradability, the proportion is at most 25% by weight, based on the total weight of the shell. Particularly preferably, the proportion of the second layer is at most 20% by weight. The proportion of the first layer in the shell, based on the total weight of the shell, is at least 40% by weight, preferably at least 50% by weight, and particularly preferably at least 60% by weight. The proportion of the third layer in the shell, based on the total weight of the shell, is at most 25%, preferably at most 20% by weight, and particularly preferably at most 15% by weight.

[0057] The size of the microcapsules according to the invention is within the range typical for microcapsules. The diameter can range from 100 nm to 1 mm. The diameter depends on the exact capsule composition and the manufacturing process. The peak maximum of the particle size distribution is regularly used as a characteristic value for the size of the capsules. Preferably, the peak maximum of the particle size distribution lies in the range of 1 µm to 500 µm. The peak maximum of the particle size distribution can be, for example, at 1 µm, 2 µm, 3 µm, 4 µm, 5 µm, 10 µm, 15 µm, 20 µm, 30 µm, 40 µm, 50 µm, 60 µm, 70 µm, 80 µm, 90 µm, 100 µm, 120 µm, 140 µm, 160 µm, 180 µm, 200 µm, 250 µm, 300 µm, 350 µm, 400 µm, 450 µm or 500 µm lay. According to a particularly preferred embodiment, the microcapsules have a peak maximum of the particle size distribution from 10 µm to 100 µm. In particular, the peak maximum of the particle size distribution lies in the range of 10 µm to 50 µm. Washing or cleaning products containing microcapsules

[0058] Due to the robustness and / or impermeability of these biodegradable capsules, they can be advantageously used in washing and cleaning agents, including fabric softeners, textile care products, solid detergents (e.g., granules or powders), liquid detergents, household cleaners, bathroom cleaners, hand dishwashing liquids, and machine dishwashing liquids.

[0059] The washing or cleaning agents of the invention preferably comprise at least one ingredient selected from the group consisting of surfactants, enzymes, builders and lifting agents.

[0060] The washing and cleaning agents may also contain anionic, non-ionic, cationic, amphoteric, or zwitterionic surfactants, or mixtures thereof. Furthermore, these agents may be in solid or liquid form. In various embodiments, the surfactants comprise, in particular, at least one anionic surfactant and / or at least one non-ionic surfactant.

[0061] Suitable nonionic surfactants are, in particular, ethoxylation and / or propoxylation products of alkyl glycosides and / or linear or branched alcohols, each with 12 to 18 carbon atoms in the alkyl moiety and 3 to 20, preferably 4 to 10, alkyl ether groups. Furthermore, corresponding ethoxylation and / or propoxylation products of N-alkylamines, vicinal diols, fatty acid esters, and fatty acid amides, which correspond to the aforementioned long-chain alcohol derivatives with respect to the alkyl moiety, as well as of alkylphenols with 5 to 12 carbon atoms in the alkyl group, are also suitable.

[0062] Suitable anionic surfactants are, in particular, soaps and those containing sulfate or sulfonate groups with preferably alkali ions as cations. Usable soaps are preferably the alkali salts of saturated or unsaturated fatty acids with 12 to 18 carbon atoms. Such fatty acids can also be used in a partially neutralized form. Suitable sulfate-type surfactants include the salts of the sulfuric acid half-esters of fatty alcohols with 12 to 18 carbon atoms and the sulfation products of the aforementioned nonionic surfactants with a low degree of ethoxylation. Usable sulfonate-type surfactants include linear alkylbenzenesulfonates with 9 to 14 carbon atoms in the alkyl moiety, alkanesulfonates with 12 to 18 carbon atoms, and olefinsulfonates with 12 to 18 carbon atoms, which are formed by the reaction of corresponding monoolefins with sulfur trioxide, as well as alpha-sulfofaticial esters, which are formed by the sulfonation of fatty acid methyl or ethyl esters.

[0063] Cationic surfactants are preferably selected from among the esterquats and / or the quaternary ammonium compounds (QACs) according to the general formula (RI< )(RI II< )(RI III< )(RI IV< )N +< X -< , where RI< to R IV< represent identical or different C1-22 alkyl groups, C7-28 arylalkyl groups, or heterocyclic groups, wherein two, or in the case of aromatic incorporation as in pyridine, even three groups together with the nitrogen atom form the heterocycle, e.g., a pyridinium or imidazolinium compound, and X -< represents halide ions, sulfate ions, hydroxide ions, or similar anions. QACs can be prepared by reacting tertiary amines with alkylating agents such as methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, or even ethylene oxide.The alkylation of tertiary amines with one long alkyl group and two methyl groups is particularly straightforward; the quaternation of tertiary amines with two long groups and one methyl group can also be carried out under mild conditions using methyl chloride. Amines with three long alkyl groups or hydroxy-substituted alkyl groups are less reactive and are quaternized, for example, with dimethyl sulfate.Examples of suitable QAVs include benzalkonium chloride (N-alkyl-N,N-dimethylbenzylammonium chloride), benzalkone B (m,p-dichlorobenzyldimethyl-C12-alkylammonium chloride), benzoxonium chloride (benzyldodecyl-bis-(2-hydroxyethyl)ammonium chloride), cetrimonium bromide (N-hexadecyl-N,N-trimethylammonium bromide), benzetonium chloride (N,N-dimethyl-N[2-[2-[p-(1,1,3,3-tetramethylbutyl)phenoxy]ethoxy]ethyl]benzylammonium chloride), dialkyldimethylammonium chlorides such as di-n-decyl-dimethylammonium chloride, didecyldimethylammonium bromide, dioctyl-dimethylammonium chloride, 1-cetylpyridinium chloride, and thiazoline iodide, as well as mixtures thereof. Preferred QAVs are the benzalkonium chlorides with C8-C22 alkyl groups, in particular... C 12 -C 14 alkyl benzyl dimethyl ammonium chloride.

[0064] Preferred esterquats are methyl-N-(2-hydroxyethyl)-N,N-di(talgacyl-oxyethyl)ammonium methosulfate, bis-(palmitoyl)-ethyl-hydroxyethyl-methyl-ammonium methosulfate, or methyl-N,N-bis(acyl-oxyethyl)-N-(2-hydroxyethyl)ammonium methosulfate. Commercially available examples include the methylhydroxyalkyldialkoyloxyalkylammonium methosulfates marketed by Stepan under the trademark Stepantex®, the products of BASF SE known under the trade name Dehyquart®, and the products of Evonik known under the name Rewoquat®.

[0065] The quantities of individual ingredients in detergents and cleaning agents are determined by the intended use of the respective composition, and those skilled in the art are generally familiar with the orders of magnitude of the quantities of ingredients to be used or can obtain this information from the relevant technical literature. Depending on the intended use of the composition, the surfactant content, for example, will be chosen to be higher or lower. Typically, the surfactant content of detergents, for instance, can range from 10 to 50 wt.%, preferably from 12.5 to 30 wt.%, and more preferably from 15 to 25 wt.%.

[0066] The washing and cleaning agents may, for example, contain at least one water-soluble and / or water-insoluble, organic and / or inorganic builder. Water-soluble organic builders include polycarboxylic acids, in particular citric acid and sugar acids; monomeric and polymeric aminopolycarboxylic acids, in particular methylglycine diacetic acid, nitrilotriacetic acid, and ethylenediaminetetraacetic acid, as well as polyaspartic acid; polyphosphonic acids, in particular aminotris(methylenephosphonic acid), ethylenediaminetetrakis(methylenephosphonic acid), and 1-hydroxyethane-1,1-diphosphonic acid; polymeric hydroxy compounds such as dextrin; and polymeric (poly)carboxylic acids, polymeric acrylic acids, methacrylic acids, maleic acids, and copolymers of these, which may also contain small amounts of polymerizable substances without carboxylic acid functionality.Suitable, though less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ethers, vinyl esters, ethylene, propylene, and styrene, in which the acid content is at least 50% by weight. The organic builders can be used, particularly for the production of liquid detergents and cleaning agents, in the form of aqueous solutions, preferably in the form of 30% to 50% by weight aqueous solutions. All the acids mentioned are generally used in the form of their water-soluble salts, especially their alkali salts.

[0067] Organic builder substances can be included, if desired, in amounts up to 40 wt.%, in particular up to 25 wt.%, and preferably from 1 wt.% to 8 wt.%. Amounts close to the aforementioned upper limit are preferably used in paste-like or liquid, especially water-containing, compositions according to the invention. Laundry after-treatment products, such as fabric softeners, can optionally also be free of organic builder.

[0068] Suitable water-soluble inorganic builder materials include, in particular, alkali silicates and polyphosphates, preferably sodium triphosphate. Water-insoluble, water-dispersible inorganic builder materials, especially crystalline or amorphous alkali aluminosilicates, can be used, if desired, in amounts of up to 50 wt.%, preferably not exceeding 40 wt.%, and in liquid compositions, particularly from 1 wt.% to 5 wt.%. Among these, crystalline sodium aluminosilicates of detergent quality, especially zeolite A, P, and optionally X, are preferred. Amounts close to the aforementioned upper limit are preferably used in solid, particulate materials. Suitable aluminosilicates, in particular, do not contain particles with a grain size greater than 30 µm and preferably consist of at least 80 wt.% of particles with a size of less than 10 µm.

[0069] Suitable substitutes or partial substitutes for the aforementioned aluminosilicate are crystalline alkali silicates, which can be present alone or in mixtures with amorphous silicates. Alkali silicates suitable as builders in detergents or cleaning agents preferably have a molar ratio of alkali oxide to SiO₂ below 0.95, particularly from 1:1.1 to 1:12, and can be amorphous or crystalline. Preferred alkali silicates are sodium silicates, especially amorphous sodium silicates, with a molar ratio of Na₂O:SiO₂ of 1:2 to 1:2.8. The crystalline silicates, which can be present alone or in mixture with amorphous silicates, are preferably crystalline layered silicates of the general formula Na 2 Si x O 2x+1 ·yH 2 O, in which x, the so-called modulus, is a number from 1.9 to 4 and y is a number from 0 to 20, and preferred values ​​for x are 2, 3 or 4.Preferred crystalline layered silicates are those in which x in the general formula mentioned above takes the values ​​2 or 3. In particular, both beta- and delta-sodium disilicates (Na₂Si₂O₅·yH₂O) are preferred. Practically anhydrous crystalline alkali silicates of the general formula mentioned above, where x is a value from 1.9 to 2.1, prepared from amorphous alkali silicates, can also be used. In a further preferred embodiment, a crystalline sodium layered silicate with a modulus of 2 to 3, such as can be produced from sand and soda, is used. Crystalline sodium silicates with a modulus in the range of 1.9 to 3.5 are used in a further preferred embodiment of the textile treatment or cleaning agent.If alkali aluminosilicate, in particular zeolite, is also present as an additional builder substance, the weight ratio of aluminosilicate to silicate, based on anhydrous active substances, is preferably 1:10 to 10:1. In compositions containing both amorphous and crystalline alkali silicates, the weight ratio of amorphous alkali silicate to crystalline alkali silicate is preferably 1:2 to 2:1 and in particular 1:1 to 2:1.

[0070] Builder substances are, if desired, preferably included in amounts up to 60% by weight, particularly from 5% by weight to 40% by weight. Laundry after-treatment agents, such as fabric softeners, are preferably free of inorganic builder.

[0071] In various embodiments, a means according to the invention further comprises at least one enzyme.

[0072] The enzyme can be a hydrolytic enzyme or another enzyme in a concentration suitable for the efficacy of the agent. One embodiment of the invention thus comprises agents comprising one or more enzymes. Preferably used as enzymes are all enzymes that can exhibit catalytic activity in the agent according to the invention, in particular a protease, amylase, cellulase, hemicellulase, mannanase, tannase, xylanase, xanthanase, xyloglucanase, β-glucosidase, pectinase, carrageenase, perhydrolase, oxidase, oxidoreductase, or a lipase, as well as mixtures thereof. Advantageously, the enzymes are each contained in the agent in an amount of 1 x 10⁻⁸ to 5 wt% based on active protein. Each enzyme is increasingly preferred in an amount of 1 x 10 -7 < -3 wt.%, of 0.00001-1 wt.%, of 0.00005-0.5 wt.%, of 0.0001 to 0.1 wt.% and particularly preferably of 0.0001 to 0.05 wt.%.-% contained in the composition according to the invention, based on active protein. The enzymes particularly preferably exhibit synergistic cleaning performance against certain types of soiling or stains, i.e., the enzymes contained in the composition mutually support each other in their cleaning performance. Synergistic effects can occur not only between different enzymes, but also between one or more enzymes and other ingredients of the composition according to the invention.

[0073] The amylase(s) is / are preferably an α-amylase. The hemicellulase is preferably a pectinase, a pullulanase, and / or a mannanase. The cellulase is preferably a cellulase mixture or a single-component cellulase, preferably or predominantly an endoglucanase and / or a cellobiohydrolase. The oxidoreductase is preferably an oxidase, in particular a choline oxidase, or a perhydrolase.

[0074] The proteases used are preferably alkaline serine proteases. They act as non-specific endopeptidases, meaning they hydrolyze any amide bonds located within peptides or proteins, thereby breaking down protein-containing soils on the items being cleaned. Their optimum pH is usually in the strongly alkaline range. In preferred embodiments, the enzyme contained in the composition according to the invention is a protease.

[0075] The enzymes used here can be naturally occurring enzymes or enzymes that have been modified by one or more mutations based on naturally occurring enzymes in order to positively influence desired properties such as catalytic activity, stability or disinfecting performance.

[0076] In preferred embodiments of the invention, the enzyme is present in the form of an enzyme product in an amount of 0.01 to 10 wt.%, preferably 0.01 to 5 wt.%, in the composition according to the invention, based on the total weight of the composition. The active protein content is preferably in the range of 0.00001 to 1 wt.%, in particular 0.0001 to 0.2 wt.%, based on the total weight of the composition.

[0077] Protein concentration can be determined using established methods, such as the BCA method (bicinchoninic acid; 2,2'-bicinolyl-4,4'-dicarboxylic acid) or the biuret method. The determination of the active protein concentration is carried out by titration of the active sites using a suitable irreversible inhibitor (for proteases, for example, phenylmethylsulfonylfluoride (PMSF)) and determination of the residual activity (see M. Bender et al., J. Am. Chem. Soc. 88, 24 (1966), pp. 5890-5913).

[0078] In the agents described herein, the enzymes to be used may also be formulated together with accompanying substances, for example from fermentation. In liquid formulations, the enzymes are preferably used as liquid enzyme formulation(s).

[0079] Enzymes are generally not supplied in the form of pure protein, but rather in the form of stabilized preparations that are suitable for storage and transport. These pre-prepared formulations include, for example, solid preparations obtained by granulation, extrusion, or lyophilization, or, particularly in the case of liquid or gel-like agents, solutions of the enzymes, advantageously as concentrated as possible, with a low water content, and / or containing stabilizers or other additives.

[0080] Alternatively, the enzymes can be encapsulated for both solid and liquid dosage forms, for example, by spray drying or extrusion of the enzyme solution together with a preferably natural polymer, or in the form of capsules, such as those in which the enzymes are enclosed as if in a solidified gel, or in core-shell type capsules in which an enzyme-containing core is coated with a protective layer impermeable to water, air, and / or chemicals. Additional active ingredients, such as stabilizers, emulsifiers, pigments, bleaching agents, or dyes, can be applied in superimposed layers. Such capsules are produced using methods known per se, for example, by shake or roll granulation or in fluid-bed processes. Advantageously, such granules are low-dust, for example, due to the application of polymeric film formers, and have a long shelf life due to the coating.

[0081] Furthermore, it is possible to combine two or more enzymes so that a single granule has multiple enzyme activities.

[0082] In various embodiments, the agent according to the invention can comprise one or more enzyme stabilizers.

[0083] Adhesion-enhancing agents are agents that improve the adhesion of microcapsules to surfaces, particularly textile surfaces. Esterquats, mentioned above, fall into this category. Further examples include so-called SRPs (soil repellent polymers), which can be nonionic or cationic. Polyethyleneimines (PEI) and their ethoxylated variants, as well as polyesters, especially esters of terephthalic acid (primarily those of ethylene glycol and terephthalic acid) or polyester / polyether compounds of polyethylene terephthalate and polyethylene glycol, are particularly noteworthy. Finally, anionic and nonionic silicones also fall into this group. Exemplary compounds are also disclosed in patent EP 2 638 139 A1.

[0084] Furthermore, the washing and cleaning agents may contain additional ingredients that further improve the application-related and / or aesthetic properties of the composition, depending on the intended use. Within the scope of the present invention, they may include, but are not limited to, bleaching agents, bleach activators, bleach catalysts, esterquats, silicone oils, emulsifiers, thickeners, electrolytes, pH adjusters, fluorescent agents, dyes, hydrotopes, foam inhibitors, anti-reposition agents, solvents, optical brighteners, anti-graying inhibitors, anti-shrinkage agents, anti-crease agents, color transfer inhibitors, color protectants, wetting agents, antimicrobial agents, germicides, fungicides, antioxidants, corrosion inhibitors, rinse aids, preservatives, antistatic agents, ironing aids, antiphobing and impregnating agents, pearlescent agents, polymers, swelling and slip-resistant agents, and UV absorbers.

[0085] Suitable ingredients and framework compositions for washing and cleaning agent compositions (for example, for detergents and fabric softeners) are disclosed, for example, in EP 3 110 393 B1. Manufacturing process

[0086] Methods for producing core / shell microcapsules are known to those skilled in the art. Typically, an oil-based core material that is insoluble or only slightly soluble in water is emulsified or dispersed in an aqueous phase containing the wall-forming agents. Depending on the viscosity of the liquid core material, a wide variety of equipment is used, ranging from simple stirrers to high-performance dispersers, to distribute the core material into fine oil droplets. The wall-forming agents then precipitate from the continuous aqueous phase onto the surface of the oil droplets and can subsequently be cross-linked. This mechanism is used in the in-situ polymerization of amino and phenolic microcapsules and in the coacervation of water-soluble hydrocolloids. In contrast, oil-soluble acrylate monomers are used for wall formation in radical polymerization.Furthermore, processes are used in which water-soluble and oil-soluble starting materials are reacted at the phase boundary of the emulsion droplets that form the solid shell.

[0087] Examples include the reaction of isocyanates and amines or alcohols to form polyurea or polyurethane walls (interface polymerization), but also the hydrolysis of silicate precursors with subsequent condensation to form an inorganic capsule wall (sol-gel process).

[0088] This document describes a process for the production of microcapsules comprising a fragrance as the core material and a shell consisting of three layers. Preferably, the very thin second layer, which serves as a diffusion barrier, is used as a template during production. Very small amounts of wall-forming agents of the type mentioned are required to build up this second layer. Preferably, after droplet formation at high stirring speeds, the sensitive templates are equipped with a negative electrical charge by suitable protective colloids (e.g., AMPS) such that neither Ostwald ripening nor coalescence can occur. After the production of this stable emulsion, the wall-forming agent, for example, a suitable precondensate based on aminoplast resin, can form a much thinner shell (layer) compared to the prior art, at a now significantly reduced stirring speed. The thickness of the shell can be further reduced, in particular, by the addition of an aromatic alcohol, e.g., a pre-condensate.B. m-Aminophenol, can be further reduced. This is followed by the formation of a productionable shell structure, which unexpectedly shows a good affinity for proteins such as gelatin or alginate upon addition and deposition on the templates without the expected problems such as gelation of the mixture, agglomeration, and incompatibility with the structure-giving agent.

[0089] The procedure includes at least the following steps: a) Producing an oil-in-water emulsion by emulsifying a core material in an aqueous phase, optionally with the addition of protective colloids; b) Adding the wall-forming component(s) of the inner shell layer, followed by deposition and curing, wherein the wall-forming component(s) of the inner shell layer are, in particular, an aldehydic component, an amine component, and an aromatic alcohol; c) Adding the wall-forming component(s) of the middle shell layer, followed by deposition and curing, wherein the wall-forming component(s) of the middle shell layer are, in particular, proteins and / or polysaccharides; and d) optionally adding the wall-forming component(s) of the outer shell layer, followed by deposition and curing, wherein the wall-forming component(s) of the outer shell layer is, in particular, an amine component.

[0090] Alternatively, steps a) and b) can be carried out as follows: a) Producing an oil-in-water emulsion by emulsifying a core material in an aqueous phase in the presence of the wall-forming component(s) of the inner shell layer, optionally with the addition of protective colloids; b) Deposition and curing of the wall-forming component(s) of the inner shell layer, wherein the wall-forming component(s) of the inner shell layer are in particular an aldehydic component, an amine component and an aromatic alcohol.

[0091] This process can be carried out either sequentially or as a so-called one-pot process. In the sequential process, only steps a) and b) are performed in the first stage, up to the point where microcapsules with only the inner layer as a shell (intermediate microcapsules) are obtained. Subsequently, a subset or the entire quantity of these intermediate microcapsules is transferred to a further reactor. The remaining reaction steps are then carried out in this reactor. In the one-pot process, all process steps are carried out in a single batch reactor. Performing the process without changing reactors is particularly time-saving.

[0092] For this to work, the entire system should be designed for the one-pot process. This allows for the correct selection of solid fractions, precise temperature control, the balanced addition of formulation components, and the sequential addition of wall-forming agents.

[0093] In one embodiment of the process, the process comprises the production of an aqueous phase by dissolving a protective colloid, in particular acrylamidosulfonate, and a methylated prepolymer in water. The prepolymer is preferably produced by reacting an aldehyde with either melamine or urea. Optionally, methanol can be used.

[0094] Furthermore, in the process according to the invention, the aqueous phase can be mixed by stirring and setting a first temperature, wherein the first temperature is in the range of 30 °C to 40 °C. Subsequently, an aromatic alcohol, in particular phloroglucinol, resorcinol or aminophenol, can be added to the aqueous phase and dissolved therein.

[0095] Alternatively, in the process according to the invention, an oil phase can be produced by mixing a fragrance composition or a phase change material (PCM) with aromatic alcohols, in particular phloroglucinol, resorcinol, or aminophenol. Alternatively, reactive monomers or diisocyanate derivatives can also be incorporated into the fragrance composition. The first temperature can then be set.

[0096] A further step could be the production of a two-phase mixture by adding the oil phase to the water phase and subsequently increasing the rotational speed.

[0097] Emulsification can then be started by adding formic acid. Regular measurement of the particle size is recommended during this process. Once the desired particle size is reached, the two-phase mixture can be stirred further, and a second temperature can be set to harden the capsule walls. This second temperature can be in the range of 55 °C to 65 °C.

[0098] Subsequently, a melamine dispersion can be added to the microcapsule dispersion and a third temperature can be set, the third temperature preferably being in the range of 75 °C to 85 °C.

[0099] Another suitable step is the addition of an aqueous urea solution to the microcapsule dispersion.

[0100] To produce the first shell, the microcapsule dispersion is added to a solution of gelatin and alginate. This would then be followed by cooling to 45 °C to 55 °C and adjusting the pH of the microcapsule dispersion to a value in the range of 3.8 to 4.3, particularly 3.9.

[0101] The microcapsule dispersion can then be cooled to a fourth temperature, which is in the range of 20°C to 25°C. It can subsequently be cooled to a fifth temperature, which is in the range of 4°C to 17°C, particularly 8°C.

[0102] Subsequently, the pH of the microcapsule dispersion would be adjusted to a value in the range of 4.3 to 5.1, and glutaraldehyde or glyoxal would be added. The reaction conditions, in particular temperature and pH, can be selected differently depending on the crosslinking agent. A person skilled in the art can derive the appropriate conditions, for example, from the reactivity of the crosslinking agent. The amount of glutaraldehyde or glyoxal added influences the crosslinking density of the first layer and thus, for example, the density and biodegradability of the microcapsule shell. Accordingly, a person skilled in the art can vary the amount precisely to adjust the property profile of the microcapsule. To produce the additional third layer, a melamine slurry can be prepared using melamine, formic acid, and water. This melamine slurry is then added to the microcapsule dispersion.Finally, the pH of the microcapsule dispersion would be adjusted to a value in the range of 9 to 12, particularly 10 to 11. EXAMPLES Example 1 - Production of the microcapsule according to the invention with a three-layer structure 1.1 Materials

[0103] Table 1: List of substances used in production Fabrics Concentration / % Quantity / g Lupasol PA140 1),*< 20 3,4 Luracoll SD 2),*< 67 1,6 Water addition 1 100 34,9 Weiroclean perfume oil *< 100 38,8 Formic acid *< Addition 1 20 0,5 Resorcinol solution 12,2 2,5 Melafin suspension 3),6)< Addition 1 27 1,9 Urea solution 16,6 4,7 Water addition 2 100 100,19 Sodium sulfate *< 100 0,5 Sodium alginate *< 100 1,4 Pork skin gelatin *< 100 6,2 Formic acid *< Addition 2 4)< 20 1,4 Sodium hydroxide solution addition 1 4)< 20 0,8 Relugan GT50 5),*< 50 1,9 Melafin suspension 3),6)< Addition 2 27 6,7 Sodium hydroxide solution addition 2 4)< 20 2,2 1) Polymer based on: Acrylamidosulfonate, Source: BASF 2) 1,3,5-Triazine-2,4,6-triamine, polymer with formaldehyde, methylated (content (w / w): >= 60% - <= 80%), in water, Source: BASF 3) Cyanuric acid triamide (melamine); Source: OCI Nitrogen BV 4) Addition depends on pH value (see manufacturing process) 5) Glutaral; glutaraldehyde; glutaraldehyde (content (w / w): 50%), water (content (w / w): 50%), Source: BASF 6) Concentration based on the acidified suspension *Quantities of components refer to the commercial product and are used as supplied 1.2 Manufacturing process

[0104] To prepare reaction mixture 1, Lupasol PA140 and Luracoll SD were weighed into a beaker with water (additive 1) and premixed using a 4 cm dissolver disc. The beaker was then placed in a water bath and stirred with the dissolver disc at 500 rpm at 30°C until a clear solution was obtained.

[0105] Once the Luracoll / Lupasol solution was clear and had reached 30–40 °C, the perfume oil was slowly added, adjusting the speed (1100 rpm) to achieve the desired particle size. The pH of this mixture was then acidified by adding formic acid.

[0106] The mixture was emulsified for 20-30 minutes, or as required, until the desired particle size of 20-30 µm (peak max) was reached. The particle size was determined using a Beckmann-Coulter instrument (laser diffraction, Fraunhofer method). Once the desired particle size was achieved, the rotational speed was reduced to ensure gentle mixing.

[0107] The resorcinol solution was then stirred in and preformed for 30–40 minutes with gentle stirring. After preformation, the emulsion temperature was increased to 50 °C within 15 minutes. Upon reaching this temperature, the mixture was increased to 60 °C over 15 minutes and held at this temperature for a further 30 minutes. Subsequently, the melafin suspension (Addition 1) was adjusted to a pH of 4.5 using 20% ​​formic acid and added to the reaction mixture over 90 minutes. The temperature was then held for 30 minutes. After 30 minutes, the temperature was first increased to 70 °C within 15 minutes. Then, the temperature was increased to 80 °C within 15 minutes and held for 120 minutes. Finally, the aqueous urea solution was added, the heat source was switched off, and the reaction mixture was cooled to room temperature.In a separate beaker, sodium sulfate was dissolved in water at 40–50 °C while stirring with a paddle stirrer. Sodium alginate and porcine skin gelatin were slowly sprinkled into the heated water. Once all solids had dissolved, reaction mixture 1 was added to the prepared gelatin / sodium alginate solution while stirring. Upon achieving a homogeneous mixture, the pH was adjusted to 3.9 by slowly adding formic acid 2 dropwise, after which the heat source was removed. The mixture was then cooled to room temperature. Once at room temperature, the reaction mixture was cooled with ice. When the temperature reached 8 °C, the ice bath was removed, and the pH was raised to 4.7 by adding sodium hydroxide solution 1. Relugan GT50 was then added, ensuring that the temperature did not exceed 16–20 °C before the addition of Relugan GT50.

[0108] Subsequently, the melafin suspension, acidified to pH 4.5 with 20% formic acid, was slowly added (Addition 2). The reaction mixture was then heated to 60 °C and held at this temperature for 60 minutes. After this holding time, the heat source was removed and the microcapsule suspension was gently stirred for 14 hours. After 14 hours, the pH of the microcapsule suspension was adjusted to 10.5 using sodium hydroxide solution (Addition 2). 1.3 Result

[0109] The microcapsule MK 1 obtained according to the invention was examined by light microscopy. Typical images are shown in Fig. 1 The results are shown in Table 2. To evaluate MK 1, the pH value, solids content, viscosity, particle size, and core material content of the slurry were determined. Table 2: Analysis results of the microcapsule MK 1 according to the invention Measurement method Example 1 pH pH electrode 8-10 Solid content [%] microwave 20 - 30 Viscosity [mPas] Brookfield viscometer < 1000 Particle size Peak max. [µm] Laser diffraction 20 - 30 Nucleus content in slurry [%] Calculation from the recipe 15-20 Example 2 - Production of a non-inventive reference microcapsule - Melamine-formaldehyde formulation 2.1 Materials

[0110] The materials used to manufacture the reference microcapsules - melamine-formaldehyde - are shown in Table 3. Table 3: List of substances used in production Example 2 Fabrics Concentration* / % Quantity / g Lupasol PA140 1)< 20 35,0 Luracoll SD 2)< 67 42,5 Weiroclean perfume oil 100 192,5 Melafin 3),4)< - Suspension 27 48,8 Urea solution 28,6 70,0 DI water for emulsion 100 187,5 Formic acid 10 8,8 1) Acrylamidosulfonate-based polymer 2) 1,3,5-Triazine-2,4,6-triamine, polymer with formaldehyde, methylated (content (w / w): >= 60% - <= 80%), in water 3) Melamine: Cyanuramides: 1,3,5-Triazine-2,4,6-triamines 4) Concentration based on the acidified suspension *Quantities of components refer to the commercial product and are used as supplied 2.2 Manufacturing process (based on BASF patent EP 1 246693 B1)

[0111] Luracoll SD was stirred into deionized water, then Lupasol PA140 was added and stirred until a clear solution was obtained. The solution was heated to 30-35 °C in a water bath. The perfume oil was added while stirring with a dissolver disc at 1100 rpm.

[0112] The pH of the oil-in-water emulsion was adjusted to 3.3–3.8 using 10% formic acid. The emulsion was then stirred at 1100 rpm for 30 minutes until a droplet size of 20–30 µm was achieved, or until the desired particle size of 20–30 µm (peak max) was reached. The particle size was determined using a Beckmann-Coulter instrument (laser diffraction, Fraunhofer method). The rotational speed was reduced depending on the viscosity to ensure thorough mixing. Stirring continued at this speed for another 30 minutes at 30–40 °C. The emulsion was then heated to 60 °C and stirred again.

[0113] The melamine suspension was adjusted to a pH of 4.5 with 10% formic acid and added to the reaction mixture. The mixture was kept at 60°C for 60 minutes and then heated to 80°C. After stirring for 60 minutes at 80°C, the urea solution was added.

[0114] After cooling to room temperature, the microcapsule dispersion was filtered through a 200 µm filter sieve. 2.3 Result

[0115] The obtained MF reference microcapsule MK 2 was examined using light microscopy. A typical image of the MK 2 is shown in Fig. 2 The results are shown in Table 4. To evaluate the obtained microcapsules, the pH value, solids content, viscosity, particle size, and core material content in the slurry were determined. Table 4: Analysis results of the non-inventive reference microcapsule MK 2 Measurement method Example 2 pH pH electrode 5,5 - 6,5 Solid content [%] microwave 37 - 41 Viscosity [mPas] Brookfield viscometer < 1000 Particle size Peak max. [µm] Laser diffraction 20 - 30 Nucleus content in slurry [%] Calculation from the recipe 30 - 35 Example 3 - Production of non-inventive reference microcapsules - Gelatin / alginate formulation (based on patent DE 3424115) 3.1 Materials

[0116] The materials used to manufacture the reference microcapsules - gelatin-alginate - are shown in Table 5. Table 5: List of substances used for production and quantity of the non-inventive reference microcapsule MK3 Example 3 Fabrics Concentration* / % Quantity / g Water addition 1 100 204,4 Sodium sulfate addition 1 100 0,9 sodium alginate 100 2,9 Pork skin gelatin 100 12,7 Sodium hydroxide solution addition 1 1)< 20 1,0 Weiroclean perfume oil 100 79,6 Sodium sulfate addition 2 100 0,8 Water addition 2 100 180,5 acetic acid 96 2,7 Sodium hydroxide solution addition 2 1)< 20 3,6 Regulan GT50 2)< 50 3,9 Sodium hydroxide solution addition 3 1)< 20 7,1 1) Addition depends on pH value (see manufacturing process) 2) Glutaral; Glutaraldehyde; Glutardialdehyde (content (w / w): 50%), Water (content (w / w): 50%) 3.2 Manufacturing process

[0117] Sodium sulfate was weighed into an 800 ml beaker and dissolved by adding 1 ounce of water while stirring with a paddle stirrer.

[0118] The perfume oil was weighed into a separate beaker and heated to 45°C while stirring.

[0119] Sodium alginate and porcine skin gelatin were slowly sprinkled into the sodium sulfate solution while stirring and dissolved. The pH was adjusted to 9.5 by adding sodium hydroxide solution (1).

[0120] To create an emulsion, the heated perfume oil was slowly added to the gelatin-alginate solution while increasing the stirrer speed to 1200 rpm. During emulsification, the droplet size was determined using a Beckmann-Coulter instrument (laser diffraction, Fraunhofer method). Once a droplet size of 20–30 µm was reached, the speed was reduced to ensure gentle mixing.

[0121] In another beaker, sodium sulfate additive 2 was dissolved in water additive 2. Concentrated acetic acid was then added to this solution and heated to 45°C while stirring.

[0122] The previously warmed acetic acid / sodium sulfate solution was poured into a dropping funnel and added to the emulsion over a period of 15 minutes. The stirring speed was selected to ensure complete mixing.

[0123] After adding the acetic acid solution, the mixture was first cooled to room temperature while stirring and then cooled to 8 °C with ice.

[0124] Once the suspension temperature reached 8 °C, the ice bath was removed and the pH was adjusted to 4.7 by adding 2 parts sodium hydroxide solution. Regulan GT50 was then added. Care was taken to ensure that the temperature of the prepared suspension did not exceed 16-20 °C before the addition of Regulan GT50.

[0125] The pH of the microcapsule suspension was then adjusted to 10.5 by slowly adding sodium hydroxide solution dropwise (additive 3) while stirring (approx. 20-30 min). 3.3 Result

[0126] The obtained gelatin reference microcapsules MK 3 were examined by light microscopy. A typical image of the MK 3 is shown in Fig. 3The results are shown in Table 8. To evaluate the obtained microcapsules, the pH value, solids content, viscosity, particle size, and core material content of the microcapsule suspension were determined. Table 6: Analysis results of the gelatin-alginate reference microcapsule MK3 Measurement method Example 3 pH pH electrode 8 - 10 Solid content [%] microwave 18-22 Viscosity [mPas] Brookfield viscometer < 1000 Particle size Peak-Max. [µm] Laser diffraction 20 - 30 Nucleus content in slurry [%] Calculation from recipe 14-18 Example 4 - Production of another microcapsule according to the invention with a three-layer structure 4.1 Materials

[0127] Table 7: List of substances used in production Fabrics Concentration / % Quantity / g Lupasol PA140 1),*< 20 3,4 Luracoll SD 2),*< 67 1,6 Water addition 1 100 34,9 Weiroclean perfume oil *< 100 38,8 Formic acid *< Addition 1 20 0,5 Resorcinol solution 12,2 2,5 Melafin suspension 3),6)< Addition 1 27 1,9 Urea solution 16,6 4,7 Water addition 2 100 100,2 Sodium sulfate *< 100 0,5 Sodium alginate *< 100 1,4 Pork skin gelatin *< 100 6,2 Formic acid *< Addition 2 4)< 20 1,4 Sodium hydroxide solution addition 1 4)< 20 0,8 Glyoxal 40% 5),*< 40 1,4 Melafin suspension 3),6)< Addition 2 27 6,7 Sodium hydroxide solution addition 2 4)< 20 2,2 1) Polymer based on: Acrylamidosulfonate, Source: BASF 2) 1,3,5-Triazine-2,4,6-triamine, polymer with formaldehyde, methylated (content (w / w): >= 60% - <= 80%), in water, Source: BASF 3) Cyanuric acid triamide (melamine); Source: OCI Nitrogen BV 4) Addition depends on pH value (see manufacturing process) 5) Glyoxal; oxalaldehyde (content (w / w): 40%), water (content (w / w): 60%), Source: Sigma Aldrich 6) Concentration based on the acidified suspension *Quantities of components refer to the commercial product and are used as supplied 4.2 Manufacturing process

[0128] To prepare reaction mixture 1, Lupasol PA140 and Luracoll SD were weighed into a beaker with water (additive 1) and premixed using a 4 cm dissolver disc. The beaker was then placed in a water bath and stirred with the dissolver disc at 500 rpm at 30°C until a clear solution was obtained.

[0129] Once the Luracoll / Lupasol solution was clear and had reached 30–40 °C, the perfume oil was slowly added, adjusting the speed (1100 rpm) to achieve the desired particle size. The pH of this mixture was then acidified by adding formic acid.

[0130] The mixture was emulsified for 20-30 minutes, or as required, until the desired particle size of 20-30 µm (peak max) was reached. The particle size was determined using a Beckmann-Coulter instrument (laser diffraction, Fraunhofer method). Once the desired particle size was achieved, the rotational speed was reduced to ensure gentle mixing.

[0131] The resorcinol solution was then stirred in and preformed for 30–40 minutes with gentle stirring. After preformation, the emulsion temperature was increased to 50 °C within 15 minutes. Upon reaching this temperature, the mixture was increased to 60 °C over 15 minutes and held at this temperature for a further 30 minutes. Subsequently, the melafin suspension (Addition 1) was adjusted to a pH of 4.5 using 20% ​​formic acid and added to the reaction mixture over 90 minutes. The temperature was then held for 30 minutes. After 30 minutes, the temperature was first increased to 70 °C within 15 minutes. Then, the temperature was increased to 80 °C within 15 minutes and held for 120 minutes. Finally, the aqueous urea solution was added, the heat source was switched off, and the reaction mixture was cooled to room temperature.In a separate beaker, sodium sulfate was dissolved in water at 40–50 °C while stirring with a paddle stirrer. Sodium alginate and porcine skin gelatin were slowly sprinkled into the heated water. Once all solids had dissolved, reaction mixture 1 was added to the prepared gelatin / sodium alginate solution while stirring. Upon achieving a homogeneous mixture, the pH was adjusted to 3.9 by slowly adding formic acid 2 dropwise, after which the heat source was removed. The mixture was then cooled to room temperature. Once at room temperature, the reaction mixture was cooled with ice. When the temperature reached 8 °C, the ice bath was removed, and the pH was raised to 4.7 by adding sodium hydroxide solution 1. Finally, the glyoxal solution was added, ensuring that the temperature did not exceed 16–20 °C before the glyoxal solution was added.

[0132] Subsequently, the melafin suspension, acidified to pH 4.5 with 20% formic acid, was slowly added (Addition 2). The reaction mixture was then heated to 60 °C and held at this temperature for 60 minutes. After this holding period, the heat source was removed and the microcapsule suspension was gently stirred for 14 hours. After 14 hours, the pH of the microcapsule suspension was adjusted to 10.5 using sodium hydroxide solution (Addition 2). 4.3 Result

[0133] The microcapsule MK 4 obtained according to the invention was examined by light microscopy. Typical images are shown in Fig. 6 The results are shown in Table 8. To evaluate MK 1a, the pH value, solids content, viscosity, particle size, and core material content of the slurry were determined. Table 8: Analysis results of the microcapsule MK 1a according to the invention Measurement method Example 1 NEW pH pH electrode 8-10 Solid content [%] microwave 20 - 30 Viscosity [mPas] Brookfield viscometer < 1000 Particle size Peak max. [µm] Laser diffraction 20 - 30 Nucleus content in slurry [%] Calculation from the recipe 15 - 20 Example 5 - Stability measurement of the microcapsules 5.1 Preliminary remarks

[0134] To determine the stability of microcapsules, they were stored in a model fabric softener formulation at 40°C for up to 12 weeks, and the concentration of fragrances diffused from the capsule interior into the surrounding formulation was determined using HS-GC / MS. Based on the measured values, the residual proportion of perfume oil still contained in the capsule was calculated.

[0135] Model fabric softener formulation based on Evonik's Rewoquat WE 18 E US, based on the formula in the corresponding product data sheet: To prepare the fabric softener base, 94 g of water were heated to 50 °C and 5.65 g of Rewoquat WE 18 E US were added to the heated water while stirring. The mixture was cooled to room temperature, and then the microcapsule dispersion was added. 5.2 Experimental Procedure

[0136] For this purpose, the microcapsule suspension (slurry) was carefully homogenized and stored at a concentration of 1 wt% in the model formulation at 40°C in an airtight container in a warming oven. The non-encapsulated odorant with an analogous odorant concentration in the model formulation served as a comparison.

[0137] After a specified storage period, the samples were removed from the incubator and an aliquot was weighed into a 20 ml headspace vial. The vial was then immediately sealed. These samples were analyzed by headspace SPME ( S oil- P hare- M micro- E The samples were examined using capillary gas chromatography (xtraction) and evaluated after detection with a mass-selective detector (MSD). 5.3 Result

[0138] The stability course of the capsule according to the invention according to Example 1 and 4 and the reference capsule according to Example 2 over 12 weeks is shown in Table 9. Table 9: Stability test measurements Storage period Capsules according to the invention (Example 1) Capsules according to the invention (Example 4) Melamine-formaldehyde capsules (Example 2) Week % stability % stability % stability 0 100 100 100 1 92 87 100 4 59 52 87 12 22 20 20

[0139] As can be seen from Table 9, the microcapsules MK 1 and MK 4 according to the invention show a stability comparable to the MF reference microcapsule MK 2 after 12 weeks of storage in a model formulation.

[0140] The gelatin / alginate reference microcapsule MK 3 shows no capsule stability in the test medium under the selected test conditions (disintegration already during sample preparation), so that it was not possible to acquire measurement values ​​for stability assessment within the required time frame.

[0141] To calculate capsule stability, changes in the concentration of 16 individual ingredients of the encapsulated fragrance were considered. A decrease in stability results in the release of the encapsulated fragrance, which can then be detected by gas chromatography using headspace SPME. Since all capsule dispersions were standardized to a defined oil content of 15 wt%, a direct comparison of the analyzed capsule samples is possible. Individual ingredients (or their gas chromatographically detected individual signals) that show higher concentrations than theoretically possible compared to the reference standard due to measurement-related fluctuations were only considered up to their theoretical maximum concentration in the evaluation. Example 6 - Biodegradability measurement of microcapsules (according to OECD 301 F) 6.1 General

[0142] This experiment serves to assess the rapid biodegradability of the microcapsules.

[0143] The standard test concentration for the samples is 1000 mg / l O₂. The measuring heads and controller measure oxygen consumption in a closed system. The consumption of oxygen and the simultaneous binding of the resulting carbon dioxide to sodium hydroxide pellets create a negative pressure within the system. The measuring heads register and store this pressure over the set measurement period. The stored values ​​are transmitted to the controller via infrared. They can then be transferred to a PC and analyzed using the Achat OC software.

[0144] To eliminate the influence of the core material on degradation, perfluorooctane was encapsulated (degradation rate = <1%). 6.2 Equipment and chemicals

[0145] Devices: OxiTop control measuring system, WTW, including OxiTop OC 110 controller with interface cable for PC, 6 OxiTop C measuring heads, 6 glass vials with a total volume of 510 ml each, 6 magnetic stirrers, 6 rubber tubes, 1 magnetic stirring system. as well as the Achat OC reading software ORI-BSB drying oven, set to 20 °C Oxygenius diffuser stones, 30 x 15 x 15 mm 3< Thomas aquarium aeration pump - ASF No. 1230053 Filter groove D=90 mm Suction bottle 2 I Whiteband filter MN 640 d, D=90mm, Macherey + Nagel Manual “System Oxi Top Controll”, WTW company Chemicals: Activated sludge from the company's own or a municipal wastewater treatment plant Ethylene glycol zA, Merck Reference sample with COD 1000 mg / l O2 Walnut shell flour, Senger Natural Raw Materials Nutrient salt solution from the company's own or a municipal wastewater treatment plant Sodium hydroxide pellets, zA > 99%, Merck company Cuvette test CSB LCK 514, Dr. Long 6.3 Implementation 6.3.1 Production of the microcapsule slurries

[0146] The microcapsules MK 1, MK 2, MK 3 and MK 4 were prepared according to the descriptions of Examples 1 to 4, with the difference that the fully persistent perfluorooctane (degradation rate <1%) was used as the core material instead of the perfume oil. This eliminates any potential influence of the core material on the experimental result.

[0147] In one embodiment, the capsule dispersion is washed after preparation by centrifugation and redispersion in water three times to separate dissolved residues. For this purpose, a 20-30 mL sample is centrifuged for 10 minutes at 12,000 revolutions per minute. After filtering off the clear supernatant, the mixture is made up with 20-30 mL of water and the sediment is redispersed by shaking. 6.3.2 Sample preparation

[0148] For the 28-day degradation tests, the microcapsule slurries were used as received from the manufacturing process. In the case of the extended 60-day degradation tests, the microcapsule slurries were washed after manufacturing by centrifugation and redispersion in water three times to remove dissolved residues. For this, a 20-30 mL sample was centrifuged for 10 minutes at 12,000 rpm. After filtering off the clear residue, the sample was made up with 20-30 mL of water, and the sediment was redispersed by shaking. 6.3.3 Preparation of the reference sample

[0149] 711.6 mg of ethylene glycol were dissolved in a 1 L volumetric flask and filled to the mark. This corresponds to a COD of 1000 mg / L O₂. Ethylene glycol is considered readily biodegradable and serves as the reference here.

[0150] Due to the rapid degradation of ethylene glycol, walnut shell flour was added as an additional reference for the extended 60-day test. Walnut shell flour consists of a mixture of biopolymers, particularly cellulose and lignin, and serves as a solid-based, bio-based reference. Because of the slow degradation of walnut shell flour, the test progress can be monitored over the entire 60-day period. For this purpose, 117.36 g of walnut shell flour were homogeneously dispersed in 1 L of water while stirring. Aliquots of this mixture were taken while stirring to determine the COD (Chemical Oxygen Demand). Based on the mean COD value of 1290 ± 33 mg / L O₂, the required amount was calculated and transferred into the OxiTop bottles while stirring. 6.3.4 Preparation of the biosludge

[0151] Activated sludge was taken from the outlet of the activated sludge basin of a company-owned or municipal wastewater treatment plant using a 20-liter bucket. After settling for 30 minutes, the supernatant was discarded.

[0152] The concentrated bio-sludge in the bucket was then continuously aerated for 3 days using the aquarium pump and an air stone. 6.3.5 Determination of the dry content of the biosludge

[0153] After 3 days, 100 ml of the concentrated biosludge was filtered off using a filter funnel via a white belt filter. The filter cake was dried for 24 hours at 105°C in a drying oven. TG = A E TG = Dry matter content of the biosludge in % E = Weight of filter cake in g A = Weight of filter cake in g c = TG x 10 c = Concentration of biosludge in g / l 6.3.6 Adjustment of samples to a COD of 1000 mg / l O2

[0154] The COD value of the samples to be tested was determined using the COD LCK 514 cuvette test. The sample is diluted with water until a COD value of 1000 mg / l O₂ is reached. 6.3.7 Preparation of the approaches

[0155] Six OxiTop bottles were used for one sample, as duplicate determinations were carried out in each case.

[0156] The following measurements were taken in two bottles each (duplicate determination): Biodegradability of the sample; Biodegradability of the ethylene glycol solution (= reference solution); Blank sample (= determination of the residual degradation of the sludge itself)

[0157] Each bottle requires: 25 ml sample with a COD of 1000 mg / l O2 (for a blank sample, 25 ml distilled water) 3.5 ml nutrient solution 44.5 mg oven-dried sludge Distilled water to top up to a total volume of 250 ml

[0158] Three sodium hydroxide pellets were placed into each rubber cup using a spatula.

[0159] After the bottles were filled with sample, nutrient solution, biosludge, and distilled water, a magnetic stir bar was placed in each bottle. Then, the rubber holders were placed on the respective bottle necks, and the measuring heads were screwed firmly onto the bottles. 6.4 Measurement and Evaluation

[0160] The programming of the OxiTop-C measuring heads and the evaluation of the data are described in detail in the manual "System OxiTop Control", WTW. 6.5 Result

[0161] The biodegradation diagram of the capsule MK 1 according to the invention, as specified in OECD 301 F, is in Fig. 4(a) depicted.

[0162] The capsule MK 1 according to the invention shows a biodegradability of 76±4% after 28 days. Furthermore, the capsule MK 1a according to the invention shows a biodegradability of 78±9% after 28 days.

[0163] After washing, the MK 1 capsule according to the invention shows a biodegradability of 47±16% after 60 days. Figure 7 A comparison of biodegradability measurements according to OECD 301F is shown. This demonstrates that the microcapsule MK1 according to the invention exhibits comparable biodegradability to the natural reference walnut shell flour, which has a biodegradability of 53% after 60 days.

[0164] In Figure 5This document presents a comparison of biodegradability measurements according to OECD 301F between the microcapsule MK 1 according to the invention, the MF reference microcapsule MK 2, and the gelatin / alginate reference microcapsule MK 3. The OECD 301F standard (according to the "Revised Introduction to the OECD Guidelines for testing of Chemicals, section 3, Part 1, dated 23 March 2006") stipulates that the substance under test must achieve a biodegradation rate of 60% within a 10-day timeframe (starting from a degradation rate of 10%). Both the microcapsule MK 1 according to the invention and the gelatin / alginate reference microcapsule MK 3 exhibit significantly faster biodegradation compared to the MF reference microcapsule MK 2. The required timeframe for a 60% degradation rate is reached after only 7 days.

[0165] It appears that, based on experience, the degradation rate of the standard MF capsules MK 2 reaches the range of 10% within a short time and forms a plateau that indicates no further degradation within the measurement period.

[0166] The cross-linked gelatin-alginate microcapsules MK 3 have proven to be readily biodegradable. They reach a biodegradability of 68±5% within 10 days.

[0167] The microcapsule MK 1 according to the invention also shows a degradation rate of 68±6% after 10 days.

[0168] In Figure 7The degradation curves of the inventive MK1, MK2, and MK3, as well as the reference substances ethylene glycol and walnut shell flour, are shown for comparison. It is evident that the rapidly biodegradable reference sample, ethylene glycol, reaches its maximum degradability between days 15 and 25 of the measurement period. Subsequently, the measured value appears to decrease, caused by inoculum processes resulting from the absence of a degradable food source. This effect can be considered a measurement artifact. A comparable behavior is observed for the readily degradable reference microcapsules MK3. The maximum degradability of sample MK3 is reached between days 25 and 45 of the measurement period and then decreases accordingly. The poorly degradable reference MK2 shows no biodegradability during the measurement period. Negative measured values ​​(which occurred particularly in the second half of the measurement period) were set to zero.The natural reference material, walnut shell flour, exhibits the typical step-like degradation of a complex mixture. Maximum biodegradability is reached around day 40 of the measurement, and this value remains constant within the range of variation until the end of the 60-day measurement period. A similar degradation behavior can be observed for the MK1 microcapsule according to the invention. A step-like progression leads to an average degradation rate of 47% after 60 days, with the absolute range of biodegradability between 30% and 65%. Table 10: Presentation of degradation values ​​according to OECD 301 (60 days) method 7 days 14 days 26 days 40 days 48 days 60 days Capsule according to the invention (MK 1), washed 1)< OECD 301 F 25±11 31±10 36±21 47±16 49±15 47±16 Melamine formaldehyde capsules (MK 2), washed 2)< OECD 301 F 1±1 0±0 0±0 0±0 0±0 0±0 Gelatin-alginate capsules (MK 3), washed 3)< OECD 301 F 46±10 55±6 72±10 82±6 74±4 63±4 Walnut shell flour 4)< OECD 301 F 17 23 43 51 52 53 1) MK1, quadruple determination 2) MK2, double determination 3) MK3, double determination 4) Walnut shell flour reference, single determination Example 7 - Biodegradability measurement of microcapsules (according to OECD 302 C) 7.1 General

[0169] This experiment serves to assess the basic biodegradability of the microcapsules.

[0170] The measurement was carried out according to the specifications of OECD 302C 1981-05 by a testing laboratory accredited according to DIN EN ISO 17025 (SGS Institut Fresenius GmbH, Taunusstein, Germany). The modified test procedure with natural inoculum and a modified detection method (direct quantification of the carbon dioxide produced) was used.

[0171] Analogous to sample preparation for biodegradability testing according to OECD 301 F (see Example 5), microcapsule slurries were produced containing perfluorooctane (degradation rate = <1%) as the core material. This prevents the core material from influencing the biodegradability of the microcapsules. 7.2 Equipment and chemicals

[0172] According to the testing laboratory, the inoculum used consists of activated sludge from the Taunusstein-Bleidenstadt wastewater treatment plant (~100 mg dry mass equivalent / L batch). Aniline was used as a control. 7.3 Implementation

[0173] First, a sample was taken from each microcapsule slurry and an analysis of the total organic carbon (TOC) was performed. Knowing the molar ratio of carbon dioxide to elemental carbon, the theoretical amount of carbon dioxide that can be released during the degradation of the test substance (TCO2, "theoretical amount of CO2") could be calculated using the TOC.

[0174] The test samples were prepared in 3500 mL volumes. The test specimen and the inoculum were incubated in this volume at room temperature in a mineral nutrient medium. Based on the total organic carbon (TOC) of the microcapsule slurry, a carbon concentration of approximately 25 mg C / L was established. Thus, only the carbon from the test specimen was available as an energy source for the microorganisms in the inoculum. The test samples were aerated with CO2-free compressed air and stirred using magnetic stirrers. The degradation of the test specimen by microorganisms converted the contained carbon into carbon dioxide. This gas evolution was collected using gas washing bottles attached to the test sample. The gas washing bottles were filled with a barium hydroxide solution, which binds the carbon dioxide produced. The amount of carbon dioxide formed in the test sample can be quantified by titration with hydrochloric acid.The degree of degradation of the test substance was then calculated by comparing the theoretically producible carbon dioxide (from the TOC measurement) with the actual amount of carbon dioxide measured. Three samples were prepared for each test substance, allowing for the determination of an average degree of degradation.

[0175] To determine the amount of carbon dioxide produced by the inoculum, two so-called blank samples containing only the inoculum, and no test substance, were measured in parallel with the test sample. The amount of carbon dioxide determined in this way was subtracted from the test sample. Analogous to the procedure described above, a sample containing a control substance (aniline) and a sample containing a mixture of the test substance and the control substance (toxicity control) were also prepared and included in the analysis.

[0176] The test lasted 28 or 60 days, with the degradation attempt being stopped on the last day by adding concentrated hydrochloric acid and the carbonates or dissolved carbon dioxide present in the mixture being driven off and also quantified in the connected gas washing bottles. 7.4 Measurement and Evaluation

[0177] After titration of the barium hydroxide solution in the gas washing bottles, the amount of carbon dioxide produced in the test mixture can be quantified and the degree of degradation of the test substrate can be calculated using the following formula: % Abbau = mg CO 2 produziert * 100 mg Prüfsubstanz im Ansatz * TCO 2 7.5 Result

[0178] Table 11: Presentation of degradation values ​​according to OECD 301 F and OECD 302 C (28 days) method 3 days 7 days 10 days 14 days 21 days 28 days Capsule according to the invention (MK 1) OECD 301 F 22±5 61±5 68±6 70±7 73±8 76±4 OECD 302 C 16±1 22±1 31±1 37±3 39±4 45±4 Capsule according to the invention (MK 1a) OECD 301 F 23±6 64±8 69±5 72±7 74±9 78±8 Melamine formaldehyde capsules (MK 2) OECD 301 F 8±1 8±1 12±4 - - - Gelatin-alginate capsules (MK 3) OECD 301 F 33±3 60±5 68±5 - - -

[0179] The biodegradation diagram according to OECD302C of the capsule MK1 according to the invention is in Figure 4(b) depicted.

[0180] The capsules according to the invention MK 1 show a degradability value of 45±4 % after 28 days.

[0181] Finally, it should be expressly pointed out that the exemplary embodiments of the device according to the invention described above serve only to discuss the claimed teaching, but do not limit it to these exemplary embodiments.

Claims

1. A washing or cleaning agent characterized in that the agent comprises: a) microcapsules comprising a core material, the core material comprising at least one fragrance, and a shell, the shell consisting of at least a first layer and a second layer, the chemical compositions of which differ from one another, and the shell having a biodegradability of at least 40%, measured according to OECD 301 F in accordance with the measurement specification from example 6 of the description, and measured over a period of 28 days, and, optionally, b) at least one further ingredient selected from surfactants, enzymes, builders and absorption-enhancing agents, the second layer being a polymer comprising an aldehydic component, an aromatic alcohol and an amine component, the second layer containing an aromatic alcohol selected from the group consisting of resorcinol, phloroglucinol and aminophenol, and the proportion of the aromatic alcohol being in the range of 1.0 to 20 wt.%, based on the total weight of the second layer, the proportion of the aldehydic component for the formation of the wall being in the range of 5 to 50 wt.%, based on the total weight of the shell, and the proportion of the amine component being in the range of 20% to 85 wt.%, based on the total weight of the second layer.

2. The washing or cleaning agent according to claim 1, wherein the shell has a biodegradability of at least 50%, preferably at least 60%, particularly preferably at least 70%, measured according to OECD 301 F in accordance with the measurement specification from example 6 of the description, and measured over a period of 28 days.

3. The washing or cleaning agent according to one of the preceding claims, wherein the first layer contains one or more biodegradable components, wherein the biodegradable components are selected from the group consisting of proteins such as gelatin; polysaccharides such as alginate, gum arabic, chitin, or starch; phenolic macromolecules such as lignin; polyglucosamines such as chitosan, polyvinyl esters such as polyvinyl alcohols and polyvinyl acetate; phosphazenes and polyesters such as polylactide or polyhydroxyalkanoate, wherein the first layer contains in particular gelatin and / or alginate.

4. The washing or cleaning agent according to one of the preceding claims, wherein the first layer contains one or more inorganic components, in particular inorganic salts such as calcium carbonate or polysilicates.

5. The washing or cleaning agent according to claim 1, wherein the second layer contains an aldehydic component selected from the group consisting of formaldehyde, glutaraldehyde, succinaldehyde, furfural and glyoxal, and preferably the proportion of the aldehydic component for the polycondensation is in the range of 10 to 30 wt.%, particularly preferably in the range of 15 to 20 wt.%, based on the total weight of the second shell.

6. The washing or cleaning agent according to one of claims 1 to 5, wherein the proportion of aromatic alcohol is in the range of 3 to 15 wt. %, particularly preferably in the range of 9 to 13 wt. %, based on the total weight of the second layer.

7. The washing or cleaning agent according to one of claims 1 to 6, wherein the second layer contains an amine component selected from the group consisting of melamine, melamine derivatives, urea and combinations thereof, and preferably the proportion of the amine component is in the range from 40 wt.% to 80 wt.%, particularly preferably in the range from 55 to 70 wt.%, based on the total weight of the second layer.

8. The washing or cleaning agent according to one of the preceding claims, wherein the second layer is arranged on the inner side of the first layer.

9. The washing or cleaning agent according to one of the preceding claims, wherein the proportion of the second layer in the shell is at most 30%, preferably at most 25 wt.%, particularly preferably at most 20 wt.%, based on the total weight of the shell.

10. The washing or cleaning agent according to one of the preceding claims, wherein the second layer has an average thickness in the range of 0.01 µm to 1 µm, preferably 0.02 µm to 0.5 µm, particularly preferably 0.05 µm to 0.30 µm.

11. The washing or cleaning agent according to one of the preceding claims, wherein the microcapsule has a third layer which is arranged on the outer side of the first layer and which contains a component selected from amines, organic salts, inorganic salts, alcohols, ethers, polyphosphazenes, and precious metals, wherein the proportion of the third layer in the shell is at most 35%, preferably at most 25 wt.%, particularly preferably at most 15 wt.%, based on the total weight of the shell.

12. The use of a washing or cleaning agent according to one of claims 1-11 in a method for cleaning textiles or hard surfaces.

Images