Bio-based core-shell microcapsules

Abstract

The present invention relates to (amino) sugar-based polyurea and / or polyurethane-based microcapsules containing at least one lipophilic active ingredient, which have a good balance of high biodegradability, stability and performance in product formulations compared to the fully synthetic based commercial state-of-the-art microcapsules. Furthermore, the present invention discloses a microcapsule slurry comprising a plurality of said core-shell microcapsules dispersed in an aqueous phase. In addition, the present invention relates to a process for the preparation of the microcapsule slurry and the bio-based core-shell microcapsules contained therein. In a further aspect, the present invention described herein relates to the use of such microcapsules according to the present invention, or a microcapsule dispersion comprising the microcapsules, for the manufacture of various consumer products. Finally, the present invention also relates to consumer products comprising such microcapsules or microcapsule dispersions.

Description

[Technical Field]

[0001] The present invention relates to bio-based core-shell microcapsules containing a natural (amino) sugar segment in the capsule wall as a component that makes the shell wall of the bio-based microcapsule according to the present invention more biodegradable than existing fully synthetic, state-of-the-art microcapsules based on non-bio-based segments. More specifically, the present invention relates to bio-based microcapsules that have a good balance between high biodegradability, stability and performance (target release characteristics) in product formulations compared to commercially available, state-of-the-art microcapsules, which contain a microcapsule shell based on a polyurea and / or polyurethane structure formed using monomers or short-chain sugars and / or amino sugars, and contain at least one lipophilic active ingredient. Furthermore, the present invention discloses a slurry containing a plurality of the bio-based core-shell microcapsules (microcapsule dispersions) dispersed in an aqueous phase. In addition, the present invention relates to a process for preparing the slurry and the core-shell microcapsules contained therein. In further embodiments, the present invention as described herein relates to the use of such microcapsules or microcapsule dispersions containing such microcapsules according to the present invention for preparing various consumer products. Finally, the present invention also relates to consumer products containing the microcapsules or microcapsule dispersions. [Background technology]

[0002] Today, many consumer products, such as detergents, fabric softeners, powder detergents, liquid detergents, shower gels, shampoos, deodorants, and lotions, are scented with aromatic substances or contain cosmetic ingredients that produce specific effects. Unfortunately, for example, the aromatic substances or cosmetic ingredients in such products often interact with other ingredients in the product formulation, or the more volatile components of the fragrance formulation tend to evaporate faster than usual. As a result, this can lead to undesirable changes and / or deterioration of the fragrance impression over time, or premature "use" of cosmetic ingredients, or even adverse reactions with other ingredients in the product formulation, resulting in a decrease in product quality and / or stability. To prevent possible interactions between fragrances or other active ingredients in a product, or to prevent, for example, the volatilization of fragrances, and to avoid distorting or reducing the desired olfactory impression, fragrances or other active ingredients can be added to the formulation in encapsulated form. In this way, for example, the desired olfactory impression can be guaranteed. Furthermore, interactions between product ingredients can be reduced, improving product quality and storage stability.

[0003] Encapsulation is a common technique used to protect active ingredients (also known as active substances or active ingredients) and to release the substance forming the core of the capsule in a targeted manner at a specific point in time. In addition, some active ingredients are often unusable as is for various reasons (e.g., due to their solubility, reactivity, stability, etc.). However, based on the encapsulation method and the selected materials, lipid-soluble or hydrophobic active ingredients, such as fragrances, cosmetic ingredients, or flavorings, can be easily and stably incorporated into various product formulations, thereby reducing or completely preventing interactions or evaporation of highly volatile aromatic components in scented products.

[0004] The contents of the core-shell microcapsule can be released by various means, such as mechanical rupture of the capsule wall by crushing or shearing, rupture of the capsule by melting the wall material, rupture of the capsule by dissolving the wall material, or diffusion of the active ingredient through the activated capsule wall. Alternatively, the shell wall may be broken by biological or enzymatic interactions, releasing the active ingredient(s) in the desired manner.

[0005] Interfacial polymerization is an efficient and common encapsulation process for the production of core-shell microcapsules, thereby creating a hydrophobic core material in water, i.e., a suspension starting from an initial emulsion or suspension of the active ingredient. Monomers or reagents in the aqueous phase diffuse across the interface and react with reactants in the oil phase, or monomers in the aqueous phase react with themselves, depositing and polymerizing on a layer around the emulsion droplet or on the dispersed liquid particles of the core material, forming a compact, crosslinked, and continuous capsule shell. Depending on the wall material and the degree of crosslinking, various properties of the microcapsule can be achieved.

[0006] Polyurea-based, polyurethane-based, or polyurea / polyurethane mixed microcapsules, formed by interfacial polymerization between a polyisocyanate dissolved in a hydrophobic phase and a polyamine and / or diol or polyol dissolved in an aqueous phase, are well-known capsules used in various technical fields, including the fragrance manufacturing industry.

[0007] Numerous polyurea-based and / or polyurethane-based encapsulated formulations currently under development involve the use of fragrances dissolved in at least one polyisocyanate dispersed in an aqueous phase containing at least one polyfunctional amine (e.g., guanidine salts, aromatic polyamines, aliphatic polyamines, or alkyl polyamines) and / or at least one polyol (glycerol, alkyl oxides, alkylene oxides, aliphatic polyols, and aromatic polyols), along with emulsion stabilizers (e.g., surfactants or protective colloids). Alternatively, the liquid core of the emulsion is stabilized by using solid particles smaller than 1 μm in size (e.g., starch, silica, metal oxides) instead of protective colloids and / or surfactants adsorbed at the interface between the two liquid phases (so-called Pickering emulsions).

[0008] Initially, the shell is rapidly formed by the diffusion of small monomers, i.e., the shell's constituent elements. However, as the shell grows, the diffusion rate of monomers through the shell toward the oil phase decreases, slowing down the shell formation reaction. In the case of larger monomers as constituent elements, diffusion into the reaction region (i.e., the oil phase) is hindered, so the reaction gradually slows down, and thus only a surface-crosslinked structure is formed, resulting in a decreased reaction of the larger constituent elements with the polyisocyanate. This, combined with reduced mechanical stability, leads to the diffusion of the active ingredient out of the capsule prior to the desired release, due to the high porosity of the capsule wall. In addition, these formulations for the preparation of oily core-shell microcapsules require the use of protective colloids as formation aids that are positioned on the surface of the emulsion's oil droplets to reduce the surface tension of the aqueous phase, such as polyvinyl alcohol (PVA), polyvinylpyrrolidone, water-soluble acrylate copolymers, modified starch, gelatin, gum arabic, cellulose derivatives such as carboxymethylcellulose, and other large polysaccharides, and / or nonionic, cationic, or anionic substances (so-called surfactants) with surface activity. As a result, the degree of diffusion of components toward the interface between the oil phase and the aqueous phase is reduced as diffusion is inhibited, limiting the interfacial polymerization reaction between the polyisocyanate in the oil phase and the polyamine and / or polyol in the aqueous phase on the surface of the oil droplet, and thus similarly resulting in a surface-crosslinked structure with a limited degree of urea / urethane-based linkage.

[0009] However, state-of-the-art core-shell microcapsules have the disadvantage that their fully synthetic shell material is largely stable to hydrolysis and resistant to environmental degradation.

[0010] As non-biodegradable plastic particles are increasingly subject to public criticism regarding their environmental impact, and as growing social pressure and new and future regulatory requirements (governments, national and local) on plastics from an environmental and health perspective increase the demand for bio-based and even biodegradable solutions, the development of new encapsulation materials is necessary to achieve the reduction of microplastics in the environment and the increased biodegradability towards more eco-sensitive products, preferably bio-based products. Therefore, today, bio-based and biodegradable materials are the focus of attention.

[0011] State-of-the-art microcapsules manufactured by interfacial polymerization are largely not biodegradable in the environment (either due to direct negative environmental impacts or the generation of non-biodegradable residues), or they do not exhibit sufficient stability for efficient encapsulation of active ingredients. These microcapsules are based on entirely synthetically derived polyurea, polyurethane, aminoplast, polyacrylate structures, or mixtures of these structures. Therefore, there is a need for microcapsules that are not only synthetic but also biodegradable in the environment and simultaneously highly stable.

[0012] Furthermore, the first step toward natural-based products involves preparing a biodegradable coating on a non-biodegradable core-shell capsule substrate called a "greenwash" to achieve a "biodegradable" impression. This is done by using high molecular weight polysaccharides and aminopolysaccharides such as high molecular weight maltodextrin and chitosan as an additional coating on a polyurethane-based core-shell substrate, instead of substances like polyaldehydes and polyvalent salts for additional stability of microcapsules. However, since chitosan dissolves in acidic solutions at a rate of only a few percent, its direct incorporation into the microparticle shell is severely limited. In addition, attempts have been made to achieve a high "biodegradable" impression by partially incorporating biodegradable starch and cellulose into synthetic polymers.

[0013] For example, WO2020 / 058044A1 (Givaudan) describes a consumer product comprising a plurality of microcapsules dispersed in a dispersion medium, wherein the shell of the microcapsules is coated with chitosan and the dispersion medium contains additional free chitosan. Thereby, the free chitosan contained in the dispersion medium preferably has a molecular weight between 500,000 g / mol and 3,000,000 g / mol, and the chitosan coating the shell of the microcapsules preferably has a molecular weight in the range of 30,000 g / mol to 300,000 g / mol.

[0014] WO2019 / 175017A1 (Givaudan) discloses a composition comprising at least one core-shell microcapsule in a suspension medium, wherein the shell comprises a hyperbranched polysaccharide having a specific ratio of 1,6-glycosidic bonds to 1,4-glycosidic bonds, selected from the group consisting of amylopectin, dextrin, hyperbranched starch, glycogen, phytoglycogen, and mixtures thereof. These microcapsules exhibit improved deposition behavior and improved resistance to rinsing on a keratin substrate.

[0015] US2020 / 0046616A1 (International Flavors and Fragrances) refers to a method for preparing a capsule composition based on a polyurea-based and polyurethane-based capsule composition, and an active emulsion containing a polyisocyanate and one or more materials selected from the group consisting of pectin, chitosan, arginine, lysine, polylysine, protein, gelatin, guar gum, and hydroxyethyl cellulose.

[0016] A microcapsule composition is disclosed in WO2019 / 210125A1 (International Flavors and Fragrances), wherein the polymer to be encapsulated contains a polyurea polymer which is a reaction product of a polyfunctional electrophile and a polyfunctional nucleophile, the polyfunctional electrophile contains a polyisocyanate, and the polyfunctional nucleophile contains a polyamine such as chitosan having a molecular weight > 30,000 g / mol.

[0017] WO2019 / 179939A1 (Firmenich) discloses microcapsules comprising an oil-based core and a shell formed from the reaction between a monomer and modified starch as the main shell material in the presence of a low level of high molecular weight chitosan (N-acetylglucosamine polymer).

[0018] US5,780,060A (Centre National de la Recherche Scientifique) relates to a microcapsule comprising a wall formed from at least one plant polyphenol crosslinked at the interface with a dioxide halogen compound crosslinking agent, and a protein, polysaccharide, polyalkylene glycol, or mixture thereof co-crosslinked with at least one plant polyphenol.

[0019] Chitosan, used in cutting-edge technology, is a natural biomacromolecule (biomolecular-weight molecule) derived from chitin, consisting of approximately 2,000 monomers (or monomer units). More specifically, it is a high-molecular-weight amino sugar (also called polyamino sugar) composed of β-1,4 glycosidically linked N-acetylglucosamine and D-glucosamine units. Commercially available chitosan typically exhibits a high molecular weight of at least 30,000 g / mol. As indicated above, chitosan has limited solubility in organic acids (e.g., formic acid, acetic acid, or citric acid), allowing for only minimal incorporation into the shell composition of microcapsules. In addition, its bulkiness hinders efficient crosslinking. As a result, large chitosan molecules form a coating rather than being components of the core-shell microparticle wall structure. Consequently, reduced stability and performance are expected for microcapsules containing such bulky polymers.

[0020] From the above perspective, the present invention addresses the complex problem of providing core-shell microcapsules, as well as processes for preparing such microcapsules, that are, on the one hand, highly biodegradable and more environmentally friendly, and on the other hand, have storage stability (especially in product formulations) and exhibit excellent release behavior of active ingredients, i.e., exhibit excellent performance.

[0021] Manufacturing microcapsules that possess both good stability and good release properties is particularly difficult. The ability of a capsule to retain active ingredients and thus prevent the loss of volatile components depends especially on the capsule's stability in the product base. The shell composition, and therefore the stability and biodegradability of the capsule, is primarily influenced by the starting materials used. The stability and release behavior of the capsule are primarily influenced by the shell's composition, morphology, and thickness. Therefore, capsules with good stability, in particular, do not naturally exhibit good biodegradability. As the degree of crosslinking increases, the stability of the microcapsule generally increases, while at the same time, the ability to biodegrade the capsule shell tends to decrease. In addition, very stable microcapsules usually exhibit poor performance as microcapsule ruptures, thus hindering the release of the active ingredient(s). However, if the microcapsule is too unstable, it will either rupture during storage or leak the active ingredient, neither of which is desirable.

[0022] Therefore, the present invention focuses on providing microcapsules based on environmentally more suitable capsule wall materials that preferably exhibit high biodegradability and, at the same time, outstanding stability as well as excellent release properties, i.e., capsule performance. It is important that not only the polymer material of the capsule wall itself, but also each of the fragments created during disintegration are more environmentally suitable.

[0023] Therefore, the object of the present invention is to provide a process for preparing a dispersion system (microcapsule slurry) of such microcapsules as well as a microcapsule containing a fragrance substance consisting of a single odor compound or a mixture of odor compounds or a perfume mixture or cosmetic ingredient, which is highly biodegradable, sustainable and environmentally friendly, and in particular contains at least one hydrophobic active ingredient, preferably exhibiting a good balance of improved biodegradability, stability and performance compared to state-of-the-art microcapsules.

[0024] An object of the present invention is also to provide environmentally sustainable microcapsules, as well as consumer products containing such microcapsules, which have the additional benefit of high biodegradability.

[0025] These and other purposes and advantages of the present invention will become clear from the following disclosure.

[0026] Surprisingly, this challenge has been found to be solvable by bio-based core-shell microcapsules according to the present invention, which contain, as a primary component of the capsule wall, cross-linked bio-based or natural low molecular weight or short-chain materials, particularly natural (amino)sugar segments having fewer than 20 monomer units, which are themselves biodegradable. The incorporation of these bio-based / natural materials into the capsule shell via reaction results in more eco-friendly capsule materials with higher biodegradability compared to state-of-the-art non-bio-based capsules. For example, such core-shell microcapsules containing active ingredients such as fragrances, cosmetics, and vitamins as a core can be efficiently formed via interfacial reactions between a reactive cross-linking agent and functional monomers, dimers, oligomers, and / or short-chain polymers having one or more -OH groups and / or one or more -NH- or -NH2 groups and / or one or more -SH groups, as (amino)sugars and / or corresponding thiosugars. In addition, these microcapsules have been found to be extremely stable (especially in product formulations) and to exhibit superior release properties, even after long-term storage in the product formulations, compared to state-of-the-art microcapsules. Remarkably, these excellent and balanced properties have also been found in microcapsules with significantly reduced shell wall portion / thickness (see Examples 11 and 12). [Overview of the Initiative]

[0027] In a first aspect, the present invention relates to a bio-based core-shell microcapsule, wherein the shell composition comprises or consists of a polymer material which is a reaction product of at least one polyisocyanate having at least two isocyanate groups, preferably a mixture of at least two such polyisocyanates, and at least one sugar and / or at least one amino sugar (i.e., repeating units or monomer (amino) sugar units) each independently having less than 20 monomer units, preferably 15 monomer units or less, and more preferably 10 monomer units or less, and the core of the capsule comprises or consists of at least one active ingredient.

[0028] In a second aspect, the present invention relates to a microcapsule slurry containing a plurality of core-shell microcapsules according to the present invention dispersed in an aqueous phase, preferably in which the concentration of microcapsules in the aqueous phase is greater than 5% and less than 70%, more preferably greater than 20% and less than 60%, and most preferably greater than 30% and less than 50%.

[0029] In a third aspect, the present invention relates to a process for preparing a microcapsule slurry (i.e., a microcapsule dispersion system), comprising the following steps: (a) A step of providing an oil phase comprising at least one polyisocyanate having at least two isocyanate groups, preferably a mixture of at least two such polyisocyanates, and one or more hydrophobic active ingredients; (b) a step of providing a first aqueous phase comprising at least one capsule-forming agent; (c) A step of providing a second aqueous phase comprising at least one sugar and / or at least one amino sugar each independently having less than 20 monomer units, and optionally the aqueous phase further comprising one or more capsule-forming aids; (d) A step of mixing the oil phase and the first aqueous phase to obtain a provisional oil-in-water emulsion; (e) A step of mixing the second aqueous phase with the provisional oil-in-water emulsion obtained in step (d) to obtain a microcapsule slurry; (f) A step of curing the microcapsules obtained in step (e).

[0030] Optionally, the process may include an additional step (f2) in which one or more suspension aids or structuring aids selected from natural gums (e.g., xanthan gum, gellan gum, diutan gum, cellulose gum) or other non-gum suspension aids, such as fine crystalline cellulose (Vivapur®, J. Rettenmeier & Soehne GmbH+Co), are added as thickeners to provide high suspension stability.

[0031] In another embodiment, the present invention relates to a process for preparing bio-based core-shell microcapsules by preparing a slurry according to the above process, comprising the steps of isolating core-shell microcapsules from the slurry following or in lieu of step (f2) and drying the isolated core-shell microcapsules as obtained.

[0032] In yet another aspect, the present invention relates to a slurry (i.e., a microcapsule dispersion) containing core-shell microcapsules obtained by the process according to the present invention as described above. Furthermore, the present invention also relates to core-shell microcapsules themselves obtained by the process according to the present invention.

[0033] In addition, the present invention relates to the use of the core-shell microcapsules and / or slurries containing the core-shell microcapsules for the preparation of various consumer products.

[0034] Finally, the present invention relates to consumer products comprising bio-based core-shell microcapsules or slurries of microcapsules according to the present invention, wherein the consumer products are selected from the group consisting of, among other things, cosmetics, personal care products, particularly skin cleansing and skin care products, shampoos, rinse-off conditioners, deodorants, antiperspirants, body lotions, fabric care products, and home care / household products, particularly liquid detergents, all-purpose cleaners, laundry and cleaning agents, fabric softeners, fragrance enhancers, fragrance enhancers in liquid or solid form, as well as pharmaceuticals.

[0035] Surprisingly, the bio-based core-shell microcapsules according to the present invention were found to exhibit high biodegradability, high mechanical, thermal, and chemical stability, and similarly excellent release properties.

[0036] These and other aspects, features and advantages of the present invention will become apparent to those skilled in the art by examining the following detailed description, drawings and patent claims. Each feature derived from one aspect of the present invention may be used in or replaced in another aspect of the present invention. The present invention is described without limitation by the examples contained herein.

[0037] The term “sugar” as used herein is to be understood to encompass the characteristics of “sugar,” “amino sugar,” and / or “thio sugar,” and for example, when referring to “sugar-based microcapsules,” it means all variations of microcapsules formed using components as defined herein, i.e., capsules formed on the basis of polymerization of sugar components, amino sugar components, and / or thio sugar components, each independently having fewer than 20 monomer units, preferably 15 monomer units or less, and even more preferably 10 monomer units or less.

[0038] The terms “at least one” or “one or more” are used herein to mean one or more and are synonymous. The terms “at least two” and “two or more” or “more than one” are used herein to mean two, three, four or more and are synonymous.

[0039] Numerical examples given in the form "x~y" include the value being mentioned. If several preferred numerical ranges are given in this form, all ranges resulting from different combinations of endpoints are also included. [Brief explanation of the drawing]

[0040] [Figure 1A] This figure shows the results of a sensory evaluation of the release characteristics of the state-of-the-art microcapsules (Comparative Example 13; relating to polyurea microcapsules) and the microcapsules according to Example 1, compared to a reference of pure fragrance oil in a fabric softener formulation, after machine drying and aging with fabric softener for one week.

[0041] [Figure 1B] This figure shows the results of a sensory evaluation of the release characteristics of the most advanced microcapsules (Comparative Example 13; relating to polyurea microcapsules) and the microcapsules according to Example 1, compared to a reference of pure aromatic oil in a fabric softener formulation, after the ropes were dried and aged for one week in a fabric softener.

[0042] [Figure 2A-B] This figure shows the results of a sensory evaluation of the release characteristics of microcapsules according to Example 2, compared to a reference of pure fragrance oil in a fabric softener formulation, after machine drying and rope drying, respectively, and then aging in a fabric softener for one week.

[0043] [Figure 3A-B] This figure shows the results of a sensory evaluation of the release characteristics of microcapsules according to Example 3, compared to a reference of pure fragrance oil in a fabric softener formulation, after machine drying and rope drying, respectively, and then aging in a fabric softener for one week.

[0044] [Figure 4A-B] This figure shows the results of a sensory evaluation of the release characteristics of microcapsules according to Example 4, compared to a reference of pure fragrance oil in a fabric softener formulation, after machine drying and rope drying, respectively, and then aging in a fabric softener for one week.

[0045] [Figure 5A-B] This figure shows the results of a sensory evaluation of the release characteristics of microcapsules according to Example 5, compared to a reference of pure aromatic oil in a fabric softener formulation, after machine drying and rope drying, respectively, and then aging in a fabric softener for one week.

[0046] [Figure 6A] This figure shows the results of a sensory evaluation of the release characteristics of state-of-the-art microcapsules (polyurea microcapsules, according to Comparative Example 13) and microcapsules, according to Example 6, compared to a reference of pure fragrance oil in fabric softener formulations, after machine drying and aging with fabric softener for one week.

[0047] [Figure 6B] This figure shows the results of a sensory evaluation of the release characteristics of state-of-the-art microcapsules (polyurea microcapsules, according to Comparative Example 13) and microcapsules, according to Example 6, compared to a reference of pure aromatic oil in a fabric softener formulation, after the ropes were dried and then aged for one week with fabric softener.

[0048] [Figure 6C] This figure shows the results of sensory evaluation of microcapsules according to Example 6, compared to a reference of pure fragrance oil in a fabric softener formulation, after machine drying and aging with fabric softener for 4 weeks.

[0049] [Figure 6D] This figure shows the results of sensory evaluation of microcapsules according to Example 6, compared to a reference of pure aromatic oil in a fabric softener formulation, after the ropes were dried and then aged for 4 weeks with the fabric softener.

[0050] [Figure 7A-B] This figure shows the results of a sensory evaluation of the release characteristics of microcapsules according to Example 7, compared to a reference of pure aromatic oil in a fabric softener formulation, after machine drying and rope drying, respectively, and aging with fabric softener for one week.

[0051] [Figure 8A-D] Figures 8A and 8B show the results of sensory evaluation of the release characteristics of microcapsules according to Example 8, compared to a reference of pure aromatic oil in a fabric softener formulation, after mechanical drying and rope drying, respectively, followed by aging in the fabric softener for one week. Figures 8C and 8D show the corresponding results of sensory evaluation of the release characteristics of capsules aged in the fabric softener for four weeks.

[0052] [Figure 9A-B] The following shows the results of sensory evaluation of the release characteristics of two microcapsule samples (Examples 9A and 9B) from Example 9, compared to a reference of pure fragrance oil in a fabric softener formulation, after being aged for one week in a fabric softener after machine drying and rope drying, respectively.

[0053] [Figure 9C-D] The following shows the results of sensory evaluation of the release characteristics of two microcapsule samples (Examples 9C and 9D) from Example 9, compared to a reference of pure fragrance oil in a fabric softener formulation, after being aged for 4 weeks in a fabric softener after machine drying and rope drying, respectively.

[0054] [Figure 10A-D] Figures 10A and 10B show the results of sensory evaluation of the release characteristics of microcapsules according to Example 10, compared to a reference of pure aromatic oil in a fabric softener formulation, after mechanical drying and rope drying, respectively, followed by aging in fabric softener for one week. Figures 10C and 10D show the corresponding results of sensory evaluation of the release characteristics of capsules that were aged in fabric softener for four weeks after drying.

[0055] [Figure 11A] The results of a subjective evaluation of the release characteristics of the most advanced microcapsules (polyurea microcapsules, according to Example 13) are shown, compared to the microcapsules according to Examples 11 and 12 in fabric softener formulations, which were aged for one week after rope drying.

[0056] [Figure 11B] The results of a subjective evaluation of the release characteristics of the most advanced microcapsules (polyurea microcapsules, according to Example 13) are shown, compared to the microcapsules according to Examples 11 and 12 in fabric softener formulations, which were aged for 4 weeks after rope drying.

[0057] [Figure 12A-D] Figures 12A and 12B show the results of sensory evaluation of the release characteristics of microcapsules according to Example 12, compared to a reference of pure aromatic oil in a fabric softener formulation, after mechanical drying and rope drying, respectively, followed by aging in fabric softener for one week. Figures 12C and 12D show the corresponding results of sensory evaluation of the release characteristics of capsules that were aged in fabric softener for four weeks after drying.

[0058] [Figure 13] This shows the increased biodegradability of the microcapsules according to Example 1 (Sample #1) in accordance with OECD 301F, compared to sodium benzoate and a toxicity control (a mixture of the microcapsules according to the present invention and sodium benzoate) during an extended incubation period of 45 days.

[0059] [Figure 14] This shows the increased biodegradability of the microcapsules according to Example 2 (Sample #2) in accordance with OECD 301F, compared to sodium benzoate and a toxicity control (a mixture of the microcapsules according to the present invention and sodium benzoate) during a 28-day incubation period.

[0060] [Figure 15] The results show the biodegradability according to OECD 301F for a fully synthetic, state-of-the-art polyurea-based microcapsule prepared according to Comparative Example 13 and corresponding to the capsule disclosed in US6,586,107B2.

[0061] [Figure 16A-M] Figure 16I shows the distribution of the median volume-based particle size of the microcapsules (polyurea microcapsules) from Examples 1 to 12 and Comparative Example 13 within the corresponding microcapsule slurry. Figure 16I corresponds to Example 9A.

[0062] [Figure 17] This shows the increased biodegradability of the microcapsules according to Example 6, in accordance with OECD 301F, compared to sodium benzoate and a toxicity control (a mixture of the microcapsules according to the present invention and sodium benzoate) during the incubation period.

[0063] [Figure 18] This shows the increased biodegradability of the microcapsules according to Example 7, in accordance with OECD 301F, compared to sodium benzoate and a toxicity control (a mixture of the microcapsules according to the present invention and sodium benzoate) during the incubation period.

[0064] [Figure 19] This shows the increased biodegradability of the microcapsules according to Example 8, in accordance with OECD 301F, compared to sodium benzoate and a toxicity control (a mixture of the microcapsules according to the present invention and sodium benzoate) during the incubation period. [Modes for carrying out the invention]

[0065] In a first aspect, the present invention relates to a bio-based or (amino) sugar-based core-shell microcapsule, wherein the shell comprises or consists of a polymer material which is a reaction product of at least one sugar and / or at least one amino sugar, each independently having less than 20 monomer units, i.e., less than 20 monomer units (monosaccharide units and / or monomer amino sugar units), or preferably consisting thereof, and the core comprises or consists of at least one active ingredient which is preferably hydrophobic in nature, for example, an aromatic compound.

[0066] Preferably, the components or constituents of the sugar and / or amino sugar are monosaccharides, disaccharides and / or (linear or branched) oligosaccharides and / or monomers, dimers and / or (linear or branched) oligomer amino sugars (also known as oligoamino sugars), or mixtures of compounds of these monomers, dimers or oligomers in any combination. However, short-chain polymer structures are also suitable as components, as long as they contain or consist of fewer than 20 monomer units, preferably 15 monomer units or less, and even more preferably 10 monomer units or less.

[0067] Therefore, short-chain (linear or branched) polysaccharides (high molecular weight sugars) and / or aminopolysaccharides (high molecular weight amino sugars) having fewer than 20 monomer units, i.e., 19 or fewer monomer units, are also preferred and can be used as components in any combination, either alone or in combination with the aforementioned monomer, dimer, or oligomer compounds, to form the capsule wall according to the present invention.

[0068] In the context of the present invention, a microcapsule is a microparticle produced by interfacial polymerization, containing at least one active ingredient as a core material inside the capsule and surrounded by a capsule shell or capsule wall. The active ingredient is preferably hydrophobic or lipophilic. Such an active ingredient is insoluble or sparingly soluble in water but highly soluble in fats and oils. The terms "microcapsule" and "capsule" are used synonymously in the context of the present invention, as are the terms "hydrophobic" and "lipophilic," and "shell" and "wall."

[0069] In the context of the present invention, the capsule shell or capsule wall is preferably based on sugars and / or amino sugars, as specified herein, which react and crosslink with isocyanates to produce a stable, highly efficient, yet highly biodegradable capsule shell with excellent release properties, i.e., release performance.

[0070] Surprisingly, the bio-based / (amino)sugar-based core-shell microcapsules of the present invention were found to exhibit superior biodegradability according to standardized OECD 301F test procedures compared to state-of-the-art microcapsules based on entirely synthetic structures, more specifically, those based on guanidine-based components (see Figures 13-15 and 16-19). While fully synthetic capsules using state-of-the-art technology exhibit virtually no biodegradability, the capsule shells of the present invention exhibit considerably high biodegradability according to the OECD 301F biodegradability standard.

[0071] Simultaneously, the microcapsules of the present invention exhibit high mechanical and thermal stability against mechanical influences such as rotary dryers or heat diffusion, as well as high chemical stability within product formulations, for example, while simultaneously enabling efficient, target signal-induced release of the active ingredient(s). In addition, sensory experiments showed that high fragrance intensity could be perceived in the case of fragrances as active ingredients, suggesting that the fragrance is efficiently encapsulated within the core-shell microcapsules of the present invention, demonstrating an efficient reduction in losses due to diffusion of the active ingredient out of the microcapsule (see Figures 1-12). At the same time, this also demonstrates an efficient balance between the performance and stability of the capsules. Furthermore, the microcapsules of the present invention showed high stability within consumer product formulations, such as fabric softeners, for at least four weeks. As a result, contrary to the teachings of state-of-the-art technology, it was possible to create highly stable microcapsules that enable efficient encapsulation of active ingredients and simultaneously high performance, despite being based on bio-based components.

[0072] As a result, the (amino) sugar components (and / or thiosugar components) serve as sites for biological attack and degradation, significantly reducing the overall environmental impact of the microcapsules according to the present invention. Consequently, the bio-based core-shell microcapsules of the present invention differ from state-of-the-art microcapsules primarily in their considerably high biodegradability, making them more environmentally friendly and even more suitable for the development of efficient consumer product formulations.

[0073] As a result, in a preferred modification, the present invention relates to a core-shell microcapsule according to a first embodiment, in which the microcapsule exhibits higher biodegradability compared to state-of-the-art microcapsules, preferably being intrinsically biodegradable, and more preferably readily biodegradable, thus exhibiting high biodegradability according to the OECD 301F biodegradability standard (pressure-breathing measurement test). In some cases, the test was extended to 45 days according to the official test procedure.

[0074] However, preferably, a mixture of two or more polyisocyanates is used to form the capsule wall, i.e., as an isocyanate component or crosslinking agent. These result in more stable and better performing microcapsules, and consequently, improved capsule properties. Furthermore, polyisocyanates having an aliphatic structure, for example, produce even more stable core-shell microcapsules that enable efficient encapsulation of volatile active ingredients, such as aromatic materials. Combinations of two or more different polyisocyanates are advantageous in terms of capsule properties, particularly when at least one of these polyisocyanates is an aliphatic polyisocyanate, or conversely, when all of the polyisocyanates in the mixture are naturally aliphatic (see, for example, Examples 3 and 4), and have been observed to enable the formation of capsules with improved stability and performance, i.e., improved properties such as release behavior.

[0075] Accordingly, alternative embodiments disclose core-shell microcapsules in which at least two isocyanate groups, i.e., at least one of one or more polyisocyanates having two or more isocyanate functionalities, comprises an aliphatic structure, preferably an alicyclic structure, as specified herein. Therefore, preferably at least one aliphatic polyisocyanate having at least two isocyanate groups is used in the preparation of core-shell microcapsules according to the present invention. In this regard, this aliphatic polyisocyanate can be used in mixtures with other aliphatic polyisocyanates, or in mixtures with aromatic polyisocyanates instead, or in mixtures with further aliphatic and aromatic polyisocyanates.

[0076] Accordingly, one embodiment of the present invention relates to a microcapsule prepared using one or more aliphatic polyisocyanates, or comprising a reaction product of at least one aliphatic polyisocyanate with at least one sugar and / or at least one amino sugar, each having fewer than 20 monomer units.

[0077] In another preferred embodiment, the capsule is prepared using a mixture of at least one aliphatic polyisocyanate and at least one aromatic polyisocyanate, resulting in a highly efficient microcapsule.

[0078] In this regard, preferably the molar ratio or weight ratio of at least one aliphatic polyisocyanate to at least one aromatic polyisocyanate, and more preferably the molar ratio, is in the range of 85:15 for microcapsules preferably based on or containing amino sugars having more than 1 monomer units (see Example 11), and more preferably 90:10 to 99:10. Therefore, the molar ratio or weight ratio of at least one aliphatic polyisocyanate to at least one aromatic polyisocyanate, and more preferably the molar ratio, is preferably higher than 85:15, and more preferably higher than 90:10, for microcapsules preferably based on or containing amino sugars having more than 1 monomer units. Based on these ratios, capsules that are highly stable but also perform well, exhibiting high stability within the product formulation (in terms of target release behavior), can be prepared.

[0079] Preferably, when a mixture of two or more polyisocyanates is used, the mixture contains or consists of more than 80 mol% of aliphatic component / polyisocyanate, i.e., the molar fraction of aliphatic component / polyisocyanate is preferably more than 80% in the isocyanate mixture for microcapsules based on or containing amino sugars having more than one monomer unit, even more preferably 81%, even more preferably at least 85 mol%, and most preferably 90 mol%. Surprisingly, microcapsules having such a high molar content of aliphatic isocyanate relative to the total isocyanate content have been found to exhibit excellent stability and performance even after aging for 4 weeks in liquid product formulations such as fabric softeners, thus showing an improved balance of overall capsule properties. These excellent properties are particularly surprising for microcapsules with a considerably reduced shell content, i.e., a considerably reduced shell thickness (see Examples 11 and 12 and Figures 11-12).

[0080] Enhanced crosslinking, and thus polymerization, of polyisocyanates may be achieved with sugars and / or amino sugars each having preferably 15 or fewer, and even more preferably 10 or fewer, monomer units independently, resulting in more stable and better performing capsules. In addition, an improved balance between stability, release performance, and biodegradability has been observed for these capsules. The same applies to the corresponding thiosugars. Even more preferably, one or more sugars and / or one or more aminosugars are monomers, most preferably glucosamine.

[0081] Therefore, core-shell microcapsules having at least one sugar and / or amino sugar in 10 or fewer monomer units are particularly preferred.

[0082] To achieve efficient encapsulation based on polymerization of constituent elements, i.e., isocyanate components(or more) and (amino)sugar components(or more), it is further necessary that at least one sugar and / or at least one amino sugar contain at least two functional groups independently selected from the group consisting of primary and secondary amine groups (-NH2, -NH-) as well as primary and secondary hydroxyl groups (-OH) that enable the formation of polyurethane and / or polyurea-based linkages.

[0083] Alternatively, or in combination with the above-mentioned (amino) sugars, thiosugars may be suitably used, having one or more functional thiol groups (-SH) that enable the formation of polythiourethane structures / links between components, or mixtures thereof with the aforementioned polyurethane and / or polyurea-based linkages.

[0084] The eco-friendly core-shell microcapsules of the present invention enable the efficient encapsulation of various active ingredients, thus allowing their incorporation into a wide range of consumer product formulations.

[0085] Suitable active ingredients include, for example, hair conditioning agents or active ingredients in skin products, such as active ingredients in cosmetics like skin moisturizers, anti-wrinkle agents, skin conditioning agents, skin whitening agents, and anti-acne agents, as well as fragrances or perfumes (also called odorous substances or aromatic substances), meaning single fragrance or perfume substances, i.e., compounds that have an odor or smell, and by extension, all natural and synthetic substances that impart an odor that can be perceived by the sense of smell, or compositions of one or more aromatic or perfume substances, i.e., mixtures of the aforementioned compounds or mixtures containing the aforementioned compounds, and / or other perfume components, fragrance oils, aromatic substances, and / or aromas. Further preferred active ingredients include, for example, pesticides, active pharmaceutical ingredients, dyes, UV active substances, optical gloss agents, thickeners, drape and form control agents, smoothing agents, antistatic agents, wrinkle inhibitors, bactericides, disinfectants, bacterial control agents, antifungal agents, mold stain inhibitors, antiviral agents, antimicrobial agents, drying agents, stain-resistant agents, antifouling agents, odor inhibitors, fabric deodorizers, dye fixatives, color maintainers, color restorers / recoverers, fade inhibitors, abrasion inhibitors, fabric preservatives, abrasion inhibitors, rinsing aids, UV protectants, sun-fading inhibitors, insect repellents, anti-allergic agents, fire resistant agents, waterproofing agents, fabric softeners, shrinkage inhibitors and / or stretch inhibitors, fluorescent paints, solvents, waxes, silicone oils, lubricants, coolants, TRPV-modifiers, and mixtures of the above-mentioned active ingredients.

[0086] However, preferably the active ingredient is a fragrance / perfume substance, or a composition as defined above, i.e., a substance or mixture of substances that impart an olfactory-perceptible scent, a fragrance oil, or a cosmetic ingredient, and preferably these fragrance / perfume substances or compositions encapsulated by the core-shell microcapsules of the present invention impart a pleasant scent to the consumer product.

[0087] The core-shell microcapsules according to the present invention preferably have a volume-based median particle size (Dv(50)) of 1 μm to 100 μm, preferably 5 μm to 55 μm, and most preferably 5 μm to 50 μm, within the microcapsule dispersion system, i.e., within the microcapsule slurry. In this regard, the (Dv(50)) value refers to the volume distribution of particles and is defined as a particle size where half of the population is below this value.

[0088] The diameter of the microcapsules is preferably determined by laser diffraction using a Malvern Mastersizer 3000 (as per the manufacturing instructions). The measured intensity values ​​of the scattered light are then calculated to a (Dv(50)) value, for example, preferably by Fraunhofer's diffraction / approximation. A (Dv(50)) value indicates that 50% of the microcapsules are finer than the (Dv(50)) value, and 50% are coarser. Therefore, the (Dv(10)) and (Dv(90)) values ​​indicate that 10% and 90% of the total volume of capsules in the sample are smaller than these values.

[0089] If the median particle size of core-shell microcapsules falls within this range, the delivery of active ingredients in applications such as fabric care products, skin care products, and personal care products is improved. Larger particles, especially those exceeding 100 μm, are less effective in delivering active ingredients to surfaces, cannot be stably incorporated into product formulations, and may aggregate. Furthermore, they are difficult to suspend in aqueous formulations or product formulations, resulting in a greater tactile (rough) feel, which is undesirable for most intended applications. In addition, if the particle size is within the range defined above, an enhanced balance between stability and release performance can be achieved.

[0090] Preferably, however, the microcapsules of the present invention are obtained and stored in the form of a slurry, i.e., as finely dispersed microcapsules in an aqueous phase (microcapsule dispersion system). The use of such a slurry facilitates application and incorporation into product formulations, enables enhanced storage without particle accumulation or oxidation, and suppresses evaporation of volatile components. Furthermore, the use of such a dispersion system allows for the efficient release of active ingredients in response to external forces such as friction, heat, or environmental changes. In addition, the stability of the active substance to environmental conditions of consumer product formulations (such as the pH of the consumer product base) can be enhanced to the release of the active substance based on the reception of release signals (friction, pH changes, heat, etc.).

[0091] Microcapsule slurry containing multiple bio-based core-shell microcapsules of the present invention can be effectively incorporated into a variety of applications, particularly in liquid (product) formulations. The core-shell microcapsules of the present invention exhibit high stability in dispersion systems (slurries), enabling long storage times and easy incorporation into consumer product formulations and application in appropriate amounts.

[0092] Therefore, another object of the present invention relates to a microcapsule slurry containing a plurality of core-shell microcapsules according to the present invention dispersed in an aqueous phase, preferably in which the concentration of microcapsules in the aqueous phase is greater than 5% by weight and less than 70% by weight, preferably greater than 20% by weight and less than 60% by weight, and most preferably greater than 30% by weight and less than 50% by weight.

[0093] In a further embodiment, the present invention relates to a process for preparing a slurry of microcapsules according to the present invention. The slurry of core-shell microcapsules, and the subsequent isolated core-shell microcapsules, are also prepared by the following steps: (a) A step of providing an oil phase comprising at least two isocyanate groups, i.e., at least one polyisocyanate having two or more isocyanate functionalities, for example, one or more linear or branched aliphatic and / or aromatic polyisocyanates or mixtures thereof, and one or more preferably hydrophobic active ingredients; (b) a step of providing a first aqueous phase comprising at least one capsule-forming agent; (c) A second aqueous phase comprising at least one sugar and / or at least one amino sugar having at least two functional reactive groups independently selected from the group consisting of primary and secondary hydroxyl groups (-OH) as well as primary and secondary amine groups (-NH2, -NH-), wherein the second aqueous phase optionally comprises one or more additional forming aids; (d) A step of mixing the oil phase with the first aqueous phase to obtain a provisional oil-in-water emulsion; (e) A step of mixing the second aqueous phase with the provisional oil-in-water emulsion obtained in step (d) to obtain a microcapsule slurry; (f) A step of curing the microcapsules obtained in step (e) within the microcapsule slurry can be obtained.

[0094] Optionally, the process includes an additional step (f2) in which one or more suspension aids or structuring aids selected from natural gums (e.g., xanthan gum, gellan gum, diutan gum, cellulose gum, preferably diutan gum) are added as thickeners to provide high suspension stability. Such substances stabilize the suspension by spontaneously forming a colloidal dispersion with water. Suitable suspension aids include, for example, Kelco-Vis® DG and Keltrol® from CP Kelco, carboxymethylcellulose (CMC), and Vivapur® (microcrystalline cellulose) from J. Rettenmaier & Soehne GmbH+Co KG.

[0095] The following details disclose suitable components similar to those of the single-process steps according to the first embodiment.

[0096] In the first step of the process according to the present invention, a provisional oil-in-water emulsion is formed. For this purpose, an internal non-aqueous phase is provided, more specifically, an oil phase comprising, or consisting of, at least one polyisocyanate having two or more isocyanate groups and at least one preferably hydrophobic active ingredient to be encapsulated.

[0097] The at least one isocyanate used in the manufacturing processes described herein, or used in the core-shell microcapsules according to the first embodiment, has at least two isocyanate groups to form a polymer network, i.e., a capsule shell or capsule wall, by polymerization. In this regard, dipolyisocyanates and / or higher-order polyisocyanates each form a stable polymer structure based on polyurethane-based and / or polyurea-based chemical bonds by interfacial polymerization with at least one sugar and / or amino sugar functional group each independently having fewer than 20 monomer units as specified herein, thereby efficiently encapsulating a hydrophobic core containing an active ingredient by forming a bio-based capsule wall that is efficient and at the same time exhibits high biodegradability compared to fully synthetic capsules according to state-of-the-art technology.

[0098] In the case of thiosaccharides, therefore, in addition to or instead of the above-mentioned bonds, thiourethane-based bonds are formed. Preferred thiosaccharides are, for example, N-acetylcysteine, 5-thio-D-glucose, or methyl 6-thio-6-deoxy-α-D-galactopyranoside. However, even more preferred substances are cysteine, homocysteine, and glutathione.

[0099] In preferred modifications, at least one polyisocyanate having at least two isocyanate groups, i.e., two or three or more functional isocyanate groups, is preferably selected from the group consisting of linear, cyclic, and branched aliphatic and aromatic polyisocyanates, as well as mixtures thereof. In this regard, dipolyisocyanates and / or higher-order polyisocyanates can include monomer, dimer, oligomer, or polymer structures having different chain lengths. For example, dipolyisocyanates and polyisocyanates often self-react to form dimers (urethidions), trimers (isocyanurates), or higher-order isocyanate oligomers. In addition, polyisocyanates can form adducts, such as Takenate® D-110N and D-120N by Mitsui Chemicals, which are aliphatic polyisocyanate adduct prepolymers.

[0100] In the context of this invention, the term "isocyanate" as used herein refers to a functional group having the formula RN=C=O. Compounds having at least two isocyanate groups, i.e., two or more isocyanate groups, are called polyisocyanates.

[0101] The molecules described herein by the term “aliphatic polyisocyanate” are non-aromatic and refer to any polyisocyanate that may be linear, branched, or cyclic, i.e., alicyclic. In these compounds, the functional isocyanate group is not directly linked to an aromatic ring. However, aliphatic isocyanates may contain aromatic structures. Furthermore, polyisocyanates may be of aromatic nature ("aromatic polyisocyanate"), i.e., they may have a structure in which the functional isocyanate group is directly linked to an aromatic ring. Polyisocyanates used within the scope of the present invention may further exhibit any substitutions, including, for example, aliphatic substituents, aromatic substituents, heteroatoms such as halogens, particularly fluorine, chlorine, bromine and / or iodine, and / or other functional groups, such as alkoxy groups. Thereafter, the cyclic structure may be heterocyclic or heteroaromatic.

[0102] In preferred modifications, the polyisocyanate is therefore preferably selected from the group consisting of linear or branched aliphatic polyisocyanates, alicyclic (heterocyclic) polyisocyanates, aromatic (or heteroaromatic) polyisocyanates, their substitution products, and mixtures of the above-mentioned monomers, dimers, or oligomer compounds, but aliphatic compounds or mixtures of aliphatic and / or aromatic polyisocyanates are preferably used.

[0103] Preferably, a mixture of at least two different polyisocyanates is used to prepare the microcapsules of the present invention, which produce microcapsules with an improved balance of capsule properties. More preferably, a mixture of two different polyisocyanates is used.

[0104] Alternatively, or even further, the corresponding polyisothiocyanates can be used to form capsules, as well as mixtures of both, i.e., compounds comprising at least one isocyanate and a mixture of at least one isothiocyanate functional groups.

[0105] According to preferred embodiments of the present invention, the linear or branched aliphatic polyisocyanate(s) may be pentamethylene diisocyanate (PDI, e.g., Stabio D-370N or D-376N by Mitsui Chemicals Inc., Japan), hexamethylene diisocyanate (HDI), e.g., Desmodur N-3400 (HDI-uretdione; Covestro Corp.), Bayhydur® (Covestro A polyisocyanate(Takenate) A compound is selected from the group consisting of 600), 1,2-bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane, methylenebis(cyclohexyl isocyanate) (H12MDI), and derivatives thereof, preferably in which case each derivative contains one or more isocyanate groups and optionally further contains one or more groups selected from the group consisting of biuretes, isocyanurates, uretdiones, iminooxadiazinediones, and trimethylolpropane adducts (e.g., TMP adducts of H6XDI, particularly Takenate D-120N by Mitsui Chemicals Inc., Japan).

[0106] Also preferred are aliphatic polyisocyanates(s) obtained from renewable sources, e.g., PDI (Stabio D-370N or D-376N by Mitsui Chemicals Inc., Japan). Such aliphatic polyisocyanates obtained from renewable sources have been found not to impair the quality / characteristics of the core-shell capsule. For example, Stabi D-370N polyisocyanate has been found to contain approximately 70% bio-based carbon, i.e., renewable and non-fossil organic carbon and only about 30% fossil-based carbon, relative to the total carbon of the material as indicated by its 14C (radiocarbon) content.

[0107] Bio-based or bio-derived reagents are preferred from a health and environmental perspective. Bio-based materials (bio-derived materials) refer to compounds containing organic carbon of renewable origin, not fossil origin such as petroleum, as defined according to the ASTM D6866 standard test, such as agricultural plants, animals, fungi, microorganisms, marine materials, and forest materials that inhabit natural environments in equilibrium with the atmosphere. Furthermore, such bio-derived compounds are defined as compounds containing carbon (organic and inorganic) of renewable origin, such as agricultural plants, animals, fungi, microorganisms, marine materials, and forest materials. Preferably, the core-shell microcapsules of the present invention include such bio-derived or bio-based, i.e., bio-derived materials. Therefore, bio-derived materials are preferably used in the preparation of core-shell microcapsules according to the present invention.

[0108] Therefore, in a more preferred variation of the present invention, preferably, bio-based polyisocyanates and / or bio-derived (amino) sugars such as STABiO® are used, i.e., components derived from natural and renewable and sustainable raw materials, i.e., bio-derived raw materials that are not primarily petrochemical.

[0109] Polymerizable aliphatic isocyanates are particularly preferred in this context due to their chemical affinity for bio-based systems. For example, lysine and 1,5-diisocyanatopentane exhibit the same degradation product, 1,5-diaminopentane, and are therefore particularly suitable for use in the production of bio-based and biodegradable microcapsules, taking environmental considerations into account.

[0110] Therefore, in preferred embodiments of the present invention, at least one aliphatic polyisocyanate is preferably used.

[0111] Preferably, derivatives of linear, branched, and / or cyclic aliphatic polyisocyanates are employed. When used herein, derivatives are broadly understood as compounds derived from a compound through chemical reactions. Examples of derivatives include oligomers and / or adducts of the linear or branched aliphatic or alicyclic polyisocyanates described above. Preferred oligomers are biuretes, isocyanurates, uretodiones, and iminooxadiazinediones, and preferred adducts are trimethylolpropane adducts. These oligomers / adducts are well known in the art and are disclosed, for example, in US4,855,490 A or US4,144,268 A. Preferably, aliphatic polyisocyanates exist in monomeric and / or dimeric or oligomeric forms.

[0112] The derivatives of linear, branched, or cyclic aliphatic polyisocyanates may also be obtained by reacting the polyisocyanate with a polyalcohol (e.g., glycerin), polyamine, polythiol (e.g., dimercaprol), and / or mixtures thereof.

[0113] Within the framework of this text, an aromatic polyisocyanate is a compound in which two or more isocyanate residues are directly bonded to an aromatic C atom and its derivative, each derivative contains one or more isocyanate groups, and further contains one or more groups selected from the group consisting of biuretes, isocyanurates, uretdiones, iminooxadiazinediones, and trimethylolpropane adducts.

[0114] Examples of aromatic dipolyisocyanates or polyisocyanates include, for example, the monomeric diphenylmethane-2,4- or -4,4'-diisocyanate (MDI) and their oligomer / polymer forms, or mixtures thereof, 2,4- and / or 2,6-toluene diisocyanate (TDI) and 1,5- or 1,8-naphthalene diisocyanate (NDI).

[0115] Among polyisocyanates, diisocyanates, i.e., isocyanates having two functional isocyanate groups, are particularly preferred and are therefore primarily used in the context of the present invention. Accordingly, preferred polyisocyanates include, for example, methylenediphenyl diisocyanate (MDI; all isomers and derivatives); toluene diisocyanate (TDI); hexamethylene diisocyanate (HDI; all isomers and derivatives); isophorone diisocyanate (IPDI); 4,4-dicyclohexylmethane diisocyanate (H12MDI); 1,5-pentamethylene diisocyanate (PDI; Stabio®); 1,3-bis(isocyanatomethyl)cyclohexane (Takenate® 600); hydrophilically modified hexamethylene diisocyanate (Bayhydur®) or mixtures thereof.

[0116] The compounds described above explicitly include different isomers, either individually or in combination, if present, and similarly, explicitly include corresponding derivatives. For example, methylenebis(cyclohexyl isocyanate) (H12MDI) includes 4,4'-methylenebis(cyclohexyl isocyanate), 2,4'-methylenebis(cyclohexyl isocyanate) and / or 2,2'-methylenebis(cyclohexyl isocyanate) or aliphatic polyisocyanate adducts, such as Takenate® D-110N and D-120N by Mitsui Chemicals.

[0117] Other particularly preferred monomer isocyanate compounds include, for example, diisocyanatobutane, 1,6-diisocyanatohexane, 1,5-diisocyanato-2,2-dimethylpentane, 2,2,4- and 2,4,4-trimethyl-1,6-diisocyanatohexane, 1,10-diisocyanatodecane, 1,3- and 1,4-diisocyanatocyclohexane, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate), 4,4'-diisocyanatodicyclohexylmethane, 2,4- and 2,6-diisocyanatomethylcyclohexane and mixtures thereof. Within the scope of the present invention, preferred polyisocyanates are both 1,5-pentanemethylene diisocyanate (PDI) (Stabio®) and / or 1,3-bis(isocyanatomethyl)cyclohexane (Takenate® 600), both derived from Mitsui Chemical, enabling the formation of highly stable and high-performing core-shell microcapsules. Adducts such as Takenate® D-110N and D-120N from Mitsui Chemicals are also preferred.

[0118] In another variation, a combination of at least two different polyisocyanates is preferred. When different polyisocyanates are used as a mixture, it has been observed that particularly stable and good, i.e., more tightly branched crosslinking is achieved within the capsule shell. In this regard, in such a mixture of isocyanates, the polyisocyanates can be a combination of all linear aliphatic, all branched aliphatic, all alicyclic, or all aromatic, or, for example, a combination of at least one aromatic polyisocyanate and at least one aliphatic polyisocyanate. In general, all conceivable combinations of the aforementioned materials are suitable for the purposes of the present invention and are suitable for achieving more tightly crosslinking, which results in more stable and efficient encapsulation, while simultaneously enabling improved performance.

[0119] However, preferably, at least one of the one or more polyisocyanates having at least two isocyanate groups is aliphatic, and more preferably alicyclic. Even more preferably, the polyisocyanate component of the oil phase is a mixture of two or more aliphatic and / or aromatic polyisocyanates, each having at least two isocyanate groups. As a result, the isocyanate component may include two or more different aliphatic polyisocyanates, two or more different aromatic polyisocyanates, or a mixture of at least one aliphatic polyisocyanate and at least one aromatic polyisocyanate. Surprisingly, such mixtures of two or more polyisocyanates have been found to result in even more stable and better performing encapsulation, particularly when used as fragrance microcapsules. Preferably, at least one of the polyisocyanates used in such a mixture is aliphatic, i.e., linear aliphatic, branched aliphatic, or alicyclic, because these enable the formation of highly stable microcapsules under mechanical stress (e.g., washing machines and dryers) and heat, particularly in consumer product formulations, while simultaneously exhibiting excellent release properties.

[0120] Furthermore, since aliphatic polyisocyanates are known to be less toxic than aromatic polyisocyanates, the resulting structures are more biocompatible than, for example, aromatic isocyanate-based polyurethanes.

[0121] Therefore, in preferred embodiments of the present invention, at least one aliphatic polyisocyanate is used to prepare the microcapsules according to the present invention, and / or the microcapsules according to the first embodiment contain a reaction product of at least one aliphatic polyisocyanate and at least one sugar and / or at least one amino sugar having less than 20 monomer units each, so that in the microcapsules according to the present invention, at least one of the one or more polyisocyanates having at least two isocyanate groups contains an aliphatic structure.

[0122] In one variation, preferably, only aliphatic polyisocyanates are used, i.e., a mixture of two or more aliphatic isocyanates that can be linear, branched, or alicyclic.

[0123] As shown above, in another variation, preferably, the capsule is prepared using a mixture of at least one aliphatic polyisocyanate and at least one aromatic polyisocyanate, i.e., the core-shell microcapsule according to the first embodiment comprises a reaction product of at least one polyisocyanate with at least one sugar and / or at least one amino sugar having fewer than 20 monomer units of at least one polyisocyanate having at least two isocyanate groups, wherein at least one of the one or more polyisocyanates contains an aliphatic structure that enables the formation of a highly effective microcapsule.

[0124] For microcapsules preferably based on or containing amino sugars having more than one monomer unit, which exhibit high stability within the product formulation even after 4 weeks of aging in the product formulation (see Example 11), enabling the formation of highly stable yet simultaneously high-performing capsules (in terms of target release behavior), the molar ratio or weight ratio of at least one aliphatic polyisocyanate to at least one aromatic polyisocyanate, preferably 85:15, and even more preferably in the range of 90:10 to 99:1.

[0125] Therefore, combinations of different polymerizable polyisocyanates result in particularly stable capsule shells or capsule walls, which in turn lead to better encapsulation of active ingredients and reduced loss during storage, while simultaneously enabling even better capsule performance (high strength and excellent odor release behavior) in areas such as the encapsulation of fragrances or odorants. Thus, in the present invention, combinations of at least two different polymerizable isocyanates are generally preferred. Even more preferably, at least one of the isocyanates is aliphatic, regardless of its (amino)sugar component.

[0126] Therefore, preferably the capsule wall is based on the reaction of at least one aliphatic polyisocyanate having at least two isocyanate groups. As a result, step (a) described above provides an oil phase which preferably comprises at least one aliphatic polyisocyanate having at least two isocyanate groups and optionally at least one aromatic polyisocyanate, preferably at least one aliphatic polyisocyanate and one or more preferably hydrophobic active ingredients.

[0127] It should be noted that the terms “polyisocyanate,” “isocyanate,” and “isocyanate component,” “isocyanate compound,” or “polyisocyanate component” are used synonymously throughout this disclosure. The same applies to the term “(poly)isothiocyanate.”

[0128] In further embodiments, a mixture of isocyanate compounds and isothiocyanate compounds can be used in the oil phase.

[0129] The ratio of the isocyanate component to the total oil phase is at least 0.2% by weight, preferably at least 0.5% by weight, or particularly preferably at least 1% by weight. In this regard, the upper limit depends on the amount of functional -NCO, -OH, -NH2 and -NH- groups so that no free isocyanate groups remain. However, the upper limit is preferably 10% by weight.

[0130] Based on the present invention, it is possible to manufacture microcapsules in which the absolute isocyanate content is a very small amount of the total capsule containing the active ingredient(s) due to the low isocyanate content. Therefore, it was possible to manufacture efficient microcapsules with significantly lower isocyanate content using the process described herein. Despite the low isocyanate content, it was possible to obtain microcapsules that are highly stable and simultaneously exhibit excellent release properties. In addition, the low isocyanate content significantly reduces health and environmental concerns. Furthermore, based on the low isocyanate content, the crosslinking density of the shell wall can be reduced without adversely affecting the stability and / or performance of the microcapsules of the present invention. As a result, the total amount of isocyanate is low relative to the total weight of the capsule.

[0131] In the process for producing bio-based microcapsules according to the present invention, at least one polymerizable isocyanate is preferably first dissolved in a hydrophobic medium together with the active ingredient(s) to be encapsulated. Preferably, the active ingredient itself, for example, an oil or fragrance substance or mixture, i.e., a substance or mixture of substances having an olfactory-perceptible odor, serves as the hydrophobic medium in which the isocyanate compound is dissolved. In the context of this description, the active ingredient to be encapsulated is therefore preferably a hydrophobic active ingredient. The selection of such an active ingredient ensures that the material to be encapsulated is in the oil phase and does not mix with the outer aqueous phase. As a result, the hydrophobic component forms a dispersed phase, and the aqueous phase is correspondingly a continuous phase. This ensures that the hydrophobic active ingredient is effectively encapsulated as a core substance within the shell of the microcapsule.

[0132] Suitable oil components for this purpose are further specified below:

[0133] The oil phase may consist of an isocyanate component as defined above and at least one active ingredient, but it may further consist of one or more oil components as a solvent having a cLogP (octanol / water partition coefficient) value of more than 2, preferably more than 3, and even more preferably more than 4, for example, (i) Saturated paraffins (mineral oil) having 15 or more carbon atoms, particularly 18 to 45 carbon atoms, in a straight or branched chain; (ii) Esters having 12 or more carbon atoms between a linear or branched fatty acid having 6 to 30 carbon atoms and a linear or branched saturated or unsaturated monool, diol, or triol having 3 to 30 carbon atoms, wherein these esters do not have free hydroxyl groups; (iii) Esters of benzoic acid with a linear or branched saturated or unsaturated monoalcohol having 8 to 20 carbon atoms; (iv) Monoesters or diesters of alcohols having 3 to 30 carbon atoms with naphthalene monocarboxylic acid or naphthalenedicarboxylic acid; especially naphthalene monocarboxylic acid C6-C18 Esters and naphthalenedicarboxylic acids C6-C 18 ester; (v) Straight-chain or branched saturated or unsaturated di-C6-C 18 -alkyl ether; (vi) Silicone oil; (vii) The following equation: [ka] In the formula, Q1 is a linear or branched alkyl radical having 6 to 24 carbon atoms, and Q2 is a linear or branched alkyl radical having 4 to 16 carbon atoms, forming a 2-alkyl-1-alkanol. It can contain.

[0134] In this regard, vLogP (partition coefficient) is defined as the ratio of the concentrations of a compound in a mixture of two immiscible solvents at equilibrium, representing a criterion for measuring the lipophilicity or hydrophobicity of a particular substance.

[0135] In the narrow sense (and preferred sense) of the present invention, the oil phase or oil component is the following group of substance: (i) Straight-chain or branched saturated paraffins having 20 to 32 carbon atoms; (ii) Esters having at least 14 carbon atoms, comprising a linear or branched saturated fatty acid having 8 to 24 carbon atoms and a linear or branched saturated or unsaturated monool, diol, or triol having 3 to 24 carbon atoms, wherein these esters do not contain free hydroxyl groups; (iii) Esters of benzoic acid with a linear or branched saturated monoalcohol having 10 to 18 carbon atoms; (iv) Alkylenediol dicaprylate caprate, especially propylenediol dicaprylate caprate; (v) Saturated di-C6-C6 in straight or branched chains 18 -Alkyl esters, especially (linear) di-C6-C 12 -alkyl ether; (vi) Silicone oils derived from cyclotrisiloxane, cyclopentasiloxane, dimethylpolysiloxane, diethylpolysiloxane, methylphenylpolysiloxane, diphenylpolysiloxane, and hybrid forms thereof; (vii) The following equation: [ka] A 2-alkyl-1-alkanol having 12 to 32 carbon atoms (wherein Q1 is a (preferably linear) alkyl radical having 6 to 18 carbon atoms, and Q2 is a (preferably linear) alkyl radical having 4 to 16 carbon atoms). It can include.

[0136] In the narrow sense (and most preferred sense) of this invention, the oil phase is the following group of substances: (i) Straight-chain or branched saturated paraffins having 20 to 32 carbon atoms, e.g., isoeicosane or squalene; (ii) Esters having at least 16 carbon atoms, comprising a linear or branched saturated fatty acid having 8 to 18 carbon atoms and a linear or branched saturated monool, diol, or triol having 3 to 18 carbon atoms, wherein these esters do not contain free hydroxyl groups; (iii) Esters of benzoic acid with a linear or branched saturated monoalcohol having 12-15 carbon atoms, particularly C benzoic acid 12 -C 15 -alkyl; (iv) Alkylenediol dicaprylate caprate, especially propylenediol dicaprylate caprate; (v) Linear di-C6-C 10 -Alkyl esters, especially di-n-octyl ethers (dicaprylyl ethers); (vi) Silicone oils derived from the group consisting of undecamethylcyclotrisiloxane, cyclomethicone, decamethylcyclopentasiloxane, dimethylpolysiloxane, diethylpolysiloxane, methylphenylpolysiloxane, and diphenylpolysiloxane; (vii) The following equation: [ka] A 2-alkyl-1-alkanol having 12 to 32 carbon atoms (wherein Q1 is a (preferably linear) alkyl radical having 6 to 18 carbon atoms, and Q2 is a (preferably linear) alkyl radical having 4 to 16 carbon atoms); It can include.

[0137] Particularly preferred components of type (i) groups in the oil phase are: isopropyl myristate, isopropyl palmitate, isopropyl stearate, isopropyl oleate, n-butyl stearate, n-hexyl laurate, n-decyl oleate, isooctyl stearate, isononyl stearate, isononyl isononanoate, 2-ethylhexyl palmitate, 2-ethylhexyl laurate, 2-hexyldecyl stearate, palmitate 2-octyldodecyl oleate, oleyl oleate, oleyl erucate, erucyl oleate, erucyl erucate, 2-ethylhexyl isostearate, isotridecyl isononanoate, 2-ethylhexyl coconut fatty acid, caprylic / capric triglyceride, alkylenediol dicaprylate caprate, especially propylenediol dicaprylate caprate, and synthetic, semi-synthetic and natural mixtures of such esters, such as jojoba oil.

[0138] Fatty acid triglycerides (type (i) oil components in the oil phase) may also be in the form of synthetic oils, semi-synthetic oils and / or natural oils, such as olive oil, sunflower oil, soybean oil, peanut oil, rapeseed oil, almond oil, palm oil, coconut oil, palm kernel oil, and mixtures thereof, or in the form of their constituent elements.

[0139] The (vii) type oil components in the oil phase are: 2-butyl-1-octanol, 2-hexyl-1-decanol, 2-octyl-1-dodecanol, 2-decyltetradecanol, 2-dodecyl-1-hexadecanol, and 2-tetradecyl-1-octadecanol.

[0140] Particularly preferred oil components in the oil phase are a mixture containing benzoic acid C 12 -C 15 -alkyl and 2-ethylhexyl isostearate, a mixture containing benzoic acid C 12 -C 15 -alkyl and isotridecyl isononanoate, a mixture containing benzoic acid C 12 -C 15 -alkyl, and a mixture containing 2-ethylhexyl isostearate and isotridecyl isononanoate, a mixture containing cyclomethicone and isotridecyl isononanoate, and a mixture containing cyclomethicone and 2-ethylhexyl isostearate.

[0141] Preferred oily substances used within the scope of the present invention are, for example, gellucire based on fatty alcohols having 6 to 18, preferably 8 to 10 carbon atoms, straight-chain or branched-chain C6-C 22 -fatty acid esters with C6-C 22 -fatty alcohols, or straight-chain or branched-chain C6-C 13 -carboxylic acid esters with C6-C 22- Esters with fatty alcohols, for example, myristyl myristate, myristyl palmitate, myristyl stearate, myristyl isostearate, myristyl oleate, myristyl behenate, myristyl erucate, cetyl myristate, cetyl palmitate, cetyl stearate, cetyl isostearate, cetyl oleate, cetyl behenate, cetyl erucate, stearyl myristate, stearyl palmitate, stearyl stearate, stearyl isostearate, stearyl oleate, stearyl behenate, stearyl erucate, isostearyl myristate, isostearyl palmitate, isos Tearyl, isostearyl isostearate, isostearyl oleate, isostearyl behenate, isostearyl oleate, oleyl myristate, oleyl palmitate, oleyl stearate, oleyl isostearate, oleyl oleate, oleyl behenate, oleyl erucate, behenyl myristate, behenyl palmitate, behenyl stearate, behenyl isostearate, behenyl oleate, behenyl behenate, behenyl erucate, erucyl myristate, erucyl palmitate, erucyl stearate, erucyl isostearate, erucyl oleate, erucyl behenate, and erucate. Also preferred are C6-C 22 - Branched-chain alcohols of fatty acids, especially esters with 2-ethylhexanol, C 18 -C 38 - Linear or branched C6-C alkylhydroxycarboxylic acid 22 - Esters with fatty alcohols, especially dioctyl maleate, polyhydric alcohols of linear and / or branched fatty acids (e.g., propylene glycol, dimethyldiol and trimeltriol) and / or Guerbet alcohols, C6-C 10 - Triglycerides based on fatty acids, C6-C 18 -Fatty acid-based liquid mono- / di- / triglycerides, C6-C 22 - Aromatic carboxylic acids of fatty alcohols and / or Guerbet alcohols, especially esters with benzoic acid, C2-C 12- Esters of dicarboxylic acids with linear or branched alcohols having 1 to 22 carbon atoms or polyols having 2 to 10 carbon atoms and 2 to 6 hydroxyl groups, vegetable oils, branched primary alcohols, substituted cyclohexane, linear or branched C6-C carbonates 22 - Fatty alcohols, such as dicaprylyl carbonate (Cetiol® CC), Guerbet carbonate based on fatty alcohols having 6 to 18, preferably 8 to 10 carbon atoms, and linear and / or branched C6-C6 benzoic acid. 22 - Esters with alcohols (e.g., Finsolv® TN), linear or branched symmetric or asymmetric dialkyl ethers having 6 to 22 carbon atoms per alkyl group, e.g., dicaprylyl ether (Cetiol® OE), ring-opening products of epoxidized fatty acid esters with polyols, silicone oils (cyclomethicone, silicone, methicone, graud, etc.) and / or aliphatic or naphthenic hydrocarbons, e.g., squalane, squalene, or dialkylcyclohexane. The most preferred oil components are triglycerides, especially those of natural origin.

[0142] In preferred embodiments, the microcapsules of the present invention are loaded with one or more (hydrophobic) active ingredients, such as fragrances or oils. For specific applications, other additives may also be used as indicated above. With respect to fragrances and oils, the polyurethane-based and / or polyurea-based capsules of the present invention allow for loading in large quantities, up to 80% of the total capsule weight. The active substance is preferably incorporated into the oil phase, but may also be incorporated into the first aqueous phase depending on its porosity.

[0143] The term “active substance” as used herein should be understood to mean a substance or component relating to a particular effect, such as a fragrance, aroma, dye, medicine, insecticide, etc. Preferably, the hydrophobic active substance is part of the oil phase, i.e., together with another component constituting the oil phase, or, as used herein, constitutes the oil component of the oil phase itself. Preferably, the hydrophobic substance and the polyisocyanate component constitute the oil phase. When used herein, fragrance and / or perfume means a single fragrance or perfume substance (also called an odorous substance or aromatic substance), i.e., a compound having an odor or smell, and by extension, all natural and synthetic substances that impart an odor that can be perceived by the sense of smell, as well as a composition of one or more fragrance or perfume substances, i.e., a mixture of the aforementioned compounds or a mixture containing the aforementioned compounds.

[0144] This list of active substances and other components is non-exclusive and may include further active substances and other components not described below.

[0145] Suitable fragrances and / or oils are, for example, single odorants or mixtures of natural and synthetic odorants. Natural perfumes include extracts from flowers (lily, lavender, rose, jasmine, neroli, ylang-ylang), stems and leaves (geranium, patchouli, petitgrain), fruits (anise, coriander, caraway, juniper), fruit peels (bergamot, lemon, orange), roots (nutmeg, angelica, celery, cardamom, costus, iris, calamus), woods (pine, sandalwood, guaiac wood, cedarwood, rosewood), herbs and grasses (tarragon, lemongrass, sage, thyme), needles and branches (spruce, fir, pine, bonsai pine), resins and balsams (galbanum, elemi, benzoin, myrrh, olibanum, opoponax). Animal sources, such as civet and beaver, may also be used. Typical synthetic perfume compounds are ester, ether, aldehyde, ketone, alcohol, and hydrocarbon type products. Examples of ester-type perfume compounds include benzyl acetate, phenoxyethyl isobutyrate, p-tert-butyl cyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethylmethylphenyl glycinate, allylcyclohexyl propionate, styraryl propionate, and benzyl salicylate. Examples of ethers include benzyl ethyl ether, while examples of aldehydes include linear alcanals containing 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lyrial, and borageonal. Examples of preferred ketones include ionone, isomethylionone, and methylcedyl ketone. Suitable alcohols include anethol, citronellol, eugenol, isoeugenol, geraniol, linalool, phenylethyl alcohol, and terpineol. Hydrocarbons mainly include terpenes and balsams. However, it is preferable to use a mixture of various perfume compounds that work together to create a perfume to one's liking. Other suitable oils are relatively low-volatility essential oils, which are primarily used as aromatic components.Examples include sage oil, chamomile oil, clove oil, melissa oil, mint oil, cinnamon leaf oil, lime blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil, ladana oil, and lavender oil. The following ingredients are preferably used individually or in mixture form: bergamot oil, dihydromyrcenol, lilial, liral, citronellol, phenylethyl alcohol, hexyl cinnamaldehyde, geraniol, benzylacetone, cyclamenaldehyde, linalool, boisamblenforte, ambroxan, indole, hedione, sandelice, citrus oil, mandhelin oil, orange oil, allylamyl glycolate, cyclobeltal, lavender oil, salvia oil, damascone, geranium oil bavone, cyclohexyl salicylate, Vertofix Coeur, Iso-E-Super, Fixolide NP, evanyl, iraldine gamma, phenylacetic acid, geranyl acetate, benzyl acetate, rose oxide, romilat, ilotyl and floramat.

[0146] However, preferably, the perfume or aromatic substances used in encapsulation are compounds used primarily for the purpose of imparting or modifying a scent or flavor. Preferably, these substances or mixtures of substances can impart or modify the scent or flavor of the composition in an active or pleasant way. For the purposes of this invention, the terms “fragrance oil” or “aroma” include combinations of fragrance and flavoring components for modifying or imparting a scent or flavor.

[0147] In addition to or in addition to the fragrance / perfume substances and oils exemplified above, at least one hydrophobic active substance is an active ingredient in aromatic substances, aromas, pesticides, cosmetics, active ingredients in active skin products such as skin moisturizers, skin or hair conditioning agents, skin whitening agents, acne inhibitors, etc., active pharmaceutical ingredients, UV active substances, optical glossing agents, thickeners, drape and form control agents, smoothing agents, antistatic agents, wrinkle inhibitors, bactericides, disinfectants, antimicrobial agents, antifungal agents, antifungal agents, antiviral agents, antimicrobial agents, drying agents, and stain-resistant substances. A broad group consisting of the above-mentioned active ingredients, as well as agents, antifouling agents, odor inhibitors, fabric deodorizers, dyes and dye fixatives, color maintenance agents, color restorers / recovery agents, antifading agents, anti-abrasion agents, abrasion-resistant agents, fabric preservatives, abrasion inhibitors, rinsing aids, UV protectants, sun-fading inhibitors, insect repellents, anti-allergic agents, flame retardants, waterproofing agents, fabric softeners, shrinkage-resistant agents, stretch-resistant agents, fluorescent paints, solvents, waxes, silicone oils, lubricants, coolants, TRPV modifiers (e.g., TRPV1 and TRPV2 modifiers), impregnating agents, stain inhibitors, friction reducers, and mixtures of the above-mentioned active ingredients can be selected.

[0148] Suitable coolants are known in the art and are, for example, menthol-based coolants such as Frescolat®. The following lists some individual coolants that are preferred for use within the framework of the present invention. Those skilled in the art can add numerous other coolants to this list; the listed coolants can also be used in combination with each other, and these are preferably listed below: menthol and menthol derivatives (e.g., L-menthol, D-menthol, racemic menthol, isomenthol, neoisomenthol, neomenthol), menthyl ethers (e.g., (l-menthoxy)-1,2-propanediol, (l-menthoxy)-2-methyl-1,2-propanediol, l-menthyl-methyl ether), menthyl glycolate acetals, menthyl glycolate ketals or mixtures of both, menthyl esters (e.g., menthyl formate, menthyl acetate, menthyl isobutyrate, menthyl hydroxyisobutyrate, menthyl lactate, L-menthyl-L-lactate, L-menthyl-D-lactate, menthyl-(2-methoxy)acetate, menthyl-(2-methoxyethoxy)acetate, menthyl pyroglutamate), menthyl carbonate (e.g., For example, menthylpropylene glycol carbonate, menthylethylene glycol carbonate, menthylglycerol carbonate or mixtures thereof), semi-esters of menthol with dicarboxylic acids or derivatives (e.g., mono-menthyl succinate, mono-menthyl glutarate, mono-menthyl malonate, O-menthyl succinate ester-N,N-(dimethyl)amide, O-menthyl succinate ester amide), menthane carboxylic acid amide (in this case, preferably menthane carboxylic acid-N-ethylamide [WS3] or Nα-(menthane carbonyl)glycine ethyl ester [WS5], menthane carboxylic acid-N-(4-cyanophenyl)amide or menthane carboxylic acid-N-(4-cyanomethylphenyl)amide, menthane carboxylic acid-N-(alkoxyalkyl)amide), menthone and menthone derivatives (e.g., L-menthylglycerol ketal), 2,3-dimethyl-2-(2-propyl)-butyric acid derivatives (e.g., 2,3-dimethyl-2-(2-propyl)-butyrate-N-methylamide [WS23]), isopuregol or its esters (I-(-)-isopulegol, I-(-)-isopulegol acetate), menthane derivatives (e.g., p-menthane-3,8-diol), cubebols or synthetic or natural mixtures containing cubebols, pyrrolidone derivatives of cycloalkyldione derivatives (e.g., 3-methyl-2(1-pyrrolidinyl)-2-cyclopenten-1-one) or tetrahydropyrimidine-2-one (e.g., WO Selected here from ishirin or related compounds as described in 2004 / 026840, further carboxamides (e.g., N-(2-(pyridine-2-yl)ethyl)-3-p-menthanecarboxamide or related compounds), (1R,2S,5R)-N-(4-methoxyphenyl)-5-methyl-2-(1-isopropyl)cyclohexane-carboxamide [WS12], oxamate and [(1R,2S,5R)-2-isopropyl-5-methyl-cyclohexyl]2-(ethylamino)-2-oxoacetate (X Cool). Preferred coolants for specific synergistic effects include L-menthol, D-menthol, racemic menthol, menthol glycerol acetal (trade name: Frescolat® MGA), menthyl lactate (preferably L-menthyl lactate, especially L-menthyl lactate (trade name: Frescolat® ML)), substituted menthyl-3-carboxamide (e.g., menthyl-3-carboxylic acid N-ethylamide), 2-isopropyl-N-2,3-trimethylbutanamide, substituted cyclohexanecarboxamide, 3-menthoxypropane-1,2-diol, 2-hydroxyethylmenthyl carbonate, 2-hydroxypropylmenthyl carbonate, and isopuregol. Particularly preferred coolants are L-menthol, racemic menthol, menthol glycerol acetal (trade name: Frescolat® MGA), menthyl lactate (preferably L-menthyl lactate, especially L-menthyl lactate (trade name: Frescolat® ML)), 3-menthoxypropane-1,2-diol, 2-hydroxyethyl menthyl carbonate, and 2-hydroxypropyl menthyl carbonate.

[0149] In addition, TRPV1 and TRPV2 modifiers, such as capsaicin and other TRPV1 and TRPV2-reactive substances known in the art, can be effectively encapsulated by the core-shell microcapsules of the present invention. Preferred capsules according to the present invention include, for example, one or more TRPV1 antagonists. Preferred compounds for alleviating cutaneous nerve hypersensitivity based on their action as TRPV1 antagonists include, for example, trans-4-tert-butylcyclohexanol, or direct TRPV1 modifiers by μ-receptors, such as acetyltetrapeptide-15.

[0150] Ingredients and / or auxiliary agents and / or additives or auxiliaries that are suitable for use as cosmetics or pharmaceuticals include, among others, abrasives, acne inhibitors, anti-aging agents for skin, anti-cellulitis agents, anti-dandruff agents, anti-inflammatory agents, antibacterial agents, anti-irritants, irritation inhibitors, antioxidants, astringents, odor absorbers, sweat inhibitors, disinfectants, antistatic agents, binders, buffers, carriers, chelating agents, cell stimulants, cleansing agents, depilatory agents, and surfactants, as further described below. Deodorizers, antiperspirants, fabric softeners, emulsifiers, enzymes, enzyme inhibitors, essential oils, fibers, film-forming agents, fixatives, foaming agents, foam stabilizers, foam inhibitors, foam boosters, gelling agents, gel-forming agents, hair care products, hair styling products, hair straightening agents, moisture supply agents, moisturizing substances, moisture-retaining substances, bleaching agents, strengthening agents, stain removers, lubricants, moisturizing creams, ointments, milking agents, plasticizers, coating agents, polishing agents, preservatives, glossing agents, green polymers and synthetic polymers, powders, proteins, substances that add oil again (re-oiling agents) Agents, abrasives, silicones, skin soothing agents, skin cleansing agents, skin care agents, skin restorers, skin whitening agents, skin protectants, skin softeners, hair protectants, coolants, skin heat dissipating agents, warming agents, skin warming agents, stabilizers, surfactants, UV absorbers, UV filters, primary sunscreen factors, secondary sunscreen factors, detergents, fabric conditioners, suspending agents, skin sunscreens, active substances that modulate skin or hair pigmentation, matrix metalloproteinase inhibitors, skin moisturizers, glycosaminoglycan stimulants, TRPV1 antagonists, exfoliants, or fat enhancers, hair growth activators or inhibitors, thickeners, rheological active substances, vitamins, oils, waxes, pearlescent waxes, fats, phospholipids, saturated fatty acids, mono- or polyunsaturated fatty acids, alpha-hydroxy acids, polyhydroxy fatty acids, liquefaction agents, dyes, color protectants, pigments, corrosion inhibitors, fragrances or fragrant oils, odorants, polyols, electrolytes, organic solvents, and mixtures of two or more of the aforementioned substances. For example, moisturizers, bio-derived active ingredients, and antioxidants can be used as active ingredients in skin products.

[0151] Suitable antifouling polymers, also called anti-redeposition agents, include, for example, nonionic cellulose ethers having a ratio of 15-30% by weight of methoxy groups and 1-15% by weight of hydroxypropyl groups based on a nonionic cellulose ether, such as methylcellulose and methylhydroxycellulose or hydroxypropylcellulose (HPC) (Klucel®), and also polymers known in the prior art of phthalic acid and / or terephthalic acid or their derivatives, particularly polymers of ethylene terephthalate and / or polyethylene glycol terephthalic acid and / or polypropylene glycol terephthalic acid, or anionic and / or nonionic modified derivatives thereof. Suitable derivatives include phthalic acid polymers and sulfonated derivatives of terephthalic acid polymers.

[0152] Optical brighteners (so-called "whitening agents") can be incorporated into capsules according to the present invention to remove graying and yellowing from the surface of treated fibers. These substances are absorbed by the fibers and brighten the fibers by converting invisible ultraviolet light into visible long-wavelength light, mimicking a bleaching effect. In this process, the ultraviolet light absorbed from sunlight is emitted as a slightly blue fluorescence, which combines with the yellow of grayed or yellowed laundry to impart a pure white color. Suitable compounds are derived, for example, from the class of substances consisting of 4,4'-diamino-2,2'-stilbendisulfonic acid (flavonic acid), 4,4'-distyryl-biphenylene, methylumbelliferone, coumarin, dihydroquinolinone, 1,3-diarylpyrazoline, naphthalimide, benzoxazole, benzisoxazole and benzimidazole, and heterocyclic-substituted pyrene derivatives.

[0153] Graying inhibitors prevent the re-adhesion of dirt by continuously removing it from fibers suspended in the liquid. Suitable for this purpose are water-soluble colloids, usually of organic properties, such as salts of ether sulfonic acid of starch or cellulose, or salts of acidic sulfonic acid esters of cellulose or starch. Also suitable for this purpose are water-soluble polyamides containing acidic groups. In addition, soluble starch preparations and starch products other than those specified above, such as decomposed starch and aldehyde starch, can be used. Polyvinylpyrrolidone can also be used. However, it is preferable to use cellulose ethers, such as carboxymethylcellulose (sodium salt), methylcellulose, hydroxyalkylcellulose, and mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose, and mixtures thereof.

[0154] Fabrics made of rayon, cellulose, cotton, and mixtures thereof may wrinkle because individual fibers are susceptible to damage from bending, folding, compression, and crushing across the fiber direction; therefore, the microcapsules according to the present invention may contain synthetic wrinkle inhibitors. These include, for example, synthetic products based on fatty acids, fatty acid esters, fatty acid amides, fatty acid alkylol esters, fatty acid alkylol amides, or fatty alcohols that typically react with ethylene oxide, or products based on lecithin or modified phosphate esters.

[0155] High comfort can be achieved by the additional use of antistatic agents. Antistatic agents enhance surface conductivity, thus enabling more easily discharged accumulated charge. Typically, antistatic agents are substances accompanied by at least one hydrophilic molecular ligand that provides a more or less hydrated film on the surface. These surface-active antistatic agents can usually be divided into nitrogen-containing (amines, amides, quaternary ammonium compounds), phosphorus-containing (phosphate esters), and sulfur-containing (alkyl sulfonates, alkyl sulfates) antistatic agents. Lauryl (or stearyl)dimethylbenzylammonium chloride is suitable as an antistatic agent for fabric surfaces or as an additive to detergents and cleaning agents, in which case additional conditioning effects are also achieved.

[0156] Moisturizers help regulate skin moisture. Preferred moisturizers according to the present invention include amino acids, pyrrolidone carboxylic acid, lactic acid and its salts, lactitol, urea and urea derivatives, uric acid, glucosamine, creatinine, collagen cleavage products, chitosan or chitosan salts / derivatives, and in particular polyols and polyol derivatives (e.g., glycerol, diglycerol, triglycerol, ethylene glycol, propylene glycol, butylene glycol, erythritol, 1,2,6-hexanetriol, polyethylene glycol (e.g., PEG-4, PEG-6, PEG-7, PEG-8, PEG-9, PEG-10, PEG-12, PEG-14, PEG-16, PEG-18) Examples include sugars and sugar derivatives (including fructose, glucose, maltose, maltitol, mannitol, inositol, sorbitol, sorbitolsilanediol, sucrose, trehalose, xylose, xylitol, glucuronic acid and its salts), ethoxylated sorbitol (Sorbeth-6, Sorbeth-20, Sorbeth-30, Sorbeth-40), honey and hydrogenated honey, hydrogenated starch hydrolysate, and mixtures of hydrogenated wheat protein and PEG-20 acetate polymer. Preferred humectants according to the present invention are glycerol, diglycerol, triglycerol, and butylene glycol.

[0157] Biologically derived agents are understood to include, for example, tocopherol, tocopherol acetate, tocopherol palmitate, ascorbic acid, (deoxy)ribonucleic acid and their fragmentation products, β-glucan, retinol, bisabolol, allantoin, phytantriol, panthenol, AHA acids, amino acids, ceramides, pseudoceramides, essential oils, plant extracts, such as plum extract, Bambara nut extract, and complex vitamin preparations.

[0158] To prevent undesirable changes on the treated fabric surface caused by the action of oxygen and other oxidative processes, the macroemulsion may contain antioxidants. Examples of compounds in this class include amino acids (e.g., glycine, histidine, tyrosine, tryptophan) and their derivatives, imidazoles (e.g., urocanic acid) and their derivatives, peptides (e.g., D,L-carnosine, D-carnosine, L-carnosine) and their derivatives (e.g., anserine), carotenoids, carotenes (e.g., α-carotene, β-carotene, lycopene) and their derivatives, chlorogenic acid and its derivatives, lipoic acid and its derivatives (e.g., dihydrolipoic acid), aurothiogluco thiols, propylthiouracil and other thiols (e.g., thioredoxin, glutathione, cysteine, cystine, cysteamine and its glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl, and lauryl, palmitoyl, oleyl, γ-linoleyl, cholesteryl, and glyceryl esters) and their salts, dilauryl thiodipropionate, distearyl thiodipropionate, thiodipropionic acid and their derivatives (esters, ethers, peptides, lipids, nucleotides, nucleosides, (and salts) and sulfoximine compounds (e.g., butionine sulfoximine, homocysteine ​​sulfoximine, butionine sulfone, penta-, hexa-, heptathonine sulfoximine) in very low permissible amounts (e.g., picomoles to micromoles / kg), further (metal) chelating agents (e.g., α-hydroxy fatty acids, palmitic acid, phytic acid, lactoferrin), α-hydroxy acids (e.g., citric acid, lactic acid, malic acid), humic acid, bile acid, bile extract, bilirubin, biliverdin, EDTA, E GTA and its derivatives, unsaturated fatty acids and their derivatives (e.g., γ-linolenic acid, linoleic acid, oleic acid), folic acid and its derivatives, ubiquinone and ubiquinol and their derivatives, vitamin C and its derivatives (e.g., ascorbyl palmitate, magnesium ascorbyl phosphate, ascorbyl acetate), tocopherol and its derivatives (e.g., vitamin E acetate), vitamin A and its derivatives (vitamin A palmitate), and coniferyl benzoate derived from benzoic acid resin, rutic acid and its derivatives,Examples of suitable derivatives according to the present invention include α-glycosylrutin, ferulic acid, furfrillidendenglucitol, carnosine, butylhydroxytoluene, butylhydroxyanisole, nordihydroguaiaretic acid, trihydroxybutyrophenone, uric acid and its derivatives, mannose and its derivatives, superoxide dismutase, zinc and its derivatives (e.g., ZnO, ZnSO4), selenium and its derivatives (e.g., selenium-methionine), stilbene and its derivatives (e.g., stilbene oxide, trans-stilbene oxide), and the above-mentioned active substances (salts, esters, ethers, sugars, nucleotides, nucleosides, peptides, and lipids).

[0159] Suitable anti-dandruff agents include piroctone olamine (1-hydroxy-4-methyl-6-(2,4,4-trimitylpentyl)-2-(1H)-pyridinone monoethanolamine salt), Baypival® (crimbazole), Ketoconazol®, (4-acetyl-1-{-4-[2-(2,4-dichlorophenyl)r-2-(1H-imidazole-1-ylmethyl)-1,3-dioxiran-c-4-ylmethoxyphenyl}piperazine, ketoconazole, and Elbio. The ingredients are sulfur, selenium disulfide, colloidal sulfur, sulfur polyethylene glycol monooleate sorbitan, sulfur ricinol polyethoxylate, sulfur-tar distillate, salicylic acid (or in combination with hexachlorophene), undecylenate sulfosuccinate monoethanolamine sodium salt, Lamepon® UD (protein-undecylenate condensate), zinc pyrithione, aluminum pyrithione, and magnesium pyrithione / dipyrithione-magnesium sulfate.

[0160] Cosmetic deodorants (deodorants) weaken, mask, or eliminate body odor. Body odor is caused by the effect of bacteria on the skin on apocrine sweating, which in turn forms unpleasant odor-causing decomposition products. Therefore, deodorants contain active ingredients that function as antibacterial agents, enzyme inhibitors, odor absorbers, and odor shielding agents.

[0161] As antibacterial agents, all substances that are active against Gram-positive bacteria include, for example, 4-hydroxybenzoic acid and its salts and esters, N-(4-chlorophenyl)-N'(3,4-dichlorophenyl)urea, 2,4,4'-trichloro-2'-hydroxy-diphenyl ether (triclosan), 4-chloro-3,5-dimethylphenol, 2,2'-methylene-bis(6-bromo-4-chlorophenol), 3-methyl-4-(1-methylethyl)-phenol, 2-benzyl-4-chlorophenol, 3-(4-chlorophenoxy)-1,2-propane Diol, 3-iodo-2-propynyl butylcarbamate, chlorohexidine, 3,4,4'-trichlorocarbanilide (TTC), antibacterial fragrance, thymol, thyme oil, eugenol, clove oil, menthol, mint oil, farnesol, phenoxyethanol, glycerol monocaprate, glycerol monocaprylate, glycerol monolaurylate (GML), diglycerol monocaprate (DMC), salicylic acid-N-alkylamide, for example, salicylic acid-n-octylamide or salicylic acid-n-decylamide are generally preferred.

[0162] Examples of suitable enzyme inhibitors are esterase inhibitors. These are preferably trialkyl citrates, such as trimethyl citrate, tripropyl citrate, triisopropyl citrate, tributyl citrate, and especially triethyl citrate (Hydagen® CAT). These substances inhibit enzyme activity and thus reduce odor formation. Further suitable substances as esterase inhibitors are sulfate sterols or phosphate sterols, such as lanosterol, cholesterol, campesterol, stigmasterolol, and sitosterol sulfate or sitosterol phosphate, dicarboxylic acids and their derivatives, such as glutaric acid, glutaric acid monoethyl ether, glutaric acid diethyl ether, adipic acid, adipic acid monoethyl ether, adipic acid diethyl ether, malonic acid and malonic acid diethyl ether, hydroxycarboxylic acids and their esters, such as citric acid, malic acid, tartaric acid or diethyl ether tartarate, and zinc glycinate.

[0163] Suitable odor absorbers are substances that can absorb and primarily retain odor-causing compounds. They reduce the diffusion rate by lowering the partial pressure of individual components. In this case, it is important that the fragrances specified herein remain unaffected. Odor absorbers have no effect on bacteria. They include, for example, zinc salt complexes of ricinoleic acid as the main component, or certain primarily odor-neutral substances known to those skilled in the art, such as "fixatives," e.g., labdanum or styrax extracts or certain abietic acid derivatives. Fragrances or fragrant oils that provide each fragrance to the deodorant in addition to their function as odor shields also act as odor shields. Examples of fragrant oils that can be mentioned are mixtures of natural and synthetic fragrances. Natural fragrances include, for example, extracts of flowers, stems and leaves, fruits, fruit peels, wood, herbs and grasses, needles and branches, and resins and balsams. Also suitable are animal-derived materials, e.g., civet and sea lion incense. Typical synthetic fragrance compounds are ester, ether, aldehyde, ketone, alcohol, and hydrocarbon type products. Examples of ester-type fragrance compounds include benzyl acetate, p-tert-butylcyclohexyl acetate, linalyl acetate, phenethyl acetate, linalyl benzoate, benzyl formate, allylcyclohexyl propionate, styraryl propionate, and benzyl salicylate. Examples of ethers include benzyl ethyl ether; examples of aldehydes include linear alcanals with 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lyrial, and borageonal; examples of ketones include ionone and methylcedyl ketone; examples of alcohols include anethol, citronellol, eugenol, isoeugenolic, geraniol, linalool, phenethyl alcohol, and terpineol; and examples of hydrocarbons mainly include terpenes and balsams. However, preferred are mixtures of various fragrances that together create a pleasant aroma.Low-volatility essential oils commonly used as flavorings are also suitable as fragrance oils, such as sage oil, chamomile oil, clove oil, melissa oil, mint oil, cinnamon leaf oil, linden flower oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil, labdanum oil, and lavandin oil. Preferred are bergamot oil, dihydromyrcenol, lilial, liral, citronellol, phenethyl alcohol, α-hexyl cinnamaldehyde, geraniol, benzylacetone, cyclamenaldehyde, linalool, boisamblenforte, ambroxan, indole, hedione, sandelice, lemon oil, mandarin oil, orange oil, allylamyl glycolate, cyclobertal, lavandin oil, clay sage oil, β-damascone, geranium oil bowlon, cyclohexyl salicylate, Vertofix Coeur, iso-E-super, Fixolide NP, evanyl, iraldine gamma, phenylacetic acid, geranyl acetate, benzyl acetate, rose oxide, Romilat, Irotyl, and Floramat, which are used alone or in combination.

[0164] Antiperspirants (perspirants) affect the activity of eccrine sweat glands, thereby reducing sweat formation by weakening underarm dampness and body odor. Aqueous or anhydrous formulations of antiperspirants typically contain the following components: astringents, oil components, nonionic emulsifiers, co-emulsifiers, thickeners, excipients, such as thickeners or complexing agents, and / or non-aqueous solvents, such as ethanol, propylene glycol, and / or glycerol. Preferred astringent antiperspirants are primary salts of aluminum, zirconium, or zinc. Suitable active ingredients with such antiperspirant activity include, for example, aluminum chloride, aluminum chlorohydrate, aluminum dichlorohydrate, aluminum sesquichlorohydrate, and their complex compounds with, for example, propylene glycol-1,2-aluminum hydroxyallantoic acid, aluminum tartrate chloride, aluminum zirconium trichlorohydrate, aluminum zirconium tetrachlorohydrate, aluminum zirconium pentachlorohydrate, and their complex compounds with amino acids such as glycine. In addition, antiperspirants may contain small amounts of common oil-soluble and water-soluble excipients. Such oil-soluble excipients may include, for example, anti-inflammatory, skin-protective, or aromatic essential oils, synthetic skin protectants, and / or oil-soluble fragrance oils.

[0165] The capsules according to the present invention may contain antimicrobial agents to combat microorganisms. In this case, distinctions are made according to the antimicrobial spectrum and the mechanism of action between bacteriostatic agents, bactericidal agents, fungicidal agents, and so on. Examples of important substances derived from these groups are benzalkonium chloride, alkylaryl sulfonate, halophenol, and phenylmercury acetate, in which case these compounds do not necessarily have to be added to the detergents and cleaning agents according to the present invention. As antimicrobial agents, all substances that are active against Gram-positive bacteria include, for example, 4-hydroxybenzoic acid and its salts and esters, N-(4-chlorophenyl)-N'(3,4-dichlorophenyl)urea, 2,4,4'-trichloro-2'-hydroxy-diphenyl ether (triclosan), 4-chloro-3,5-dimethylphenol, 2,2'-methylene-bis(6-bromo-4-chlorophenol), 3-methyl-4-(1-methylethyl)-phenol, 2-benzyl-4-chlorophenol, and 3-(4-chlorophenoxy)-1,2-propane Diol, 3-iodo-2-propynyl butylcarbamate, chlorohexidine, 3,4,4'-trichlorocarbanilide (TTC), antibacterial fragrance, thymol, thyme oil, eugenol, clove oil, menthol, mint oil, farnesol, phenoxyethanol, glycerol monocaprate, glycerol monocaprylate, glycerol monolaurylate (GML), diglycerol monocaprate (DMC), salicylic acid-N-alkylamide, for example, salicylic acid-n-octylamide or salicylic acid-n-decylamide are generally preferred.

[0166] Among the compounds that serve as bleaching agents that generate H2O2 in water, sodium perborate tetrahydrate and sodium perborate monohydrate are particularly important. Further useful bleaching agents include, for example, sodium percarbonate, peroxypyrrophosphates, citrate perhydrates, and peracidic salts or peracids that generate H2O2, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacids, or diperdodecanediic acid. Compounds that produce aliphatic peroxocarboxylic acids and / or optionally substituted perbenzoic acids, preferably having 1 to 10 carbon atoms, particularly 2 to 4 carbon atoms, under hyperhydrolysis conditions can be used as bleaching activators. Preferably, substances have O-acyl groups and / or N-acyl groups along with the aforementioned number of carbon atoms and / or optionally substituted benzoyl groups. Preferred materials include polyacylated alkylenediamines, particularly tetraacetylethylenediamine (TAED); acylated triazine derivatives, particularly 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT); acylated glycolyls, particularly tetraacetylglycolyl (TAGU); N-acylimides, particularly N-nonanoylsuccinimide (NOSI); acylated sulfonic acid phenols, particularly N-nonanoyl or isononanoyl oxybenzenesulfonic acid (n- or iso-NOBS); carboxylic anhydrides, particularly phthalic anhydrides; and acylated polyhydric alcohols, particularly triacetin, ethylene glycol diacetate, and 2,5-diacetoxy-2,5-dihydrofuran. In addition to, or instead of, conventional bleaching activators, so-called bleaching catalysts can also be incorporated into the textile treatment agent via the capsules of the present invention. These substances are transition metal salts or complexes that enhance bleaching, such as Mn-, Fe-, Co-, R-, or Mo- salt complexes or -carbonyl complexes. Mn-, Fe-, Co-, Ru-, Mo-, Ti-, V-, and Cu- complexes and Co-, Fe-, Cu-, and Ru-amine complexes with nitrogen-containing tripod-type ligands can also be used as bleaching catalysts.

[0167] The capsules according to the present invention may also contain preservatives. Examples include sorbic acid and its salts, benzoic acid and its salts, salicylic acid and its salts, phenoxyethanol, 3-iodo-2-propynyl butylcarbamate, sodium N-(hydroxymethyl)glycinate, biphenyl-2-ol, and mixtures thereof. A preferred preservative is a solvent-free aqueous combination of diazolidinyl urea, sodium benzoate, and potassium sorbate (available from Schulke and Mayr as Euxyl® K 500), which may be used in a pH range up to 7. Preservatives based on organic acids and / or their salts are particularly suitable for preserving skin-friendly detergents and the capsules according to the present invention.

[0168] Silicone derivatives may be used in textile treatment, for example, to improve re-wetting properties and facilitate ironing of the treated fabric surface. They also improve the rinsing behavior of detergents and cleaning agents due to their foam-suppressing properties. Preferred silicone derivatives are, for example, polydialkylsiloxanes or alkylarylsiloxanes that have 1 to 5 C atoms in the alkyl group and are fully or partially fluorinated. Preferred silicones are polydimethylsiloxanes that can optionally be derivatized and then amino-functionalized, or quaternized, or have Si-OH, Si-H and / or Si-Cl bonds. The viscosity of preferred silicones at 25°C is in the range of 100 mPas to 100,000 mPas.

[0169] The capsules according to the present invention may also contain an insect repellent. Suitable insect repellents include, for example, N,N-diethyl-m-toluamide, 1,2-pentanediol or ethylbutylacetyl aminopropionate, 1-(1-methylpropoxycarbonyl)-2-(2-hydroxyethyl)piperidine, p-menthane-3,8-diol, 2-undecanone, as well as essential oils, such as citronella oil, lemongrass oil, lavender oil, neem oil and eucalyptus oil, in particular p-menthane-3,8-diol and essential oils, such as citronella oil, lemongrass oil, lavender oil, neem oil and eucalyptus oil.

[0170] The capsules according to the present invention may also include a UV absorber that can be absorbed onto the surface of the treated fabric and improves the photostability of the fibers. The term UV photoprotective factor is understood to refer to an organic substance that is, for example, a liquid or crystalline substance at room temperature (a photoprotective filter) that absorbs ultraviolet light and can emit the absorbed energy in the form of long-wavelength radiation, such as heat. The UV photoprotective factor is usually present in an amount of 0.1% to 5% by weight, preferably 0.2% to 1% by weight. The UVB filter may be oil-soluble or water-soluble. Examples of oil-soluble substances include, for example, 3-benzylidene camphor or 3-benzylidenenorcamphor and their derivatives, such as 3-(4-methylbenzylidene) camphor, 4-aminobenzoic acid derivatives, preferably 3-(4-dimethylamino)benzoate-2-ethylhexyl, 4-(dimethylamino)benzoate-2-octyl, and 4-(dimethylamino)benzoate amyl; cinnamic acid esters, preferably 4-methoxycinnamate-2-ethylhexyl, 4-methoxycinnamate propyl, 4-methoxycinnamate isoamyl, and 2-cyano-3,3-phenylcinnamate-2-ethylhexyl (octocrylene); salicylic acid esters, preferably salicylate-2-ethylhexyl, salicylate-4-propylbenzyl, and salicylate Examples include homomethyl cylate; derivatives of benzophenone, preferably 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, and 2,2'-dihydroxy-4-methoxybenzophenone; esters of benzylmalonic acid, preferably di-2-ethylhexyl 4-methoxybenzylmalonate; triazine derivatives, such as 2,4,6-trianilino-(p-carbo-2'-ethyl-1'-hexyloxy)-1,3,5-triazine and octyltriazone or dioctylbutamidetriazone (Uvasorb® HEB); propane-1,3-dione, such as 1-(4-tert.-butylphenyl)-3-(4'-methoxyphenyl)propane-1,3-dione; and ketotricyclo(5.2.1.0)decane derivatives.

[0171] In particular, suitable UVA filters include benzoylmethane derivatives, such as 1-(4'-tert-butylphenyl)-3-(4'-methoxyphenyl)propane-1,3-dione, 4-tert-butyl-4'-methoxydibenzoylmethane (Parsol® 1789), 2-(4-diethylamino-2-hydroxybenzoyl)-hexyl benzoate (Uvinul® A Plus), 1-phenyl-3-(4'-isopropylphenyl)-propane-1,3-dione, and enamine compounds. UVA and UVB filters can, of course, be used in combination. Particularly favorable combinations consist of benzoylmethane derivatives combined with cinnamic acid esters, preferably 4-methoxycinnamate-2-ethylhexyl and / or 4-methoxycinnamate propyl and / or 4-methoxycinnamate isoamyl, such as 4-tert-butyl-4'-methoxydibenzoylmethane (Parsol® 1789) and 2-cyano-3,3-phenylcinnamate-2-ethylhexyl (octocrylene). Advantageously, these combinations are used with water-soluble filters, such as 2-phenylbenzimidazole-5-sulfonic acid and its alkali salts, alkaline earth salts, ammonium salts, alkylammonium salts, alkanolammonium salts, and glucammonium salts.

[0172] In addition to the soluble substances described above, insoluble photoprotective dyes, specifically finely dispersed metal oxides or metal salts, are also suitable for this purpose. Examples of suitable metal oxides include zinc oxide and titanium oxide, as well as oxides and mixtures thereof of iron, zirconium, silicon, manganese, aluminum, and cerium. Silicates (talc), barium sulfate, or zinc stearate may be used as salts. Oxides and salts are used in the form of dyes for skincare and skin protection emulsions and cosmetic products. In this case, the particles should have an average diameter of less than 100 nm, preferably 5 nm to 50 nm and especially 15 nm to 30 nm. They may have a spherical shape, but particles with an elliptical shape or other shapes deviating from the spherical shape may also be used. Dyes can also exist in a surface-treated, i.e., hydrophilic or hydrophobic form. Typical examples include coated titanium dioxide, such as titanium dioxide T805 (Degussa) or Eusolex® T2000, Eusolex® T, Eusolex® T-ECO, Eusolex® T-Aqua, Eusolex® T-45D (all Merck), and Uvinul TiO2 (BASF). In this context, suitable hydrophobic coating agents are mainly silicones, specifically trialkoxyoctylsilane or simethicone. In sunscreens, so-called micropigments or nanopigments are preferably used. Preferably, micronized zinc oxide, such as Z-COTE® or Z-COTE HP1®, is used.

[0173] In addition, a substance that complexes heavy metals may be encapsulated within the capsule according to the present invention. Suitable heavy metal complexing agents include, for example, alkali salts of ethylenediaminetetraacetic acid (EDTA) or nitrilotriacetic acid (NTA), and alkali metal salts of anionic polyelectrolytes, such as polymaleic acid and polysulfonic acid. A preferred class of complexing agents is phosphonates, which are included in a preferred fabric treatment agent in an amount of 0.01 to 2.5% by weight, preferably 0.02 to 2% by weight, and particularly 0.03 to 1.5% by weight. Examples of these preferred compounds include organophosphonates in particular, such as 1-hydroxyethane-1,1-diphosphonic acid (HEDP), aminotri(methylenephosphonic acid) (ATMP), diethylenetriaminepenta(methylenephosphonic acid) (DTPMP or DETPMP), and 2-phosphonobutane-1,2,4-tricarboxylic acid (PBS-AM), which are usually used in the form of ammonium salts or alkali metal salts.

[0174] The preferred hydrophobic substances identified above can be used alone or in mixtures of two, three, four or more of the above substances.

[0175] According to certain and preferred modifications, if the capsule of the present invention is to be used to impart, i.e., deliver or transfer, a fragrance or aroma, i.e., if it is dispersed in the oil phase of the present invention, the hydrophobic active substance comprises or consists of perfume or aromatic substances or at least one fragrance oil or aroma, i.e., a corresponding mixture of the aforementioned substances, as specified herein.

[0176] Possible further components generally include all compounds for which applications exist in the field of microencapsulation. Such components are well known in the art. However, fragrant active substances such as fragrances and perfumes, which are of both synthetic and natural origin, are preferred. Preferred is the core-shell microcapsule according to the present invention, in which the core contains as an activator (may be one or more) one or more odorous substances / fragrances selected from the group consisting of extracts of natural raw materials such as essential oils, concretes, absolutes, resins, resinous substances, balsams, and tinctures containing non-primary or secondary alcohols. Preferably, these substances impart a pleasant scent.

[0177] The ratio of the active ingredient to the total oil phase is approximately 15 to 100% by weight, preferably 30 to 100% by weight, even more preferably 40 to 100% by weight, and most preferably 50 to 100% by weight, relative to the total weight of the oil phase.

[0178] Therefore, the process described herein makes it possible to efficiently encapsulate a considerable amount of active ingredient(s).

[0179] Alternatively, and preferably, the active ingredient itself can serve as an oil component that dissolves at least one polyisocyanate, for example, a fragrance oil.

[0180] The eco-friendly core-shell microcapsules of the present invention enable the efficient encapsulation of various active ingredients, thus facilitating the preparation of numerous products and their incorporation into a wide range of product formulations.

[0181] Furthermore, the first step of the process described herein requires the provision of at least one capsule-forming agent, i.e., a first aqueous phase comprising one or more capsule-forming agents. For this purpose, the capsule-forming agents are dissolved in an aqueous solvent (preferably pure water) to form the first aqueous phase.

[0182] Capsule-forming aids (multiple) used within the scope of the present invention include, for example, surfactants (or emulsifiers) and / or colloidal protective agents.

[0183] Generally, surfactants, or simply surfactants, are amphiphilic substances that reduce the surface tension between two different phases and usually possess both hydrophobic and hydrophilic functional groups. As a result, these substances can be positioned at the interface between the oil phase and the water phase, for example, around droplets in an oil-in-water emulsion, allowing for the stabilization of individual oil droplets that are finely spread in the surrounding water phase, thus avoiding aggregation of the oil droplets. Therefore, these surfactants may also act as emulsifiers, that is, as substances that stabilize the emulsion by increasing its dynamic stability and reducing the interfacial tension between the two phases.

[0184] Therefore, to facilitate emulsification, it may be useful to add such emulsifiers, selected from the group consisting of nonionic, anionic, amphoteric, and / or cationic surfactants and mixtures thereof, to the first aqueous phase as capsule-forming aids.

[0185] Suitable nonionic emulsifiers include, for example, • Linear C 8-22 C to fatty alcohols 12-22 Addition products of 2 to 30 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide to fatty acids and alkylphenols containing 8 to 15 carbon atoms in the alkyl group; • Addition product of 1 mole to 30 moles of ethylene oxide to glycerol 12 / 18 Fatty acid monoesters and diesters; Glycerol monoesters and diesters and sorbitan monoesters and diesters of saturated and unsaturated fatty acids containing 6 to 22 carbon atoms and their ethylene oxide loading products; • Addition product of 15 to 60 moles of ethylene oxide to castor oil and / or hydrogenated castor oil; Polyol esters, particularly polyglycerol esters, such as polyglycerol polyricinoleate, polyglycerol poly-12-hydroxystearate, or polyglycerol dimerate isostearate. Mixtures of compounds derived from some of these classes are also preferred; • Addition product of 2 to 15 moles of ethylene oxide to castor oil and / or hydrogenated castor oil; • Linear, branched, unsaturated or saturated C 6 / 22 Partial esters based on fatty acids, ricinolenic acid and 12-hydroxystearic acid, and glycerol, polyglycerol, pentaerythritol, dipentaerythritol, sugar alcohols (e.g., sorbitol), alkyl glucosides (e.g., methyl glucoside, butyl glucoside, lauryl glucoside), and polyglucosides (e.g., cellulose); Mono-, di-, and trialkyl phosphates and mono-, di-, and tri-PEG-alkyl phosphates and their salts; Wool wax alcohol; • Polysiloxane / polyalkyl polyester copolymers and corresponding derivatives; Pentaerythritol, fatty acids, mixed esters of citric acid and fatty alcohols and / or C 6-22 Fatty acids, methyl glucose and polyols, preferably glycerol, or mixed esters of polyglycerol; • Polyalkylene glycol; and Glycerol carbonate It includes.

[0186] Addition products of ethylene oxide and / or propylene oxide to fatty alcohols, fatty acids, alkylphenols, glycerol mono- and diesters of fatty acids, and sorbitan mono- and diesters, or to castor oil are known commercially available products. These are homologous mixtures, and their average degree of alkoxylation corresponds to the ratio of the amounts of ethylene oxide and / or propylene oxide to the substrate on which the addition reaction takes place. C 12 / 18Fatty acid monoesters and diesters are known as lipid layer enhancers for cosmetic formulations. Preferred emulsifiers are described in more detail below:

[0187] Partial glycerides: Typical examples of suitable partial glycerides are monoglycerides hydroxystearate, diglycerides hydroxystearate, monoglycerides isostearate, diglycerides isostearate, monoglycerides oleate, diglycerides oleate, monoglycerides ricinoleate, diglycerides ricinoleate, monoglycerides linoleate, diglycerides linoleate, monoglycerides linolenic acid, diglycerides linolenic acid, monoglycerides erucate, diglycerides erucate, monoglycerides tartaric acid, diglycerides tartaric acid, monoglycerides citrate, diglycerides citrate, monoglycerides malic acid, diglycerides malic acid, and technical mixtures thereof that may still contain small amounts of triglycerides derived from the manufacturing process. Addition products of 1 to 30 moles, preferably 5 to 10 moles, of ethylene oxide to the mentioned partial glycerides are also suitable.

[0188] Sorbitan esters: Suitable sorbitan esters include sorbitan monoisostearate, sorbitan sesquiisostearate, sorbitan diisostearate, sorbitan triisostearate, sorbitan monooleate, sorbitan sesquioleate, sorbitan dioleate, sorbitan trioleate, sorbitan monoerucate, sorbitan sesquierucate, sorbitan dierucate, sorbitan trierucate, sorbitan monoricinoleate, sorbitan sesquiricinoleate, sorbitan diricinoleate, and sorbitan triricinoleate. These include sorbitan, sorbitan monohydroxystearate, sorbitan sesquihydroxystearate, sorbitan dihydroxystearate, sorbitan trihydroxystearate, sorbitan monotartrate, sorbitan sesquitartrate, sorbitan ditartrate, sorbitan tritartrate, sorbitan monocitrate, sorbitan sesquicitrate, sorbitan dicitrate, sorbitan tricitrate, sorbitan monomaleate, sorbitan sesquimaleate, sorbitan dimaleate, sorbitan trimaleate, and technical mixtures thereof. Addition products of 1 to 30 moles, preferably 5 to 10 moles, of ethylene oxide to the sorbitan esters mentioned are also preferred.

[0189] Polyglycerol esters: Typical examples of suitable polyglycerol esters include polyglyceryl-2 dipolyhydroxystearate (Dehymuls® PGPH), polyglycerin-3-diisostearate (Lameform® TGI), polyglyceryl-4 isostearate (Isolan® GI 34), polyglyceryl-3 oleate, diisostearoyl polyglyceryl-3 diisostearate (Isolan® PDI), polyglyceryl-3 methyl glucose distearate (Tego Care® 450), polyglyceryl-3 beeswax (Cera Bellina®), polyglyceryl-4 caprate (polyglycerol T2010 / 90), polyglyceryl-3 cetyl ether (Chimexane® NL), and polyglyceryl-3 distearate (Cremophor® GS 32) and polyglyceryl polyricinoleate (Admul® WOL 1403), polyglyceryl isostearate dimer acid, and mixtures thereof. Examples of suitable polyol esters are monoesters, diesters, and triesters of lauric acid, coco fatty acid, tallow fatty acid, palmitic acid, stearic acid, oleic acid, behenic acid, etc., obtained by reacting trimethylolpropane or pentaerythritol with any 1 to 30 moles of ethylene oxide.

[0190] Tetraalkylammonium salts: Cationic surfactants, which are cationic and active, contain hydrophobic polymer groups necessary for surface activity due to dissociation in aqueous solutions. An important representative group of cationic surfactants is the general formula (R 1 R 2 R 3 R 4 N + )X - It is a tetraalkylammonium salt of . Here, R 1 represents C1-C8 alkyl (alkenyl), R 2 , R 3 and R 4Each of these independently represents an alkyl (alkenyl) radical having 1 to 22 carbon atoms. X is preferably a counterion selected from the group consisting of halogen compounds, alkyl sulfates, and alkyl carbonates. Cationic surfactants in which the nitrogen group is substituted with two long acyl groups and two short alkyl (alkenyl) groups are particularly preferred.

[0191] Esterquats: A further class of cationic surfactants particularly useful as co-surfactants for the present invention is represented by so-called esterquats. Esterquats are generally understood to be quaternized fatty acid triethanolamine ester salts. These are known compounds that can be obtained by relevant methods of prepared organic chemistry. In this regard, refer to international patent application WO91 / 01295A1, which describes the partial esterification of triethanolamine with a fatty acid in the presence of hypophosphorous acid, passing air through the reaction mixture, and then quaternizing the whole with dimethyl sulfate or ethylene oxide. In addition, German patent DE4308794C1 describes a process for producing solid esterquats in which the quaternization of triethanolamine ester is carried out in the presence of a suitable dispersant, preferably a fatty alcohol.

[0192] Typical examples of ester quats suitable for use according to the present invention are products in which the acyl component is derived from a monocarboxylic acid corresponding to the formula RCOOH, where RCO is an acyl group containing 6 to 10 carbon atoms, and the amine component is triethanolamine (TEA). Examples of such monocarboxylic acids are caproic acid, caprylic acid, capric acid, and technical mixtures thereof, e.g., so-called head-fractionated fatty acids. Ester quats derived from monocarboxylic acids in which the acyl component contains 8 to 10 carbon atoms are preferably used. Other ester quats are derived from dicarboxylic acids such as malonic acid, succinic acid, maleic acid, fumaric acid, glutaric acid, sorbic acid, pimelic acid, azelaic acid, sebacic acid and / or dodecanedioic acid, but preferably from adipic acid. In general, ester quats derived from mixtures of monocarboxylic acids containing 6 to 22 carbon atoms and adipic acid are preferably used. The molar ratio of monocarboxylic acid to dicarboxylic acid in the final ester quat may be in the range of 1:99 to 99:1, preferably in the range of 50:50 to 90:10, and more specifically in the range of 70:30 to 80:20. Besides quaternated fatty acid triethanolamine ester salts, other suitable ester quats are quaternated ester salts of mono- / dicarboxylic acid mixtures with diethanolalkylamine or 1,2-dihydroxypropyldialkylamine. Ester quats may be obtained from both fatty acids and corresponding triglycerides in mixtures with the corresponding dicarboxylic acids. One such process, intended to be representative of the relevant prior art, is proposed in European Patent EP0750606B1. To produce quaternated esters, mixtures of monocarboxylic acid and dicarboxylic acid with triethanolamine may be used in molar ratios of 1.1:1 to 3:1 based on the available carboxyl function. Considering the performance characteristics of the ester quats, ratios of 1.2:1 to 2.2:1, preferably 1.5:1 to 1.9:1, have been found to be particularly advantageous. A preferred ester quat is a technical mixture of monoesters, diesters, and triesters with an average degree of esterification of 1.5 to 1.9.

[0193] Further preferred surfactants include nonionic polymers, such as sorbitan ester ethoxylates (Tween®) and / or polypropylene oxide / ethylene copolymers, Tergitol®, Triton® (Dow Chemicals), and alcohol ethoxylates.

[0194] The use of anionic and / or amphoteric surfactants in combination with one or more nonionic surfactants is even more advantageous. In preferred embodiments of the present invention, the composition further does not cause aggregation in the required product formulation. • Alkyl phosphate derivatives; • Glyceryl citrate oleate derivatives; • Glyceryl citrate derivative of stearate; • Stearic acid ester; • Sorbitan ester; • Ethoxylated sorbitan ester; • Ethoxylated mono-, di-, and triglycerides; Methyl glucose ester It contains an emulsifier selected from the group consisting of the following.

[0195] Alternatively, or even better, a colloidal protective agent (so-called protective colloid) can be dissolved in the first aqueous phase as a capsule-forming aid.

[0196] Preferably, the first aqueous phase contains one or more colloidal protective agents as capsule-forming aids.

[0197] Therefore, in a preferred modification of the present invention, one or more colloidal protective agents are used as at least one capsule-forming aid.

[0198] In an alternative embodiment, both at least one colloidal protective agent and at least one surfactant are used in the first aqueous phase.

[0199] Preferably, one or more colloidal protective agents are selected from the group consisting of polymers, for example, polyvinyl alcohol (hydrolysis: 70% or more), for example, Selvol® (Sekisui Specialty Chemicals), polyvinylpyrrolidone, polyvinyl acetate, chemically modified biopolymers, preferably chemically modified starch, modified gum arabic, modified cellulose or cellulose derivatives, for example, methylcellulose, hydroxypropyl methylcellulose and hydroxyethylcellulose, gelatin, casein, acrylate polymers or mixtures thereof. Also preferred are, for example, starch (often derived from corn, quinoa, oats, barley, or potatoes), gum arabic, or cellulose chemically modified with, for example, octenyl succinate anhydride (OSA). Typical products are available, for example, as Capsul® Starch or Hi-CAP® 100 (Ingredion Inc.).

[0200] Preferably, the colloidal protective agent(s) is selected from the group consisting of known protective colloids, such as polyvinyl alcohol, polyvinylpyrrolidone, hydroxyethylcellulose, methylcellulose, gelatin, casein, polymethacrylic acid, and mixtures thereof.

[0201] Polyvinyl alcohol was found to be a suitable protective colloid for all types of bio-based microcapsules according to the present invention (see Examples 1-12). Furthermore, since polyvinyl alcohol is biodegradable under both aerobic and anaerobic conditions, it is particularly suitable for the preparation of biodegradable microcapsules, and thus environmentally friendly microcapsules.

[0202] Furthermore, the protective colloid may preferably be an anionic or amphiphilic polymer selected from the group consisting of modified gum arabic, starch modified with octenyl succinic anhydride (OSA), for example, Capsu®, HiCap®, soy protein, sodium caseinate, gelatin, bovine serum albumin, sugar beet pectin, hydrolyzed soy protein, hydrolyzed sericin, pseudocollagen, biopolymer SA-N, pentacarea-NAPF, a mixture of gum arabic and revitalin, and mixtures thereof.

[0203] Preferably, the protective colloid is a biomacromolecule (biomacromolecule), i.e., a substance extracted from a renewable source or produced by a living organism (i.e., of biological origin), such as a polysaccharide, such as starch or cellulose. Biomacromolecules are characterized by a molecular weight distribution ranging from 1,000 daltons to 1,000,000,000 daltons and can be, for example, carbohydrates (sugar-based), proteins (amino acid-based), or a combination of both, and can be linear or branched. Derivatives of biomacromolecules (bio-based polymers) are compounds derived from such biomacromolecules by chemical derivatization. These substances are usually also biodegradable. Preferably, one or more protective colloids are selected from the group consisting of modified gum arabic, starch modified with octenyl succinic anhydride (OSA), such as Capsu®, HiCap®, or (modified / derivativeized) soy protein.

[0204] In consideration of the objectives of the present invention, at least one capsule-forming aid used within the scope of the present invention is preferably a colloidal protective agent, in which case biopolymer compounds are particularly preferred as capsule-forming aids, taking into account a particularly eco-friendly approach.

[0205] A comparison between Example 1 and Example 5 demonstrates that such bio-based protective colloids can be suitably used in the preparation of bio-based microcapsules according to the present invention, which exhibit high stability and high release characteristics simultaneously.

[0206] Therefore, in a preferred variation, the present invention relates to a process for preparing a core-shell microcapsule or a slurry containing a core-shell microcapsule according to the present invention, wherein at least one forming aid is a biopolymer or a derivative of a biopolymer, preferably a derivative of a biopolymer.

[0207] However, in a more preferred variation, at least one capsule-forming agent is polyvinyl alcohol, enabling the formation of highly stable and high-performing microcapsules as described above.

[0208] Based on these substances identified herein as colloidal protective agents, it is possible to prepare environmentally friendly and efficient microcapsules with ideally balanced properties.

[0209] The microcapsules according to the present invention can be prepared by using one or more colloidal protective agents and / or one or more surfactants as specified herein. Preferably, one or more colloidal protective agents are used. Even more preferably, these colloidal protective agents are biodegradable and / or bio-based or biologically derived.

[0210] Typically, capsule-forming aids(s) are included in the first aqueous phase in an amount of 0.1 to 5% by weight, preferably 0.5 to 5% by weight.

[0211] If capsule-forming aids, such as protective colloids, are included in these amounts, a high degree of stabilization of oil droplets in a continuous aqueous phase can be achieved. Furthermore, precipitation is avoided and the coagulation effect is reduced, so that the oil particles are finely dispersed in the surrounding aqueous phase, thereby ensuring homogeneous encapsulation and a homogeneous size distribution of the resulting microcapsules.

[0212] In addition, continuous stirring during the preparation process according to the present invention helps to avoid aggregation, and consequently clumping, of the particles and / or microcapsules obtained according to the present invention, as well as the precipitation of the microcapsules.

[0213] Furthermore, the pH value of the first aqueous phase is preferably 7 or higher. Preferably, the pH is approximately 8 or higher. To achieve these pH values, the corresponding acidic or basic substance can be added to the first aqueous phase, or alternatively, to the provisional oil-in-water emulsion. Alternatively, pH adjustment (if necessary) can be performed in the second aqueous phase or after the addition of the second aqueous phase.

[0214] Furthermore, the process of the present invention requires the provision of a second aqueous phase comprising at least one sugar and / or amino sugar as a component having less than 20 monomer units (or repeating units), i.e., 19 monomer units or less, preferably 15 monomer units or less, and even more preferably 10 monomer units or less, each independently, and optionally the second aqueous phase further comprising one or more additional capsule-forming aids. For this purpose, at least one sugar and / or amino sugar having less than 20 monomer units, preferably 15 monomer units or less, and even more preferably 10 monomer units or less, each independently, and optionally capsule-forming aids, are dissolved in an aqueous solvent (preferably pure water).

[0215] However, alternative variations of the process of the present invention may omit the step of directly adding (amino) sugar to the first aqueous phase to provide a second aqueous phase and the preparation of an intermediate oil-in-water emulsion. Thereafter, the oil phase containing isocyanate and the aqueous phase containing (amino) sugar and a forming aid are mixed to obtain an oil-in-water emulsion, which is then cured. If necessary, the pH value is adjusted by adding an alkaline solution.

[0216] The (amino) sugar components of the core-shell microcapsules of the present invention, as well as the corresponding components used in the process of the present invention, will be described below.

[0217] Typically, such monomers, dimers, oligomers, and small, i.e., short-chain polymer (amino) sugars have a molecular weight of 3500 Da or less, preferably less than 3000 Da. Therefore, within the scope of the present invention, amino sugars and / or sugars having a molecular weight of 3500 Da or less, preferably less than 3000 Da, are used as components in the preparation of highly stable and efficient bio-based core-shell microcapsules.

[0218] The present invention uses specific ratios of monosaccharides, disaccharides, oligosaccharides, and small, i.e., short-chain polysaccharides that react with polyisocyanates to form structural segment units that form the shell wall in core-shell microcapsules. Suitable sugars within the scope of the present invention are carbohydrates or their derivatives, i.e., derivatives of biomolecules consisting of carbon, hydrogen, and oxygen atoms. These sugars can generally be divided into four chemical groups based on the number of monomer units, i.e., monomer sugar components: monosaccharides (1 monomer unit), disaccharides (2 monomer units), oligosaccharides (3 to 10 monomer units), and polysaccharides (more than 10 monomer units). In this regard, monomer units, i.e., sugar components, have two or more hydroxyl groups (-OH). Oligosaccharides are defined as short polymers of monosaccharide residues linked by glycosidic bonds having a degree of polymerization (DP) (IUPAC definition) of 3 to 10 units. They may be linear or branched and usually contain hexoses or pentoses individually or in mixtures. Other monosaccharides, including uronic acid, sialic acid, and anhydrous sugars, may be present. Disaccharides, oligosaccharides, and high molecular weight sugars may consist of one type of monomer unit, or more than one type of monomer unit, i.e., two or more structurally different monomer units.

[0219] Such carbohydrates most preferably used within the scope of the present invention are sugars (colloquial: sugars) having fewer than 20 monomer units, i.e., fewer than 20 linked monosaccharide residues, preferably 15 monomer units or less, and even more preferably 10 monomer units or less, such as monosaccharides (glucose, fructose, galactose), disaccharides (sucrose, lactose, maltose), linear or branched oligosaccharides (raffinose, stachyose) and / or linear or branched short-chain polysaccharides as defined herein.

[0220] As used herein, the term sugar includes not only sugars obtained from natural sources, but also synthetically produced sugars and their derivatives having structures equivalent to those of natural sugars.

[0221] However, preferably, the crosslinked sugar components used within the scope of this application are monosaccharides, disaccharides and / or oligosaccharides and / or short-chain polysaccharides as defined herein. Preferably, these sugars are derived from natural sources.

[0222] Even smaller molecules allow for enhanced diffusion toward the oily core containing isocyanate linkers surrounded by capsule-forming aids, enabling denser crosslinking and enhanced interfacial polymerization. This results in improved performance and greater capsule stability, enabling efficient encapsulation of the active ingredient(s) as the core material. Simultaneously, bio-based capsule components allow for improved biodegradability of the capsule wall material compared to commercially available, fully synthetic, state-of-the-art microcapsules. The performance, as well as capsule stability, is improved compared to microcapsules based on larger components such as starch or chitosan.

[0223] Generally, amine or alcohol components permeate from the aqueous phase into the organic phase for wall formation. In this regard, the permeation rate is mainly controlled by the solubility and diffusion rate of the component, and the molecular size of the component significantly affects the diffusion rate and, consequently, the permeation rate. For larger components such as commercially available starch or chitosan, the diffusion and permeation rates decrease considerably, resulting in a decrease in crosslinking density, inefficient encapsulation, and reduced capsule stability. As a result, the release performance of microcapsules based on larger components such as starch and / or chitosan is also significantly reduced.

[0224] In the corresponding amino sugars, one or more hydroxyl groups in the sugar structure are substituted with amine groups (-NH2 or -NH-, preferably -NH2). Such amino-functional monosaccharides, disaccharides, oligosaccharides, and polysaccharides include, for example, glucosamine, mannosamine, galactosamine, polyglucosamine, and oligoglucosamine, oligochitosan, also known as chitose, chito-oligosaccharide, or chitosan oligosaccharide (having fewer than 20 monomer units) and chitosan (having 20 or more monomer units), and N-acetyl-substituted amino sugars. Preferably, the amino sugars used within the scope of the present invention have fewer than 20 monomer units, i.e., 19 monomer units or less, preferably 15 monomer units or less, and even more preferably 10 monomer units or less. Therefore, the amino sugars used in the context of the present invention are preferably amino monosaccharides (one monomer unit), amino disaccharides (two monomer units), linear or branched amino oligosaccharides (oligomer amino sugars: 3 to 10 monomer units) and / or short-chain amino polysaccharides (polymer amino sugars: more than 10 monomer units) having a chain length of less than 20 monomer units, preferably 15 or less monomer units, and being branched or linear. Amino disaccharides, amino oligosaccharides and amino polysaccharides may be composed of one type of monomer unit or more than one type of monomer unit, i.e., two or more structurally different monomer units.

[0225] Correspondingly, in preferred modifications, the crosslinked amino sugar components used within the scope of this application are preferably amino monosaccharides, amino disaccharides, amino oligosaccharides and / or short-chain polymer amino sugars, as defined herein, derived from natural sources.

[0226] As used herein, the term amino sugar includes not only amino sugars obtained from natural sources, but also amino sugars produced synthetically and derivatives thereof having structures equivalent to those of natural amino sugars. However, preferably, within the scope of the present invention, amino sugars derived from natural sources are used.

[0227] Furthermore, sugars containing or consisting of a mixture of amine-free monomer units and amine-containing monomer units are suitably used within the scope of the present invention and are also called "amino sugars." However, preferably in amino sugars, all monomer units contain an amine group.

[0228] In a more preferred variation, the sugar and / or amino sugar components, each independently having fewer than 20 monomer units, are either linear or branched. For the formation of the capsule wall, combinations of two or more linear and / or branched components can be used, i.e., a mixture of one or more linear sugars, one or more linear amino sugars, one or more branched sugars and / or one or more branched amino sugars, as well as a mixture of linear and branched sugars and / or amino sugars.

[0229] According to a preferred modification of the present invention, the capsule shell is formed from a polymer material which is a reaction product of at least one polyisocyanate having at least two isocyanate groups, i.e., a single isocyanate compound or a mixture of two or more different isocyanate compounds, each having two or more isocyanate functional groups, and at least one sugar as defined herein, each independently having less than 20 monomer units, preferably 15 or fewer monomer units, and even more preferably 10 or fewer monomer units.

[0230] Alternatively, the capsule shell is formed from a polymer material which is a reaction product of at least one polyisocyanate having at least two isocyanate groups, i.e., a single isocyanate compound or a mixture of two or more different isocyanate compounds, each having two or more isocyanate functional groups, and one or more amino sugars each independently having less than 20 monomer units, preferably 15 or fewer monomer units, and even more preferably 10 or fewer monomer units, as defined herein.

[0231] However, in a more preferred variation, the capsule shell is formed of a polymer material which is a reaction product of at least one polyisocyanate having at least two isocyanate groups, i.e., a single isocyanate compound or a mixture of two or more different isocyanate compounds, each having two or more isocyanate functional groups, and at least one sugar and at least one amino sugar, less than 20 monomer units, preferably 15 monomer units or less, even more preferably 10 monomer units, i.e., at least one (i.e., one or more) sugar component and at least one (i.e., one or more) amino sugar component, a combination or mixture of sugars and amino sugars.

[0232] Based on these polymer materials, highly efficient microcapsules exhibiting high biodegradability can be prepared (i.e., microcapsules that are stable against mechanical shock or heat or in product formulations, and can efficiently encapsulate active ingredients until the target release begins, while simultaneously exhibiting high release performance).

[0233] In this regard, (amino) sugar units, due to their high degradability surpassing that of state-of-the-art microcapsules, serve as sites for biological attack and, consequently, biodegradation, thereby reducing the environmental impact of capsule materials and thus enabling the preparation of highly efficient, and at the same time more environmentally compatible, and ultimately more environmentally friendly microcapsule alternatives.

[0234] The capsule shell of the core-shell microcapsule of the present invention is formed by interfacial polymerization between the functional groups of polyisocyanate and the functional hydroxyl groups and / or amine groups of (amino) sugar units, resulting in a polymeric structure around a polyurethane-based and / or polyurea-based crosslink, and consequently a core containing the active ingredient as specified above. Thereafter, the isocyanate units serve as "crosslinked" or "rigid" segments, while the (amino) sugar units serve as hydrophilic "soft" segments that form the majority of the shell material.

[0235] According to the present invention, the term "sugar" refers to both sugar structures containing a hydroxyl functional group and / or sugars containing one or more amine functional groups, i.e., amino sugars, for the sake of simplicity.

[0236] The polyaddition reaction of at least one polyisocyanate with the hydroxyl group of at least one (amino)sugar results in the formation of a so-called urethane crosslink (-NH-CO-C-) by the addition of the hydroxyl group (-OH) of the (amino)sugar(s) to the carbon atoms of the carbon-nitrogen bond of the isocyanate group (-N=C=O). Alternatively, or simultaneously, the formation of polyurea crosslinks is carried out in a manner similar to that of polyurethane crosslinks by the polyaddition of the amine group (-NH2, -NH-) of the (amino)sugar(s) to the isocyanate functional group of the polyisocyanate(s). Alternatively, in the case of the corresponding thiosugars, a polythiourethane crosslink is formed.

[0237] Therefore, a tightly crosslinked capsule shell can be formed as a polymer material from crystalline polar segments and / or tightly crosslinked segments with reduced polyisocyanate content, preventing the diffusion or penetration of the hydrophobic active ingredient (or mixture of active ingredients) encapsulated in the capsule as the core material. In the case of fragrances and perfumes, for example, this leads to the effective encapsulation of a sensory-perceptible active ingredient (a mixture of fragrances or a single fragrance substance), which is effectively released, for example, by mechanical activation, or by changes in the external environment, such as changes in pH or temperature, or through biological attack. This further requires that the capsule exhibits sufficient stability to achieve high performance. Based on the bio-based core-shell microcapsule of the present invention, it is possible to provide a highly stable capsule that enables efficient encapsulation of the active ingredient(s) without loss due to evaporation and / or interaction with other components of the product formulation, and / or premature destruction during application (e.g., in a washing machine). At the same time, the bio-based capsule of the present invention exhibits high performance, enabling the efficient and targeted release of the active ingredient(s). In addition, they exhibit high biodegradability without negatively impacting stability or performance.

[0238] Furthermore, surprisingly, it was found that highly stable, bio-based, and eco-friendly microcapsules could be prepared with a significantly reduced shell material (see Examples 11 and 12). These capsules exhibit high mechanical, thermal, and chemical stability despite the reduced shell material and low isocyanate content due to efficient crosslinking of (amino) sugar segments as defined herein.

[0239] The greater the number of cross-linking functional groups, the greater the steric cross-linking, and the more stable the capsule shell or capsule wall of the resulting final microcapsules. In addition to the number of functional groups, i.e., the number of branched chains, the chain length of the individual components has a significant impact on the mechanical properties, i.e., the stability of the capsules. However, overly high cross-linking will enhance the stability of the capsules, but at the same time will adversely affect the biodegradability and performance of the capsule material and the capsules themselves, i.e., the release behavior. However, based on the processes described herein according to the first aspect and the (amino) sugars specified herein, it is possible to achieve microcapsules having improved or more ideal balances of these properties, so these components enable the preparation of highly stable microcapsules with excellent performance and high biodegradability suitable for stable incorporation in various consumer product formulations.

[0240] The microcapsules of the present invention according to the first aspect exhibit high mechanical stability (thermal stability) against mechanical effects, such as rotary dryers or heat dominance, while at the same time enabling efficient, targeted release of the active ingredient induced by the signal. In addition, sensory experiments show that in the case of fragrances as active ingredients, high aroma intensities can be perceived, which suggests that the fragrance is efficiently encapsulated within the core-shell microcapsules of the present invention, and shows an efficient reduction in losses due to diffusion of the active ingredient outside the microcapsules even after aging within the consumer product formulation. The shell contains at least one sugar and / or at least one amino sugar each independently having less than 20 monomer units as defined herein, and the bio-based core-shell microcapsules are highly stable and enable efficient encapsulation and high performance of the active ingredient despite being based on bio-based components. At the same time, they exhibit high biodegradability compared to commercially available state-of-the-art microcapsules.

[0241] It has further been found that different combinations of sugars and / or amino sugars can be used efficiently to adjust the crosslink density in the shell wall and thus the resulting capsule properties.

[0242] Thus, the present invention mainly focuses on (amino) sugar-based core-shell microcapsules. And more specifically, in (amino) sugar-based core-shell microcapsules, the shell comprises, or consists of, a polymeric material which is the reaction product of at least one polyisocyanate having at least two isocyanate groups and at least one (amino) sugar, i.e., at least one sugar and / or at least one amino sugar each independently having less than 20 monomer units, and the core comprises, or consists of, at least one active ingredient.

[0243] The sugar-based within the scope of the present invention means that at least one sugar and / or at least one amino sugar as specified herein is used as a component for the formation of the capsule shell.

[0244] Bio-based or biogenic within the scope of the present invention means that the materials used within the scope of this application are preferably derived from renewable biological sources that are replenishable, more specifically, sources such as crops, agricultural waste, or wood. For example, the (amino) sugars described herein refer to natural biological compounds (i.e., compounds of biological origin), more specifically classes of natural molecules. Surprisingly, these biogenic materials have been found to be suitably used as major components for the preparation of stable and efficient bio-based / biogenic or (amino) sugar-based core-shell microcapsules and thus as a bio-based and more environmentally friendly alternative to fossil-based microcapsules.

[0245] In this regard, short-chain high molecular weight (amino) sugars, such as certain (amino) monosaccharides, (amino) disaccharides, and (amino) oligosaccharides as specified herein, for example, low molecular weight maltodextrins having fewer than 20 monomer units (or repeating units), preferably 15 monomer units or less, and even more preferably 10 monomer units or less, are particularly advantageous in shell formation of the bio-based core-shell microcapsules. These low molecular weight (amino) sugars diffuse more readily to the reaction interface compared to high molecular weight poly(amino) sugars. Diffusion is less hindered, and wall formation is promoted, enabling the formation of more advanced crosslinks, resulting in more stable and simultaneously better-performing microcapsules. The capsules efficiently encapsulate the active ingredient(s) without loss due to diffusion and can be stably incorporated into various formulations, particularly consumer products such as detergents and fabric softeners. Furthermore, these bio-based microcapsules exhibit high performance, namely, excellent fragrance release properties in the case of fragrance capsules or odor capsules, and high biodegradability.

[0246] Amino sugars are widely present in nature and are found in a wide range of compounds, such as structural polysaccharides, mucopolysaccharides, bacterial capsule polysaccharides, teicoic acid, lipopolysaccharides, glycolipids, mucoproteins, and nucleotides.

[0247] Chitosan is a biopolymer based on β(1-4) linked D-glucosamine monomer units and N-acetyl-D-glucosamine monomer units, generally non-toxic, biodegradable, and biocompatible polysaccharides, with molecular weights ranging from 30,000 Da to 50,000 Da. This polymer contains 20 or more monomer units, i.e., glucosamine-based monomer units (D-glucosamine monomer units or N-acetyl-D-glucosamine monomer units; each considered individually), and usually more than 100 monomer units. However, chitosan has poor solubility in water or organic solvents, and is only soluble in a few percent (1-3%) of acidic organic solutions such as acetic acid, propionic acid, citric acid, and formic acid. In addition, acidified chitosan solutions are very unresponsive to polyisocyanates in interfacial reactions. Therefore, chitosan itself is not suitable for the preparation of core-shell microcapsules. In addition, due to the large molecular structure, diffusion toward the isocyanate reactant is hindered, resulting in loosely connected crosslinks, which reduces stability and leads to inefficient encapsulation.

[0248] However, surprisingly, it has now been discovered that certain low molecular weight chitosan oligomers, also known as oligochitosan (or chito-oligosaccharide), which are degradation products of chitosan or chitin prepared by enzymatic or chemical hydrolysis of chitosan (Carbosynth-Biosynth® LTD, England) and its derivatives, having fewer than 20 monomer units, preferably 15 or fewer monomer units, and even more preferably 10 or fewer monomer units, overcome poor solubility in both acidic and alkaline solvents, enabling high levels of solubility exceeding 10%.

[0249] By definition, according to the present invention, chitosan derivatives having a degree of polymerization (DP) of less than 20 and an average molecular weight of less than approximately 3900 Da are called chitosan oligomers, chito-oligomers, oligochitoses, or chito-oligosaccharides (COS). These terms are used synonymously. The definition of what constitutes a chitosan oligomer may deviate from the classical definition of an oligomer structure as defined above, having less than 10 monomer units. However, according to the present invention, since chitosan oligomers are defined as having less than 20 monomer units, they are also called "oligo-amino sugars" or "oligomer-amino sugars" or, instead, "short-chain amino polysaccharides."

[0250] The uniqueness of low molecular weight chitosan oligomers (MW < 3900 g / mol, preferably < 3000 g / mol; also called chito-oligosaccharides or oligochitoses) lies in their high solubility in both acidic and alkaline media compared to general chitosans with molecular weights of 30,000 g / mol to 5,000,000 g / mol or more. In addition, chito-oligosaccharides are readily soluble in water due to their short chain length, and therefore depending on the degree of polymerization (DP). Chitosan oligomers with molecular weights less than 3000 g / mol are based on 10 to 15 monomeric glucosamine units (D-glucosamine monomer units or N-acetyl-D-glucosamine monomer units). These amino sugars efficiently polymerize with crosslinking agents, i.e., polyisocyanates, forming structural units in the shell wall, thus increasing the reaction with the isocyanate component and allowing direct incorporation as segments into the shell of core-shell microcapsules, as opposed to coating. Furthermore, even smaller components allow for even denser crosslinking. Therefore, these compounds are suitable for the preparation of sugar-based or bio-based core-shell microcapsules. As a result, chitosan in oligosaccharide form is preferably used within the scope of the present invention. Therefore, for example, the crosslinking density and properties of the shell wall can be adjusted using formulations of various mixtures of glucosamine and oligochitoses.

[0251] Preferably, the chito-oligosaccharides and their derivatives suitable for use in the context of the present invention have a molecular weight of 3000 g / mol or less than 3000 Da.

[0252] In a more preferred variation, the chito-oligosaccharide contains fewer than 20 monomer units, preferably 15 or fewer monomer units, and even more preferably 10 or fewer monomer units.

[0253] In addition, even smaller molecules facilitate diffusion toward an oily core containing an isocyanate linker surrounded by a bio-based crosslinking agent, i.e., a capsule-forming aid that enables efficient crosslinking between the isocyanate component and sugars and / or amino sugars each having fewer than 20 monomer units, preferably 15 or fewer monomer units, and even more preferably 10 or fewer monomer units. This results in the formation of a bio-based or (amino) sugar-based polymer material as a reaction product that forms a capsule shell.

[0254] As described above, bio-based reagents are preferred from a health and environmental perspective. Therefore, the sugars and / or amino sugars and / or polyisocyanates used in the preparation of the core-shell microcapsules of the present invention are preferably of biological origin. Preferably, the capsule-forming aids are also of biological origin or at least biodegradable.

[0255] Furthermore, small alkaline or neutral chitosan oligomers, i.e., chito-oligosaccharides, as described above, enable improved interfacial reactions with isocyanate crosslinking agents dissolved in the oil phase compared to long-chain chitosan. It has also been found that polyisocyanates react more favorably with amino sugars, such as glucosamine and the amino groups of short-chain chitosan oligomers, under basic, i.e., alkaline conditions than under acidic conditions. Therefore, the pH value is preferably kept above 8 during the preparation process described herein. Accordingly, the pH of the first and / or second aqueous phases is preferably in the alkaline range, and preferably above 8.

[0256] Therefore, in preferred variations of the present invention, the (amino) sugars preferred to be used within the scope of the present invention are (amino) sugars having independently less than 20 monomer units, preferably 15 monomer units or less, and even more preferably 10 monomer units or less. According to the present invention, at least one such sugar and / or at least one amino sugar reacts with a polyisocyanate(s).

[0257] In another preferred embodiment, a mixture of at least one sugar and at least one amino sugar, as defined herein, is preferably used.

[0258] Preferably, the core-shell microcapsule of the present invention comprises or consists of a polymer material which is a reaction product of at least one polyisocyanate having at least two isocyanate groups and at least one sugar and at least one amino sugar, each independently having less than 20 monomer units, selected from the following group: glucosamine, maltodextrin and / or chito-oligosaccharides, wherein the core comprises or consists of at least one active ingredient.

[0259] These (amino) components, individually or in mixtures, enable the formation of highly stable yet high-performing microcapsules that are stable for extended periods (at least 4 weeks) in consumer product formulations and exhibit high biodegradability. See Examples 2 and 3 for chito-oligosaccharide-based capsules, and Examples 6-8 and 10 for maltodextrin-based capsules.

[0260] However, in an even more preferred embodiment, the constituent of at least one (amino)sugar component having fewer than 20 monomer units is a monomer (i.e., a monosaccharide or aminomonosaccharide), and an even more preferred (amino)sugar-based component is glucosamine (see Examples 1 or 5).

[0261] Glucosamine can be used as the only (amino) sugar component or can be suitably combined with other (amino) sugar components as defined herein, such as maltodextrin and / or chito-oligosaccharide. Glucosamine is a monomeric amino sugar compound and is one of the most common monosaccharides further used as a dietary supplement. Core-shell microcapsules prepared based on glucosamine exhibit excellent stability, high release performance, and improved biodegradation properties within the product formulation.

[0262] Generally within the scope of the present invention, small molecules such as glucosamine or glucose can freely mix with larger (amino) disaccharides, (amino) oligosaccharides, or short-chain (amino) sugars as defined herein due to their structural similarity.

[0263] Thus, in a preferred embodiment, there is disclosed a core-shell microcapsule comprising, or consisting of, a polymeric material that is a reaction product of at least one polyisocyanate having at least two isocyanate groups and at least one sugar and / or at least one amino sugar each independently having less than 20 monomer units, wherein at least one sugar and / or at least one amino sugar is glucosamine and the core comprises, or consists of, at least one active ingredient.

[0264] The reaction of polyisocyanates with available amino and / or hydroxyl groups of sugars and / or amino sugars having less than 20 monomer units, preferably 15 or less monomer units, more preferably 10 or less monomer units, by forming urea-based and / or urethane-based crosslinks is exemplified below for amino sugar components.

Chemical Formula

[0265] As a result, core-shell microcapsules can be obtained based on the reaction of a polyisocyanate as defined herein with a (amino) sugar as defined herein, wherein the shell material comprises or consists of a bio-based polymer material which is a reaction product of at least one sugar and / or at least one amino sugar, each independently having less than 20 monomer units, preferably 15 monomer units or less, and even more preferably 10 monomer units or less, i.e., less than 20, 15 or less, or 10 or less monomer units, respectively, and the core comprises or consists of at least one active ingredient, e.g., a fragrance compound.

[0266] In this regard, preferably, at least one polyisocyanate is aliphatic. Even more preferably, a mixture of two or more polyisocyanates is used, in which case preferably at least one or all of the polyisocyanates are aliphatic. Alternatively, at least one or all of the polyisocyanates in the mixture of polyisocyanates are aromatic. In a further alternative, a mixture of two or more polyisocyanates is used, in which case at least one of the polyisocyanates is aliphatic and at least one of the polyisocyanates is aromatic. Preferably, when a mixture of two or more polyisocyanates is used, the mixture preferably contains or consists of more than 80 mol% aliphatic component / polyisocyanate. In the latter case, preferably, the molar ratio or weight ratio of aliphatic polyisocyanates(plural) to aromatic polyisocyanates(plural) is in the range of 85 to 15, and even more preferably in the range of 90 to 10 to 99:1.

[0267] The isocyanate components are preferably selected independently of the (amino) sugar components. As a result, due to the significant difference in reactivity between aromatic isocyanates and aliphatic isocyanates, the aliphatic / aromatic isocyanates form regional stratification in the shell, independent of the amine / alcohol components.

[0268] Accordingly, in a further embodiment, the present invention relates to a core-shell microcapsule comprising, or consisting of, a polymer material which is a reaction product of at least one polyisocyanate having at least two isocyanate groups and at least one sugar and / or at least one amino sugar each independently having less than 20 monomer units, and the core comprising, or consisting of, at least one active ingredient.

[0269] In this regard, combinations of one or more sugars and / or amino sugars are particularly preferred, as they allow for adjustment of the crosslink density and, consequently, the resulting capsule properties. This results in varying lengths of crosslinks between the constituent elements, which affect the crosslink density, and allows for different functionalities of the capsule due to the different functional groups of the constituent elements. Furthermore, various degrees of polymerization and crosslinking are achieved, providing a more flexible capsule wall composition and positively impacting the overall capsule properties.

[0270] Polymerization involves the reaction of active hydrogen of the corresponding (amino) sugar(s) for crosslinking. To achieve efficient encapsulation based on the polymerization of the constituent elements, it is therefore further necessary that at least one sugar and / or at least one amino sugar have at least two functional groups independently selected from the group consisting of primary and secondary hydroxyl groups (-OH) as well as primary amine groups (-NH2) and secondary amine groups (-NH-), enabling the formation of polyurethane-based and / or polyurea-based bonds.

[0271] A primary hydroxyl group is a hydroxyl group (-OH) in which one carbon atom is directly bonded to a primary carbon atom, while a secondary hydroxyl group is in which two carbon atoms are directly bonded to a secondary carbon atom.

[0272] On the other hand, primary amines can be derived from ammonia by replacing one of the three hydrogen atoms with a non-hydrogen group; that is, the nitrogen atom bonds with a non-hydrogen atom, such as a carbon-containing group, leaving two hydrogen atoms. When referring to secondary amines, two of the three hydrogen atoms are substituted with non-hydrogen groups; that is, in these secondary substituted amines, nitrogen is bonded with two non-hydrogen atoms, and only one hydrogen atom remains bonded to nitrogen.

[0273] Preferably, at least one sugar has at least two hydroxyl groups, while at least one amino sugar has at least two functional groups selected from the list identified above, in which case at least one of these functional groups is an amine group for the formation of polyurethane-based and / or polyurea-based bonds, so as to provide enhanced stability and a more tightly crosslinked capsule shell while simultaneously enabling enhanced capsule release performance, i.e., release behavior.

[0274] In a more preferred variation, the present invention relates to a core-shell microcapsule according to the present invention, in which at least one sugar and / or at least one amino sugar having less than 20 monomer units is a monosaccharide, for example, glucose, galactose, fructose, xylose, mannose, arabinose, erythrose, threose, ribose, arabinose, lyxose, allose, altrose, talose, fucose, rhamnose, amino monosaccharide, for example, glucosamine, galactosamine, N-acetylglucosamine, disaccharide. For example, selected from the group consisting of sucrose, lactose, maltose, isomaltulose, trehalose, lactulose, cellobiose, chitobiose, isomaltose, isomaltulose, maltulose, amino disaccharides, linear and / or branched oligosaccharides, for example, malto-oligosaccharides, for example, maltodextrin, raffinose, stachyose, fructo-oligosaccharides, merisitose, umbelliferose, cyclodextrin, oligoamino sugars (oligomeric amino sugars), for example, chito-oligosaccharides, or mixtures thereof.

[0275] Alternatively, or in combination with the (amino) sugars specified above, thiosugars having at least two functional groups independently selected from the group consisting of primary and secondary hydroxyl groups (-OH) and thiol groups (-SH), having fewer than 20 monomer units, preferably 15 monomer units or less, and even more preferably 10 monomer units or less, can be suitably used. Preferably, these thiosugars have one or more functional thiol groups (-SH) that enable the formation of polythiourethane structures / bonds. Preferably, at least one thiol group and at least one hydroxyl group are present to enable the formation of both polythiourethane-based and polyurethane-based structures.

[0276] The combination of at least one thiosaccharide with at least one sugar and / or amino sugar results in a polymeric structure based on polythiourethane bonds, polyurethane bonds, and / or polyurea bonds between the constituent elements.

[0277] Another preferred variation of the present invention therefore describes a core-shell microcapsule comprising or consisting of a polymer material which is a reaction product of at least one polyisocyanate having at least two isocyanate groups, preferably a mixture of two or more polyisocyanates, and at least one sugar and / or at least one amino sugar and / or at least one thio sugar, each independently having less than 20 monomer units, and the core comprising or consisting of at least one active ingredient.

[0278] As a further alternative, sugar alcohols containing one hydroxyl group (-OH) linked to each carbon atom, such as sorbitol or mannitol, can also be used as components for reaction with isocyanate components.

[0279] The ratio of at least one sugar and / or at least one amino sugar and / or at least one thio sugar, i.e., the (amino) sugar and / or thio sugar components to the total oil phase, is at least 0.2% by weight, preferably at least 0.5% by weight, or particularly preferably at least 1% by weight, of the total weight of the oil phase. The upper limit is in the range of 5 to 10% by weight. However, to ensure that all polyisocyanate molecules react, an excess of (amino) sugar and / or thio sugar components in the aqueous phase, i.e., unreacted components, is generally desired.

[0280] The ratio of sugar components (multiple components are possible) (sugars, amino sugars, thiosugars) to the total second aqueous phase is 1 to 30% by weight, preferably 5 to 20% by weight. If the ratio of sugar components (multiple components are possible) is within the above range, ideal reaction conditions for efficient encapsulation can be achieved.

[0281] As shown above, the second aqueous phase is optional and may include one or more additional forming aids, such as colloidal protective agents and / or surfactants as specified above, which may be added to the second aqueous phase in an amount of approximately 0.1 to 5% by weight, preferably 0.2 to 2% by weight.

[0282] The second aqueous phase may, for example, contain at least one surfactant, in which case the surfactant is preferably a nonionic and / or cationic and / or anionic polymer, as described above.

[0283] Generally, the capsule-forming agent(s) added to the second aqueous phase may be the same as, or different from, the capsule-forming agent(s) used in the first aqueous phase.

[0284] Preferably, one or more capsule-forming aids used in the first and / or second aqueous phases of a process for preparing a bio-based core-shell microcapsule or a slurry containing the core-shell microcapsule according to the present invention are therefore surfactants and / or colloidal protective agents, preferably colloidal protective agents as specified above. Furthermore, preferably, the capsule-forming aids used are based on biopolymers.

[0285] Therefore, the microcapsules according to the present invention may be manufactured using at least one aqueous phase containing a capsule-forming aid(s). The amount of active substance(s) is, for example, in the range of 0.1 to 5% by weight based on each phase.

[0286] Alternatively, these substances may be added to the final microcapsule slurry to enhance the stability of the microcapsules, which are finely dispersed in the aqueous phase.

[0287] Suitable polymers that may be added instead to or further to the second aqueous phase or final capsule slurry to improve the spreadability of the composition on skin or hair, or to improve the water resistance and / or sweat resistance and / or peel resistance of the formulation, and to improve the protective factors of the composition are, for example, VP / Eicosene copolymer sold by International Speciality Products under trade name Antaron® V-220, VP / Hexadecene copolymer sold by International Speciality Products under trade names Antaron® V-216 and Antaron® V-516, International Speciality Tricontanyl PVP sold by Products under the trade name Antaron® WP-660, isohexadecane and ethylene / propylene / styrene copolymer and butylene / styrene copolymer sold by Penreco under the trade names Versagel® MC and MD, hydrogenated polyisobutene and ethylene / propylene / styrene copolymer and butylene / styrene copolymer sold by Penreco under the trade name Versagel® ME, acrylate / octylacrylamide copolymer sold by AkzoNobel under the trade names Dermacryl® 79, Dermacryl® AQF and Dermacryl® LT, and Avalure® UR 450 & Polyurethanes sold under 525, for example, PPG-17 / IPDI / DMPA copolymer, polyurethanes sold by Lubrizol under trade names Avalure® UR-405, -410, -425, -430 and -445, polyurethanes-2 and -4 sold under -525, polyurethanes-5 sold by Lubrizol under trade names Avalure® UR-510 and -525, and butyl acetate and isopropyl alcohol, and polyurethanes sold by BASF under trade name Luviset® PURPolyurethane-1 and -6, sold under the brand name Cosmedia® DC, are hydrogenated dimer dilinoleyl / dimethyl carbonate copolymer.

[0288] Furthermore, the pH of the second aqueous phase is preferably in the range of 8 to 11 and can be adjusted by using an alkaline solution, for example, a solution of potassium hydroxide or sodium hydroxide. Even more preferably, the pH of the second aqueous phase is greater than 9 and less than 11. If the pH is within this range, the reaction of the crosslinking agent(s), i.e., isocyanates(s), with (amino)sugars(s) in the organic phase is promoted. In the case of amine-containing components, a high pH, ​​i.e., a pH greater than 8 and up to 9, causes the conversion of amine hydrochlorides to free amines (-NH2, NH-). Since amine hydrochloride bases react more slowly with isocyanates than free amine groups, a high pH is generally preferred. If sugar-based components are used, similarly, a pH higher than 8 is advantageous. The pH can be adjusted accordingly by adding alkaline water-soluble hydroxyls and / or basic catalysts such as DABCO®.

[0289] Next, in step (d), the oil phase and the first aqueous phase are mixed to obtain a provisional oil-in-water emulsion with finely dispersed and stabilized individual droplets. In this step, the oil phase (containing isocyanate components, active ingredients, and optionally additional oil components) and the first aqueous phase (containing capsule-forming aids) are mixed to form finely diffused oil droplets in a continuous aqueous phase.

[0290] Emulsions containing two phases can be further divided into two different types. In oil-in-water (O / W) emulsions, oil droplets are dispersed in water. This is the most common type of emulsion. Conversely, water-in-oil (W / O) emulsions contain finely dispersed water droplets in oil. In the context of the present invention, the emulsion is an oil-in-water (O / W) emulsion in which the oil phase is dispersed in the aqueous phase. Preferably, the active ingredient is hydrophobic and is therefore included as the core material in the core-shell microcapsule of the present invention.

[0291] Alternatively, a corresponding water-in-oil emulsion can be prepared for the encapsulation of hydrophilic active substances.

[0292] In order to achieve an interfacial reaction between isocyanate components and amino sugar components, it is necessary that the isocyanate components are mainly water-insoluble, while the amino sugar components are water-soluble.

[0293] Core-shell capsules are typically manufactured by the fine dispersion of core material(s) in an aqueous phase. Based on the reaction between isocyanate components and sugar and / or amino sugar components in the oil phase near the interface between the aqueous and oil phases, polymer wall material forms around finely dispersed / individual oil droplets. This results in a suspension containing as-is microcapsules with shell walls and oil cores. Therefore, the size of the oil droplets directly determines the size of the subsequently formed capsule core. High rotational speeds allow for the formation of finely dispersed, individual, homogeneous oil droplets, resulting in homogeneous core-shell microcapsule sizes.

[0294] As indicated above, advantageous stirring is applied throughout the entire preparation process.

[0295] The formation of an emulsion in the case of a liquid active ingredient or a suspension in the case of a solid active ingredient according to the present invention, i.e., emulsification or suspension of an internal non-aqueous or oily phase by an external aqueous or hydrophilic phase, is carried out under high turbulence or strong shear, thereby determining the diameter of the microcapsules at which the intensity of turbulence or shear is obtained. The production of microcapsules can be continuous or discontinuous. With increasing viscosity of the aqueous phase or decreasing viscosity of the oily phase, the size of the resulting capsules usually decreases.

[0296] Preferably, emulsification, i.e., the formation of a provisional oil-in-water emulsion, is preferably carried out by subjecting the mixture to high-speed shearing using, for example, Ultra-Turrax® from IKA®Works at 3000 rpm to 5000 rpm for about 20 to 120 seconds, in order to achieve a homogeneous provisional oil-in-water emulsion in which the individual particle sizes are uniform. Subsequently, to prevent particle aggregation, the shearing rate was reduced to 300 rpm to 800 rpm, preferably 600 rpm to 650 rpm, using, for example, an overhead mixer.

[0297] In that regard, the temperature is preferably kept within the range of 0°C to 50°C, and more preferably between 20°C and 40°C.

[0298] Once a provisional oil-in-water emulsion is prepared, it is mixed with a second aqueous phase containing at least one sugar and / or at least one amino sugar and / or at least one thio sugar, each independently having less than 20 monomer units, preferably 15 monomer units or less, and even more preferably 10 monomer units or less, as defined above, in order to form a bond between the isocyanate functional group of the isocyanate component and at least two functional groups, namely a hydroxyl group and / or an amine group and / or a thiol group, and / or a polythiourethane base.

[0299] The second aqueous phase is preferably added at a stirring speed of 300 rpm to 800 rpm, preferably 600 rpm to 650 rpm. Preferably, the second aqueous phase is added at a temperature between 0°C and 50°C, preferably 20°C to 40°C.

[0300] In the process according to the present invention, at least one sugar and / or amino sugar has at least two functional groups independently selected from the group consisting of primary and secondary hydroxyl groups (-OH) as well as primary and secondary amine groups (-NH2, -NH-).

[0301] Preferably, a sugar component and / or an amino sugar component and / or a thio sugar component having at least two functional reactive groups independently selected from the group consisting of primary and secondary hydroxyl groups (-OH), as well as primary and secondary amine groups (-NH2, -NH-) or thiol (-SH) groups.

[0302] Preferably, in a process for preparing a core-shell microcapsule or a slurry or microcapsule containing a core-shell microcapsule according to the first embodiment, the molar ratio or weight ratio, preferably in the range of 1:3 to 1:1, preferably 1:3 to 1:2, of at least one polyisocyanate having at least two isocyanate groups to at least one sugar and / or amino sugar and / or at least one thiosugar having at least two functional reactive groups independently selected from the group consisting of primary and secondary hydroxyl groups (-OH), as well as primary and secondary amine groups (-NH2, -NH-) or thiol (-SH) groups, which have fewer than 20 monomer units, is in the range of 1:3 to 1:1, preferably 1:3 to 1:2.

[0303] If the ratio of isocyanate to (amino) sugar is within the range specified above, efficient crosslinking and, consequently, highly stable yet still excellent release properties of microcapsules can be achieved.

[0304] Finally, the microcapsules obtained in step (e) in the form of a microcapsule slurry need to be cured.

[0305] Once the provisional oil-in-water emulsion is mixed with the second aqueous phase, polyaddition occurs, forming crude microcapsules that encapsulate the active substance. Capsule-forming aids are understood to be incorporated into the capsule shell or bound to the capsule surface. Simultaneously, since the microcapsules exhibit insufficient stability in the dispersion, a final curing step is required: after the completion of the crosslinking process, the prepared microcapsules exist as raw microcapsules in the form of an aqueous dispersion, with soft and flexible capsule shells or walls. Therefore, it is subsequently necessary to subject the microcapsules to an additional curing step to cure, i.e., harden, the shells or walls of the still soft, flexible, and unstable single-layer microcapsules, thereby consuming isocyanates and growing polymers to provide sufficient stability. Typically, curing is carried out by treating the resulting dispersion at a high temperature of about 50°C to about 90°C for a period of about 1 to 12 hours. To avoid aggregation and subsequent clumping of crude microcapsules, it is advantageous to continuously stir the dispersion system at 300 rpm to 1000 rpm using a non-high-speed shear blade during the curing process. Preferably, the stirring speed is approximately 650 rpm during the curing process.

[0306] If desired, the solvent can be removed to obtain "pure" capsules, which typically have an average diameter of about 5 to 50 microns.

[0307] As a result, the process of preparing bio-based core-shell microcapsules by preparing a slurry is optional and may include an additional step of isolating the microcapsules themselves from the slurry / dispersion system (step (g)), preferably in a dry form.

[0308] This can be achieved, for example, by filtration. Further common techniques suitable for this purpose include, for example, filtration or spray drying, freeze-drying or vacuum drying, for removing the solvent(s) and obtaining isolated microcapsules. Centrifugation and subsequent drying may also be an option.

[0309] Optionally, the process may include an additional step (f2) instead of isolating the microcapsules after step (f), in which one or more suspension or structuring aids selected from natural gums (e.g., xanthan gum, gellan gum, diutan gum; cellulose gum) are added as thickeners to provide high suspension stability.

[0310] In this regard, the thickener(s) are preferably added while stirring at approximately 1200 rpm to 1500 rpm for 1 to 5 minutes, after which the stirring speed is reduced to less than 1000 rpm, preferably about 850 rpm. This provides stability to the slurry against "creaming" or precipitation of particles by adding the thickener or structuring agent.

[0311] Preferably, the resulting capsules are then cured again in an additional step, and optionally, the microcapsules are then isolated from the slurry as described above.

[0312] In addition, preferably, catalysts(s) may be added to facilitate the reaction between (amino) sugar components and isocyanate crosslinkers, particularly with respect to the formation of polyurethane-based structures. Suitable catalysts are, for example, tin, zinc, bismuth, or metal-ligand catalysts based on tertiary amines such as DABCO® (1,4-diazabicyclo[2.2.2]octane; Air Products & Chemicals, Inc; supplier: Sigma-Aldrich Corp. St. Louis, MO, USA).

[0313] Preferably, the catalyst(s) are added to the oil phase and / or to one or both of the aqueous phases and / or directly to the (provisional) oil-in-water emulsion. Preferably, for the synergistic effect of the catalysts, approximately 0.03 to 0.1% by weight of a metal-based catalyst (bismuth neodecanoate) is added to the organic / oil phase, and further approximately 0.03 to 0.1% by weight of a tertiary amine (e.g., DABCO®) is added to one of the aqueous phases or directly to the (provisional) oil-in-water emulsion. Preferably, bismuth neodecanoate is used as the catalyst because this compound is preferred due to its lower toxicity compared to other metal-ligand catalysts.

[0314] Overall, the processes described herein enable significant savings of shell material for more efficient crosslinking, allowing for a further reduction in the required isocyanate content compared to state-of-the-art capsules without adversely affecting capsule stability or performance. This enables the preparation of stable and high-performing bio-based or sugar-based core-shell microcapsules. In addition, capsules manufactured in this manner have excellent substrate compatibility and high biodegradability, particularly in light of the growing health and environmental awareness in today's society. It is particularly suitable for use in various consumer goods.

[0315] Therefore, another object of the present invention is to provide a slurry containing bio-based core-shell microcapsules obtained by the process described above, as well as the bio-based core-shell microcapsules themselves obtained by the process described above.

[0316] In addition, the bio-based core-shell microcapsules and / or slurry containing the core-shell microcapsules of the present invention are suitable for use in the preparation of various consumer products.

[0317] Accordingly, the present invention also relates to the use of core-shell microcapsules according to the present invention for preparing consumer products. The core-shell microcapsules of the present invention are suitable for use in, but are not limited to, cosmetics, personal care products, especially skin cleansing and skincare products, shampoos, rinse-off conditioners, deodorants, antiperspirants, body lotions, fabric care products and home care / household products, especially liquid detergents, all-purpose cleaners, laundry and detergents, fabric softeners, fragrance enhancers and pharmaceuticals.

[0318] Finally, the present invention also relates to preferably scented consumer products comprising core-shell microcapsules or slurries of microcapsules according to the present invention, wherein the consumer products are selected from the group comprising, or consisting of, cosmetics, personal care products, particularly skin cleansing and skincare products, shampoos, rinse-off conditioners, deodorants, antiperspirants, body lotions, fabric care products and home care / household products, particularly liquid detergents, all-purpose cleaners, laundry and cleaning agents, fabric softeners, fragrance enhancers, and pharmaceuticals.

[0319] Examples of personal care products include shampoos, rinses, hair conditioners, soaps, creams, body washes such as shower salts or bath salts, body soaps, generally solid and liquid soaps, body liquids, mousses, oils or gels, hygiene products, generally cosmetics, body lotions; leave-in personal care products including hair fragrances and lotions, personal cleansers or disinfectants, pre-shaving products, splash colognes and scented refreshing wipes, shower gels, shaving soaps, shaving foams, bath oils, cosmetic emulsions, such as skin creams and lotions, facial creams and lotions. Examples of products include sunscreens, sunscreens and lotions, after-sun creams and lotions, hand creams and hand lotions, foot creams and foot lotions, hair removal creams and lotions, after-shaving creams and lotions, sunscreens and lotions, hair care products such as hair sprays, hair gels, hair lotions, hair conditioners, permanent and semi-permanent hair dyes, hair styling agents such as cold perms and straighteners, hair tonics, hair creams and lotions, deodorants and antiperspirants such as underarm sprays, roll-ons, deodorant sticks, deodorant creams, or cosmetic products. Wash-off products may be liquids, solids, pastes or gels in any physical form.

[0320] Examples of home care products include solid or liquid detergents, all-purpose cleaners, fabric softeners and coolants, ironing water and detergents, fabric softeners and dryers, with liquid, powder and tablet detergents, fragrances and fabric softeners being preferred. Further examples include floor cleaners, window cleaners, dishwashing detergents, bath and sanitary cleaners, rinse lotions, solid and liquid toilet cleaners, powder and foam carpet cleaners, liquid and powder detergents for dishwashing or various surface cleaning, laundry pretreatment agents such as bleaches, soaking agents and stain removers, fabric softeners, fabric coolants, cleaning soaps, cleaning tablets, disinfectants, surface disinfectants and air purifiers in liquid, gel-like or solid carrier form, aerosol sprays, waxes and polishes such as furniture polishes, floor waxes and shoe polishes.

[0321] Preferred laundry / fabric care products include, in particular, fabric care products and detergent-containing preparations, such as powder and liquid detergents and fabric softeners.

[0322] This core-shell microcapsule enables the efficient encapsulation of a wide range of active ingredients, such as fragrances, thereby reducing or completely preventing interactions with other components in the product formulation in scented products, as well as reducing or completely preventing the evaporation of potentially slightly volatile components. The use of microcapsules allows for the targeted release of a component(s) under precisely defined conditions. For example, in the case of microcapsules containing fragrance substances, fragrances that are generally sensitive to environmental conditions (oxidative effects caused by air or other components in the product formulation) can be encapsulated, so that the fragrance substance is stable during storage. The microcapsule is broken by applying a specific signal or trigger (e.g., mechanical stress) only when the desired fragrance is to be released, thereby efficiently releasing the fragrance and exhibiting good sensory performance as defined herein. The capsules of the present invention allow for controlled release of the active ingredient (without loss during storage) upon rupture of the capsule shell, while simultaneously providing sufficient stability to the capsule over long periods, and exhibiting higher biodegradability compared to state-of-the-art capsules.

[0323] [Examples]

[0324] Preparation of core-shell microcapsules

[0325] The following encapsulated particles (core-shell microcapsules) were prepared as described below. Based on the preparations described below, a corresponding microcapsule slurry was obtained containing multiple bio-based / (amino) sugar-based core-shell microcapsules dispersed in an aqueous phase, exhibiting higher biodegradability, superior release properties, and capsule stability even during long-term storage, compared to fully synthesized, state-of-the-art (non-bio-based) microcapsules.

[0326] Table 1 summarizes the equivalent amounts and functional group content of isocyanate components used in the context of the present invention and its examples.

[0327] [Table 1]

[0328] Table 2 summarizes the relative weight and molar ratios of the isocyanate compounds used in the context of the present invention and its examples.

[0329] [Table 2]

[0330] Example 1: Glucosamine-based microcapsules I

[0331] Microcapsules according to the present invention were prepared using glucosamine as a polyfunctional nucleophile and polyvinyl alcohol (PVA, Selvol® 523, Sekisui Specialty Chemicals, Japan) as a capsule-forming aid.

[0332] More specifically, 210 g of fragrance material, in this case TomCap® (Symrise, Teterboro, NJ), was weighed into a 250 ml beaker and combined with 6.29 g of Desmodur® N-3400 isocyanate monomer (hexamethylene diisocyanate uretidione, HDI-uretidione, aliphatic polyisocyanate; equivalent: 193) and 1.57 g of Mondur® M flake (monomer diphenylmethane-4,4'-diisocyanate; aromatic polyisocyanate; equivalent: 125.2), both derived from Covestro Corporation, to form an oil phase containing aliphatic and aromatic polyisocyanates in a relative weight ratio of 80:20 or a relative molar ratio of 72.3:27.7, respectively. Next, 0.3 g of oil-soluble catalyst (bismuth neodecanoate, Aldrich Chemical Corporation, St. Louis, MO, US) was added. In a separate 800 ml beaker, a solution (322 g) containing 32.2 g of polyvinyl alcohol (PVA, Selvol® 523, Sekisui Specialty Chemicals, Japan) in water was prepared to form the first aqueous phase. Next, the oil phase was emulsified into the aqueous phase by applying shear force (Ultra Turrax®, T-50, commercially available from IKA® Werke, Staufen, Germany) by stirring at 3500 rpm for approximately 20 to 60 seconds in the presence of 0.3 g of DABCO® (1,4-diazabicyclo[2.2.2]octane, Aldrich Chemical Corporation, St. Louis, MO, USA) to obtain an oil-in-water fragrance emulsion with an average particle size of 5 to 50 microns. That is, the catalyst is added to the provisional oil-in-water emulsion after emulsification. The particle size of the finely dispersed oil particles was measured using a Mastersizer® 3000 particle size analyzer (Malvern Instruments, 117 Flanders Road, Westborough, MA, USA). Preferably, the median particle size of the finely dispersed oil droplets in the aqueous phase is in the range of 20 μm to 30 μm.

[0333] The resulting provisional oil-in-water emulsion was placed in an overhead mixer and stirred at 600 rpm while gradually adding 60 g of 10% glucosamine solution (second aqueous phase). The glucosamine solution used was prepared by dissolving 6 g of glucosamine HCl (Biosynth Carbosynth®, United Kingdom) in 54 g of deionized water. The pH was adjusted to approximately 9.5-10.5 by adding potassium hydroxide. The resulting capsule slurry was cured by heating at 70°C for at least 3 hours. Microcapsules in the suspension will separate over time due to the density difference between the aqueous phase (water) and the microcapsules. To avoid this process, a structuring agent is added to provide solution viscosity. Therefore, to stabilize the resulting microcapsules in the aqueous phase, the slurry was stirred at 1200 rpm for approximately 2-4 minutes, with 0.60 g of Kelco-vis® DG (diutane gum, CP Kelco Inc.) added at the end. The stirring speed was then reduced to 850 rpm, followed by curing for a further 1 hour.

[0334] The fact that the obtained microcapsules have a fairly narrow particle size distribution range in the aqueous phase indicates that the bio-based core-shell microcapsules have a uniform particle size. The core-shell microcapsules have a median volume-based particle size of 25.3 μm (Dv(50)) (see Figure 16A).

[0335] Furthermore, the resulting microcapsules exhibit high mechanical and chemical stability in product formulations (such as fabric softeners), and demonstrate superior release properties that clearly surpass those of state-of-the-art, non-biobased microcapsules (see Figures 1A and 1B). Moreover, the as-is microcapsules show significantly enhanced biodegradability compared to state-of-the-art microcapsules that are not biodegradable at all.

[0336] Example 2: Chito-oligosaccharide-based microcapsules I

[0337] Microcapsules according to the present invention were prepared using chitosan oligosaccharide (chito-oligosaccharide) as a polyfunctional nucleophile and polyvinyl alcohol (PVA, Selvol® 523, Sekisui Specialty Chemicals, Japan) as a capsule-forming aid.

[0338] More specifically, 210 g of fragrance material, in this case TomCap® (Symrise, Teterboro, NJ), was weighed into a 250 ml beaker and combined with 6.29 g of Desmodur® N-3400 isocyanate monomer (hexamethylene diisocyanate uretidione, HDI-uretidione, aliphatic polyisocyanate; equivalent: 193) and 1.57 g of Mondur® M flake (monomer diphenylmethane-4,4'-diisocyanate; aromatic polyisocyanate; equivalent: 125.2), both derived from Covestro Corporation, to form an oil phase containing aliphatic and aromatic polyisocyanates in a relative weight ratio of 80:20 or a relative molar ratio of 72.3:27.7, respectively. Next, 0.3 g of oil-soluble catalyst (bismuth neodecanoate, Aldrich Chemical Corporation, St. Louis, MO, US) was added. In a separate 800 ml beaker, a solution (302 g) containing 3.02 g of polyvinyl alcohol (PVA, Selvol® 523, Sekisui Specialty Chemicals, Japan) in water was prepared to form the first aqueous phase. Then, in the presence of 0.3 g of DABCO® (1,4-diazabicyclo[2.2.2]octane, Aldrich Chemical Corporation, St. Louis, MO, USA), the oil phase was emulsified into the aqueous phase by applying shear force (Ultra Turrax® T-50, commercially available from IKA® Werke, Staufen, Germany) by stirring at 3500 rpm for approximately 20 to 60 seconds, thereby obtaining an oil-in-water fragrance emulsion with an average particle size in the range of 5 to 50 microns. The particle size of the finely dispersed oil particles was measured using a Mastersizer® 3000 particle size analyzer (Malvern Instruments, 117 Flanders Road, Westborough, MA, USA).

[0339] The resulting provisional oil-in-water emulsion was placed in an overhead mixer and stirred at 600 rpm while gradually adding 80 g of a 10% chitosan oligosaccharide solution (second aqueous phase). The chitosan oligosaccharide solution was prepared by dissolving 8 g of chitosan oligosaccharide HCl (molecular weight <3000 Da, Biosynth Carbosynth®, United Kingdom) in 72 g of deionized water. The pH was adjusted to approximately 10-11 by adding potassium hydroxide. The resulting capsule slurry was cured at 70°C for at least 3 hours. Finally, 0.60 g of Kelco-vis® DG (diutan gum, CP Kelco Inc.) was added to the slurry while stirring at 1200 rpm for approximately 2-4 minutes, then the stirring speed was reduced to 850 rpm, followed by a further curing for 1 hour.

[0340] The final core-shell microcapsules have a volume-based median particle size (Dv(50)) of 22.9 μm in the slurry (see Figure 16B), and exhibit good stability and release characteristics even when dryer-dried and aged with a softener (see Figures 2A and 2B).

[0341] Example 3: Chito-oligosaccharide-based microcapsules II

[0342] Microcapsules according to the present invention were prepared using chitosan oligosaccharide (chito-oligosaccharide) as a polyfunctional nucleophile and polyvinyl alcohol (PVA, Selvol® 523, Sekisui Specialty Chemicals, Japan) as a capsule-forming aid.

[0343] More specifically, 210 g of fragrance material, in this case TomCap® (Symrise, Teterboro, NJ), was weighed into a 250 ml beaker and combined with 1.57 g of STABiO® D-370N (aliphatic polyisocyanurate based on bio-based 1,5-pentamethylene diisocyanate (PDI); equivalent: 168.24) and 1.57 g of Takenate® 600 (1,3-bis(isocyanatomethyl)cyclohexane; aliphatic polyisocyanate; equivalent: 97.14), both derived from Mitsui Chemicals (Japan), to form an oil phase containing aliphatic polyisocyanates in a relative weight ratio of 50:50 or a relative molar ratio of 36.6:63.4. Subsequently, 0.3 g of oil-soluble catalyst (bismuth neodecanoate, Aldrich Chemical Corporation) was added. In a separate 800 ml beaker, a solution (302 g) containing 3.02 g of polyvinyl alcohol (PVA, Selvol® 523, Sekisui Specialty Chemicals, Japan) in water was prepared to form the first aqueous phase. Next, the oil phase was emulsified into the aqueous phase by applying shear force by stirring at 3500 rpm (Ultra Turrax® T-50, commercially available from IKA® Werke, Staufen, Germany) for approximately 20 to 60 seconds in the presence of 0.3 g of DABCO® (1,4-diazabicyclo[2.2.2]octane, Aldrich Chemical Corporation), thereby obtaining an oil-in-water fragrance emulsion with an average particle size in the range of 5 to 50 microns. The particle size of the finely dispersed oil particles was measured using a Mastersizer® 3000 particle size analyzer (Malvern Instruments, 117 Flanders Road, Westborough, MA, USA).

[0344] The resulting provisional oil-in-water emulsion was placed in an overhead mixer and stirred at 600 rpm while gradually adding 80 g of a 10% chitosan oligosaccharide solution. The chitosan oligosaccharide solution was prepared by dissolving 8 g of chitosan oligosaccharide HCl (molecular weight <3000 Da, Biosynth Carbosynth®, United Kingdom) in 72 g of deionized water. The pH was adjusted to approximately 9.5-10.5 by adding potassium hydroxide. The resulting capsule slurry was cured at 70°C for at least 3 hours. Finally, 0.60 g of Kelco-vis® DG (diutan gum, CP Kelco Inc.) was added to the slurry while stirring at 1200 rpm for approximately 2-4 minutes, then the stirring speed was reduced to 850 rpm, followed by a further curing for 1 hour.

[0345] The final core-shell microcapsules had a volume-based median particle size (Dv(50)) of 25.9 μm in the slurry (see Figure 16C) and exhibited excellent release characteristics, particularly after rope drying, following aging in a fabric softener solution for one week (see Figures 3A and 3B). In this particular case, increasing the amount of aliphatic isocyanate appears to have a positive effect on stability compared to Example 2.

[0346] Example 4: Microcapsules I based on chito-oligosaccharide and glucosamine

[0347] Microcapsules according to the present invention were prepared using glucosamine and chitosan oligosaccharide as polyfunctional nucleophiles, and polyvinyl alcohol (PVA) (Selvol® 523, Sekisui Specialty Chemicals, Japan) as a capsule-forming aid.

[0348] More specifically, 210 g of fragrance material, in this case TomCap® (Symrise, Teterboro, NJ), was weighed into a 250 ml beaker and combined with 3.93 g of STABiO® D-370N (aliphatic polyisocyanurate based on bio-based 1,5-pentamethylene diisocyanate (PDI); equivalent: 168.24) and 3.93 g of Takenate® 600 (1,3-bis(isocyanatomethyl)cyclohexane; aliphatic polyisocyanate; equivalent: 97.14), both derived from Mitsui Chemicals (Japan), to form an oil phase containing aliphatic polyisocyanates in a relative weight ratio of 50:50 or a relative molar ratio of 36.6:63.4. Subsequently, 0.3 g of oil-soluble catalyst (bismuth neodecanoate, Aldrich Chemical Corporation) was added. In a separate 800 ml beaker, a solution (302 g) containing 3.02 g of polyvinyl alcohol (PVA, Selvol® 523, Sekisui Specialty Chemicals, Japan) in water was prepared to form the first aqueous phase. Next, the oil phase was emulsified into the aqueous phase by applying shear force (Ultra Turrax® T-50, commercially available from IKA® Werke, Staufen, Germany) by stirring at 3500 rpm for approximately 20 to 60 seconds in the presence of 0.3 g of DABCO® (1,4-diazabicyclo[2.2.2]octane, Aldrich Chemical Corporation), thereby obtaining an oil-in-water fragrance emulsion with an average particle size in the range of 5 to 50 microns. The particle size of the finely dispersed oil particles was measured using a Mastersizer® 3000 particle size analyzer (Malvern Instruments, 117 Flanders Road, Westborough, MA, USA).

[0349] The resulting provisional oil-in-water emulsion was placed in an overhead mixer and stirred at 600 rpm while gradually adding 80 g of a solution mixture of 5% chitosan oligosaccharide (molecular weight <3000 Da; equivalent to approximately 12-15 monomer units) and 5% glucosamine (both from Biosynth Carbosynth®, United Kingdom). The mixed chitosan oligosaccharide / glucosamine solution was prepared by dissolving 4 g of chitosan oligosaccharide and 4 g of glucosamine HCl in 72 g of deionized water. The pH was adjusted to 10-11 by adding potassium hydroxide. The resulting capsule slurry was cured at 70°C for at least 3 hours. Finally, 0.60 g of Kelco-vis(trademark) DG (diutan gum, CP Kelco Inc.) was added to the slurry while stirring at 1200 rpm for approximately 2-4 minutes, after which the stirring speed was reduced to 850 rpm and the mixture was allowed to cure for another hour.

[0350] The final core-shell microcapsules have a volume-based median particle size (Dv(50)) of 22.6 μm in the slurry (see Figure 16D), exhibit excellent performance (release characteristics) after drying, and similarly show high stability in the formulation and during the drying process.

[0351] Example 5: Glucosamine-based microcapsules II

[0352] Microcapsules according to the present invention were prepared using glucosamine (Biosynth Carbosynth®, United Kingdom) as a polyfunctional nucleophile and Capsul® starch (commercially available from Ingredion Inc.) as a capsule-forming aid.

[0353] More specifically, 210 g of fragrance material, in this case TomCap® (Symrise, Teterboro, NJ), was weighed into a 250 ml beaker and combined with 6.29 g of Desmodur® N-3400 isocyanate monomer (hexamethylene diisocyanate uretidione, HDI-uretidione, aliphatic polyisocyanate; equivalent: 193) and 1.57 g of Mondur® M flake (monomer diphenylmethane-4,4'-diisocyanate; aromatic polyisocyanate; equivalent: 125.2), both derived from Covestro Corporation. These were then combined to form an oil phase containing aliphatic and aromatic polyisocyanates in a relative weight ratio of 80:20 or a relative molar ratio of 72.3:27.7. Subsequently, 0.6 g of oil-soluble catalyst (bismuth neodecanoate, Aldrich Chemical Corporation) was added. In a separate 800 ml beaker, a solution (322 g) containing 6.44 g of octenyl succinate (OSA) starch anhydride (Capsul®, Ingredion Inc.) in water was prepared to form the first aqueous phase. Then, in the presence of 0.6 g of DABCO® (1,4-diazabicyclo[2.2.2]octane, Aldrich Chemical Corporation), the oil phase was emulsified into the aqueous phase by applying shear force by stirring at 3500 rpm (Ultra Turrax®, T-50, commercially available from IKA® Werke, Staufen, Germany) for approximately 20 to 60 seconds, thereby obtaining an oil-in-water fragrance emulsion with an average particle size in the range of 5 to 50 microns. The particle size of the finely dispersed oil particles was measured using a Mastersizer® 3000 particle size analyzer (Malvern Instruments, 117 Flanders Road, Westborough, MA, USA).

[0354] The resulting provisional oil-in-water emulsion was placed in an overhead mixer and stirred at 600 rpm while gradually adding 60 g of 10% glucosamine solution. The glucosamine solution was prepared by dissolving 6 g of glucosamine HCl (Biosynth Carbosynth®, United Kingdom) in 54 g of deionized water. The pH was adjusted to 10-11 by adding potassium hydroxide. The resulting capsule slurry was cured at 70°C for at least 3 hours. Finally, 1.8 g of Keltrol® (xanthan gum, CP Kelco Inc.) was added to the slurry while stirring at 1200 rpm for approximately 2-4 minutes, then the stirring speed was reduced to 850 rpm, followed by a further curing for 1 hour.

[0355] The final core-shell microcapsules have a volume-based median particle size (Dv(50)) of 32.1 μm in the slurry (see Figure 16E) and exhibit outstanding capsule performance as well as mechanical and chemical stability, especially after rope drying. The use of starch, i.e., a bio-based capsule-forming aid, as a capsule-forming aid appears to have a positive effect on the capsule stability and release characteristics of the core-shell microcapsules of the present invention.

[0356] Example 6: Maltodextrin-based microcapsules I

[0357] Microcapsules according to the present invention were prepared using maltodextrin DE8 as a polyfunctional nucleophile and polyvinyl alcohol (PVA, Selvol® 523, Sekisui Specialty Chemicals, Japan) as a capsule-forming aid.

[0358] More specifically, 210 g of fragrance material, in this case TomCap® (Symrise, Teterboro, NJ), was weighed into a 250 ml beaker and combined with 6.29 g of Desmodur® N-3400 isocyanate monomer (hexamethylene diisocyanate uretidione, HDI-uretidione, aliphatic polyisocyanate; equivalent: 193) and 1.57 g of Mondur® M flake (monomer diphenylmethane-4,4'-diisocyanate; aromatic polyisocyanate; equivalent: 125.2), both derived from Covestro Corporation. These were then combined to form an oil phase containing aliphatic and aromatic polyisocyanates in a relative weight ratio of 80:20 or a relative molar ratio of 72.3:27.7. Subsequently, 0.7 g of oil-soluble catalyst (bismuth neodecanoate, Aldrich Chemical Corporation) was added. In a separate 800 ml beaker, a 1% PVA solution (approximately 241 g) (i.e., a PVA solution with a concentration of 1%) (Selvol® 523, Sekisui Specialty Chemicals, Japan) was prepared to form the first aqueous phase. This solution was prepared by mixing 6.5 g of 10% PVA solution (therefore, equivalent to 0.65 g of pure PVA) with 235.2 g of deionized water. The as-prepared solution represented 0.25% of the total PVA added during the experiment (i.e., one-quarter of the total PVA added). The oil phase was then emulsified into the aqueous phase by applying shear force by stirring at 3500 rpm (Ultra Turrax® T-50, commercially available from IKA® Werke, Staufen, Germany) for approximately 20-60 seconds, yielding an oil-in-water fragrance emulsion with an average particle size in the range of 4-50 microns. The particle size of the finely dispersed oil particles was measured using a Mastersizer® 3000 particle size analyzer (Malvern Instruments, 117 Flanders Road, Westborough, MA, USA).

[0359] The resulting provisional oil-in-water emulsion was placed in an overhead mixer and stirred at 650 rpm, while the remaining 0.75% PVA solution (i.e., the remaining three-quarters of the total addition of 1% PVA containing approximately 1.96 g of PVA in deionized water) (Selvol® 523, Sekisui Specialty Chemicals, Japan) was added, along with 0.7 g of oil-soluble catalyst (bismuth neodecanoate, Aldrich Chemical Corporation) and 60 g of 10% maltodextrin DE8 solution. A total of 2.61 g of PVA was added. The maltodextrin DE8 solution was prepared by dissolving 6 g of maltodextrin having 8 dextrose equivalents in 54 g of deionized water. The resulting capsule slurry was cured at 70°C for at least 30 minutes. Subsequently, an additional 60 g of 10% maltodextrin DE8 prepared in the same manner as previously described was added. The slurry was cured again at 70°C for another 30 minutes. Finally, 0.60 g of Kelco-vis(trademark) DG (diutan gum, CP Kelco Inc.) was added to the slurry while stirring at 1200 rpm for approximately 2-4 minutes, after which the stirring speed was reduced to 850 rpm and the temperature was raised to 80°C for another hour.

[0360] The fact that the obtained microcapsules have a narrow particle size distribution range in the aqueous phase indicates that the bio-based core-shell microcapsules have a uniform particle size. The core-shell microcapsules have a median volume-based particle size of 27.6 μm (Dv(50)) (see Figure 16F). The core-shell microcapsules according to Example 6 exhibit significantly improved stability and release characteristics compared to the non-bio-based state-of-the-art microcapsules according to Comparative Example 13 (see Examples 6A and 6B). Furthermore, they exhibit improved biodegradability compared to the completely synthetic state-of-the-art microcapsules (see Example 17).

[0361] Example 7: Maltodextrin-based microcapsules II

[0362] Microcapsules according to the present invention were prepared using maltodextrin DE8 as a polyfunctional nucleophile and polyvinyl alcohol (PVA, Selvol® 523, Sekisui Specialty Chemicals, Japan) as a capsule-forming aid.

[0363] More specifically, 210 g of fragrance material, in this case TomCap® (Symrise, Teterboro, NJ), was weighed into a 250 ml beaker and combined with 7.07 g of Bayhydur® 305 isocyanate monomer (hydrophilic aliphatic polyisocyanate based on hexamethylene diisocyanate (HDI), Covestro Corporation; equivalent: 259.6) and 0.785 g of Takenate® 600 (1,3-bis(isocyanatomethyl)cyclohexane; aliphatic polyisocyanate, Mitsui Chemicals; equivalent: 97.14), respectively, to form an oil phase containing aliphatic polyisocyanates in a relative weight ratio of 90:10 or a relative molar ratio of 77.1:22.9. Subsequently, 0.7 g of oil-soluble catalyst (bismuth neodecanoate, Aldrich Chemical Corporation) was added. In a separate 800 ml beaker, a 1% PVA aqueous solution (241 g) was prepared to form the first aqueous phase, which represented 0.25% of the total added 1% PVA (Selvol® 523, Sekisui Specialty Chemicals, Japan) (see Example 6). Next, the oil phase was emulsified into the aqueous phase by applying shear force by stirring at 3500 rpm (Ultra Turrax® T-50, commercially available from IKA® Werke, Staufen, Germany) for approximately 20 to 60 seconds, yielding an oil-in-water fragrance emulsion with an average particle size in the range of 4 to 50 microns. The particle size of the finely dispersed oil particles was measured using a Mastersizer® 3000 particle size analyzer (Malvern Instruments, 117 Flanders Road, Westborough, MA, USA).

[0364] The resulting provisional oil-in-water emulsion was placed in an overhead mixer and stirred at 650 rpm, while the remaining 0.75% of the PVA addition (1% PVA solution in deionized water) (Selvol® 523, Sekisui Specialty Chemicals, Japan) was added, along with 0.7 g of oil-soluble catalyst (bismuth neodecanoate, Aldrich Chemical Corporation) and 60 g of 10% maltodextrin DE8 solution. The maltodextrin DE8 solution was prepared by dissolving 6 g of maltodextrin having 8 dextrose equivalents (DE) in 54 g of deionized water. The resulting capsule slurry was cured at 70°C for at least 30 minutes. Then, an additional 60 g of 10% maltodextrin DE8 solution, prepared in the same manner as previously described, was added. The slurry was again cured at 70°C for a further 30 minutes. Finally, 0.60 g of Kelco-vis(trademark) DG (diutan gum, CP Kelco Inc.) was added to the slurry while stirring at 1200 rpm for approximately 2-4 minutes. Then, the stirring speed was reduced to 850 rpm, and the temperature was raised to 80°C for another hour.

[0365] The fact that the resulting microcapsules exhibit a sharp particle size distribution range in the aqueous phase indicates that the bio-based core-shell microcapsules have a uniform particle size. The core-shell microcapsules have a median volume-based particle size of 51.5 μm (Dv(50)) (see Figure 16G). Furthermore, their biodegradability is improved compared to state-of-the-art, fully synthetic microcapsules (see Figure 18).

[0366] Example 8: Maltodextrin-based microcapsules III

[0367] Microcapsules according to the present invention were prepared using maltodextrin DE8 as a polyfunctional nucleophile and polyvinyl alcohol (PVA, Selvol® 523, Sekisui Specialty Chemicals, Japan) as a capsule-forming aid.

[0368] More specifically, 210 g of fragrance material, in this case TomCap® (Symrise, Teterboro, NJ), was weighed into a 250 ml beaker and combined with 6.29 g of Desmodur® N-3400 isocyanate monomer (hexamethylene diisocyanate uretidione, HDI-uretidione, aliphatic polyisocyanate; equivalent: 193) and 1.57 g of Mondur® M flake (monomer diphenylmethane-4,4'-diisocyanate; aromatic polyisocyanate; equivalent: 125.2), both derived from Covestro Corporation. These were then combined to form an oil phase containing aliphatic and aromatic polyisocyanates in a relative weight ratio of 80:20 or a relative molar ratio of 72.3:27.7. Subsequently, 0.7 g of oil-soluble catalyst (bismuth neodecanoate, Aldrich Chemical Corporation) was added. In a separate 800 ml beaker, a 1% PVA aqueous solution (241 g) was prepared to form the first aqueous phase, which represented 0.25% of the total added 1% PVA (Selvol® 523, Sekisui Specialty Chemicals, Japan) (see previous examples). Next, the oil phase was emulsified into the aqueous phase by applying shear force by stirring at 3500 rpm (Ultra Turrax® T-50, commercially available from IKA® Werke, Staufen, Germany) for approximately 20 to 60 seconds, thereby obtaining an oil-in-water fragrance emulsion with an average particle size in the range of 4 to 50 microns. The particle size of the finely dispersed oil particles was measured using a Mastersizer® 3000 particle size analyzer (Malvern Instruments, 117 Flanders Road, Westborough, MA, USA).

[0369] The resulting provisional oil-in-water emulsion was placed in an overhead mixer and stirred at 650 rpm, while the remaining 0.75% of the PVA addition (1% PVA solution in deionized water) (Selvol® 523, Sekisui Specialty Chemicals, Japan) was added, along with 0.7 g of catalyst DABCO® (1,4-diazabicyclo[2.2.2]octane, Aldrich Chemical Corporation) and 60 g of 10% maltodextrin DE8 solution. The maltodextrin DE8 solution was prepared by dissolving 6 g of maltodextrin having 8 dextrose equivalents (DE) in 54 g of deionized water. The resulting capsule slurry was cured at 70°C for at least 30 minutes. Then, an additional 60 g of 10% maltodextrin DE8 solution prepared in the same manner as previously described was added. The slurry was again cured at 70°C for a further 30 minutes. Finally, 0.60 g of Kelco-vis(trademark) DG (diutan gum, CP Kelco Inc.) was added to the slurry while stirring at 1200 rpm for approximately 2-4 minutes. Then, the stirring speed was reduced to 850 rpm, and the temperature was raised to 80°C for another hour.

[0370] The fact that the resulting microcapsules exhibit a sharp particle size distribution range in the aqueous phase indicates that the bio-based core-shell microcapsules have a uniform particle size. The core-shell microcapsules have a median volume-based particle size of 26.4 μm (Dv(50)) (see Figure 16H) and exhibit improved biodegradability (see Figure 19). Furthermore, the capsules of the present invention exhibit high stability and performance even after drying in the product formulation and aging for 4 weeks (see Figures 6A-6D, 8A-8D). Examples 6 and 8 use different catalysts.

[0371] Example 9: Maltodextrin and glucosamine-based microcapsules

[0372] Microcapsules according to the present invention were prepared using maltodextrin DE8 and glucosamine as polyfunctional nucleophiles, and polyvinyl alcohol (PVA, Selvol® 523, Sekisui Specialty Chemicals, Japan) as a capsule-forming aid.

[0373] More specifically, 210 g of fragrance material, in this case TomCap® (Symrise, Teterboro, NJ), was weighed into a 250 ml beaker and combined with 6.29 g of Desmodur® N-3400 isocyanate monomer (hexamethylene diisocyanate uretidione, HDI-uretidione, aliphatic polyisocyanate; equivalent: 193) and 1.57 g of Mondur® M flake (monomer diphenylmethane-4,4'-diisocyanate; aromatic polyisocyanate; equivalent: 125.2), both derived from Covestro Corporation. These were used to form an oil phase containing aliphatic and aromatic polyisocyanates in a relative weight ratio of 80:20 or a relative molar ratio of 72.3:27.7. Subsequently, 0.5 g of oil-soluble catalyst (bismuth neodecanoate, Aldrich Chemical Corporation) was added. In a separate 800 ml beaker, a 1% PVA aqueous solution (241 g) was prepared to form the first aqueous phase, which represented 0.25% of the total added 1% PVA (Selvol® 523, Sekisui Specialty Chemicals, Japan) (see previous examples). Next, the oil phase was emulsified into the aqueous phase by applying shear force by stirring at 3500 rpm (Ultra Turrax® T-50, commercially available from IKA® Werke, Staufen, Germany) for approximately 20 to 60 seconds, thereby obtaining an oil-in-water fragrance emulsion with an average particle size in the range of 4 to 50 microns. The particle size of the finely dispersed oil particles was measured using a Mastersizer® 3000 particle size analyzer (Malvern Instruments, 117 Flanders Road, Westborough, MA, USA).

[0374] The resulting provisional oil-in-water emulsion was placed in an overhead mixer and stirred at 650 rpm, while the remaining 0.75% of PVA (1% PVA solution in deionized water) was added, followed by 0.5 g of catalyst DABCO® (1,4-diazabicyclo[2.2.2]octane, Aldrich Chemical Corporation) and 60 g of 10% glucosamine solution. The glucosamine solution was prepared by dissolving 6 g of glucosamine HCl (Biosynth Carbosynth®, United Kingdom) in 54 g of deionized water, and then the pH was adjusted to 7-8 by adding KOH. The resulting capsule slurry was cured at 70°C for 30 minutes, followed by the addition of an additional 60 g of 10% maltodextrin DE8 solution. A maltodextrin DE8 solution was prepared by dissolving 6 g of maltodextrin having 8 dextrose equivalents (DE) in 54 g of deionized water. The resulting capsule slurry was cured at 70°C for a further 30 minutes. Finally, 0.60 g of Kelco-vis® DG (diutan gum, CP Kelco Inc.) was added to the slurry while stirring at 1200 rpm for approximately 2-4 minutes, after which the stirring speed was reduced to 850 rpm and the temperature was raised to 80°C for a further 1 hour. This procedure corresponds to Example 9B.

[0375] In parallel, a microcapsule slurry was prepared according to the process described above, but with the difference that 30 g of the corresponding glucosamine solution and 30 g of the corresponding maltodextrin solution were added simultaneously before the first curing step, and an additional 30 g of glucosamine solution and 30 g of maltodextrin solution were added after the first curing step (corresponding to Example 9A).

[0376] The fact that the resulting microcapsules exhibit a sharp particle size distribution range in the aqueous phase indicates that the bio-based core-shell microcapsules have a uniform particle size. The core-shell microcapsules have a median volume-based particle size of 27.0 μm (Dv(50)) (see Figure 16I corresponding to Example 9A) and exhibit satisfactory performance and stability (see Figures 9A and 9B).

[0377] Example 10: Maltodextrin-based microcapsules IV

[0378] Microcapsules according to the present invention were prepared using maltodextrin DE8 as a polyfunctional nucleophile and polyvinyl alcohol (PVA, Selvol® 523, Sekisui Specialty Chemicals, Japan) as a capsule-forming aid.

[0379] More specifically, 210g of fragrance material, in this case TomCap® (Symrise, Teterboro, NJ), is weighed into a 250ml beaker, and 3.93g of Bayhydur® 305 isocyanate monomer (hydrophilic aliphatic polyisocyanate based on hexamethylene diisocyanate (HDI), Covestro Corporation; equivalent: 259.6), 1.57g of Takenate® 600 (1,3-bis(isocyanatomethyl)cyclohexane; aliphatic polyisocyanate, Mitsui Chemicals; equivalent: 97.14), and 2.36g of STABiO® 370-N (polyisocyanate based on 1,5-pentamethylene diisocyanate (PDI); aliphatic polyisocyanate, Mitsui Combined with chemicals (equivalent: 168.24), an oil phase was formed containing three aliphatic polyisocyanates in relative weight ratios of 50:20:30 or relative molar ratios of 33.4:35.7:30.9. Subsequently, 0.7 g of oil-soluble catalyst (bismuth neodecanoate, Aldrich Chemical Corporation, St. Louis, MO, US) was added. In a separate 800 ml beaker, a 1% PVA aqueous solution (241 g) was prepared to form the first aqueous phase, which corresponds to 0.2% of the total addition of 1% PVA (Selvol (trademark) 523, Sekisui Specialty Chemicals, Japan) (see previous examples). Next, the oil phase was emulsified into the aqueous phase by applying shear force by stirring at 3500 rpm (Ultra Turrax® T-50, commercially available from IKA® Werke, Staufen, Germany) for approximately 20 to 60 seconds, thereby obtaining an oil-in-water fragrance emulsion with an average particle size in the range of 4 to 50 microns. The particle size of the finely dispersed oil particles was measured using a Mastersizer® 3000 particle size analyzer (Malvern Instruments, 117 Flanders Road, Westborough, MA, USA).

[0380] The resulting provisional oil-in-water emulsion was placed in an overhead mixer and stirred at 650 rpm, while the remaining 0.75% of the PVA addition (1% PVA solution in deionized water) (Selvol® 523, Sekisui Specialty Chemicals, Japan) was added, along with 0.7 g of catalyst DABCO® (1,4-diazabicyclo[2.2.2]octane, Aldrich Chemical Corporation) and 60 g of 10% maltodextrin DE8 solution. The maltodextrin DE8 solution was prepared by dissolving 6 g of maltodextrin having 8 dextrose equivalents in 54 g of deionized water. The resulting capsule slurry was cured at 70°C for at least 30 minutes. Then, an additional 60 g of 10% maltodextrin DE8 solution, prepared in the same manner as previously described, was added. The slurry was again cured at 70°C for a further 30 minutes. Finally, 0.60 g of Kelco-vis(trademark) DG (diutan gum, CP Kelco Inc.) was added to the slurry while stirring at 1200 rpm for approximately 2-4 minutes. Then, the stirring speed was reduced to 850 rpm, and the temperature was raised to 80°C for another hour.

[0381] The fact that the resulting microcapsules exhibit a sharp particle size distribution range in the aqueous phase indicates that the bio-based core-shell microcapsules have a uniform particle size. The core-shell microcapsules have a median volume-based particle size of 13.7 μm (Dv(50)) (see Figure 16J). Furthermore, the core-shell microcapsules exhibit excellent release characteristics and good performance and stability, even after long-term storage in product formulations or under mechanical stress from washing machines or heat (see Figures 10A-10D). The combination of three different aliphatic polyisocyanates appears to have a positive effect on stability and performance.

[0382] Example 11: Chito-oligosaccharide and glucosamine-based microcapsules II (90 / 10 HDI / MDI; shell wall reduction)

[0383] Furthermore, bio-based microcapsules exhibiting reduced shell wall thickness have been prepared. Shell wall volume is calculated based on equivalent weight. In Examples 1-10, the shell wall volume / thickness is equivalent to that of current state-of-the-art microcapsules. In Examples 11 and 12, the shell wall volume is reduced to approximately half in terms of weight or thickness compared to state-of-the-art. By reducing the isocyanate content, the capsule thickness could be significantly reduced, and the formation of even thinner shell walls could be achieved.

[0384] Microcapsules according to the present invention were prepared using chitosan oligosaccharide and glucosamine as polyfunctional nucleophiles, and polyvinyl alcohol (PVA, Selvol® 523, Sekisui Specialty Chemicals, Japan) as a capsule-forming aid.

[0385] More specifically, 210 g of fragrance material, in this case TomCap® (Symrise, Teterboro, NJ), was weighed into a 250 ml beaker and combined with 4.27 g of Desmodur® N-3400 isocyanate monomer (hexamethylene diisocyanate uretidione, HDI-uretidione, aliphatic polyisocyanate; equivalent: 193) and 0.48 g of Mondur® M flake (monomer diphenylmethane-4,4'-diisocyanate; aromatic polyisocyanate; equivalent: 125.2), both derived from Covestro Corporation. These were used to form an oil phase containing aliphatic and aromatic polyisocyanates in a relative weight ratio of 90:10 or a relative molar ratio of 85.4:14.6. Subsequently, 0.6 g of oil-soluble catalyst (bismuth neodecanoate, Aldrich Chemical Corporation) was added. In a separate 800 ml beaker, a solution (302 g) containing 3.02 g of polyvinyl alcohol (PVA, Selvol® 523, Sekisui Specialty Chemicals, Japan) in water was prepared to form an aqueous phase. Next, the oil phase was emulsified into the aqueous phase by applying shear force (Ultra Turrax® T-50, commercially available from IKA® Werke, Staufen, Germany) by stirring at 3500 rpm for approximately 20 to 60 seconds in the presence of 0.3 g of DABCO® (1,4-diazabicyclo[2.2.2]octane, Aldrich Chemical Corporation, St. Louis, MO, USA), thereby obtaining an oil-in-water fragrance emulsion with an average particle size in the range of 5 to 50 microns. The particle size of the finely dispersed oil particles was measured using a Mastersizer® 3000 particle size analyzer (Malvern Instruments, 117 Flanders Road, Westborough, MA, USA).

[0386] The resulting oil-in-water emulsion was placed in an overhead mixer and stirred at 600 rpm, while 80 g of a solution mixture of 5% chitosan oligosaccharide (molecular weight <3000 Da) and 5% glucosamine (both from Biosynth Carbosynth®, United Kingdom) was immediately added. The mixed chitosan oligosaccharide / glucosamine solution was prepared by dissolving 4 g of chitosan oligosaccharide and 4 g of glucosamine HCl in 72 g of deionized water. The pH was adjusted to approximately 10-11 by adding potassium hydroxide. The resulting capsule slurry was cured by heating at 70°C for at least 3 hours. Finally, 0.60 g of Kelco-vis® DG (diutan gum, CP Kelco Inc.) was added to the slurry while stirring at 1200 rpm for approximately 2-4 minutes, then the stirring speed was reduced to 850 rpm, followed by a further curing for 1 hour.

[0387] The final core-shell microcapsules have a median volume-based particle size (Dv(50)) of 22.6 μm in the slurry (see Figure 16K). Although the capsule shell is significantly reduced, the microcapsules according to the present invention exhibit excellent release properties and stability in product formulations, especially after 4 weeks of aging, which is comparable to that of the completely synthetic conventional microcapsules according to Comparative Example 13 (see Figures 11A and 11B). Although the as-prepared capsules exhibit considerably thinner shell walls compared to standard capsule shells, the microcapsules according to the present invention in Example 11 (and Example 12) exhibit excellent release properties and stability in the corresponding product formulations, even after 4 weeks of aging. The capsule properties are comparable to those of state-of-the-art capsules (e.g., those of Comparative Example 13) with capsule shells nearly twice as thick.

[0388] Example 12: Chito-oligosaccharide and glucosamine-based microcapsules III (86 / 14 HDI / MDI; shell wall reduction)

[0389] Microcapsules according to the present invention were prepared using chitosan oligosaccharide and glucosamine as polyfunctional nucleophiles, and polyvinyl alcohol (PVA, Selvol® 523, Sekisui Specialty Chemicals, Japan) as a capsule-forming aid. Furthermore, these capsules exhibit a final capsule shell composed of a reduced shell wall, which represents a considerable reduction compared to microcapsules using state-of-the-art technology (for example, according to Example 13, the shell is approximately twice as large as in Examples 11 and 12).

[0390] More specifically, 210 g of fragrance material, in this case TomCap® (Symrise, Teterboro, NJ), was weighed into a 250 ml beaker and combined with 4.09 g of Desmodur® N-3400 isocyanate monomer (hexamethylene diisocyanate uretidione, HDI-uretidione, aliphatic polyisocyanate; equivalent: 193) and 0.66 g of Mondur® M flake (monomer diphenylmethane-4,4'-diisocyanate; aromatic polyisocyanate; equivalent: 125.2), both derived from Covestro Corporation. These were then combined to form an oil phase containing aliphatic and aromatic polyisocyanates in a relative weight ratio of 86:14 or a relative molar ratio of 80.1:19.9. Subsequently, 0.6 g of oil-soluble catalyst (bismuth neodecanoate, Aldrich Chemical Corporation) was added. In a separate 800 ml beaker, a solution (302 g) containing 3.02 g of polyvinyl alcohol (PVA, Selvol® 523, Sekisui Specialty Chemicals, Japan) in water was prepared to form an aqueous phase. Next, the oil phase was emulsified into the aqueous phase by applying shear force (Ultra Turrax® T-50, commercially available from IKA® Werke, Staufen, Germany) by stirring at 3500 rpm for approximately 20 to 60 seconds in the presence of 0.3 g of DABCO® (1,4-diazabicyclo[2.2.2]octane, Aldrich Chemical Corporation, St. Louis, MO, USA), thereby obtaining an oil-in-water fragrance emulsion with an average particle size in the range of 5 to 50 microns. The particle size of the finely dispersed oil particles was measured using a Mastersizer® 3000 particle size analyzer (Malvern Instruments, 117 Flanders Road, Westborough, MA, USA).

[0391] The resulting oil-in-water emulsion was placed in an overhead mixer and stirred at 600 rpm, while 80 g of a solution mixture of 5% chitosan oligosaccharide (molecular weight <3000 Da) and 5% glucosamine (both from Biosynth Carbosynth®, United Kingdom) was immediately added. The mixed chitosan oligosaccharide / glucosamine solution was prepared by dissolving 4 g of chitosan oligosaccharide and 4 g of glucosamine HCl in 72 g of deionized water. The pH was adjusted to approximately 10-11 by adding potassium hydroxide. The resulting capsule slurry was cured at 70°C for at least 3 hours. Finally, 0.60 g of Kelco-vis® DG (diutan gum, CP Kelco Inc.) was added to the slurry while stirring at 1200 rpm for approximately 2-4 minutes, then the stirring speed was reduced to 850 rpm, followed by a further curing for 1 hour.

[0392] The final core-shell microcapsules have a median volume-based particle size (Dv(50)) of 22.8 μm in the slurry (see Figure 16L). Although the capsule shell is significantly reduced, the microcapsules according to the present invention exhibit excellent release properties and mechanical and chemical stability in product formulations, particularly after 4 weeks of aging, which are comparable to those of the completely synthetic conventional microcapsules described in Comparative Example 13 (see Figures 11A and 11B).

[0393] Example 13: Guanidine carbonate-based microcapsules (Comparative example: Polyurea-based microcapsules)

[0394] In the comparative example, microcapsules were prepared using guanidine carbonate as a polyfunctional nucleophile and polyvinyl alcohol (PVA, Selvol® 523, Sekisui Specialty Chemicals, Japan) as a capsule-forming aid.

[0395] More specifically, 210 g of fragrance material, in this case TomCap® (Symrise, Teterboro, NJ), was weighed into a 250 ml beaker and combined with 6.29 g of Desmodur® N-3400 isocyanate monomer (hexamethylene diisocyanate uretidione, HDI-uretidione, aliphatic polyisocyanate; equivalent: 193) and 1.57 g of Mondur® M flake (monomer diphenylmethane-4,4'-diisocyanate; aromatic polyisocyanate; equivalent: 125.2), both derived from Covestro Corporation, to form an oil phase containing aliphatic and aromatic polyisocyanates in a relative weight ratio of 80:20 or a relative molar ratio of 72.3:27.7, respectively. In a separate 800 ml beaker, a solution (322 g) containing 1% polyvinyl alcohol (PVA, Selvol® 523, Sekisui Specialty Chemicals, Japan) in water was prepared to form the first aqueous phase. Next, by applying shear force (Ultra Turrax® T-50, commercially available from IKA® Werke, Staufen, Germany) by stirring at 3500 rpm for approximately 20-60 seconds, the oil phase was emulsified into the aqueous phase, obtaining an oil-in-water fragrance emulsion with an average particle size of 5-50 microns. The particle size of the finely dispersed oil particles was measured using a Mastersizer® 3000 particle size analyzer (Malvern Instruments, 117 Flanders Road, Westborough, MA, USA).

[0396] The resulting oil-in-water emulsion was placed in an overhead mixer and stirred at 600 rpm while gradually adding 28 g of 15% guanidine carbonate solution. The guanidine carbonate solution was prepared by dissolving 3.2 g of guanidine carbonate in 24 g of deionized water. The resulting capsule slurry was cured at 70°C for at least 2 hours. Finally, 0.60 g of Kelco-vis® DG (diutane gum, CP Kelco Inc.) was added to the slurry while stirring at 1200 rpm for approximately 2-4 minutes, then the stirring speed was reduced to 850 rpm, followed by further curing at 80°C for 1 hour.

[0397] The final core-shell microcapsules have a median volume-based particle size (Dv(50)) of 20.6 μm in the slurry (see Figure 16M) and are not biodegradable (see Figure 15).

[0398] Sensory evaluation of fragrance core-shell microcapsules

[0399] For sensory evaluation, the microcapsules according to the present invention were compared with microcapsules related to state-of-the-art technology (Comparative Example 13), that is, the slurries of microcapsules manufactured as described above were compared.

[0400] 0.3 g of the obtained core-shell microcapsules were dispersed in 30 g of commercially available fabric softener (Downy® Ultra Free & Gentle® Liquid Fabric Conditioner, Proctor & Gamble) and aged for at least one week, preferably for one, two, and four weeks, respectively (shown as the one-week sample, two-week sample, etc. in the figure). To evaluate the sensory properties, each of the different fabric softener samples (each containing different microparticles) was added to 10 cotton-based face towels (small towels) and 10 cotton-based hand towels (large towels). For reference, 0.1 g of aromatic oil (TomCap® Symrise, Teterboro, NJ) was directly dispersed in 30 g of fabric softener.

[0401] The washing instructions are as follows: Place the towel (cotton cloth) in the washing machine, age the fabric softener containing the corresponding core-shell microcapsules or pure unencapsulated fragrance oil (see reference) for the time indicated above, add it to the fabric softener dispenser, and start the washing program (device: automatic washer-dryer: Whirlpool® (USA); washing cycle: normal wash; washing temperature: warm (32-44°C); load: normal).

[0402] After washing, the towels were divided into two groups and air-dried by hanging them on a clothesline (indicated as "rope drying" in the diagram) or mechanically dried in a dryer (indicated as "dryer drying" in the diagram). The towels were then labeled correspondingly and stored in a large plastic bag until testing.

[0403] The fragrance was released in three steps, and the intensity of the released fragrance was evaluated by 10 trained panelists. Intensity was determined by blind evaluation on a scale ranging from 1 (odorless) to 6 (very strong). Step 1 describes smelling an untreated, as-prepared towel. Step 2 describes smelling a lightly crumpled towel; for this purpose, the towel was subjected to slight mechanical stress by rubbing. Step 3 describes smelling a towel after it has been vigorously rubbed back and forth between the hands several times, mechanically breaking the capsules and releasing the encapsulated aromatic oil. After each step, the panelists evaluated the fragrance intensity.

[0404] The composition of the microcapsules used for comparison is summarized in Table 3 below.

[0405] [Table 3-1] [Table 3-2] [Table 3-3]

[0406] The formulations of the microcapsules prepared according to Examples 1-6 (Figures 1A / B and 6A / 6B) were compared with those of standard polyurea microcapsules prepared according to Comparative Example 13.

[0407] The performance of bio-based (amino)sugar-based microcapsules using sugars and / or amino sugars having fewer than 20 monomer units as constituent elements is comparable to, and even slightly better than, the performance of guanidine-crosslinked polyurea-based microcapsules relating to state-of-the-art synthesis techniques after mechanical drying. However, for rope-dried samples, significantly higher fragrance intensity was observed in samples treated with the fabric softener containing the bio-based (amino)sugar-based microcapsules of the present invention. Mechanical stress and heat were thought to increase the release of volatile substances from the emulsion-treated fabric. The lower fragrance intensity of towel samples dried in a dryer can be explained by increased microcapsule rupture due to mechanical shock in the dryer and increased evaporation due to heat.

[0408] However, the bio-based microcapsules of the present invention appear to be more stable than state-of-the-art, fully synthetic microcapsules, and can more efficiently suppress the evaporation of volatile fragrance components. The significant increase in strength after crumpling and / or rubbing (considerably greater than the capsules of the comparative example) indicates efficient encapsulation of fragrance substances. This is particularly evident based on Figures 6A and 6B. Experiments demonstrate the high mechanical and thermal stability (washer, dryer) of the capsules of the present invention while still allowing for the targeted release of active ingredients. Furthermore, the microcapsules of the present invention exhibit high chemical stability when incorporated into, for example, consumer product formulations and subjected to aging, enabling efficient encapsulation of active ingredients and effectively maintaining long-term product quality. Thus, the capsules of the present invention enable efficient encapsulation and excellent and targeted release of active ingredients. In addition, the microcapsules of the present invention are less affected by the drying process in a dryer compared to state-of-the-art, fully synthetic microcapsules. As a result, the bio-based core-shell microcapsules of the present invention are highly suitable for incorporation into various consumer product formulations.

[0409] Furthermore, samples of fabric softener containing a slurry of 0.3 wt% of each fragrance microcapsule of the present invention, as described in Examples 1-12, which contained 33 wt% active fragrance oil (equivalent to 0.1 wt% pure fragrance oil), were compared to 0.1 wt% fragrance oil directly incorporated into the fabric softener as a reference, and were compared on both machine-dried and rope-dried towels (Figures 1-12). While the free, unencapsulated fragrance oil evaporated rapidly and was undetectable after the drying process and storage, the bio-based microcapsules according to the present invention enabled stable encapsulation of fragrance substances, exhibiting excellent and targeted release behavior, resulting in a highly detectable fragrance intensity (i.e., high sensory performance).

[0410] The fact that efficient encapsulation of fragrance substances could be observed even after four weeks of aging in the fabric softener demonstrates the high stability of the core-shell microcapsules of the present invention within the fabric softener and, consequently, within the formulation of consumer products (see, for example, Figures 8A-8D; 10A-10D; 11A and 11B; and 12A-12D).

[0411] Furthermore, the microcapsules according to the present invention, having a shell with reduced thickness (see Examples 11 and 12), exhibit excellent performance and stability comparable to state-of-the-art microcapsules with considerably thicker shell walls.

[0412] As a result, it can be concluded that the bio-based core-shell microcapsules according to the present invention are more stable against mechanical shock and heat while simultaneously enabling the targeted release of the encapsulated active substance (see mechanically dried sample). Furthermore, the bio-based microcapsules of the present invention efficiently encapsulate active substances for more than four weeks in consumer product formulations, while state-of-the-art capsules suffer considerable loss of active substances over time (see rope-dried sample). Therefore, it can be concluded that the bio-based microcapsules according to the present invention demonstrate an improved balance of efficient encapsulation, stability, and targeted release characteristics / performance.

[0413] Evaluation of the biodegradation of the core-shell microcapsules of the present invention

[0414] The biodegradability of the core-shell microcapsules of the present invention was determined as follows.

[0415] The biodegradation of microcapsule slurries in the environment includes the biological degradation of polymer shells according to the present invention. The measurement of the biological activity or degradation of the shell material can be determined under different environmental conditions, particularly in soil, ocean, water, or sludge, under OECD guidelines.

[0416] OECD tests that can be used to determine the readily biodegradable nature of organic chemicals include six test methods described in OECD Testing Guideline 301AF: the DOC Die-Away test (TG301A), the CO2 evaluation test (TG301B), the modified MITI test (I) (TG301C), the sealed bottle test (TG301D), the modified OECD screening test (TG301E), and the pressure breathing measurement test (TG301F). The following pass levels of biodegradation obtained within 28 days may be considered evidence of readily biodegradable nature: 70% DOC removal (TG301A and TG301E); 60% theoretical carbon dioxide (ThCO2) (TG301B); and 60% theoretical oxygen demand (ThOD) (TG301C, TG301D, and TG301F). Further details can be found in the official OECD guidelines for testing chemicals: OECD (2006), Revised Introduction to the OECD Guidelines for Testing of Chemicals, Section 3, OECD Publishing, Paris.

[0417] Testing System

[0418] The test methods and test systems (inoculants) used for analyzing the biodegradability of microcapsules according to the present invention are consistent with the standard test guidelines and procedures in accordance with OECD 301F biodegradability testing.

[0419] Isolation of shell material (sample preparation)

[0420] The shell walls, which constitute 1-10% by weight of the entire core-shell microcapsule (after subtracting water), were obtained by removing water-soluble reagents (protective colloids, unreacted (amino) sugars and salts) by withdrawing and washing the payload (i.e., the core).

[0421] Shell isolation involves the following steps: 1) A step of washing with water to remove any soluble materials, followed by isolating the shell by centrifugation; 2) A step of solvent extraction of the hydrophobic "core" using an organic solvent, such as a lower alcohol or acetone; 3) This was achieved by a multi-step process that included the steps of heat-drying the obtained shell material to remove the remaining solvent and water, and then grinding it to obtain shell powder, i.e., shell material in powder form.

[0422] The isolation of the shell wall can also be achieved using other processes, such as freeze-drying, vacuum drying, or spray drying, or even more complex processes, such as supercritical CO2 extraction.

[0423] Biodegradation tests were performed on the isolated microcapsule shell powder as obtained, and the tests were conducted according to the standardized OECD 301F procedure. In the first biodegradation test, the microcapsule shell material from Example 1 was analyzed for its easy biodegradability using a pressure-breathing measurement test according to the standardized OECD 301F procedure, in accordance with the OECD Guidelines for Chemical Test No. 301F (1992) (Sample #1). According to the test guidelines, the biodegradation curve of the test item showed that biodegradation had begun but had not reached a plateau by day 28 of exposure, so the test was extended to day 45. Sample #1 was found to exhibit intrinsic primary biodegradability. In addition, the test item did not have an inhibitory effect on the activity of activated sludge microorganisms at the tested concentration of 100 mg / L. However, a second sample of the microcapsule shell material from Example 1 (Sample #2) showed that easy biodegradability was almost achieved (see Figures 13 and 14).

[0424] Analysis of comparative test samples corresponding to capsule shells prepared according to Comparative Example 13 and capsules disclosed in US6,586,107B2 indicates that these fully synthetic guanidine-based capsule materials are not biodegradable at all (see Figure 15). Therefore, based on the degradation curves, it can be concluded that the core-shell microcapsules according to the present invention are more biodegradable than the most advanced microcapsules currently available, and thus more preferable as a more eco-friendly consumer product.

[0425] consumer product formulation

[0426] The following describes various suitable consumer product formulations according to the present invention, including the core-shell microcapsules of the present invention, which enable efficient encapsulation and excellent release of active ingredients.

[0427] [Table 4]

[0428] [Table 5]

[0429] [Table 6]

[0430] [Table 7]

[0431] [Table 8]

[0432] [Table 9]

[0433] Table 10

[0434] Table 11

Claims

1. A core-shell microcapsule, wherein the shell comprises or consists of a polymer material which is a reaction product of two or more polyisocyanates having at least two isocyanate groups and at least one sugar and / or at least one amino sugar having less than 20 monomer units, wherein at least one of the two or more polyisocyanates having at least two isocyanate groups comprises an aliphatic structure, and the core comprises or consists of at least one active ingredient.

2. The core-shell microcapsule according to claim 1, wherein the sugar(s) and / or amino sugar(s)(s) are of biological origin.

3. The core-shell microcapsule according to claim 1 or 2, wherein the at least one sugar and / or at least one amino sugar has 15 or fewer monomer units.

4. The core-shell microcapsule according to claim 3, wherein the at least one sugar and / or at least one amino sugar has 10 or fewer monomer units.

5. The core-shell microcapsule according to any one of claims 1 to 4, wherein the at least one sugar and / or at least one amino sugar having less than 20 monomer units is selected from the group consisting of monosaccharides, aminomonosaccharides, disaccharides, aminodisaccharides, linear and / or branched oligosaccharides, and linear and / or branched oligomeric aminosaccharides.

6. The core-shell microcapsule according to claim 5, wherein the monosaccharide is selected from the group consisting of glucose, galactose, fructose, xylose, mannose, arabinose, erythrose, threose, ribose, lyxose, allose, altrose, talose, fucose, and rhamnose.

7. The core-shell microcapsule according to claim 5, wherein the amino monosaccharide is selected from the group consisting of glucosamine, galactosamine, and N-acetylglucosamine.

8. The core-shell microcapsule according to claim 5, wherein the disaccharide is selected from the group consisting of sucrose, lactose, maltose, isomaltulose, trehalose, lactulose, cellobiose, chitobiose, isomaltose, and maltulose.

9. The core-shell microcapsule according to claim 5, wherein the linear and / or branched oligosaccharide is selected from the group consisting of maltodextrin, raffinose, stachyose, fructo-oligosaccharide, merisitose, umbelliferose, and cyclodextrin.

10. The aforementioned at least one sugar and / or at least one amino sugar has primary and secondary amine groups (-NH) as well as primary and secondary hydroxyl groups (-OH). ２ A core-shell microcapsule according to any one of claims 1 to 9, having at least two functional groups independently selected from the group consisting of , -NH-.

11. The above-mentioned at least one active ingredient is a cosmetic active ingredient, pesticide, perfume substance, fragrance oil, aroma substance, aroma, active pharmaceutical ingredient, dye, UV active substance, optical gloss agent, thickener, drape and form control agent, smoothing agent, antistatic agent, wrinkle inhibitor, bactericide, disinfectant, bacterial control agent, antifungal agent, mold stain inhibitor, antiviral agent, antibacterial agent, drying agent, stain-resistant agent, stain-resistant agent (soil release agent), odor inhibitor, fabric deodorizer, dye fixative. Core-shell microcapsules according to any one of claims 1 to 10, selected from the group consisting of agents, color maintenance agents, color restorers / recovery agents, fade inhibitors, abrasion inhibitors, anti-wear agents, fabric preservatives, anti-wear agents, rinsing aids, UV protectants, sun-fading inhibitors, insect repellents, anti-allergic agents, fire retardants, waterproofing agents, fabric softeners, shrinkage inhibitors and / or stretch inhibitors, fluorescent paints, waxes, silicone oils, lubricants, coolants, and TRPV modifiers.

12. The core-shell microcapsule according to any one of claims 1 to 11, wherein the microcapsule has a volume-based median particle size (Dv(50)) of 1 μm to 100 μm.

13. The core-shell microcapsule according to claim 12, wherein the microcapsule has a volume-based median particle size (Dv(50)) of 5 μm to 55 μm.

14. The core-shell microcapsule according to claim 12 or 13, wherein the microcapsule has a volume-based median particle size (Dv(50)) of 5 μm to 50 μm.

15. The core-shell microcapsule according to any one of claims 1 to 14, wherein the shell of the microcapsule is intrinsically biodegradable in accordance with the OECD 301F biodegradability standard (pressure-breathing measurement test).

16. A microcapsule slurry comprising a plurality of core-shell microcapsules according to any one of claims 1 to 15 dispersed in an aqueous phase, wherein the concentration of the microcapsules in the aqueous phase is greater than 5% by weight and less than 70% by weight.

17. A microcapsule slurry according to claim 16, wherein the concentration of the microcapsules in the aqueous phase is greater than 20% by weight and less than 60% by weight.

18. A microcapsule slurry according to claim 16 or 17, wherein the concentration of the microcapsules in the aqueous phase is greater than 30% by weight and less than 50% by weight.

19. A process for preparing a slurry of core-shell microcapsules, comprising the following steps: (a) A step of providing an oil phase comprising a mixture of two or more polyisocyanates having at least two isocyanate groups, wherein at least one of the two or more polyisocyanates having at least two isocyanate groups includes an aliphatic structure, and one or more active ingredients; (b) Providing a first aqueous phase comprising at least one forming aid, which is a surfactant and / or colloidal protective agent; (c) A step of providing a second aqueous phase comprising at least one sugar and / or at least one amino sugar having less than 20 monomer units; (d) A step of mixing the oil phase and the first aqueous phase to obtain a provisional oil-in-water emulsion; (e) A step of mixing the second aqueous phase with the provisional emulsion obtained in step (d) to obtain a slurry of core-shell microcapsules; The process comprising (f) a step of curing the core-shell microcapsules obtained in step (e).

20. A process for preparing core-shell microcapsules by a process for preparing a slurry of core-shell microcapsules according to claim 19, wherein the process follows the process according to claim 19 (g) The process comprising the step of isolating the core-shell microcapsules from the slurry.

21. A process for preparing a slurry of core-shell microcapsules according to claim 19, wherein the molar ratio of at least one polyisocyanate having at least two isocyanate groups and including an aliphatic structure to at least one amino sugar having less than 20 monomer units is in the range of 1:3 to 1:

1.

22. A process for preparing a core-shell microcapsule according to claim 20, wherein the forming aid(s)(s)(s) are biopolymer derivatives(s). Or a process for preparing a slurry of core-shell microcapsules according to claim 19 or 21.

23. A consumer product comprising a core-shell microcapsule according to any one of claims 1 to 15, or a slurry of microcapsules according to any one of claims 16 to 18, wherein the product is selected from the group comprising cosmetics, personal care products, fabric care products and home care / household products, and pharmaceuticals, or the group comprising them.

24. The consumer product according to claim 23, wherein the personal care product is selected from the group consisting of skin cleansing products, shampoos, rinse-off conditioners, deodorants, antiperspirants, and body lotions.

25. The consumer product according to claim 23, wherein the fabric care product and home care / household product are selected from the group consisting of liquid detergents, all-purpose cleaning agents, laundry detergents and cleaning agents, fabric softeners, fragrance enhancers, and fragrance enhancers.

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