Bio-based core-shell microcapsules

Abstract

The present invention provides core-shell microcapsules, as well as processes for preparing such microcapsules, which are, on the one hand, highly biodegradable and 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 superior performance. [Solution] The present invention relates to (amino) sugar-based polyurea and / or polyurethane-based microcapsules containing at least one lipid-soluble active ingredient. Furthermore, it discloses a microcapsule slurry comprising a plurality of the core-shell microcapsules dispersed in an aqueous phase. In addition, the present invention relates to a process for preparing microcapsule slurries and bio-based core-shell microcapsules contained therein. The present invention relates to the use of such microcapsules according to the present invention, or microcapsule dispersion systems containing microcapsules, for the manufacture of various consumer products.

Description

[Technical Field]

[0001] This invention is based on existing fully synthetically produced segments that are not bio-based. The bio-based microcapsules according to the present invention have a larger market share than state-of-the-art microcapsules. To further biodegrade the capsule wall, natural (amino) sugar segments are added to the capsule wall. This relates to bio-based core-shell microcapsules containing [the specified substance]. More specifically, this [the specified substance] The invention relates to polyureas formed using monomers or short-chain sugars and / or amino sugars. It includes a microcapsule shell based on a polyurethane structure as a component. and containing at least one lipid-soluble active ingredient, commercially available state-of-the-art microcapsules In comparison to the high biodegradability, stability and performance (target release characteristics) in the product formulation. This invention relates to bio-based microcapsules having a good balance. Furthermore, the present invention relates to Multiple bio-based core-shell microcapsules (microcapsules) dispersed in the aqueous phase The present invention discloses a slurry containing a capsule dispersion system. In addition, the present invention discloses a slurry and itself This relates to a process for preparing core-shell microcapsules contained within. In a further embodiment, The present invention as described herein is for preparing various consumer products. Such microcapsules or microcapsule dispersions containing microcapsules Regarding the use of. Finally, the present invention also relates to the use of the microcapsules or microcapsules. This also applies to consumer products, including distributed systems. [Background technology]

[0002] Today, for example, there are many consumer products such as detergents, fabric softeners, powder detergents, and liquid detergents. Detergents, shower gels, shampoos, deodorants, lotions, etc. are scented with aromatic substances. It contains cosmetic ingredients that produce or have a specific effect. Unfortunately, for example, The fragrance substances or cosmetic ingredients in the product may interact with other ingredients in the product, or the fragrance may not be compatible with other ingredients in the product. Furthermore, the volatile components tend to evaporate faster than usual. This refers to the undesirable change and / or decline of the fragrance impression over time, or the cosmetic composition. This can lead to faster-than-usual "use" of the product, or furthermore, adverse interactions with other ingredients in the product formulation. This may cause a reaction that leads to a decrease in product quality and / or stability. Other components of the product To prevent possible interactions between fragrances or other active ingredients, or, for example, the volatilization of fragrances To prevent this and to avoid distorting or reducing the desired olfactory impression, fragrance or other effective The ingredients can be added to the formulation in an encapsulated form. Thus, for example, desired It can guarantee the olfactory impression. Furthermore, it reduces interactions between product ingredients and improves product quality. Furthermore, it can improve storage stability.

[0003] Encapsulation protects the active ingredient (also known as an active substance or active ingredient) and caps To release the material forming the cell core in a targeted manner at a specific point in time. It is a common technique used. In addition, some active ingredients are used for various reasons. Often, they cannot be used as is (for example, due to their solubility, reactivity, stability, etc.). However, based on the encapsulation method and the selected material, the effectiveness of lipophilic or hydrophobic encapsulation depends on the method. Ingredients, such as fragrances, cosmetic ingredients, or flavorings, can be easily and stably incorporated into various product formulations. Because it can be absorbed, it can interact with scented products or highly volatile fragrances. Reduces or completely prevents evaporation of the components.

[0004] The contents of core-shell microcapsules can be released by various methods, for example crushing or shearing to mechanically break the capsule wall, break the capsule by melting the wall material, break the capsule by dissolving the wall material, or diffusion of the active ingredient through the capsule wall after activation . Alternatively, biological or enzymatic interactions may break the shell wall to release the active ingredient(s) in a targeted manner.

[0005] Interfacial polymerization is an efficient and common encapsulation process for producing core-shell microcapsules, by which a suspension starting from an initial emulsion or suspension of hydrophobic core material, that is the active ingredient, in water is produced. A monomer or reagent in the aqueous phase diffuses across the interface and reacts with a reactant in the oil phase, or the monomer in the aqueous phase reacts with itself, depositing on the layer around emulsion droplets or on dispersed liquid particles of the core material and polymerizes to form a compact crosslinked and continuous capsule shell. Depending on the wall material and the degree of crosslinking, various properties of the microcapsules can be achieved.

[0006] Polyurea-based, polyurethane-based, or mixed polyurea / polyurethane 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 capsules currently under development For compounding, emulsion stabilizers (e.g., surfactants or protective colloids) are used along with , at least one polyfunctional amine (e.g., guanidine salt, aromatic polyamine, aliphatic) Polyamines, or alkyl polyamines) and / or at least one polyol ( (Riceol, alkyl oxides, alkylene oxides, aliphatic polyols, and aromatic polyols) The use of fragrances dissolved in at least one polyisocyanate dispersed in an aqueous phase containing Use is involved. Alternatively, the liquid core of the emulsion adsorbs to the interface between the two liquid phases. Instead of protective colloids and / or surfactants, solid particles smaller than 1 μm in size (e.g.) It is stabilized by using starch, silica, and metal oxides (so-called pitting). (Culling emulsion).

[0008] The shell initially forms rapidly through the diffusion of small monomers, i.e., the components of the shell. This is accomplished. However, as the shell grows, mono flows through the shell towards the oil phase. The diffusion rate of the mer decreases, and the rate of the shell formation reaction decreases. In the case of a large monomer, on the other hand, diffusion into the reaction region (i.e., the oil phase) is hindered, The process gradually slows down, and therefore only the surface-crosslinked structure is formed, resulting in the aforementioned larger structure. This leads to a decrease in the reaction of the element with polyisocyanate, and together with the reduced mechanical stability, the capsule Due to the high porosity of the capsule wall, the active ingredient diffuses out of the capsule prior to its intended release. This causes... In addition, these formulations for the preparation of oily core-shell microcapsules... It is retained as a forming aid that is placed on the surface of the oil droplets in the emulsion to reduce the surface tension of the aqueous phase. Protective colloids, for example, polyvinyl alcohol (PVA), polyvinylpyrrolidone, water-soluble. Acrylate copolymer, modified starch, gelatin, acacia gum, carboxymethyl carboxylate Cellulose derivatives such as luluose, and other large polysaccharides, and / or surface-active The use of nonionic, cationic, or anionic substances (so-called surfactants) is required. Therefore, as diffusion is hindered, the constituent elements toward the interface between the oil phase and the aqueous phase Due to the reduced degree of basic diffusion, polyisoscia in the oil phase on the surface of the oil droplet Interfacial polymerization reactions between the nate and polyamines and / or polyols in the aqueous phase are limited. Therefore, similarly, a surface-crosslinked structure with a limited degree of urea / urethane-based linkage To occur.

[0009] However, state-of-the-art core-shell microcapsules are made from their completely synthetic shell material. However, they have the disadvantage of being mostly stable to hydrolysis and resistant to environmental degradation.

[0010] Non-biodegradable plastic particles are increasingly facing public criticism regarding their environmental impact. This is because it can lead to increasing social pressure, as well as environmental and health issues. New and future regulations by regulatory authorities (governments, national and local) regarding plastics Therefore, the demand for bio-based and even biodegradable solutions is increasing, Reducing microplastics and further developing eco-sensitive products, preferably bio-based products. To achieve increased biodegradability, the development of new encapsulation materials is necessary. Therefore, today, bio-based and biodegradable materials are the focus of attention.

[0011] These state-of-the-art microcapsules, manufactured by interfacial polymerization, are largely biodegradable in the environment. There is no direct negative environmental impact or the production of non-biodegradable residues. (By doing so), or by demonstrating sufficient stability for efficient encapsulation of the active ingredient No, polyurea, polyurethane, aminoplast, polyacrylate are derived entirely through synthesis. Based on the structure of a ring, or a mixture of these structures. Therefore, not only synthesis, but also rings. There is a growing need for microcapsules that are both biodegradable and highly stable.

[0012] Furthermore, the first step toward natural-based products is, for example, the addition of microcapsules. Instead of substances like polyaldehydes and polyvalent salts for qualitative analysis, a polyurethane-based solution is used. As an additional coating on the Ashel substrate, high molecular weight maltodextrin and chitosa By using high molecular weight polysaccharides and aminopolysaccharides such as n, the "biodegradability" label is created. A non-degradable core-shell capsule base called "greenwash" to achieve elephants This is done by preparing a biodegradable coating on the material. However, Tosan dissolves in acidic solutions at a rate of only a few percent, so it can be directly incorporated into the shells of microparticles. Incorporation is strictly restricted. Furthermore, biodegradable starch and cellulose are used in synthetic polymers. Attempts were made to partially incorporate it to achieve the impression of high "biodegradability."

[0013] For example, WO2020 / 058044A1 (Givaudan) is dispersed in a dispersion medium. The text describes consumer products containing multiple microcapsules, and in doing so, the microcapsules The shell is coated with chitosan, and the dispersion medium contains additional free chitosan. Therefore, the amount of free chitosan contained in the dispersion medium is preferably 500,000 g / mol ~ 3. It has a molecular weight between 000,000 g / mol and coats the microcapsule shell. The chitosan used is preferably in the molecular weight range of 30,000 g / mol to 300,000 g / mol. The quantity differs.

[0014] WO2019 / 175017A1 (Givaudan) requires at least 1 in the suspension medium. A composition comprising a core-shell microcapsule is disclosed, wherein the shell is Myropectin, dextrin, hyperbranched starch, glycogen and phytoglycogen and A 1,4-glycosidic bond of 1,6-glycosidic bonds selected from the group consisting of mixtures thereof. These microcapsules contain hyperbranched polysaccharides with a specific ratio of side bonds. It exhibits improved precipitation behavior and improved rinsing resistance on the Chin substrate.

[0015] US2020 / 0046616A1 (International Flavor and Aroma) is polyurea-based and Polyurethane-based capsule composition, as well as polyisocyanate, pectin, chito Sun, arginine, lysine, polylysine, protein, gelatin, guar gum, and hydr An activated emulsion containing one or more materials selected from the group consisting of oxyethylcellulose. The text describes a method for preparing capsule compositions based on the formula.

[0016] Microcapsule composition conforms to WO2019 / 210125A1 (International Flavor and Aroma). This is disclosed, and in this case, the polymer to be encapsulated is a polyfunctional electrophile and a polyfunctional It contains a polyurea polymer, which is a reaction product with a nucleophile, and the polyfunctional electrophile is a polyurea polymer. It contains lyisocyanate, and the polyfunctional nucleophile has a molecular weight of >30,000 g / mol. It contains polyamines such as chitosan.

[0017] WO2019 / 179939A1 (Firmenich) has an oil-based core and low-voltage Monomers and A shell formed from the reaction between modified starch, which serves as the main shell material. The microcapsule is being disclosed.

[0018] US5,780,060A(Centre National de la Rech (erche Scientifique) is crosslinked at the interface by a halogenated dioxide compound crosslinking agent. Cross-linked at least one plant polyphenol and at least one plant polyphenol Co-crosslinked proteins, polysaccharides, polyalkylene glycols, or mixtures thereof, etc. This relates to microcapsules containing a wall formed from them.

[0019] Chitosan used in cutting-edge technology is derived from approximately 2000 monomers (or monomer units). It is a natural biopolymer (biomolecule) derived from chitin, and more specifically, β It consists of units of N-acetylglucosamine and D-glucosamine linked by -1,4 glycosidic bonds. It is a high-molecular-weight amino sugar (also called polyamino sugar). Commercially available chitosan is usually low in quantity. It exhibits a high molecular weight of at least 30,000 g / mol. As shown above, chitosan Organic acids are only able to be incorporated into the microcapsule shell composition in a small amount. For example, there are limitations to its solubility in formic acid, acetic acid, or citric acid. In addition, the bulkiness of the substance. This hinders efficient crosslinking. As a result, large chitosan molecules become co-shells. The wall structure of the microparticles forms a coating rather than being a component of the particle itself. As a result, For microcapsules containing bulky polymers like the one described above, there is a decrease in stability and performance. It is expected.

[0020] From the above perspective, the present invention is, on the one hand, highly biodegradable and more environmentally friendly, and On the other hand, storage stability (especially in product formulations) and excellent release behavior of the active ingredient are important. In other words, a core-shell microcapsule that exhibits superior performance, as well as such a microphone This is based on the complex challenge of providing a process for preparing locapsules.

[0021] Manufacturing microcapsules that possess both good stability and good release characteristics is particularly difficult. The capsule's ability to retain the active ingredients and thus prevent the loss of volatile components is essential for the product. It particularly depends on the stability of the capsule in the formulation. Shell composition, and therefore the capsule The stability and biodegradability of the capsule are primarily influenced by the starting materials used. The release behavior is primarily influenced by the shell's composition, morphology, and thickness. Capsules with good qualitative properties do not exhibit good biodegradability in the natural course of events. Degree of cross-linking As the amount increases, the stability of the microcapsules generally improves, while at the same time, the capsule size The ability to biodegrade the material tends to decrease. In addition, the highly stable microcapsules Therefore, it exhibits low performance in destroying microcapsules, so the release of active ingredients (multiple ingredients possible) It will be disrupted. However, if the microcapsules are too unstable, they will already be destroyed during storage. This results in either leakage of the active ingredient or other issues, and neither method works.

[0022] Therefore, the present invention preferably exhibits high biodegradability and, at the same time, outstanding stability and A capsule wall that exhibits superior release characteristics, i.e., capsule performance, and is more environmentally compatible. We are focusing on providing microcapsules based on materials. Rather, each of the fragments created during the collapse must also be environmentally compatible. It is essential.

[0023] Therefore, the objective of the present invention is to provide a sustainable and environmentally friendly mineral with high biodegradability. Kurocapsules, particularly at least one hydrophobic active ingredient, preferably state-of-the-art microcapsules Compared to capsules, it exhibits a good balance of improved biodegradability, stability, and performance, and has a single odor. Aromatic substances consisting of compounds or mixtures of odor compounds or perfume mixtures or cosmetic ingredients Similar to microcapsules, a dispersion system of such microcapsules (microcapsules The objective is to provide a process for preparing a slurry.

[0024] The object of this invention is also environmentally sustainable microclaving, which has the added benefit of high biodegradability. The objective is to provide consumer products containing microcapsules, similar to capsules.

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

[0026] Surprisingly, this substance, as a major component in the capsule wall, is biodegradable itself. Cross-linked bio-based or natural low molecular weight or short-chain materials, especially 20 The present invention contains a natural (amino) sugar segment having a monomer unit of less than a certain amount. It has been found that this can be solved by io-based core-shell microcapsules. The incorporation of these bio-based / natural materials into the capsule shell via reaction was achieved. Compared to cutting-edge non-biobased capsules, it has superior biodegradability and is even more beneficial to the ecosystem. It produces a capsule material that contains active ingredients such as fragrances, cosmetics, and vitamins. Such core-shell microcapsules containing as A contain a reactive crosslinking agent and one or more -OH group and / or one or more -NH- or -NH2 groups and / or one or more -SH groups Functional monomers, dimers, oligomers and / or short-chain polymers having (amino ) Can be efficiently formed via interfacial reactions between sugars and / or corresponding thiosugars. In addition, these microcapsules are very (especially in product formulations) It is stable, and even after long-term storage in the aforementioned product formulation, the state-of-the-art microcapsules remain intact. It was found to exhibit superior emission characteristics compared to the previous method. The shell wall portion was significantly reduced. Even with microcapsules having a certain thickness, these excellent and balanced capsules are also remarkable. The following characteristics have been identified (see Examples 11 and 12). [Overview of the initiative]

[0027] In a first aspect, the present invention relates to bio-based core-shell microcapsules. Yes, and in that case, the shell composition has at least 1 isocyanate group having at least 2 isocyanate groups One polyisocyanate, preferably at least two such polyisocyanates A mixture and less than 20 monomer units, preferably 15 monomer units or less, more preferably or at least one sugar and / or having 10 or fewer monomer units independently. with at least one amino sugar (i.e., repeating unit or monomer (amino) sugar unit) The capsule contains or consists of a polymer material which is a reaction product, and the capsule core is small It contains or consists of at least one active ingredient.

[0028] In a second aspect, the present invention provides a plurality of core-shell micro-electrode This relates to a slurry of microcapsules containing capsules, preferably containing water. The concentration of microcapsules within the phase is greater than 5% but less than 70%, preferably greater than 20%. Less than 60%, most preferably more than 30% but less than 50%.

[0029] In a third aspect, the present invention relates to a slurry of microcapsules (i.e., microcapsules This relates to the process of preparing a dispersed system, and the steps are as follows: (a) at least one polyisocyanate having at least two isocyanate groups Preferably a mixture of at least two such polyisocyanates and one or more, The process involves providing an oil phase containing hydrophobic active ingredients (multiple ingredients are possible); (b) a step of providing a first aqueous phase comprising at least one capsule-forming agent; (c) At least one sugar having less than 20 monomer units each independently and / or It contains at least one amino sugar, and optionally the aqueous phase further comprises one or more capsule-forming aids. A step of providing a second aqueous phase containing (or multiple) elements; (d) A step of mixing the oil phase and the first aqueous phase to obtain a provisional oil-in-water emulsion; (e) Mix the second aqueous phase with the provisional oil-in-water emulsion obtained in step (d) and micro The process of obtaining the capsule slurry; (f) A step of curing the microcapsules obtained in step (e).

[0030] Optionally, the process may include an additional step (f2), in which natural gum (e.g., xanthan gum) may be added. Gum, gellan gum, diutan gum, cellulose gum) or other non-gum suspension aids, for example For example, microcrystalline cellulose (Vivapur®, J. Rettenmeier) One or more suspension aids or structuring aids selected from & Soehne GmbH+Co) It is added as a thickening agent to provide high suspension stability.

[0031] In another embodiment, the present invention relates to a process following or in place of process (f2). (g) Isolate core-shell microcapsules from the slurry and obtain the isolated core as is. A slurry is prepared, which includes a step of drying the shell microcapsules as described above. This relates to a process for preparing bio-based core-shell microcapsules. ru.

[0032] In yet another aspect, the present invention is obtained by the process according to the present invention as described above. Regarding slurries containing core-shell microcapsules (i.e., microcapsule dispersion systems) Furthermore, the present invention also provides a coacheal sheath obtained by the process according to the present invention. This also relates to microcapsules.

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

[0034] Finally, the present invention relates to a bio-based core-shell microcapsule or the present invention. This relates to a consumer product containing a slurry of microcapsules according to the invention, and in that case, Consumer products include, in particular, cosmetics, personal care products, and especially skin cleansing and skin care products. Shampoo, rinse-off conditioner, deodorant, antiperspirant, body lotion, fabric care A products, and home care / household products, especially liquid detergents, all-purpose cleaners, laundry detergents and cleaning agents, fabrics This consists of fabric softeners, fragrances, aroma enhancers in liquid or solid form, as well as pharmaceuticals. Selected from the group.

[0035] Surprisingly, the bio-based core-shell microcapsules according to the present invention have high bioavailability. It exhibits decomposability while simultaneously showing high mechanical, thermal, and chemical stability, as well as excellent release properties. It was found to indicate sex.

[0036] These and other aspects, features and advantages of the present invention are described in the following detailed description, drawings and patent credits. This will become clear to those skilled in the art by examining the framework. Each feature derived from one aspect of the present invention is This invention may be used or replaced in other embodiments of the present invention. The present invention will be described without limiting itself to the embodiments described herein.

[0037] The term "sugar" is used herein to mean "sugar," "amino sugar," and / or " It is understood that it encompasses the characteristic of "thiosaccharides," for example, "sugar-based" When referring to "microcapsules of," use components as defined herein. This refers to all deformations of the microcapsules formed, i.e., less than 20 monomers. Units, preferably 15 monomer units or less, and even more preferably 10 monomer units or less per layer Sugar components, amino sugar components, and / or thio sugar components, each having an independent position. It refers to a capsule formed based on polymerization.

[0038] When the terms "at least one" or "one or more" are used herein, they mean one or more. It refers to and is used synonymously with "at least two" and "two or more" or "more than one". When used in this specification, the term refers to 2, 3, 4 or more, and is used synonymously.

[0039] Numerical examples given in the form "x~y" include the values ​​mentioned. Some preferred numbers When the range is given in this form, it also includes all ranges resulting from different combinations of endpoints. Born. [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 the first aspect, the present invention relates to a bio-based or (amino) sugar-based core shell. This relates to microcapsules, in which the shell contains at least two isocyanates. At least one polyisocyanate having a t group, preferably at least two each A mixture of at least two polyisocyanates having an isocyanate group, and less than 20 Each monomer unit has independently, that is, less than 20 monomer units (monosaccharide units) A minimum of (a) containing (a) and / or monomer amino sugar units) and preferably consisting thereof. It also contains polymer materials that are reaction products with one sugar and / or at least one amino sugar. or consisting thereof, the core preferably having at least one which is hydrophobic in nature It contains or consists of an active ingredient, such as 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) oligomeric amino sugars (also known as oligoamino sugars), or mixtures of these monomers, dimers, or oligomers in any combination. It is a substance. However, they are less than 20 monomer units, preferably 15 or fewer. Mer units, more preferably containing 10 or fewer monomer units, or composed of therefrom As far as possible, short-chain polymer structures are also suitable as constituent elements.

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

[0068] In the context of the present invention, the microcapsule contains at least one core material inside the capsule. It contains one or more active ingredients and is enclosed by a capsule shell or capsule wall. These are microparticles produced by interfacial polymerization. The active ingredient is preferably hydrophobic. Alternatively, it is a lipid-soluble active ingredient. Such active ingredients are insoluble or sparingly soluble in water. However, it is highly soluble in fats and oils. The terms are used synonymously within the context of this invention, and the terms "hydrophobic" and "lipid-soluble," and " The terms "shell" and "wall" are similar examples.

[0069] In the context of the present invention, the capsule shell or capsule wall is preferably as specified herein. As described above, it reacts and is crosslinked by isocyanate, resulting in excellent release properties, that is, A capsule with release capabilities that is stable, highly efficient, and at the same time highly biodegradable. Based on sugars and / or amino sugars that produce sugars.

[0070] Surprisingly, the present invention's bio-based / (amino) sugar-based core-shell micro The capsule is based on a completely synthetic structure, more specifically, a guanidine-based component. Compared to state-of-the-art microcapsules based on the standardized OECD 301F test procedure It was found that it has high biodegradability according to the following (see Figures 13-15 and 16-19). It was revealed that while completely synthetic capsules using cutting-edge technology exhibit almost no biodegradability, The capsule shell of the present invention exhibits considerably high biodegradability according to the OECD 301F biodegradability standard. This indicates.

[0071] At the same time, the microcapsules of the present invention appear to be dispersed by a rotary dryer or heat. It exhibits high mechanical and thermal stability against mechanical influences, and similarly, for example, in product formulations. It exhibits high chemical stability within the body, while simultaneously ensuring efficient distribution of the active ingredient(s) and targeting of the target area. Gunar enables release. In addition, sensory experiments in the case of fragrance as an active ingredient Although a high aroma intensity could be detected, this was because the aroma was contained within the core-shell microcapsule of the present invention. This suggests that the fragrance is efficiently encapsulated, and that the active ingredients do not diffuse out of the microcapsules. This demonstrates an efficient reduction of losses caused by (see Figures 1-12). At the same time, this This also demonstrates an efficient balance between the performance and stability of the aforementioned capsule. Furthermore, the microcapsules of the present invention are used in consumer products such as fabric softeners for at least four weeks. It showed high stability within the molecule. As a result, contrary to the teachings of cutting-edge technology, the bio-based composition Despite being based on minute-by-minute calculations, it enables efficient encapsulation of active ingredients and simultaneously high performance. This made it possible to create extremely stable microcapsules.

[0072] As a result, (amino) sugar components (and / or thio sugar components) are subjected to biological attack and Since it serves as a site for decomposition, the overall environmental impact of the microcapsules according to the present invention A significant reduction was found. As a result, the bio-based core-shell microphone of the present invention Rocapsules differ from state-of-the-art microcapsules primarily in their significantly high biodegradability. Furthermore, it is more environmentally friendly and even more suitable for developing efficient consumer product formulations.

[0073] As a result, in a preferred modification, the present invention relates to a core-shell microcapsule according to the first embodiment. This relates to the fact that, in this case, the microcapsules are more advanced compared to state-of-the-art microcapsules. It exhibits biodegradability, preferably is intrinsically biodegradable, and more preferably is readily biodegradable. Therefore, it has high biodegradability according to the OECD 301F biodegradability standard (pressure breathing measurement test). It indicates sex. In some cases, the exam was extended to 45 days according to the official examination procedures. .

[0074] However, preferably a mixture of two or more polyisocyanates is used for the formation of the capsule wall. , in other words, they are used as isocyanate components or crosslinking agents. These are even more stable Furthermore, it produces high-performance microcapsules, and consequently, improved capsule characteristics. For example, polyisocyanates having an aliphatic structure are volatile materials such as aromatic materials. More stable core-shell microcapsules that enable efficient encapsulation of active ingredients. This results in a combination of two or more different polyisocyanates, which in terms of capsule properties is particularly If at least one of these polyisocyanates is an aliphatic polyisocyanate or, instead, all of the polyisocyanates contained in the mixture are aliphatic in nature. This is advantageous in cases where (see, for example, Examples 3 and 4), and in terms of stability and performance, that is, It has been observed that this enables the formation of capsules with improved properties, such as release behavior. It is.

[0075] Therefore, in an alternative embodiment, a core-shell microcapsule is disclosed, In this case, at least two isocyanate groups, i.e., two or more isocyanate functionalities At least one of the one or more polyisocyanates is, as specified herein, It includes an aliphatic structure, preferably an alicyclic structure. Therefore, preferably at least two a The core of the present invention is at least one aliphatic polyisocyanate having a socianate group. It is used in the preparation of shell microcapsules. In that regard, this aliphatic polyisocyanate The phosphate is a mixture with other aliphatic polyisocyanates, or alternatively, aromatic polyisocyanates. A mixture with anate, or a mixture with further aliphatic and aromatic polyisocyanates. It can be used in [location / service].

[0076] Therefore, one embodiment of the present invention uses one or more aliphatic polyisocyanates to prepare A product is made of, or at least one aliphatic polyisocyanate, each with less than 20 mo Reaction with at least one sugar and / or at least one amino sugar having nomeric units. This invention relates to microcapsules containing a product according to the present invention.

[0077] In another preferred embodiment, the capsule contains at least one aliphatic polyisocyanate It is prepared using a mixture of at least one aromatic polyisocyanate and is highly efficient. It produces microcapsules.

[0078] In that regard, preferably at least one aliphatic polyisocyanate The molar ratio or weight ratio to aromatic polyisocyanate, more preferably the molar ratio Preferably based on an amino sugar having more than one monomer unit. For microcapsules containing (see Example 11), the ratio is 85:15, and further layers are used. Preferably, the ratio is in the range of 90:10 to 99:10. Therefore, at least one aliphatic compound is present. The molar ratio or weight of at least one polyisocyanate to one aromatic polyisocyanate The quantity ratio, and more preferably the molar ratio, is preferably greater than 1 monomer unit. For microcapsules preferably based on or containing amino sugars, 85: Higher than 15, preferably higher than 90:10. Based on these ratios, stability is high. However, at the same time, it is a capsule that exhibits superior performance and high stability within the product formulation (target release rate). (In terms of movement) it can be prepared.

[0079] Preferably, when a mixture of two or more polyisocyanates is used, the mixture is Contains or consists of more than 80 mol% aliphatic components / polyisocyanates. In other words, the mole fraction of the aliphatic component / polyisocyanate is preferably greater than 1. For microcapsules based on or containing amino sugars having units, see Isosia. The mixture of nates contains more than 80%, even more preferably 81%, and even more preferably less At least 85 mol%, and most preferably 90 mol%, is preferable. Surprisingly Having such a high molar content of aliphatic isocyanates relative to the total isocyanate content The microcapsules were aged for 4 weeks in a liquid product such as fabric softener. It exhibits excellent stability and performance even after the process, thus improving the overall balance of the capsule characteristics. It was found that these superior properties are achieved with a significantly reduced shell content. This is particularly surprising for microcapsules whose shell thickness has been significantly reduced. This is the case (see Examples 11 and 12 and Figures 11-12).

[0080] Enhanced crosslinking, and therefore polymerization, of polyisocyanates is preferably 15 Hereinafter, more preferably sugars having 10 or fewer monomer units independently, and / Alternatively, this may be achieved with respect to amino sugars, and furthermore, a stable and high-performing capsule may be produced. To drip. In addition, for these capsules, the balance between stability, release performance and biodegradability is favorable. The above balance could be observed. The same is true for the corresponding thiosaccharides. Furthermore, it is even more preferable Or, one or more sugars and / or one or more amino sugars are monomers, most preferably so This is glucosamine.

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

[0082] The constituent elements, namely isocyanate components (multiple) and (amino) sugar components (multiple) To achieve efficient encapsulation based on polymerization with (several possible) sugars, at least one sugar and / or at least one amino sugar is a polyurethane and / or polyurea-based binder. Primary and secondary hydroxyl groups (-OH) that enable the formation of primary and secondary hydroxyl groups (-OH) At least two functional groups independently selected from the group consisting of mine groups (-NH2, -NH-) It is also necessary that the group be included.

[0083] Alternatively, or in combination with the above-mentioned (amino) sugars, thiosaccharides can be suitably used. This can be done, and it involves a polythiourethane structure / connection between the components, or the aforementioned polyurethane It is possible to form these mixtures with 1 or more polyurea-based links. It has the functional thiol group (-SH) shown above.

[0084] The eco-friendly core-shell microcapsules of the present invention efficiently contain various active ingredients. Because it enables cell formation, it can be incorporated into a wide range of consumer product formulations.

[0085] Suitable active ingredients include, for example, hair conditioning agents or active ingredients in skin products. For example, skin moisturizers, anti-wrinkle agents, skin conditioning agents, skin whitening agents, anti-acne agents. Fragrance refers to a single fragrance substance or perfume substance, as well as the active ingredient in cosmetics such as agents. A fragrance or perfume (also called an odorant or aromatic substance), that is, a substance that has a smell or odor. This includes all compounds that impart odors, and by extension, all natural and synthetic substances that impart odors that can be perceived by the sense of smell. or a composition of one or more aromatic or perfumed substances, that is, a mixture of the aforementioned compounds or a mixture containing the aforementioned compounds, and / or other perfume components, fragrance oils, aromatic substances, and / or aroma. Further suitable active ingredients include, for example, pesticides, active pharmaceutical ingredients, Dyes, UV-active substances, optical gloss agents, thickeners, drape and foam control agents, Lubricant, antistatic agent, wrinkle preventative, disinfectant, antibacterial agent, antifungal agent, antifungal agent, mold stain remover Inhibitors, antiviral agents, antibacterial agents, desiccants, stain-resistant agents, anti-fouling agents, odor inhibitors, fabric deodorizers, Dye fixatives, color maintenance agents, color restorers / recovery agents, fade prevention agents, abrasion prevention agents, wear-resistant agents, Fabric preservative, abrasion inhibitor, rinsing aid, UV protectant, sun-fading inhibitor, insect repellent, anti-allergic agent. Energy agents, fire retardants, waterproofing agents, fabric softeners, shrinkage and / or stretching agents, fluorescent paints, solvents The above-mentioned effective solutions include fertilizers, waxes, silicone oils, lubricants, coolants, TRPV preparations, and others. It is a mixture of components.

[0086] However, preferably the active ingredient is a fragrance / perfume substance, or as defined above. Such compositions, i.e., substances or mixtures of substances that impart an olfactoryly perceptible odor. , fragrance oil or cosmetic ingredient, preferably formed by the core-shell microcapsules of the present invention These encapsulated fragrance / perfume substances or compositions give consumer products a pleasant scent. It is being granted.

[0087] The core-shell microcapsules according to the present invention are preferably contained within the microcapsule dispersion system. In other words, within the microcapsule slurry, 1 μm to 100 μm, preferably 5 μm A volume-based median particle size (Dv(50)) of ~55 μm, most preferably 5 μm to 50 μm. It possesses. In that regard, the (Dv(50)) value refers to the volume distribution of particles, and half of the population has this It is defined as a particle size that falls below a certain value.

[0088] The diameter of the microcapsules is preferably Malvern Mastersizer 3 Determined by laser diffraction using 000 (according to the manufacturing instructions). The measured intensity values ​​of the scattered light are, for example, preferably, used in Fraunhofer's diffraction / approximation. Therefore, we calculate the (Dv(50)) value. The (Dv(50)) value is 50 microcapsules. The product percentage is finer than the (Dv(50)) value, and 50 volume% is coarser. Therefore, ( The Dv(10) and Dv(90) values ​​represent the total volume of capsules in the sample, respectively. 10% and 90% indicate values ​​smaller than these.

[0089] If the median particle size of the core-shell microcapsules is within this range, then fabric care products and skin care products are suitable. This improves the delivery of active ingredients in applications such as care products and personal care products. Large particles, especially those larger than 100 μm, do not have much effect on the delivery of active substances to the surface. It is not effective, cannot be stably incorporated into product formulations, and may aggregate. Furthermore, they are difficult to suspend in aqueous formulations or product formulations, and have a large tactile (roughness) This results in a problem that is unfavorable for most intended uses. In addition, the particle size is fixed as described above. Within the defined range, an enhanced balance between stability and release performance can be achieved. .

[0090] Preferably, however, the microcapsules of the present invention are in the form of a slurry, that is, It is obtained as finely dispersed microcapsules in the aqueous phase (microcapsule dispersion system). , and are stored. The use of such slurries allows for the application and incorporation into product formulations. This makes storage easier and allows for enhanced storage without particle buildup or oxidation. Furthermore, the use of such dispersion systems is protected from friction, heat, or rings. It enables the efficient release of active ingredients in response to external forces such as environmental changes. In addition, consumers The stability of active substances in relation to environmental conditions of the product formulation (such as the pH of the consumer product base) is determined by the release process. It is possible to enhance the release of active substances based on the reception of signals (friction, pH changes, heat, etc.). Cut.

[0091] The present invention relates to a microcapsule comprising multiple bio-based core-shell microcapsules. Rally can be effectively incorporated into a variety of different applications, particularly in liquid (product) formulations. The core-shell microcapsules of the present invention exhibit high stability within a dispersion system (slurry) and long-term This allows for extended storage time and easy incorporation into consumer product formulations and application.

[0092] Therefore, another object of the present invention is a plurality of core shells according to the present invention dispersed in an aqueous phase. This relates to a slurry of microcapsules containing chlorocapsules, preferably the In this process, the concentration of microcapsules in the aqueous phase is preferably more than 5% by weight and less than 70% by weight. More than 20% by weight and less than 60% by weight, most preferably more than 30% by weight and less than 50% by weight. That is the case.

[0093] In a further embodiment, the present invention provides a method for preparing a slurry of microcapsules according to the present invention. Regarding the process. Slurry of core-shell microcapsules, and subsequent isolation Core-shell microcapsules are also produced through the following process: (a) at least two isocyanate groups, i.e., two or more isocyanate functionalities It contains at least one polyisocyanate, for example, one or more linear or branched fats. Polyisocyanates (or mixtures thereof) of the genus and / or aromatic group, and one or more A step of providing an oil phase containing a preferably hydrophobic active ingredient(s); (b) a step of providing a first aqueous phase comprising at least one capsule-forming agent; (c) Less than 20 monomer units, preferably 15 monomer units or less, even more preferably Each of the monomer units independently comprises 10 or fewer monomer units, preferably primary and secondary hydro A group consisting of primary and secondary amine groups (-NH2, -NH-) similar to the xyl group (-OH). At least one sugar having at least two functional reactive groups independently selected from and / or provide a second aqueous phase containing at least one amino sugar, and optionally the second aqueous phase further A step comprising 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) Mix the second aqueous phase with the provisional oil-in-water emulsion obtained in step (d) The process of obtaining a slurry of microcapsules; (f) The microcapsules obtained in step (e) within the microcapsule slurry are cured. It can be obtained based on the process.

[0094] Optionally, the process may include an additional step (f2), in which natural gum (e.g., xanthan gum) may be added. Selected from gum, gellan gum, diutan gum, cellulose gum (preferably diutan gum). One or more selected suspension aids or structuring aids are added as thickeners to provide high suspension stability. Such substances spontaneously form colloidal dispersions with water, thus stabilizing the suspension. To stabilize. Suitable suspension aids include, for example, Kelco-Vis (commercial) derived from CP Kelco. (Mark) DG and Keltrol (registered trademark), carboxymethylcellulose (CMC) and Viva from J.Rettenmaier & Soehne GmbH+Co KG It is pur(trademark) (microcrystalline cellulose).

[0095] The following details disclose suitable components similar to those of the single-process steps in the first embodiment. It is being done.

[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, two or more isocyanate groups At least one polyisocyanate having and a few which are to be encapsulated An oil phase is provided which contains or consists of at least one preferably hydrophobic active ingredient. It can be done.

[0097] Coasting used in the manufacturing process described herein or according to the first embodiment At least one isocyanate used in the ELL microcapsules is polymerized to a high degree Less Both have two isocyanate groups. In relation to this, dipolyisocyanates and / or Furthermore, higher-order polyisocyanates are each as specified herein, such as 20. A sugar and / or amino sugar having each monomer unit independently Chemical bonding of polyurethane-based and / or polyurea-based structures occurs through interfacial polymerization with functional groups. It forms a stable polymer structure based on this, which is efficient, but at the same time, it is fully integrated with cutting-edge technology. By forming a bio-based capsule wall that exhibits higher biodegradability compared to conventional capsules, This efficiently encapsulates the hydrophobic core containing the active ingredients.

[0098] In the case of thiosaccharides, therefore, in addition to the above bond, or instead, thiourethanebe A thiosaccharide bond is formed. Suitable thiosaccharides include, for example, N-acetylcysteine ​​and 5-thiosaccharides. -D-glucose, or methyl 6-thio-6-deoxy-α-D-galactopyranoside However, more suitable substances are cysteine, homocysteine, and glutathione. It is.

[0099] In the preferred modification, at least two isocyanate groups, i.e., two or three or more functional groups are present. The at least one polyisocyanate having a cyclic isocyanate group is preferably linear, ring-linked. Composed of crystalline and branched aliphatic and aromatic polyisocyanates, as well as mixtures thereof. Selected from the group. In that regard, dipolyisocyanates and / or higher-order poly Lyisocyanates are monomers, dimers, oligomers, or polymers with different chain lengths. It may have the structure of For example, dipolyisocyanates and polyisocyanates They self-react to form dimers (urethidione), trimers (isocyanurate), or even higher-order dimers. It often forms isocyanate oligomers. In addition, polyisocyanates are attached Additives, for example, aliphatic polyisocyanate adduct prepolymers, Mitsui C Chemicals form Takenate® D-110N and D-120N. It is possible.

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

[0101] The molecules described herein by the term "aliphatic polyisocyanate" are non Any aromatic poly(A) which may be linear, branched, or cyclic, i.e., alicyclic. This refers to isocyanates. In these compounds, the functional isocyanate group is directly connected to the aromatic ring. It is not linked to. However, aliphatic isocyanates (plural) contain aromatic structures. This is possible. Furthermore, polyisocyanates can be aromatic in nature (" Aromatic polyisocyanates, that is, functional isocyanate groups directly in the aromatic ring. It can be a structure that is connected. Polyisocyanates used within the scope of the present invention The te also includes, for example, aliphatic substituents, aromatic substituents, for example, halogens, especially fluorine, Heteroatoms such as chlorine, bromine and / or iodine, and / or other functional groups, for example, Any substitutions including an alkoxy group may be shown. Thereafter, the cyclic structure is heterocyclic or It can also be heteroaromatic.

[0102] In a preferred modification, therefore, at least one polyisocyanate is preferred. Monomers, dimers, or oligomers (linked polyisocyanates) in a linear or fractional manner Branched aliphatic polyisocyanates, alicyclic (heterocyclic) polyisocyanates, aromatic ( (or heteroaromatic) polyisocyanates, their substitution products, as well as the monomers mentioned above. Selected from the group consisting of a mixture of dimer or oligomer compounds, but an aliphatic compound Alternatively, a mixture of aliphatic and / or aromatic polyisocyanates is preferably used. .

[0103] Preferably, a mixture of at least two different polyisocyanates is used to improve the capsule properties. Used in the preparation of microcapsules of the present invention that produce microcapsules with the above balance. More preferably, a mixture of two different polyisocyanates is used. .

[0104] Alternatively, or even better, the corresponding polyisothiocyanate is used for capsule formation, and A mixture of both, i.e., at least one isocyanate and at least one iso It can be used to form compounds containing a mixture of thiocyanate functional groups.

[0105] According to a preferred embodiment of the present invention, linear or branched aliphatic polyisocyanates ( (Multiple names are possible) Pentamethylene diisocyanate (PDI, for example, Mitsui Che Stabiio D-370N or D-37 by micals Inc., Japan 6N), hexamethylene diisocyanate (HDI), e.g., Desmodur N- 3400(HDI-uretdione;Covestro Corp.), Bayhy dur® (Covestro Corp.), ethyl ether lysine triiso From the group consisting of cyanates, lysine diisocyanate ethyl ethers and their derivatives Selected, and preferably each derivative, comprises one or more isocyanate groups. Optionally, further viuret, isocyanurate, urethione, iminooxadiazinedione It comprises one or more groups selected from the group consisting of and trimethylolpropane adducts, and / or cyclic aliphatic polyisocyanates (plural) are isophorone diisocyanates (I PDI), 1,3-bis(isocyanatomethyl)cyclohexane (H6XDI, for example, Takenate 6 by Mitsui Chemicals Inc., Japan 00), 1,2-bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyan atomethyl)cyclohexane, methylenebis(cyclohexyl isocyanate) (H12 MDI), and derivatives thereof, wherein the derivatives are preferably selected from the group consisting of the above, and in this case, each of the derivatives comprises more than one isocyanate group, and optionally further comprises one or more groups selected from the group consisting of biuret, isocyanurate , uretdione, iminooxadiazinedione and trimethylolpropane adducts (for example , TMP adducts of H6XDI, particularly Takenate D-120N from Mitsui Chemicals Inc., J apan). comprises the above-mentioned one or more groups.

[0106] Also preferred are aliphatic polyisocyanate(s) obtained from renewable sources , for example PDI (from Mitsui Chemicals Inc., Japan Stabio D-370N or D-376N). It has been found that such aliphatic polyisocyanates obtained from renewable sources do not impair the quality / characteristics of core-shell capsules . For example, Stabio D-370N polyisocyanate has approximately 70% biobased carbon relative to the total carbon of the substance, as indicated by the 14C (radiocarbon) content, that is, approximately only 30% fossil-based carbon, with the remainder being renewable and non-fossil organic carbon .

[0107] Biobased or biologically derived reagents are preferred in consideration of health and environmental aspects. Biobased materials (biologically derived materials), for example, as defined in ASTM D686 , include agricultural crops, animals, fungi, microorganisms, marine materials and forest materials that live in the natural environment in equilibrium with the atmosphere Renewable origins that are not of fossil origin, such as petroleum, as defined according to standard tests. This refers to compounds containing organic carbon. Furthermore, such bio-derived compounds are found in agricultural plants. Carbon from renewable sources such as animals, fungi, microorganisms, marine materials and forest materials (organic and non-organic) It is defined as a compound containing (of the machine). Preferably, the core shell of the present invention Kurocapsule is made from such bio-derived or bio-based materials. Includes. Therefore, bio-derived materials are preferably the core-shell microcapsules according to the present invention. Used in cell preparation.

[0108] Therefore, in a more preferred variation of the present invention, preferably, STABiO(trademark) such bio-based polyisocyanates and / or bio-derived (amino) sugars, that is, and natural and renewable, and sustainable raw materials, i.e., mainly The components used are derived from bio-based raw materials that do not originate from petrochemicals.

[0109] Polymerizable aliphatic isocyanates are due to their chemical affinity for bio-based systems. In this context, it is particularly preferable. For example, lysine and 1,5-diisocyanatopentane are the same Since it exhibits 1,5-diaminopentane as a decomposition product, environmental considerations must be taken into account when using biobaking. It is particularly suitable for use in the manufacture of biodegradable microcapsules.

[0110] Therefore, in a preferred embodiment of the present invention, preferably, at least one aliphatic poly Lyisocyanate is used.

[0111] Preferably, derivatives of linear, branched, and / or cyclic aliphatic polyisocyanates are used. Used. When used herein, derivatives are, in a broad sense, derived from compounds by chemical reactions. It is understood as a compound that performs this function. Examples of derivatives include the linear or branched aliphatic compounds mentioned above. This includes oligomers and / or adducts of alicyclic polyisocyanates. The preferred oligomers are biuret, isocyanurate, urethidion, and iminooxadi. These are azines, and the preferred adduct is a trimethylolpropane adduct. Oligomers / adducts are well known in the art, for example, US4,855,490 A Or disclosed in US4,144,268 A. Preferably, aliphatic polyisothex The nate exists in monomer and / or dimer or oligomer forms.

[0112] The derivatives of linear, branched, or cyclic aliphatic polyisocyanates are the same as the polyisocyanates. Anate polyalcohols (e.g., glycerin), polyamines, polythiols (e.g., It may also be obtained by reaction with dimercaprol, and / or mixtures thereof. .

[0113] Within the framework of this text, aromatic polyisocyanates are defined as having two or more isocyanate residues A isocyanate is directly bonded to the aromatic carbon atom and its derivative, and each of the derivatives has more than 1 isocyanate. It contains a tetrapropyl group, and further contains biuret, isocyanurate, urethion, and iminooxadia. One or more selected from the group consisting of zingione and trimethylolpropane adducts, etc. It is a compound containing a group.

[0114] Examples of aromatic dipolyisocyanates or polyisocyanates include, for example, monomers. Diphenylmethane-2,4- or -4,4'-diisocyanate (MDI) and its oligomeric / polymeric forms of the foregoing, or mixtures thereof, 2,4- and / or 2,6- toluene diisocyanate (TDI) and 1,5- or 1,8-naphthalene diisocyanat e (NDI).

[0115] Among polyisocyanates, diisocyanates, i.e., isocyanates having two functional isocyanate groups, are particularly preferred and therefore are mainly used in the context of the present invention. Accord ingly, suitable polyisocyanates include, for example, methylene diphenyl diisocyanate (MDI; all isomers and derivatives thereof); toluene diisocyanate (TDI); hexa methylene diisocyanate (HDI; all isomers and derivatives thereof); isophorone diiso cyanate (IPDI); 4,4-dicyclohexylmethane diisocyanate (H12M DI); 1,5-pentamethylene diisocyanate (PDI; Stabio™); 1,3-bis(isocyanatomethyl)cyclohexane (Takenate™ 600 ); hydrophilic modified hexamethylene diisocyanate (Bayhydur® ) or mixtures thereof.

[0116] The above-mentioned compounds explicitly include, if present, different isomers alone or in combination , and also explicitly include the corresponding derivatives. For example, methylenebis(cyclohexy l isocyanate) (H12MDI) is 4,4'-methylenebis(cyclohexyl iso cyanate), 2,4'-methylenebis(cyclohexyl isocyanate) and / or 2,2'-methylenebis(cyclohexyl isocyanate) or aliphatic polyisocyanate Adductors, for example, Takenate (trademark) by Mitsui Chemicals. This includes D-110N and D-120N.

[0117] Other particularly preferred monomer isocyanate compounds include, for example, 1,4-diisocyana Tobutane, 1,6-diisocyanatohexane, 1,5-diisocyanato-2,2-dimethicone Lupentane, 2,2,4- and 2,4,4-trimethyl-1,6-diisocyanatohexa n, 1,10-diisocyanatodecane, 1,3- and 1,4-diisocyanatocyclohex San, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohex San (isophorone diisocyanate), 4,4'-diisocyanate dicyclohexylmeth , 2,4- and 2,6-diisocyanatomethylcyclohexane and mixtures thereof It is a diisocyanate. Within the scope of the present invention, preferred polyisocyanates are both 1,5-pentanemethylene diisocyanate (P) derived from Mitsui Chemical DI) (Stabio (trademark)) and / or 1,3-bis(isocyanatomethyl) cyclamate It is hexahexane (Takenate® 600), which is very stable and has good performance. It enables the formation of core-shell microcapsules. Also preferred is Mitsui C Like Takenate(trademark) D-110N and D-120N by chemicals. It is an accretionary compound.

[0118] In another variation, a combination of at least two different polyisocyanates is preferred. When different polyisocyanates are used as a mixture, they are particularly stable within the capsule shell. Furthermore, it was observed that good, i.e., more densely branched bridges could be achieved. Regarding such mixtures of isocyanates, polyisocyanates are linear aliphatic All combinations of all branched-chain aliphatic, all alicyclic, or all aromatic compounds, or for example If, then, at least one aromatic polyisocyanate and at least one aliphatic polyisocyanate It can be a combination of nates. In general, all possible combinations of the aforementioned substances This is suitable for the purpose of the present invention, and furthermore, it provides more stable and efficient encapsulation, and a tighter density It is suitable for achieving crosslinking while simultaneously enabling improved performance.

[0119] However, preferably, one or more poly(I) having at least two isocyanate groups. At least one of the socianates is aliphatic, and more preferably alicyclic. More preferably, the polyisocyanate components of the oil phase each contain at least two isocyanates. A mixture of two or more aliphatic and / or aromatic polyisocyanates having an anneate group. Yes. As a result, the isocyanate component consists of two or more different aliphatic polyisocyanates, 2 The above different aromatic polyisocyanates, or at least one aliphatic polyisocyanate It may include a mixture of the compound and at least one aromatic polyisocyanate. Such mixtures of two or more polyisocyanates should be used, especially for fragrance microcapsules. When used as a cell, it provides more stable and better-performing encapsulation. It was found. Preferably, a small amount of polyisocyanate used in such mixtures. Both are aliphatic, that is, linear aliphatic, branched aliphatic, or alicyclic, but these In particular, in consumer product formulations, under mechanical stress (e.g., washing machines and dryers) and heat, This is because it enables the formation of highly stable microcapsules while simultaneously exhibiting excellent release characteristics. ru.

[0120] Furthermore, aliphatic polyisocyanates have lower toxicity compared to aromatic polyisocyanates. Since it is known that the resulting structure is, for example, an aromatic isocyanate-based poly It is more biocompatible than uretan.

[0121] Therefore, in a preferred embodiment of the present invention, at least one aliphatic polyisocyanate The material is used in the preparation of microcapsules according to the present invention, and / or according to the first embodiment. Each microcapsule contains at least one aliphatic polyisocyanate and less than 20 of each. with at least one sugar and / or at least one amino sugar having monomer units Since it contains reaction products, the microcapsules according to the present invention contain at least two isocyanates At least one of the polyisocyanates having a nate group contains an aliphatic structure.

[0122] In one variation, preferably only aliphatic polyisocyanates, i.e., straight A mixture of two or more aliphatic isocyanates, which can be chain-type, branched-chain-type, or alicyclic-type. It will be used.

[0123] As shown above, in another variation, preferably at least one aliphatic poly Using a mixture of socianate and at least one aromatic polyisocyanate, encapsulation A solution is prepared, that is, the core-shell microcapsule according to the first embodiment is at least At least one sugar and / having less than 20 monomer units of one polyisocyanate or a reaction product with at least one amino sugar, in which case at least two iso At least one of the one or more polyisocyanates having a cyanate group is a very effective m It contains an aliphatic structure that enables the formation of microcapsules.

[0124] Even after 4 weeks of aging in the product formulation, it exhibits high stability within the aforementioned product formulation. (See Example 11), a capsule that is very stable but also performs well at the same time (target) Preferably, more than one monomer unit enables the formation of (in terms of release behavior) Microcapsules preferably based on or containing amino sugars are preferred. More specifically, at least one aliphatic polyisocyanate and at least one aromatic poly The molar ratio or weight ratio to the socianate, preferably the molar ratio is 85:15, and further Preferably, the ratio is in the range of 90:10 to 99:1.

[0125] Therefore, combinations of different polymerizable polyisocyanates are particularly stable capsules. This results in a shell or capsule wall, which in turn provides a better capsule for the active ingredient. This is reflected in the reduction of losses during processing and storage, but at the same time, for example, the caps of fragrances or odorous substances. Further improved performance of capsules in the cellular domain (high strength and excellent odor substance release behavior). This makes it possible. Therefore, in the present invention, at least two polymerizable different isocyanates A combination of the isocyanates is generally preferred. Even more preferably, a small amount of the isocyanate is preferred. At least one of them is the aliphatic property, regardless of whether it is an (amino) sugar component.

[0126] Therefore, preferably the capsule wall has at least two isocyanate groups It is based on the reaction of at least one aliphatic polyisocyanate. As a result, as described above In step (a), preferably, at least two isocyanate groups are present. One aliphatic polyisocyanate and optionally at least one aromatic polyisocyanate Preferably, at least one aliphatic polyisocyanate and one or more preferably hydrophobic An oil phase containing an active ingredient is provided.

[0127] "Polyisocyanate", "Isocyanate", and "Isocyanate component", "Iso The terms “cyanate compound” or “polyisocyanate component” are used throughout this disclosure. It should be noted that they are used synonymously. The same applies to words.

[0128] Further embodiments include mixtures of isocyanate compounds and isothiocyanate compounds. It can be used in an oil phase.

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

[0130] Based on the present invention, because the isocyanate component content is low, the absolute isocyanate content This process involves manufacturing microcapsules that make up a very small portion of the total capsule containing the active ingredient(s)(or multiple active ingredients). It is possible to do so in the process described herein, isocyanates It was possible to produce efficient microcapsules with significantly lower isosorbent content. Despite its low anate content, it exhibits extremely stable and excellent release characteristics. It was possible to obtain chlorocapsules. In addition, because the isocyanate content is low, Furthermore, health and environmental concerns are significantly reduced. Based on this, adversely affecting the stability and / or performance of the microcapsules of the present invention This can reduce the crosslinking density of the shell wall. As a result, the total amount of isocyanate in the capsule It is low relative to the total weight.

[0131] The process for producing bio-based microcapsules according to the present invention includes at least Another polymerizable isocyanate is preferably first encapsulated. It is dissolved in a hydrophobic medium together with the active ingredient(s). Preferably, the active ingredient itself For example, perfumed oils or fragrance substances or mixtures, that is, substances that have an odor that can be detected by the sense of smell. A mixture of substances or materials serves as a hydrophobic medium in which isocyanate compounds dissolve. Therefore, in the context described herein, the active ingredients that are to be encapsulated are preferred. The active ingredient is hydrophobic. The selection of such an active ingredient is based on the fact that the material being encapsulated is oil. It is in a phase that ensures it does not mix with the outer aqueous phase. As a result, the hydrophobic component is dispersed in the phase. It forms a layer, and the aqueous phase is a continuous phase. This means that the hydrophobic active ingredient acts as the core material. This ensures that the substance is effectively encapsulated within the microcapsule shell.

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

[0133] The oil phase consists of an isocyanate component as defined above and at least one active ingredient It may consist of more than 2, preferably more than 3, even more preferably As a solvent having a cLogP (octanol / water partition coefficient) value greater than 4 One or more oil components, for example, (i) A linear or branched chain having 15 or more carbon atoms, particularly having 18 to 45 carbon atoms. Saturated paraffin (mineral oil); (ii) Straight-chain or branched fatty acids having 6 to 30 carbon atoms and having 3 to 30 carbon atoms With linear or branched saturated or unsaturated monools, diols, or triols Esters having 12 or more carbon atoms, in which case these esters have free hydroxyl groups Do not possess; (iii) Benzoic acid and a linear or branched saturated or unsaturated chain having 8 to 20 carbon atoms. Esters of monoalcohols; (iv) Alcohols having 3 to 30 carbon atoms and naphthalene monocarboxylic acid or naphth Monoesters or diesters with talenedicarboxylic acids; especially naphthalene monoesters C6-C 18 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 C atoms, and Q 2 is a linear or branched alkyl radical having 4 to 16 C atoms, 2-alkyl Ru-1- Alkanol It can contain.

[0134] In that regard, vLogP (partition coefficient) is a measure of the lipophilicity or hydrophobicity of a particular substance. The ratio is the ratio of the concentrations of a compound in a mixture of two immiscible solvents at equilibrium. It is defined as follows.

[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) Straight-chain or branched saturated fatty acids having 8 to 24 carbon atoms and having 3 to 24 carbon atoms With linear or branched saturated or unsaturated monools, diols, or triols Esters having at least 14 C atoms, wherein these esters are free hydroxy Esters that do not contain syl groups; (iii) Saturated monoalcohols, either linear or branched, containing benzoic acid and 10-18 carbon atoms. Ester of Ru; (iv) Alkylenediol dicaprylate, especially procaprylate dicaprylate Pyrenediol; (v) Saturated di-C6-C6 in straight or branched chains 18 -alkyl esters, especially (linear) di- C6-C 12 -alkyl ether; (vi) Cyclotrisiloxane, cyclopentasiloxane, dimethylpolysiloxane, di Ethylpolysiloxane, methylphenylpolysiloxane, diphenylpolysiloxane, and Silicone oils derived from a group of hybrid forms thereof; (vii) The following equation: [ka] 2-alkyl-1-alkanol having 12-32 C atoms (wherein Q1 is 6-18) A (preferably linear) alkyl radical having a C atom, where Q2 is a C radical with 4 to 16 C atoms. (A linear alkyl radical having a derivative) 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., iso-e Icosane or squalene; (ii) Straight-chain or branched saturated fatty acids having 8 to 18 carbon atoms and having 3 to 18 carbon atoms At least one saturated monool, diol, or triol in a straight or branched chain. Esters having 6 carbon atoms, these esters contain free hydroxyl groups. No, Esther; (iii) Saturated monoalcohols, either linear or branched, containing benzoic acid and 12-15 carbon atoms. Esters with benzoic acid, especially C benzoate. 12 -C 15 -alkyl; (iv) Alkylenediol dicaprylate, especially procaprylate dicaprylate Pyrenediol; (v) Linear di-C6-C 10 -Alkyl esters, especially di-n-octyl ethers (Dica Prilyl ether; (vi) Undecamethylcyclotrisiloxane, cyclomethicone, decamethylcyclopene Tasiloxane, Dimethylpolysiloxane, Diethylpolysiloxane, Methylphenylpoly Silicone oils derived from siloxanes and diphenylpolysiloxanes; (vii) The following equation: [ka] 2-alkyl-1-alkanol having 12-32 C atoms (wherein Q1 is 6-18) A (preferably linear) alkyl radical having a C atom, where Q2 is a C radical with 4 to 16 C atoms. It is an alkyl radical (preferably linear) having a derivative; It can include.

[0137] Particularly preferred components of type (i) groups in the oil phase are: isopropyl myristate, Isopropyl palmitate, isopropyl stearate, isopropyl oleate, ste n-butyl oleate, n-hexyl laurate, n-decyl oleate, stearate Sooctyl, Isononyl Stearate, Isononyl Isononanoate, 2-Ethyl Palmitate 2-ethylhexyl laurate, 2-hexyldecyl stearate, palmite 2-octyldodecyl tinate, oleyl oleate, oleyl erucate, erucate Syl, Erucyl erucate, 2-ethylhexyl isostearate, Isotrisine isononanoate Decyl, 2-ethylhexyl cocoate, caprylic / capric triglyceride, dica Alkylenediol caprate, especially propylenediol dicaprylate The synthetic, semi-synthetic and natural mixtures of such esters, for example, jojoba oil. ru.

[0138] Fatty acid triglycerides (type (i) oil components in the oil phase) are also synthetic oils, semi-synthetic oils and Beverages and / or natural oils, such as olive oil, sunflower oil, soybean oil, peanut oil, natto oil. In the form of coconut 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 component in the oil phase is: 2-butyl-1-octano ol, 2-hexyl-1-decanol, 2-octyl-1-dodecanol, 2-decylte tradecanol, 2-dodecyl-1-hexadecanol and 2-tetradecyl-1-oc tadecanol.

[0140] Particularly preferred oil components in the oil phase are C benzoate 12 -C 15 -alkyl and isostear a mixture comprising 2-ethylhexyl phosphate and C benzoate 12 -C 15 -alkyl and isono a mixture comprising isotridecyl nananoate and C benzoate 12 -C 15 -alkyl and isostear a mixture comprising 2-ethylhexyl alate and isotridecyl isononanoate, cyclomethi cone and a mixture comprising isotridecyl isononanoate, and a mixture comprising cyclomethicone and 2-ethylhexyl isostearate .

[0141] Preferred oily bodies used within the scope of the present invention are, for example, 6 to 18, preferably 8 to 10 Guerbet alcohols based on fatty alcohols having carbon atoms, C6-C 22 -fatty acid linear or branched C6-C 22 -esters with fatty alcohols, or branched C6-C 13 -linear or branched C6-C carboxylic acids 22 -esters with fatty alcohols, for example for example, myristyl myristate, myristyl palmitate, myristyl stearate, my ristyl isostearate, myristyl oleate, myristyl behenate, myristyl eruc ate, cetyl myristate, cetyl palmitate, cetyl stearate, cetyl isostear ate, cetyl oleate, cetyl behenate, cetyl erucate, stearyl myristate Lyl, stearyl palmitate, stearyl stearate, stearyl isostearate Stearyl oleate, stearyl behenate, stearyl erucate, iso myristate Stearyl, Isostearyl Palmitate, Isostearyl Stearate, Isostearyl Isostearyl oleate, isostearyl behenate, oleic acid Isostearyl, oleyl myristate, oleyl palmitate, oleyl stearate Oleyl isostearate, oleyl oleate, oleyl behenate, oleyl erucate Behenyl myristate, behenyl palmitate, behenyl stearate, isostearate Behenyl phosphate, behenyl oleate, behenyl behenate, behenyl erucate, myristyl Erusyl palmitate, erusyl palmitate, erusyl stearate, erusyl isostearate These include erucyl oleate, erucyl behenate, and erucyl erucate. Also preferred are Also, C6-C 22 - Branched-chain alcohols of fatty acids, especially with 2-ethylhexanol. Stel, C 18 -C 38 - Linear or branched C6-C2 alkylhydroxycarboxylic acids Esters with 2-fatty alcohols, especially dioctyl maleate, linear and / or branched chains Polyhydric alcohols of fatty acids (e.g., propylene glycol, dimethyl diol and trimel) Esters with rutriol and / or guerbet alcohols, C6-C 10 -Based on fatty acids Triglycerides, C6-C 18 -Fatty acid-based liquid mono- / di- / triglycerides , C6-C 22 - Aromatic carboxylic acids of fatty alcohols and / or Guerbet alcohols, particularly Ester with benzoic acid, C2-C12 - A dicarboxylic acid having 1 to 22 carbon atoms Alcohols in chain or branched chain form, or having 2 to 10 carbon atoms and 2 to 6 hydroxyl groups. Polyol esters, vegetable oils, branched-chain primary alcohols, substituted cyclohexane , straight-chain or branched-chain C6-C carbonate 22 - Fatty alcohols, e.g., dicaprylyl carbonate ( Cetiol (registered trademark) CC), a lipid having 6 to 18, preferably 8 to 10, carbon atoms. Guerbet carbonate based on benzoic acid, straight-chain and / or branched-chain C6-C6 of benzoic acid 22 - Esters with alcohols (e.g., Finsolv® TN), alkyl groups A linear or branched symmetric or asymmetric dialkylate having 6 to 22 carbon atoms. For example, dicaprylyl ether (Cetiol® OE), polyols Ring-opening products of epoxidized fatty acid esters, silicone oil (cyclomethicone, silicone) (e.g., methicone, gravy, etc.) and / or aliphatic or naphthenic hydrocarbons, for example The most preferred oil component is squalane, squalene, or dialkylcyclohexane. These are triglycerides, especially those of natural origin.

[0142] In preferred embodiments, the microcapsules of the present invention contain one or more (hydrophobic) active ingredients, e.g. For example, it is loaded with fragrances or fragrant oils. For specific applications, other additives may also be used as described above. It can be used as directed. With regard to fragrances and fragrance oils, the polyurethane of the present invention The cost of urea-based and / or polyurea-based capsules was calculated based on the total weight of the capsule. This allows for loading large amounts, up to 80%. The active substance is preferably incorporated into the oil phase. It can be incorporated into the first aqueous phase, depending on its porosity.

[0143] When the term "active substance" is used herein, it refers to a substance relating to a particular effect or It should be understood to mean ingredients, such as fragrances, aromas, dyes, medicines, and insecticides. Preferably, the hydrophobic active substance is part of the oil phase, that is, another component that makes up the oil phase. It is accompanied by, or when used herein, constitutes the oil component of the oil phase. Preferably, Hydrophobic substances and polyisocyanate components constitute the oil phase. Fragrances and / or perfumes are present. When used in fine writing, it refers to a single fragrance or perfume substance (also known as an odorous or aromatic substance). (called), that is, a compound that has an odor or smell, and by extension, an odor that can be perceived by the sense of smell. All natural and synthetic substances that impart fragrance, as well as one or more fragrance or perfume substances. This refers to a composition, that is, 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 will be further explored below. It may also contain further active substances and other components that have not been identified.

[0145] Suitable fragrances and / or oils include, for example, single odor substances or natural and synthetic odors. It is a mixture of substances. Natural perfumes include flowers (lily, lavender, rose, jasmine, nero). Li, Ylang-ylang), stems and leaves (geranium, patchouli, petitgrain), fruit (anise, Coriander, caraway, juniper), fruit peel (bergamot, lemon, orange), root ( Nutmeg, angelica, celery, cardamom, costus, iris, calamus), wood ( Pine wood, sandalwood, guaiac wood, cedarwood, rosewood), herbs and grasses (tarragon) Lemongrass, surge, thyme), needles and branches (spruce, fir, pine, bonsai pine), resin and balsam (galbanum, elemi, benzoin, myrrh, olibanum, opoponax) Extracts of the following can be used. Animal-derived materials, such as civet and beaver, may also be used. Typical synthetic perfume compounds include esters, ethers, aldehydes, ketones, alcohols, and These are hydrocarbon-type products. Examples of ester-type perfume compounds include benzyl acetate and fructose isobutyrate. Phenoxyethyl acetate, p-tert-butyl cyclohexyl acetate, linalyl acetate, dimethyl acetate Rubenzyl carvinyl, phenylethyl acetate, linalyl benzoate, benzyl formate, glycy Ethylmethylphenyl phosphate, allylcyclohexyl propionate, styralyl propionate These are benzyl salicylate and benzyl ether. Examples of ethers include benzyl ethyl ether. On the other hand, aldehydes include, for example, linear alkanas containing 8 to 18 carbon atoms. Citral, citronellal, citronellyloxyacetaldehyde, cyclamen Examples include aldehydes, hydroxycitronellal, lirial, and borageonal. Suitable examples of ketones are ionone, isomethylionone, and methylcedyl ketone. Suitable alcohols include anetol, citronellol, eugenol, isoeugenol, These are geraniol, linalool, phenylethyl alcohol, and terpineol. Hydrogenated compounds mainly include terpenes and balsams. However, perfumes that suit your taste It is preferable to use a mixture of various perfume compounds that work together to produce the desired effect. Fragrance oils are essential oils with relatively low volatility that are primarily used as aromatic components. An example is selenite. Lime oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, lime oil Rossum oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil, radianum Oils, and lavender oil. Below: Bergamot oil, dihydromyrcenolate, lilial Lilar, citronellol, phenylethyl alcohol, hexyl cinnamaldehyde Geraniol, benzylacetone, cyclamenaldehyde, linalool, voisamble Inforte, ambroxan, indole, hedione, sandelice, citrus oil, mande Phosphorus oil, orange oil, allylamyl glycolate, cyclobeltal, lavender oil, sa Rubia oil, damascone, geranium oil, cyclohexyl salicylate, Verto fix Coeur, Iso-E-Super, Fixolide NP, Evernil, Iraldein gamma, phenylacetic acid, geranyl acetate, benzyl acetate, rose oxide, ro Milat, Irotyl, and Floramat are preferably used individually or in mixture form. ru.

[0146] However, preferably, the perfume or aromatic substance used for encapsulation is odor It is a compound used primarily for the purpose of imparting or modifying flavor. Preferably, These substances or mixtures of substances give off an odor in a positive or pleasant way. Alternatively, flavor can be imparted or modified. For the purposes of the present invention, "fragrance oil" or "a The term "roma" refers to flavorings used to alter or impart a smell or flavor. It contains a combination of ingredients that enhance flavor.

[0147] In addition to or in addition to the fragrance / perfume substances and oils listed above as examples, there are a few other At least one hydrophobic active substance is used in aromatic substances, aromatherapy, pesticides, and as an active ingredient in cosmetics, for example. For example, skin moisturizers, skin or hair conditioning agents, skin whitening agents, acne preventatives, etc. What are the active ingredients in skin products, active pharmaceutical ingredients, UV active substances, and optical components? Glossing agents, thickeners, drape and form control agents, smoothing agents, antistatic agents, wrinkle inhibitors, anti-static agents Antimicrobial agents, disinfectants, antibacterial agents, mold inhibitors, white mold inhibitors, antiviral agents, antimicrobial agents, desiccants stain-resistant agents, anti-fouling agents, odor-preventing agents, fabric deodorizers, dyes and dye fixatives, color maintenance agents, Color restorer / recovery agent, anti-fading agent, anti-abrasion agent, wear-resistant agent, fabric preservative, wear prevention Agents, rinsing aids, UV protection agents, sun-fading inhibitors, insect repellents, anti-allergic agents, flame retardants, anti- Water-based 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), impregnation Select from a broad group consisting of mixtures of the above-mentioned active ingredients, as well as agents, stain inhibitors, and friction reducers. It is possible.

[0148] Suitable coolants are known in the art, for example, Frescolat®. These are menthol-based coolants such as the above. Preferred individual for use within the framework of the present invention The following is a list of coolants. Those skilled in the art can add many other coolants to this list. The listed coolants can also be used in combination with each other, and they are preferable. The following is a list of menthol and menthol derivatives (e.g., L-menthol, D-menthol) Menthol, racemic menthol, isomenthol, neoisomenthol, neomenthol ) Menthyl ether (for example, (l-menthoxy)-1,2-propanediol, (l- Menthoxy)-2-methyl-1,2-propanediol, l-menthyl-methyl ether ), menthong glyceryl acetal, menthong glyceryl ketal, or a mixture of both, Menthyl esters (e.g., menthyl formate, menthyl acetate, menthyl isobutyrate, hydroxyl Menthyl cyisobutyrate, menthyl lactate, L-menthyl-L-lactate, L-menthyl-D -Lactate, Menthyl-(2-methoxy)acetate, Menthyl-(2-methoxyeth Xyl(acetate, menthyl pyroglutamate), menthyl carbonate (for example, menthyl carbonate) Propylene glycol, menthyl ethylene glycol carbonate, menthyl glycerol carbonate (or mixtures thereof), semi-esters of menthol dicarboxylic acid or its derivatives (For example, mono-menthyl succinate, mono-menthyl glutarate, mono-menthylma Lonate, O-menthyl succinate ester-N,N-(dimethyl)amide, O-menthyl succinic acid ester amide), menthane carboxylic acid amide (in this case, menthane carboxylic acid amide is preferred) Carboxylic acid-N-ethylamide [WS3] or Nα-(menthanecarbonyl)glycine Ethyl ester [WS5], menthanecarboxylic acid-N-(4-cyanophenyl)amide or menthanecarboxylic acid-N-(4-cyanomethylphenyl)amide, menthanecarbon Acid-N-(alkoxyalkyl)amide), menthone and menthone derivatives (e.g., L- Menthol glycoside ketal, 2,3-dimethyl-2-(2-propyl)-butyrate derivative (e.g., 2,3-dimethyl-2-(2-propyl)-butyrate-N-methylamide [WS 23]), isopuregol or its ester (I-(-)-isoplegol, I-(- )-Isoplegol acetate), menthane derivatives (e.g., p-menthane-3,8-diol) ), cubebol or a synthetic or natural mixture containing cubebol, cycloalkyldi Pyrrolidone derivatives of ion derivatives (e.g., 3-methyl-2(1-pyrrolidinyl)-2-syl Clopenten-1-one) or tetrahydropyrimidine-2-one (e.g., WO20) Icilin or related compounds as described in 04 / 026840, further cal Boxamide (for example, N-(2-(pyridine-2-yl)ethyl)-3-p-menthanka (Ruboxamide 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-cyclo From hexyl]2-(ethylamino)-2-oxoacetate (X Cool) to here Selected. Preferred coolants for specific synergistic effects are L-menthol and D-menthol. Le, racemic menthol, menthol glycerol acetal (product name: Frescol) at(registered trademark)MGA), menthyl lactate (preferably L-menthyl lactate, especially L-lactic acid L-menthyl (trade name: Frescolat(registered trademark)ML)), substituted menthyl -3-Carboxamide (e.g., menthyl-3-carboxylic acid N-ethylamide), 2- Sopropyl-N-2,3-trimethylbutanamide, substituted cyclohexane carboxy Thamide, 3-menthoxypropane-1,2-diol, 2-hydroxyethylmenthoxy The components are 2-hydroxypropylmenthyl carbonate and isopuregol. Particularly preferred cooling The ingredients are L-menthol, racemic menthol, and menthol glycerol acetal (product name). :Frescolat(registered trademark) MGA), menthyl lactate (preferably L-menthyl lactate) In particular, L-menthyl L-lactic acid (product name: Frescolat(registered trademark)ML) 3-Mentoxypropane-1,2-diol, 2-hydroxyethyl menthyl carbonate and It is 2-hydroxypropylmenthyl carbonate.

[0149] In addition, capsaicin and other TRPV1 and 2-reactive compounds known in the relevant technology. TRPV1 and TRPV2 modifiers, such as substances, are incorporated into the core-shell microcapsules of the present invention. Therefore, it can be effectively encapsulated. A preferred capsule according to the present invention is, for example, one or more. Contains a TRPV1 antagonist. Based on its action as a TRPV1 antagonist. A suitable compound for alleviating skin nerve hypersensitivity is, for example, trans-4-tert-butyl Cyclohexanol, or μ-receptors, such as acetyl tetrapeptide-15 This includes direct modifiers for TRPV1.

[0150] Ingredients that are suitable for use as cosmetics or pharmaceuticals and / or Or auxiliary agents and / or additives or auxiliaries, in particular, are further described below, for example. Abrasives, acne preventatives, anti-aging medications for the skin, anti-cellulitis agents, anti-dandruff agents Anti-inflammatory agent, antibacterial agent, anti-irritant, irritation inhibitor, antioxidant, astringent, odor absorber, sweat inhibitor Inhibitors, disinfectants, antistatic agents, binders, buffers, carriers, chelating agents, cell stimulants, washing Cleaning agents, hair removal agents, surfactants, deodorants, antiperspirants, fabric softeners, emulsifiers, enzymes, enzyme inhibitors, essences Oils, fibers, film-forming agents, adhesives, foaming agents, foam stabilizers, foam inhibitors, foam boosters, gelling agents Gel-forming agent, hair care agent, hair styling agent, hair straightening agent, moisture supply agent, moisturizing substance, moisture retainer Additives, bleaches, strengtheners, stain removers, lubricants, moisturizing creams, ointments, emulsions, plasticizers, Coating agents, polishing agents, preservatives, glossing agents, green polymers and synthetic polymers, powders, proteins Oil-based substances, re-oiling agents, abrasives, silicone Skin soothing agents, skin cleansers, skincare agents, skin restorers, skin whitening agents, skin protectants, Skin softener, hair protectant, coolant, skin heat dissipation agent, warming agent, skin warming agent, stabilizer, surfactant Agents, UV absorbers, UV filters, primary sunscreen factors, secondary sunscreen factors, detergents, fabrics Modifiers, suspenders, skin sunscreens, active substances that modify skin or hair pigmentation, matrix Calcium metalloproteinase inhibitors, skin moisturizers, glycosaminoglycan stimulants, TRP V1 antagonist, stripping agent, or fat enhancer, hair growth activator or inhibitor, growth enhancer Mucus, rheologically active substances, vitamins, oils, waxes, pearlescent waxes, fats, Phospholipids, saturated fatty acids, mono- or polyunsaturated fatty acids, alpha-hydroxy acids, polyhydro Xy fatty acids, liquefaction agents, dyes, color protectants, pigments, corrosion inhibitors, fragrances or fragrant oils, odorants A substance, polyol, electrolyte, organic solvent, and a mixture of two or more of the aforementioned substances. Skin products For example, use of humectants, bio-derived active ingredients, antioxidants, etc. It is possible.

[0151] Suitable antifouling polymers, also called anti-redeposition agents, are, for example, nonionic polymers in each case. Based on cellulose ether, 15-30% by weight of methoxy groups and 1-15% by weight of hydroxycellulose ether Nonionic cellulose ethers having a ratio of droxypropyl groups, for example, methyl cellulose Rose and methylhydroxycellulose or hydroxypropylcellulose (HPC) (Klucel®), and also phthalates and / or terephthalates or so These derivatives are polymers known in the prior art, particularly ethylene terephthalate polymers. - and / or polyethylene glycol terephthalic acid and / or polypropylene glycol terephthalic acid, or its anionic and / or nonionic modified derivatives. It is a body. Suitable derivatives include sulfonated derivatives of phthalate polymers and terephthalate polymers. Conductors are an example.

[0152] Optical brighteners (so-called "whitening agents") remove graying and yellowing from the treated fiber surface. These materials can be incorporated into capsules according to the present invention for removal. It absorbs invisible ultraviolet light and converts it into visible long-wavelength light, thereby brightening the fibers and preventing bleaching. It mimics the whitening effect, but in the process, the ultraviolet light absorbed from sunlight is emitted as a slightly blue fluorescence. This combines the yellow of grayed or yellowed laundry to create a pure white color. Suitable compounds include, for example, 4,4'-diamino-2,2'-stilbendisulfonic acid ( Lavonic acid, 4,4'-distyryl-biphenylene, methylumbelliferone, coumarin , dihydroquinolinone, 1,3-diarylpyrazoline, naphthalimide, benzoxy Systems of sazole, benzisoxazole and benzimidazole, and heterocyclic substituted pi It originates from the material class of len derivatives.

[0153] The graying inhibitor continuously removes dirt from the fibers floating in the liquid, thus preventing the dirt from reattaching. It has a role in this. Suitable for this purpose are water-soluble colloids, usually, with properties such as, for example, The ingredients are organic matter, starch or cellulose ether sulfonic acid salts, or cellulose. Alternatively, it is a salt of an acidic sulfonic acid ester of starch. Suitable for this purpose is also an acid It is a water-soluble polyamide containing a property group. In addition, it contains soluble ions other than those specified above. Starch preparations and starch products, such as hydrolyzed starch and aldehyde starch, are used. It is possible to use it. It is also possible to use polyvinylpyrrolidone. However, However, cellulose ethers, such as carboxymethylcellulose (sodium salt), Hydroxycellulose, hydroxyalkylcellulose, and mixed ethers, for example, methyl cellulose Droxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose It is preferable to use chill cellulose and mixtures thereof.

[0154] Fabrics made from rayon, cellulose, cotton, and mixtures thereof have individual fibers that are aligned in the direction of the fibers. It is prone to creasing because it is easily damaged by bending, folding, compression, and crushing across the surface. Because it may have such properties, the microcapsules according to the present invention may contain a synthetic wrinkle-preventing agent. These include, for example, fatty acids, fatty acid esters, and fats that normally react with ethylene oxide. Acid amides, fatty acid alkylol esters, fatty acid alkylolamides, or fatty acid alkyl Synthetic products based on kohl, or products based on lecithin or modified phosphate esters. These are some examples.

[0155] High comfort can be achieved by adding an antistatic agent. The agent enhances surface conductivity, thus enabling easier discharge of accumulated charge. Typically, band The antistatic agent provides a more or less watery film on the surface, containing at least one hydrophilic molecule. These are substances that cause static electricity. These antistatic agents, which are usually surface-active, contain nitrogen (amines, Amides, quaternary ammonium compounds), phosphorus-containing (phosphate esters) and sulfur-containing (sulfur It can be divided into alkyl phosphates and alkyl sulfates as antistatic agents. Lauryl chloride ( Dimethylbenzylammonium (or stearyl) is used as an antistatic agent on the surface of textiles, or It is suitable as an additive to detergents and cleaning agents, and in doing so, it also provides an additional conditioning effect. It will be achieved.

[0156] Moisturizers help regulate skin moisture. Preferred moisturizers according to the present invention include ami No acids, pyrrolidone carboxylic acids, lactic acid and its salts, lactitol, urea and urea derivatives, urine Acids, glucosamine, creatinine, collagen cleavage products, chitosan or chitosan salts / Derivatives, and in particular, polyols and polyol derivatives (e.g., glycerol, diglycerol) Cerol, triglycerides, ethylene glycol, propylene glycol, butylene glycol Recall, erythritol, 1,2,6-hexanetriol, polyethylene glycol (e.g. PEG-4, PEG-6, PEG-7, PEG-8, PEG-9, PEG-1 0, PEG-12, PEG-14, PEG-16, PEG-18, PEG-20), sugar and Sugar derivatives (fructose, glucose, maltose, maltitol, mannitol, i Nositol, sorbitol, sorbitol silanediol, sucrose, trehalose, Xylose, xylitol, glucuronic acid and its salts), ethoxylated sorbitol (Sorbeth-6, Sorbeth-20, Sorbeth-30, Sorbeth-40), honey and hard Honey, hydrogenated starch hydrolysate, hydrogenated wheat protein, and PEG-20 acetate Examples include mixtures of polymers. Preferred as a suitable humectant according to the present invention is glycerin. These are cerol, diglycerol, triglycerol, and butylene glycol.

[0157] Examples of bio-derived agents include tocopherol, tocopherol acetate, and tocopheryl palmitate. Rollol, ascorbic acid, (deoxy)ribonucleic acid and their fragmentation products, β-glucan Retinol, Bisabolol, Allantoin, Phytantriol, Panthenol, AH Acid A, amino acids, ceramides, pseudoceramides, essential oils, plant extracts, e.g., plum extract. It is understood to refer to the substance, Bambara nut extract, and complex vitamins.

[0158] Undesirable conditions on the treated fabric surface caused by the action of oxygen and other oxidative processes. To prevent changes, macroemulsions may contain antioxidants. Examples of compounds include amino acids (e.g., glycine, histidine, tyrosine, tryptophan). ) and their derivatives, imidazoles (e.g., urocanic acid) and their derivatives, Butides, for example, D,L-carnosine, D-carnosine, L-carnosine and their derivatives Conductors (e.g., anserine), carotenoids, carotenes (e.g., α-carotene, β-carotene) Rotenoids, lycopene, and their derivatives, chlorogenic acid and its derivatives, lipoic acid and its derivatives Derivatives (e.g., dihydrolipoic acid), aurothioglucose, propylthiouracil and Other thiols (e.g., thioredoxin, glutathione, cysteine, cystine, cyste Amines and their glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, and butyl compounds. , and lauryl, palmitoyl, oleyl, γ-linoleyl, cholesteryl, and glyceryl (Lyl esters) and their salts, dilauryl thiodipropionate, di thiodipropionate Stearyl, thiodipropionic acid and their derivatives (esters, ethers, peptides, Lipids, nucleotides, nucleosides, and salts) as well as very low permissible doses (e.g., , sulfoximine compounds (e.g., butionine sulfoximine) in picomoles to micromoles / kg Hoximin, homocysteine ​​sulfoximin, butionine sulfone, penta-, hexa- (, heptathonine sulfoximine), further (metal) chelating agents (e.g., α-hydro Xy fatty acids, palmitic acid, phytic acid, lactoferrin), α-hydroxy acids (for example) Citric acid, lactic acid, malic acid, humic acid, bile acid, bile extract, bilirubin, bilirubin Din, EDTA, EGTA and their derivatives, unsaturated fatty acids and their derivatives (for example) For example, gamma-linolenic acid, linoleic acid, oleic acid, folic acid and its derivatives, ubiquinone and Ubiquinol and its derivatives, vitamin C and its derivatives (e.g., palmitin) Ascorbyl acid, magnesium ascorbyl phosphate, ascorbyl acetate), tocopherol and so These derivatives (e.g., vitamin E acetate), vitamin A and its derivatives (vitamin A phosphate) Lumitinate salts, coniferyl benzoate derived from benzoic acid resin, rutinic acid, and its derivatives α-glycosylrutin, ferulic acid, furfrilliliden glucitol, carnosine, buty Hydroxytoluene, Butylhydroxyanisole, Nordihydroguaiaretinic acid, Trihydroxybutyrophenone, uric acid and its derivatives, mannose and its derivatives, sulphur Peroxide dismutase, zinc and its derivatives (e.g., ZnO, ZnSO4), cele Nium and its derivatives (e.g., selenium methionine), stilbene and its derivatives ( For example, stilbene oxide, trans-stilbene oxide) and the above-mentioned active substances (salts, etc.) The present invention relates to esters, ethers, sugars, nucleotides, nucleosides, peptides, and lipids. Suitable derivatives include the following.

[0159] A suitable anti-dandruff agent is piroctone olamine (1-hydroxy-4-methyl-6-(2,4 ,4-trimitylpentyl)-2-(1H)-pyridinone monoethanolamine salt), B aypival (registered trademark) (crimbazol), Ketoconazol (registered trademark) ,(4-acetyl-1-{-4-[2-(2,4-dichlorophenyl)r-2-(1H- Imidazole-1-ylmethyl)-1,3-dioxirane-c-4-ylmethoxypheny Lupiperazine, ketoconazole, erbiol, selenium disulfide, colloidal sulfur Sulfur polyethylene glycol monooleate sorbitan, sulfur ricinol polyethylene Xylates, sulfur-tar distillates, salicylic acid (or combinations with hexachlorophene) (Waseda), undecylenate sulfosuccinate monoethanolamine sodium salt, Lamepo n(registered trademark)UD (protein-undecylenate condensate), zinc pyrithione, aluminum These are umpyrithione and magnesiumpyrithione / dipyrithione-magnesium sulfate.

[0160] Cosmetic deodorants (deodorizers) weaken, mask, or eliminate body odor. Body odor is caused by skin This is caused by the effect of bacteria on apocrine sweating, and in the process, it produces the decomposition products of unpleasant odors. Therefore, the deodorant is an antibacterial agent, an enzyme inhibitor, an odor absorber, and an odor shielding agent. It contains active ingredients that function in this way.

[0161] As an antimicrobial agent, any substance that is active against Gram-positive bacteria is, for example, 4-Hydro Loxybenzoic 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'-meth Len-bis(6-bromo-4-chlorophenol), 3-methyl-4-(1-methyleth (Lu)-phenol, 2-benzyl-4-chlorophenol, 3-(4-chlorophenoxy )-1,2-propanediol, 3-iodo-2-propynylbutylcarbamate, chloro Lohexidine, 3,4,4'-Trichlorocarbanilide (TTC), Antimicrobial fragrance, Thymol Thyme oil, eugenol, clove oil, menthol, mint oil, farnesol, fe Noxyethanol, glycerol monocaprate, glycerol monocaprylate, mono Glycerol urylate (GML), diglycerol monocaprate (DMC), salicylate Acid-N-alkylamides, for example, salicylic acid-n-octylamide or salicylic acid- n-decylamides are generally preferred.

[0162] Examples of suitable enzyme inhibitors are esterase inhibitors. These are preferably citrate inhibitors. Lyalkyl, for example, trimethyl citrate, tripropyl citrate, triisopropyl citrate Ropil, tributyl citrate and especially triethyl citrate (Hydagen® registered trademark) These substances inhibit enzyme activity, thus reducing odor formation. Further substances suitable as terase inhibitors include sterol sulfate or sterol phosphate. For example, lanosterol, cholesterol, campesterol, stigmasterol Sitosterol sulfate or sitosterol phosphate, dicarboxylic acids and their derivatives For example, glutaric acid, monoethyl glutarate, diethyl glutarate adipic acid, monoethyl adipic acid ether, diethyl adipic acid ether, malonic acid and diethyl malonate, hydroxycarboxylic acids and their esters, for example, These are citric acid, malic acid, tartaric acid or diethyl ether tartarate, and zinc glycinate. .

[0163] Suitable odor absorbers are those that can absorb odor-causing compounds and primarily retain them. These are substances that can do this. They reduce the partial pressure of the individual components, thus slowing down the diffusion rate. This reduces the odor. In this case, the fragrances specified herein must remain unaffected. It is important that this is not the case. Odor absorbers do not affect bacteria. They are, for example, For example, the main component is a zinc salt complex of ricinoleic acid, or a "fixative," such as labdanum. Alternatively, as known to those skilled in the art as an extract of Styrax or a specific abietic acid derivative. It contains certain substances that are primarily odor-neutral. In addition to their function as odor-blocking agents, they also act as deodorizers. The fragrances or oils that provide each aroma act as odor masking agents. Examples of oils that may be mentioned It is a mixture of natural and synthetic fragrances. Natural fragrances include, for example, flowers, stems and leaves, fruits, and berries. These include extracts of bark, wood, herbs and grasses, needles and branches, and resins and balsams. Preferred are Also, animal-derived ingredients, such as civet and sea lion incense. Typical synthetic fragrance compounds are... The products are of the form of esters, ethers, aldehydes, ketones, alcohols, and hydrocarbons. Examples of stereotype fragrance compounds include benzyl acetate and p-tert-butylcyclohexyl acetate. Syl, linalyl acetate, phenethyl acetate, linalyl benzoate, benzyl formate, propionic acid These are allylcyclohexyl, styraryl propionate, and benzyl salicylate. Examples of ethers include benzyl ethyl ether, and examples of aldehydes include 8-18 carbon Linear alcanal, citral, citronellal, and citronellyloxyacetate containing elementary atoms Toaldehyde, cyclamenaldehyde, hydroxycitronellal, lirial and boula Examples include geonal, and examples of ketones include ionone and methylcedyl ketone. Alcohol contains anetol, citronellol, eugenol, isoeugenol, and Examples include laniol, linalool, phenethyl alcohol, and terpineol, and carbonized water. The main components are terpenes and balsams. However, what is preferable is a pleasant feeling It is a mixture of various fragrances that work together to create an aroma. It is usually used as a flavoring component. Low-potency essential oils include perfumed oils such as sage oil, chamomile oil, clove oil, melissa oil, and mi. Flour oil, cinnamon leaf oil, linden flower oil, juniper berry oil, vetiver oil, Libanum oil, galbanum oil, labdanum oil, and lavandin oil are also suitable. The ingredients are bergamot oil, dihydromyrcenol, lilial, citronellol. Phenethyl alcohol, α-hexyl cinnamaldehyde, geraniol, benzyl Acetone, cyclamenaldehyde, linalool, Boisam Blenforte, Ambroxa Indole, hedione, sandelice, lemon oil, mandarin oil, orange oil, glyco Allylamyl oxalate, cyclobeltal, lavandin oil, clay sage oil, β-Damascotol Geranium oil, cyclohexyl salicylate, Vertofix Coeu r, iso-E-super, Fixolide NP, evernyl, iraldine gamma, Phenylacetic acid, geranyl acetate, benzyl acetate, rose oxide, Romilat, Iro These are tyl and Floramat, which are used individually or in combination.

[0164] Antiperspirants (perspirants) affect the activity of eccrine sweat glands, thus causing dampness in the armpits and body odor. By weakening the sweat glands, sweat formation is reduced. The water-based or anhydrous formulations of antiperspirants typically contain the following: Ingredients: Astringent, oil component, nonionic emulsifier, coemulsifier, thickener, excipient, e.g., thickener Agent or complexing agent and / or non-aqueous solvent, e.g., ethanol, propylene glycol, and / or containing glycerol. Suitable astringent antiperspirants include aluminum, di It is a primary salt of licorice or zinc. Examples of active substances with such suitable antiperspirant activity include For example, aluminum chloride, aluminum chlorohydrate, aluminum dichlorohydrate, A Luminium sesquichlorohydrate, and, for example, hydroxyallantoic acid propylene Recall-1,2-aluminum, aluminum chloride tartrate, aluminum zirconium Trichlorohydrate, aluminum zirconium tetrachlorohydrate, aluminum zirconium Their complex compounds with nium pentachlorohydrate, and with amino acids such as glycine. These are complex compounds. In addition, antiperspirants contain small amounts of common oil-soluble and water-soluble excipients. It may contain such oil-soluble excipients, for example, anti-inflammatory, skin-protective, or aromatic. It may contain essential oils, synthetic skin protectants and / or oil-soluble fragrance oils.

[0165] The capsule according to the present invention may contain an antimicrobial agent to combat microorganisms. , the spectrum of antimicrobial activity and the relationship between bacteriostatic agents, bactericidal agents, fungicidal agents, etc. Distinctions are made according to the mechanism of use. Examples of important substances derived from these groups include benzoyl chloride. The compounds are nzalkonium, alkylaryl sulfonate, halophenol, and phenylmercury acetate. In this case, these compounds do not necessarily have to be added to the entire detergent and cleaning agent according to the present invention. As a biological agent, all substances that are active against Gram-positive bacteria include, for example, 4-hydroxy cybenzoic acid and its salts and esters, N-(4-chlorophenyl)-N'(3,4-dichlorobenzoic acid Loropetine)urea, 2,4,4'-trichloro-2'-hydroxy-diphenyl A Tel(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-Propanediol, 3-Iodo-2-Propynnylbutylcarbamate, Chlorohe Xyzidine, 3,4,4'-trichlorocarbanilide (TTC), antibacterial fragrance, thymol, ta Immuno oil, eugenol, clove oil, menthol, mint oil, farnesol, phenoxyethanol Citrate, glycerol monocaprate, glycerol monocaprylate, monolauric acid Glycerol glycerate (GML), diglycerol monocaprate (DMC), salicylic acid - N-alkylamides, for example, salicylic acid-n-octylamide or salicylic acid-n- Decylamide is generally preferred.

[0166] Among the compounds that serve as bleaching agents, producing H2O2 in water, sodium perborate tetrahydrate is one of them. Japanese chloride and sodium perborate monohydrate are of particular importance. Further useful bleaching agents include, for example, Then, sodium percarbonate, peroxypyrrophosphate, citrate perhydrate, and H2O2 The resulting peracid salts or peracids include perbenzoates, peroxophthalates, and diper. These are azelaic acid, phthaloimino peracid, or diperdodecanediic acid, under conditions of hyperhydrolysis. Aliphatic peroxocarboxylic acid having preferably 1 to 10 carbon atoms, particularly 2 to 4 carbon atoms. Compounds that produce perbenzoic acid, and / or optionally substituted perbenzoic acid, are used as bleach activators. This is possible. Preferably, the above number of C atoms and / or optionally substituted benzos. A substance having an O-acyl group and / or an N-acyl group together with an yl group. Preferably, Polyacylated alkylenediamines, especially tetraacetylethylenediamine (TAED) , acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydr Ro-1,3,5-triazine (DADHT), acylated glycolyllyl, especially tetraacetate Tylglycoryl (TAGU), N-acylimide, especially N-nonanoylsuccinimide (NOSI), acylated sulfonic acid phenol, especially oxybenzenesulfonic acid N- Nonanoyl or isononanoyl (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, and acylated polyhydric alcohols, particularly triacetin, ethylene diacetate, Recall and 2,5-diacetoxy-2,5-dihydrofuran. Conventional bleach activation In addition to, or instead of, the so-called bleaching agent to the textile treatment agent via the capsules of the present invention. White catalysts can also be incorporated. These substances are transition metal salts or transition gold that enhance bleaching. Group complexes, e.g., Mn-, Fe-, Co-, R-, or Mo- salt complexes or -carbon complexes It is a complex with nitrogen-containing tripod-type ligands Mn-, Fe-, Co-, Ru-, Mo- Ti-, V-, and Cu- complexes and Co-, Fe-, Cu-, and Ru-amine complexes are also bleached. It can be used as a catalyst.

[0167] The capsules according to the present invention may also contain preservatives. Examples include sorbic acid and its salts, and ammonium compounds. Salicylic acid and its salts, salicylic acid and its salts, phenoxyethanol, butylcarbamic acid 3-iodo-2-propynyl, sodium N-(hydroxymethyl)glycinate, bifer These are yl-2-ol and mixtures thereof. Suitable preservatives are used in a pH range up to 7. Diazolidinyl urea, sodium benzoate, and potassium sorbate may be used as solvents. Water-based combinations that do not contain (Schulke and Mayr Euxyl (registered trademark) (Available as standard K 500). Preservatives based on organic acids and / or their salts are It is particularly suitable for storing skin-friendly detergents and capsules according to the present invention.

[0168] Silicone derivatives, for example, improve re-wetting properties and iron the treated fabric surface. They may also be used in textile processing to smooth the fabric. Furthermore, due to their foam-suppressing properties... This improves the rinsing behavior of detergents and cleaning agents. Preferred silicone derivatives are, for example, A Polydialkyl groups having 1 to 5 carbon atoms and being fully or partially fluorinated. The preferred silicone is a siloxane or alkylarylsiloxane. It can be converted, and then be amino-functionalized, or quaternized, or Si-O It is a polydimethylsiloxane having H, Si-H and / or Si-Cl bonds. The viscosity of the silicone at 25°C is in the range of 100 mPas to 100,000 mPas. be.

[0169] The capsules according to the present invention may also contain an insecticide. A suitable insecticide is, for example, N N-diethyl-m-toluamide, 1,2-pentanediol, or aminopropionic acid Ethylbutylacetyl, 1-(1-methylpropoxycarbonyl)-2-(2-hydroxyl Similar to cyethyl)piperidine, p-menthane-3,8-diol, and 2-undecanone. Essential oils, such as citronella oil, lemongrass oil, lavender oil, neem oil, and eucalyptus oil. In particular, p-menthane-3,8-diol, essential oils, such as citronella oil and lemongrass. These are oils, lavender oil, neem oil, and eucalyptus oil.

[0170] The capsules according to the present invention can also be absorbed into the surface of the treated fabric, and the photostability of the fibers. The term UV photoprotective factor may also include UV absorbers that improve UV protection. For example, at room temperature. It is a liquid or crystalline substance (a light-protective filter) that absorbs ultraviolet light and the absorbed energy It is understood to refer to organic substances that can emit long-wavelength radiation, for example, in the form of heat. The UV light protection factor is usually 0.1% to 5% by weight, preferably 0.2% to 1% by weight. It is present in a certain percentage of amount. UVB filters can be oil-soluble or water-soluble. Examples of substances containing 3-benzylidene camphor or 3-benzylidene norcamphor are available. Calcium and its derivatives, for example, 3-(4-methylbenzylidene)camphor, 4-amino Benzoic acid derivatives, preferably 3-(4-dimethylamino)benzoate-2-ethyl-hexyl Luester, 4-(dimethylamino)benzoate-2-octyl ester and 4-(dimeth Amyl aminobenzoate ester; cinnamic acid ester, preferably 4-methoxycinnamic acid -2-ethylhexyl ester, 4-methoxy-propyl cinnamate, 4-methoxy -Isoamyl cinnamate, and 2-Cyano-3,3-phenylcinnamate-2-ethyl Xyl ester (octocrylene), salicylic acid ester, preferably salicylic acid-2 -Ethylhexyl ester, 4-propylbenzyl salicylate, and salicylate Acid homomethyl esters; derivatives of benzophenone, preferably 2-hydroxy-4-methyl esters. Xybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, and 2,2'-Dihydroxy-4-methoxybenzophenone; ester of benzylmalonic acid Preferably, di-2-ethylhexyl 4-methoxybenzylmalonate; triad Derivatives, for example, 2,4,6-trianilino-(p-carbo-2'-ethyl-1'- Xyloxy)-1,3,5-triazine and octyltriazone or dioctylbuta Midotriazone (Uvasorb® HEB); propane-1,3-dione, e.g. For example, 1-(4-tert.-butylphenyl)-3-(4'methoxyphenyl)propane Examples include n-1,3-dione and ketotricyclo(5.2.1.0)decane derivatives.

[0171] In particular, suitable UVA filters include benzoylmethane derivatives, for example, 1-(4 '-tert.-butylphenyl)-3-(4'-methoxyphenyl)propane-1,3 -Dione, 4-tert-butyl-4'-methoxydibenzoylmethane (Parsol( (Registered Trademark) 1789), 2-(4-diethylamino-2-hydroxybenzoyl)-benzoyl Hexyl phosphate (Uvinul® A Plus), 1-phenyl-3- Examples include (4'-isopropylphenyl)-propane-1,3-dione and enamine compounds. UVA and UVB filters can, of course, be used in combination. A particularly favorable combination is an ester of cinnamic acid, preferably 4-methoxycinnamic acid-2- Ethylhexyl ester and / or propyl 4-methoxycinnamate and / or A derivative of benzoylmethane combined with 4-methoxycinnamate isoamyl ester, for example , 4-tert-butyl-4'-methoxydibenzoylmethane (Parsol (Registered Trademark) Standard 1789) and 2-Cyano-3,3-phenylcinnamate-2-ethyl-hexyl ester It is composed of octocrylene. Advantageously, these combinations are water-soluble Fi Luther, for example, 2-phenylbenzimidazole-5-sulfonic acid and its alkali salts Alkaline earth salts, ammonium salts, alkylammonium salts, alkanol ammonia It is used together with ammonium salts and glucan ammonium salts.

[0172] In addition to the soluble substances mentioned above, insoluble photoprotective dyes, specifically finely dispersed metal acids, are also present. Metal oxides or metal salts are also suitable for this purpose. Examples of suitable metal oxides include, in particular, zinc oxide and Titanium oxide, as well as iron, zirconium, silicon, manganese, aluminum, and cerium. These are oxides and mixtures thereof. Silicates (talc), barium sulfate or stearin Zinc oxide may also be used as a salt. Oxides and salts are used in skincare and skin protection emulsions. It is used in the form of a pigment for cosmetic and decorative purposes. In this case, the particles are less than 100 nm in size. It should have an average diameter of 5 nm to 50 nm, and more preferably 15 nm to 30 nm. Yes, they exist. They can have a spherical shape, but they can also deviate from an elliptical or spherical shape. Particles having a different form may be used. The dye is surface-treated, i.e., hydrophilic. It can also exist in a hydrophobic form. A typical example is a coated two Titanium dioxide, for example, titanium dioxide T805 (Degussa) or Eusolex ( (Registered Trademark) T2000, Eusolex(Registered Trademark) T, Eusolex(Registered Trademark) T -ECO, Eusolex (registered trademark) T-Aqua, Eusolex (registered trademark) T- These are 45D (all Merck) and Uvinul TiO2 (BASF). In this context... Suitable hydrophobic coating agents are mainly silicones, specifically trialkoxyoctyl It is either or simethicone. In sunscreens, it is a so-called micropigment or nanopigment. Preferably, micronized zinc oxide, for example, Z-COTE( The registered trademark () or Z-COTE HP1 (registered trademark) is used.

[0173] In addition, a substance that complexes heavy metals may be encapsulated within the capsule according to the present invention. Examples of heavy metal complexing agents include ethylenediaminetetraacetic acid (EDTA) or nitrilotriacetic acid. Alkali salts of (NTA), and anionic polyelectrolytes, such as polymaleic acid and poly It is an alkali metal salt of a sulfonic acid. The preferred class of complexing agent is phosphonates, and This is 0.01 to 2.5% by weight, preferably 0.02 to 2% by weight, and especially 0.03 to 1.5% by weight. They are included in preferred textile treatment agents in a certain percentage of amount. Examples of these preferred compounds include, in particular, O Luganophosphonates, for example, 1-hydroxyethane-1,1-diphosphonic acid (HEDP) ), aminotri(methylenephosphonic acid) (ATMP), diethylenetriaminepenta(me (Tylenephosphonic acid) (DTPMP or DETPMP) and 2-phosphonobutane-1,2 Examples include ,4-tricarboxylic acids (PBS-AM), which are usually ammonium salts. It is also used in the form of alkali metal salts.

[0174] The preferred hydrophobic active substances identified above can be used alone or in combination of two or three of the above substances. Alternatively, it can be used in a mixture of four or more people.

[0175] According to certain and preferred modifications, the capsules of the present invention impart fragrance or aroma. In other words, if it is to be used for delivery or transfer, that is, if it is this If dispersed in the oil phase of the invention, the hydrophobic active substance will have a fragrance as specified herein. A water substance or an aromatic substance or at least one fragrance oil or aroma, i.e., the aforementioned It contains or consists of a corresponding mixture of qualities.

[0176] Possible additional ingredients generally have applications in the field of microencapsulation. All compounds are included. Such components are well known in the art. However, Odorous active substances such as fragrances and perfumes, which are of both synthetic and natural origin, are preferred. Preferably is a core-shell microcapsule according to the present invention, in which case the core is an essential oil Concrete, absolute, resin, resinous substance, balsam, non-grade 1 or grade 2 aluminum One of the following is selected from the group consisting of extracts of natural raw materials such as tinctures containing kohl. The above odor substances / fragrances are contained as activators (multiple activators are possible). Preferably, these substances are heart It imparts a pleasant scent.

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

[0178] Therefore, the processes described herein involve a considerable amount of active ingredients (or multiple active ingredients). It is possible to efficiently encapsulate )

[0179] Alternatively, and preferably, the active ingredient itself may be, for example, a fragrance oil may contain at least one poly It can serve as an oil component that dissolves isocyanates.

[0180] The eco-friendly core-shell microcapsules of this invention efficiently contain various active ingredients. Because it enables the preparation of numerous products and its incorporation into a wide range of product formulations, it can be used in many applications. This makes it possible.

[0181] Furthermore, the first step of the process described herein is at least one capsule-shaped This requires the provision of a first aqueous phase containing a capsule-forming aid, i.e., one or more capsule-forming aids. For this purpose, the capsule-forming aid is dissolved in an aqueous solvent (preferably pure water) to form a first aqueous phase. To accomplish.

[0182] Capsule-forming aids used within the scope of the present invention include, for example, surfactants (vaginal surfactants). It is a surfactant or emulsifier and / or a colloidal protective agent.

[0183] Generally, surfactants, or simply surfactants, reduce the surface tension between two different phases. Furthermore, a substance that usually possesses both hydrophobic and hydrophilic functional groups, and is amphiphilic in nature. It is of quality. As a result, these substances form at the interface between the oil phase and the water phase, for example, in an oil-in-water emulsion. It can be placed around the droplet, stabilizing the individual oil droplets that have spread finely in the surrounding aqueous phase. This makes it possible, thus avoiding the aggregation of the oil droplets. Therefore, these surfactants emulsify It may also act as an agent, that is, to enhance dynamic stability and reduce the interfacial tension between the two phases. It may also act as a substance that stabilizes the emulsion by causing it to settle.

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

[0185] Suitable nonionic emulsifiers include, for example, • Linear C 8-22 C to fatty alcohols 12-22 8 fatty acids and alkyl groups 2 to 30 moles of ethylene oxy to alkylphenol containing ~15 carbon atoms Addition products of propylene oxide and / or 0 to 5 moles of propylene oxide; • Addition product of 1 mole to 30 moles of ethylene oxide to glycerol 12 / 18 fat monoesters and diesters of phytophosphates; • Saturated and unsaturated fatty acids containing 6 to 22 carbon atoms and their ethylene oxide load products Glycerol monoesters and diesters and sorbitan monoesters and diesters Lu; • Add 15 to 60 moles of ethylene oxide to castor oil and / or hydrogenated castor oil. additive products; • Polyol esters, especially polyglycerol esters, for example, polyricinoleate Liglycerol, polyglycerol poly-12-hydroxystearate, or dimer Polyglycerol isostearate. Compounds derived from some of these classes. Mixtures are also preferred; • Addition of 2 to 15 moles of ethylene oxide to castor oil and / or hydrogenated castor oil. product; • Linear, branched, unsaturated or saturated C 6 / 22 Fatty acids, ricinolenic acid and 12-hydrox Cystearic acid and glycerol, polyglycerol, pentaerythritol, dipenta Erythritol, sugar alcohols (e.g., sorbitol), alkyl glucosides (e.g., , methyl glucoside, butyl glucoside, lauryl glucoside) and polyglucoside (e.g.) For example, partial esters based on cellulose; • Mono-, di- and trialkyl phosphates and mono-, di- and tri-PEG-al phosphates Kill 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 is C 6-22 Fatty acids, methyl glucose and polyols, preferably glycerol, Polyglycerol mixed esters; • Polyalkylene glycol; and Glycerol carbonate It includes.

[0186] Fatty alcohols, fatty acids, alkylphenols, glycerol mono- and die-glycerols of fatty acids Ethylene oxide to esters and sorbitan mono- and diesters, or to castor oil The addition products of and / or propylene oxide are known commercially available products. These are a mixture of homologs, and their average degree of alkoxylation is that of ethylene oxide and / or This corresponds to the ratio of the amount of propylene oxide to the amount of the substrate on which the addition reaction takes place. The addition product of ethylene oxide to C 12 / 18 Fatty acid monoesters and diesters are It is known as a lipid layer strengthening agent for cosmetic formulations. Below, preferred emulsifiers are further Details are provided below:

[0187] Partial glycerides: A typical example of a suitable partial glyceride is monoglyceryl hydroxystearate. Lido, diglyceride hydroxystearate, monoglyceride isostearate, isos Diglyceride thearate, monoglyceride oleate, diglyceride oleate, licin Linoleic acid monoglyceride, ricinoleic acid diglyceride, linoleic acid monoglyceride, linoleic acid Diglycerides of erucic acid, monoglycerides of linolenic acid, diglycerides of linolenic acid, monoglycerides of erucic acid Glycerides, diglyceride erucate, monoglyceride tartarate, diglyceride tartarate, cucumber Malate monoglycerides, citrate diglycerides, malate monoglycerides, malate diglycerides These may still contain cerides and small amounts of triglycerides derived from the manufacturing process. It is a technical mixture. 1 to 30 moles, preferably 5 moles, of the mentioned partial glycerides. Addition products of 10 moles of ethylene oxide are also preferred.

[0188] Sorbitan esters: Suitable sorbitan esters are sorbitan monoisostearate, Sorbitan sesquiisostearate, sorbitan diisostearate, triisostearate Sorbitan oleate, sorbitan monooleate, sorbitan sesquioleate, diolein Sorbitan acid, sorbitan trioleate, sorbitan monoerucate, sorbitan sesquierucate Rubitan, sorbitan dielcate, sorbitan trierucate, sorbitan monolicinoleate Sorbitan sesquiricinoleate, sorbitan diricinoleate, sorbitan triricinoleate Vitan, sorbitan monohydroxystearate, sorbitan sesquihydroxystearate Tan, sorbitan dihydroxystearate, sorbitan trihydroxystearate, Sorbitan monotartrate, sorbitan sesquitartrate, sorbitan ditartrate, sorbitan tritartrate Sorbitan monocitrate, sorbitan sesquicitrate, sorbitan dicitrate, tri Sorbitan citrate, sorbitan monomaleate, sorbitan sesquimaleate, dimale These are sorbitan iodine, sorbitan trimalate, and technical mixtures thereof. 1 mole to 30 moles, preferably 5 moles to 10 moles, of ethyl acetate to the sorbitan ester. Addition products of ylene oxides are also suitable.

[0189] Polyglycerol esters: Typical examples of suitable polyglycerol esters include dipolyhydr Polyglyceryl-2 oxystearate (Dehymuls® PGPH), Liglycerin-3-diisostearate (Lameform® TGI), iso Polyglyceryl-4 stearate (Isolan® GI 34), oleic acid Polyglyceryl-3, Diisostearoyl Polyglyceryl-3 Diisostearate (Is olan(registered trademark) PDI), polyglyceryl-3 methyl glucose distearate ( Tego Care (registered trademark) 450), Polyglyceryl-3 beeswax (Cera Bel) lina(registered trademark), polyglyceryl-4 caprate (polyglycerol caprate) T2010 / 90), Polyglyceryl-3 Cetyl Ether (Chimexane (Registered Trademark) (Registered Trademark) NL), Polyglyceryl-3 Distearate (Cremophor® GS 32) and polyglyceryl polyricinoleate (Admul(registered trademark) WOL 140 3) Polyglyceryl isostearate dimer acid and mixtures thereof. Examples of lyol esters are trimethylolpropane or pentaerythritol. Lauric acid, coco fatty acids, and tallow fat reacted with 1 to 30 moles of ethylene oxide. Monoesters and dienes formed by acids, palmitic acid, stearic acid, oleic acid, behenic acid, etc. These are ster and triester.

[0190] Tetraalkylammonium salts: Cationic and active surfactants in aqueous solutions It contains hydrophobic polymer groups necessary for surface activity at the cation level through dissociation. Cationic A group of important representative surfactants is the general formula (R 1 R 2 R 3 R 4 N + )X - Tetraalkyl It is a monium salt. Here, R 1 represents C1-C8 alkyl (alkenyl), R 2 , R 3 and R 4 Each of these is an alkyl (alkenyl) group having 1 to 22 carbon atoms independently. This represents a gal. X is preferably from the group consisting of halogen compounds, alkyl sulfates, and alkyl carbonates. The selected counterion. The nitrogen group consists of two long acyl groups and two short alkyl (alkyl) groups. Cationic surfactants substituted with a nyl group are particularly preferred.

[0191] Esterquat: A cationic surfactant particularly useful as a co-surfactant for the present invention. Further classes of agents are represented by so-called ester quats. Ester quats are It is generally understood to be a quaternized fatty acid triethanolamine ester salt. These are known compounds that can be obtained by relevant methods of prepared organic chemistry. In this regard, international patent application WO91 / 01295A1 is referenced, and accordingly, hypophosphorus hypochlorite In the presence of an acid, triethanolamine is partially esterified by a fatty acid, and is exposed to air. The mixture is passed through the appropriate solution, and then the whole is quaternized with dimethyl sulfate or ethylene oxide. In addition, German patent DE4308794C1 relates to a quaternary triethanolamine ester. The solid ester quad is prepared in the presence of a suitable dispersant, preferably a fatty alcohol. This describes the manufacturing process of [product name].

[0192] A typical example of an ester quat suitable for use according to the present invention is one in which the acyl component is RC Monocarbons corresponding to formula RCOOH, where O is an acyl group containing 6 to 10 carbon atoms. It is a product derived from an acid, with triethanolamine (TEA) as the amine component. Examples of monocarboxylic acids include caproic acid, caprylic acid, capric acid, and their technical mixtures. Compounds, such as so-called head-fractionated fatty acids. The acyl component is a carbon base of 8-10. Ester quats derived from monocarboxylic acids containing the ester are preferably used. Sterkwat contains acyl components such as malonic acid, succinic acid, maleic acid, fumaric acid, and glutaric acid. Acids such as sorbic acid, pimelic acid, azelaic acid, sebacic acid and / or dodecanediic acid. It is derived from a dicarboxylic acid, but preferably from adipic acid. Generally speaking, The sil component is derived from a mixture of monocarboxylic acid and adipic acid containing 6 to 22 carbon atoms. A monocal ester quat is preferably used in the final ester quat. The molar ratio of benzoic acid to dicarboxylic acid is in the range of 1:99 to 99:1, preferably 50:50 to 9 The range is 0:10, or more specifically, 70:30 to 80:20. (Classification to Grade 4) In addition to fatty acid triethanolamine ester salts, other suitable ester quats are mono - / Diethanolalkylamine or 1,2-dihydroxypropyl dicarboxylic acid mixture It is a quaternization ester salt with a pyru-dialkylamine. Ester quat is the corresponding di They may be obtained from both fatty acids and the corresponding triglycerides in a mixture with carboxylic acids. One such process, intended to be representative of the relevant prior art, is a European patent. This is proposed in EP0750606B1. To produce quaternary esters, monocal A mixture of benzoic acid and dicarboxylic acid with triethanolamine can be used for carboxyl function. It may be used in a molar ratio of 1.1:1 to 3:1 based on the performance characteristics of ester quat. Considering the properties, a ratio of 1.2:1 to 2.2:1, preferably 1.5:1 to 1.9:1, is particularly suitable. It has been found to be advantageous. The preferred ester quat is an average of 1.5 to 1.9. This is a technical mixture of monoesters, diesters, and triesters based on their degree of esterification.

[0193] Even more suitable surfactants are nonionic polymers, such as sorbitan ester ethoxy Rate (Tween® registered trademark) and / or polypropylene oxide / ethylene copolymer Rimmer, Tergitol(TM), Triton(TM) (Dow Chemical s) and alcohol ethoxylates.

[0194] Combinations of anionic and / or amphoteric surfactants with one or more nonionic surfactants The use of wasabi is even more advantageous. In a preferred embodiment of the present invention, the composition is further, The required product formulation does not cause aggregation. • 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, colloidal protective agents (so-called protective colloids) aid in capsule formation. It can be dissolved in the first aqueous phase as an agent(s).

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

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

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

[0199] Preferably, one or more colloidal protective agents are polymers, such as polyvinyl alcohol. (Hydrolysis: 70% or more), for example, Selvol (trademark) (Sekisui Spec ialty Chemicals), polyvinylpyrrolidone, polyvinyl acetate, chemical modification Modified biopolymers, preferably chemically modified starch, modified gum arabic, modified Decorated cellulose or cellulose derivatives, e.g., methylcellulose, hydroxypropylcellulose Ropil methylcellulose and hydroxyethylcellulose, gelatin, casein, acrylic acid Selected from the group consisting of rate polymers or mixtures thereof. Also preferred are, for example, Starch (derived from corn, quinoa, oats, barley, or potatoes) (Often), gum arabic, or for example, octenyl succinate anhydride (OSA) It is cellulose that has been chemically modified. A typical product is, for example, Capsul. (Registered Trademark) Starch or Hi-CAP (Registered Trademark) 100 (Ingredients) It is available from Inc.

[0200] Preferably, the colloidal protective agent(s) is, for example, a known protective colloid, for example, Polyvinyl alcohol, polyvinylpyrrolidone, hydroxyethylcellulose, methylcellulose Selected from the group consisting of lurose, gelatin, casein, polymethacrylic acid, and mixtures thereof. It will be selected.

[0201] Polyvinyl alcohol is used in all types of bio-based microcapsules according to the present invention. It was found to be a suitable protective colloid (see Examples 1-12). Furthermore, since polyvinyl alcohol is biodegradable under both aerobic and anaerobic conditions, It is particularly suitable for preparing biodegradable microcapsules, and consequently, microcapsules that are environmentally friendly. That is the case.

[0202] Furthermore, the protective colloid is preferably modified gum arabic, anhydrous octenyl succinate Acid-modified starch (OSA), e.g., Capsu (registered trademark), HiCap (trademark). ), soy protein, sodium caseinate, gelatin, bovine serum albumin, sugar beets Topectin, hydrolyzed soy protein, hydrolyzed sericin, pseudocollagen, biological High molecular weight SA-N, Pentacare-NAPF, a mixture of gum arabic and revitalin, and The polymer is an anionic or amphiphilic polymer selected from the group consisting of mixtures of these. can.

[0203] Preferably, the protective colloid is a biopolymer (biomolecule), i.e., a regenerative Extracted from a source or produced by an organism (i.e., of biological origin; bio-derived) These are substances, such as polysaccharides, such as starch or cellulose. Biomacromolecules are It is characterized by a molecular weight distribution ranging from 1,000 Daltons to 1,000,000,000 Daltons. For example, carbohydrates (sugar-based), proteins (amino acid-based), or a combination of both. It can be linear or branched. Biopolymer derivatives (biomers) O-based polymers are derived from such biomacromolecules through chemical derivatization. These are compounds. These substances are usually also biodegradable. Preferably, one or more protective compounds are present. Colloids are modified gum arabic, octenyl succinic anhydride, and other materials. Punpun (OSA), for example, Capsu (registered trademark), HiCap (trademark), or (modified) Selected from the group consisting of (decorated / derivativeized) soy proteins.

[0204] In consideration of the object of the present invention, at least one capsule shape used within the scope of the present invention The auxiliary agent is preferably a colloidal protective agent, in which case the biopolymer compound is particularly beneficial to the ecosystem. It is particularly preferred as a capsule-forming aid, considering a gentle approach.

[0205] A comparison between Example 1 and Example 5 shows that such bio-based protective colloids are high Preparation of bio-based microcapsules exhibiting both stability and high release characteristics according to the present invention This indicates that it can be suitably used in [the specified field].

[0206] Therefore, in a preferred modification, the present invention provides a core-shell microcapsule according to the present invention. This relates to a process for preparing a slurry containing core-shell microcapsules. In this case, at least one forming aid is a biopolymer or a derivative of a biopolymer, preferably It is a derivative of a biomolecule.

[0207] However, in a more preferred modification, at least one capsule-forming agent is polyvinyl It is a nitrile alcohol, and is a microphone with high stability and excellent performance as described above. This enables the formation of capsules.

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

[0209] The microcapsules according to the present invention are one or more colloids as specified herein. It can be prepared by using a protective agent and / or one or more surfactants. Preferably, one or more colloidal protective agents are used. Even more preferably, these The colloidal protective agent is biodegradable and / or bio-based or of biological origin. .

[0210] Typically, the capsule-forming aid(s) are 0.1 to 5% by weight, preferably 0.5 to 5% by weight. It is included in the first aqueous phase in this quantity.

[0211] Capsule-forming aids (multiple), such as protective colloids (multiple), are contained in these amounts. This allows for a high degree of stabilization of oil droplets in a continuous aqueous phase. Furthermore, sedimentation Because the swarm is avoided and the coagulation effect is reduced, the oil particles are finely dispersed in the surrounding aqueous phase, This ensures homogeneous encapsulation and uniform size distribution of the resulting microcapsules. do.

[0212] In addition, continuous stirring during the preparation process according to the present invention results in particles and / or obtains according to the present invention. The aggregation and subsequent clumping of microcapsules, as well as the precipitation of microcapsules, It helps to avoid it.

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

[0214] Furthermore, the process of the present invention uses fewer than 20 monomer units (or repeating units), i.e. , 19 monomer units or less, preferably 15 monomer units or less, even more preferably At least one sugar as a component having 10 or fewer monomer units independently and / or a second aqueous phase containing amino sugars is required, and optionally the second aqueous phase is Furthermore, it includes one or more additional forming aids. For this purpose, fewer than 20 monomers Preferably 15 or fewer monomer units, and even more preferably 10 or fewer monomer units. At least one sugar and / or amino sugar each independently having, and optionally a capsule Forming aids (or multiple aids) are dissolved in an aqueous solvent (preferably pure water).

[0215] However, in an alternative variation of the process of the present invention, the (amino) sugar is directly added to the first aqueous phase. Additionally, the steps of providing a second aqueous phase and preparing an intermediate oil-in-water emulsion can be omitted. It is possible. This allows for the formation of an oil phase containing isocyanates, (amino) sugars, and forming aids. The aqueous phase is mixed with the oil-in-water emulsion, which is then cured. The pH value is adjusted by adding an alkaline solution.

[0216] In the following, the (amino) sugar component of the core-shell microcapsule of the present invention is similar to the present invention. This section describes the corresponding components used within the process.

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

[0218] This invention relates to monosaccharides, disaccharides, oligosaccharides, and similar small molecules that react with polyisocyanates. In other words, using a specific ratio of short-chain polysaccharides, the shell wall in core-shell microcapsules It forms structural segment units that form a structure. Suitable sugars within the scope of the present invention are carbohydrates or The derivatives are, in other words, derivatives of biomolecules consisting of carbon atoms, hydrogen atoms, and oxygen atoms. These sugars are generally based on the number of monomer units, i.e., the number of monomer sugar components. Four chemical groups: monosaccharides (one monomer unit), disaccharides (two monomer units), oligosaccharides ( It can be divided into monomer units (3-10) and polysaccharides (more than 10 monomer units). In that regard, monomer units, that is, sugar components, consist of two or more hydroxyl groups (-O It contains H). Oligosaccharides have a degree of polymerization (DP) of 3 to 10 units (IUPAC definition). It is defined as a short polymer of monosaccharide residues linked by glycosidic bonds. These may be linear or branched, and are usually hexose or in mixtures, individually or in combination. It contains pentoses. Other monosaccharides, including uronic acid, sialic acid, and anhydrous sugar, may also be present. Disaccharides, oligosaccharides, and high molecular weight sugars are defined as one type of monomer unit, or more than one type of monomer unit. It can be composed of nomeric units, that is, two or more structurally distinct monomer units.

[0219] Such carbohydrates most preferably used within the scope of the present invention are those with fewer than 20 monomer units. Position, i.e., less than 20 linked monosaccharide residues, preferably 15 or fewer monomer units, one layer More preferably, it is a sugar (colloquial: sugar) having 10 or fewer monomer units, for example, Monosaccharides (glucose, fructose, galactose), disaccharides (sucrose, lactose, ma) Lutoses), linear or branched oligosaccharides (raffinose, stachyose) and / or These are short-chain polysaccharides, either linear or branched, as defined herein.

[0220] When the term sugar is used herein, it refers not only to sugars obtained from natural sources, but also to synthetic sugars. This includes sugars manufactured using chemical processes and derivatives thereof that have a structure equivalent to naturally occurring 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 are surrounded by isocyanates, which are capsule-forming aids. This facilitates diffusion toward the oily core containing the carbide, resulting in further reinforcement through denser crosslinking. This enables interfacial polymerization and efficient encapsulation of the active ingredient(s) as a core material. This enhances performance and simultaneously provides a more stable capsule. The base capsule components are compared to commercially available, fully synthetic, state-of-the-art microcapsules. This enables improved biodegradability of capsule wall materials. Its performance, as well as the stability of the capsule, is, for example, For example, microcapsules based on larger components such as starch or chitosan. This is an improvement compared to the previous version.

[0223] Generally, amine or alcohol components move from the aqueous phase to the organic phase for wall formation. It penetrates. In that regard, the penetration rate is mainly determined by the solubility and diffusion rate of the constituent elements. Controlled, the molecular size of the constituent elements significantly influences the diffusion rate, and consequently, the penetration rate. For larger components such as commercial starch or chitosan, the diffusion rate and filtration The permeability is significantly reduced, as is the decrease in crosslink density and inefficient encapsulation, as well as the capsules. This results in a decrease in stability. As a result, even larger substances such as starch and / or chitosan... The release performance of microcapsules based on their constituent elements also decreases significantly.

[0224] In the corresponding amino sugars, one or more hydroxyl groups in the sugar structure are amine groups (-NH2 or Substituted with -NH-, preferably -NH2). Such amino-functional monosaccharides, di Sugars, oligosaccharides, and polysaccharides include, for example, glucosamine, mannosamine, galactosamine, and polysaccharides. Glucosamine and oligoglucosamine, for example, chitose, chito-oligosaccharide, or chitosan Oligosaccharides (containing fewer than 20 monomer units) and chitosan (containing 20 or more monomer units) Oligochitosan, also known as an N-acetyl-substituted amino sugar, is preferred. In the scope of this invention, amino sugars have fewer than 20 monomer units, i.e., 19 or fewer. The monomer units below, preferably 15 or fewer monomer units, and even more preferably 10 or fewer units in the layer below. It has monomer units. Therefore, amino sugars used in the context of the present invention are preferred These are amino monosaccharides (one monomer unit), amino disaccharides (two monomer units), linear or segmented molecules. Chain-linked aminooligosaccharides (oligomeric amino sugars: 3-10 monomer units) and / or 2 Having a chain length of less than 0 monomer units, preferably 15 monomer units or less, and branched or It is a straight-chain short-chain amino polysaccharide (polymer amino sugar: more than 10 monomer units). Mino disaccharides, amino oligosaccharides, and amino polysaccharides are defined as one monomer unit or more than one. It can be composed of different types of monomer units, that is, two or more structurally different monomer units. .

[0225] In corresponding cases, preferred modifications involve crosslinked amino sugar components used within the scope of this application. The element is preferably derived from a natural source, such as an amino monosaccharide as defined herein. These are amino disaccharides, amino oligosaccharides, and / or short-chain high molecular weight amino sugars.

[0226] As used herein, the term amino sugar refers to amino sugars obtained from natural sources. Not only that, but also synthetically produced amino sugars and their derivatives with structures equivalent to natural amino sugars. It is included. However, preferably, within the scope of the present invention, amino acids derived from natural sources. Sugar is used.

[0227] Furthermore, it includes a mixture of monomer units that do not contain amines and monomer units that do contain amines. Sugars composed of such sugars are preferably 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] A more preferred variation involves sugar components each having fewer than 20 monomer units independently. The amino sugar components are either linear or branched. Capsule wall shape Regarding the composition, it is a combination of two or more linear and / or branched chain components, i.e., 1 The above linear sugars, one or more linear amino sugars, one or more branched sugars and / or one or more fractions A mixture of branched amino sugars, as well as a mixture of straight-chain and branched-chain sugars and / or amino sugars. It can be used.

[0229] According to a preferred modification of the present invention, the capsule shell comprises at least two isocyanates At least one polyisocyanate having a group, i.e., each having two or more isocyanates A single isocyanate compound having a nate functional group or two or more different isocyanates A mixture of compounds, less than 20 monomer units, preferably 15 monomer units or less, in a single layer More preferably, each monomer unit independently comprises 10 or fewer monomer units as defined herein. It is formed from a polymer material that is a reaction product with at least one sugar, such as the one described above.

[0230] Alternatively, the capsule shell has at least two isocyanate groups One polyisocyanate, that is, having two or more isocyanate functional groups. A single isocyanate compound or a mixture of two or more different isocyanate compounds, and Less than 20 monomer units, preferably 15 or fewer monomers, as defined in the specification. One or more units, each independently having monomer units, more preferably 10 or fewer. It is formed from polymer materials that are reaction products with amino sugars.

[0231] However, in a more preferred variation, the capsule shell has at least two isosyl At least one polyisocyanate having an anneate group, i.e., two or more each A single isocyanate compound having an isocyanate functional group or two or more different isocyanates A mixture of anate compounds and at least one sugar and a small amount as defined herein. At least one amino sugar, less than 20 monomer units, preferably 15 or fewer monomer units Even more preferably, each monomer unit independently comprises 10 or fewer monomer units, that is, at least one (i.e., one or more) sugar component and at least one (i.e., A combination of one or more amino sugar components, sugars (multiple), and amino sugars (multiple) or It is formed from polymer materials that are reaction products with a mixture.

[0232] Based on these polymer materials, micro-materials exhibit high efficiency and high biodegradability. Capsules (i.e., stable against mechanical shock or heat or in the product formulation, target) It can efficiently encapsulate the active ingredient until its release begins, but at the same time, high Microcapsules exhibiting release properties can be prepared.

[0233] In that regard, (amino) sugar units have a higher decomposition rate than even the most advanced microcapsules. Because of its properties, it serves as a site for biological attack and ultimately for biodegradation, so the ring of the capsule material It reduces the impact on the environment, and therefore, is more efficient and at the same time more environmentally friendly. This will enable the preparation of even more environmentally friendly microcapsule alternatives.

[0234] The capsule shell of the core-shell microcapsule of the present invention is functionalized with polyisocyanate. Interfacial polymerization between the group and the functional hydroxyl group and / or amine group of the (amino) sugar unit This is formed by crosslinking with polyurethane-based and / or polyurea-based crosslinks, and consequently, as described above. This creates a polymeric structure around a core containing the identified active ingredient. While isocyanate units serve as "crosslinking" or "rigid" segments (A The MINOS (sugar units) act as hydrophilic, "soft" segments that form the majority of the shell material. stand.

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

[0236] At least one polyisocyanate hydroxyl of at least one (amino) sugar The polyaddition reaction with the group involves the carbon atom in the nitrogen bond of the isocyanate group (-N=C=O). The addition of a hydroxyl group (-OH) to an amino sugar (plural) results in what is known as urethane. This results in the formation of crosslinks (-NH-CO-C-). Alternatively, or simultaneously, polyurea crosslinks Formation involves the addition of (amino) sugars to the isocyanate functional groups of polyisocyanates. Similar to the formation of polyurethane crosslinks by polyaddition of amine groups (-NH2, -NH-) (possible). This is done by the method described above. Instead, in the case of the corresponding thiosaccharide, a polythiourethane crosslink is formed. ru.

[0237] Therefore, the strongly cross-linked capsule shell is enclosed in the capsule as the core material. A crystalline electrode that prevents the diffusion or penetration of hydrophobic active ingredients (or mixtures of active ingredients). Strongly crosslinked segments with reduced sex segment and / or polyisocyanate content It can be formed from the ion as a polymer material. In the case of fragrances and perfumes, for example, this Effective encapsulation of sensory-perceptible active ingredients (fragrance mixtures or single fragrance substances) This can be triggered, for example, by mechanical activation or by changes in the external environment, such as They are effectively released by changes in pH or temperature, or through biological attack. This further requires that the capsule exhibit sufficient stability in order to achieve high performance. Based on the bio-based core-shell microcapsules of the present invention, active substances (multiple) Due to evaporation (possible) and / or interaction with other components of the product formulation, and / or during application There is no loss due to premature destruction (for example, in a washing machine), and the effectiveness of the active ingredients (multiple ingredients are possible). It is possible to provide highly stable capsules that enable efficient encapsulation. Furthermore, the bio-based capsules of the present invention exhibit high performance, enabling efficient distribution of active substances (multiple substances are possible). Moreover, it enables the target release. In addition, they do not negatively affect stability or performance. It exhibits high biodegradability without any issues.

[0238] Furthermore, remarkably, the significantly reduced shell material results in a highly stable bio-based material. Furthermore, it was found that eco-friendly microcapsules can be prepared (Examples 11 and 1 See 2). These capsules contain (amino) sugars as defined herein. For efficient segment crosslinking, a reduction in shell material and a low isocyanate content are also required. Nevertheless, it exhibits high mechanical stability, thermal stability, and chemical stability.

[0239] The more cross-linking functional groups there are, the greater the spatial cross-linking becomes, and the final microphone The resulting capsule shell or capsule wall becomes more stable. Number of functional groups In other words, in addition to the number of branched chains, the chain length of each individual component is a mechanical property, i.e., caps It has a significant impact on cell stability. However, excessive cross-linking affects capsule stability. This will improve the biodegradability and performance of the capsule material and the capsule itself, that is, This adversely affects the release behavior. However, as described herein in accordance with the first aspect Based on the processes and (amino) sugars specified herein, these properties It is possible to achieve microcapsules with an improved or even more ideal balance. Therefore, these components are suitable for stable incorporation into various consumer product formulations. This enables the preparation of highly stable microcapsules with excellent performance and high biodegradability. do.

[0240] The microcapsules of the present invention according to the first aspect are resistant to mechanical influences, for example, rotary dryers. It exhibits high mechanical stability (thermal stability) against heat-dominant substances, but at the same time, the active ingredient It enables efficient, targeted, signal-induced release. In addition, sensory experiments are available. In the case of fragrances as active ingredients, it can be perceived that high fragrance intensity is possible, which indicates that the fragrance is the original This suggests that the core shell microcapsules are efficiently encapsulated within the Ming genus, and consumption Even after aging within the product formulation, this is due to the diffusion of active ingredients outside the microcapsules. It demonstrates an efficient reduction in losses. The shell is less than 20 as defined herein. At least one sugar and / or at least one each having monomer units independently The bio-based core-shell microcapsules containing amino sugars are highly stable. Furthermore, despite being based on bio-based components, it enables efficient encapsulation of active ingredients and It enables high performance. At the same time, they offer superior performance compared to commercially available state-of-the-art microcapsules. It is biodegradable.

[0241] Crosslinking in shell walls by efficiently using combinations of different sugars and / or amino sugars It was further discovered that the density, and consequently the resulting capsule properties, can be adjusted.

[0242] Therefore, the present invention primarily uses (amino) sugar-based core-shell microcapsules. To place a point. And more specifically, with (amino) sugar-based core-shell microcapsules The shell has at least one polyisocyanate having at least two isocyanate groups. An anneal and at least one (amino) sugar, i.e., less than 20 monomer units. Reaction with at least one sugar and / or at least one amino sugar, each independently present. The product comprises or consists of a polymer material, and the core has at least one active ingredient. It includes or consists of.

[0243] Within the scope of the present invention, a sugar base is at least one sugar as specified herein. and / or at least one amino sugar as a component for forming the capsule shell It means to be used.

[0244] Within the scope of this invention, bio-based or biologically derived materials used within the scope of this application Preferably, from a replenishable, natural source, more specifically, crops, agricultural waste, This means that it originates from a renewable, bio-based source such as wood. The (amino) sugars listed in the document are naturally occurring biocompounds (i.e., compounds of biological origin). ), and more specifically, it refers to a class of natural molecules. Surprisingly, these bio-derived materials The ingredients are stable and efficient bio-based / biological or (amino) sugar-based coacin. As a key component for the preparation of fossil-based microcapsules, Suitable as a bio-based and more environmentally friendly alternative to rocapsules. Something was found to be gained.

[0245] In that regard, certain (amino) monosaccharides, (amino) disaccharides, as specified herein Sugars and (amino)oligosaccharides, as well as short-chain high-molecular-weight (amino) sugars, for example, monomers with a molecular weight of less than 20. - Unit (or repeating unit), preferably 15 or fewer monomer units, even more preferably Low molecular weight maltodextrins having 10 or fewer monomer units are coaches derived from the aforementioned organisms. These are particularly advantageous in the formation of microcapsule shells. These low molecular weight (amino) sugars are Compared to high molecular weight poly(amino) sugars, it diffuses more easily to the reaction interface. Diffusion is hindered. This makes it more difficult, and wall formation is promoted, which in turn makes it possible to form even more advanced bridges. As a result, more stable and simultaneously high-performing microcapsules can be obtained. The active ingredients are efficiently encapsulated without loss due to diffusion of the ingredients(s), and various... It can be stably incorporated into formulations, especially consumer products, such as detergents and fabric softeners. Furthermore, these bio-based microcapsules offer high performance, namely, fragrance capsules. Alternatively, in the case of fragrance capsules, they exhibit excellent fragrance release properties and high biodegradability.

[0246] Amino sugars are widely present in nature and comprise a broad range of compounds, such as structural polysaccharides and mucopolysaccharides. Bacterial capsule polysaccharides, teicoic acid, lipopolysaccharides, glycolipids, mucoproteins, nucleotides, etc. It has been discovered.

[0247] Chitosan is, for example, a generally non-toxic, biodegradable, and biocompatible polysaccharide, i.e., 30 β(1-4) linked D-glucoglycans having molecular weights in the range of 1,000 Da to 50,000 Da Biometrics based on samine monomer units and N-acetyl-D-glucosamine monomer units It is a child, and as a result, the polymer has 20 or more monomer units, i.e., glucosam Glucosamine-based monomer units (D-glucosamine monomer units or N-acetyl-D-glucosamine monomer units) Cosamine monomer units (each considered individually as a monomer unit), usually 10 It contains more than 0 monomer units. However, chitosan is poor in water or organic solvents. It is only soluble and can be found in acidic organic solutions such as acetic acid, propionic acid, citric acid, and formic acid at a concentration of a few percent. It is only (1-3%) soluble. In addition, the acidified chitosan solution undergoes an interfacial reaction with poly It is very unreactive with isocyanates. Therefore, chitosan itself is not a core-shell micro It is not suitable for capsule preparation. In addition, due to the large molecular structure, isocyanate Diffusion toward the reactants is hindered, leading to the formation of less dense crosslinks, thus reducing stability. This also results in inefficient encapsulation.

[0248] However, surprisingly, there are now fewer than 20 monomer units, preferably 15 or fewer. Oligochitosan having monomer units, and more preferably 10 or fewer monomer units ( Chitosan (Carbosynth-Bios), also known as chito-oligosaccharide Enzymatic or chemical processing of ynth (registered trademark) LTD, England) and its derivatives Certain low molecular weight chitosan is a degradation product of chitosan or chitin, prepared by hydrolysis. The oligomer overcomes its poor solubility in both acidic and alkaline solvents, achieving a 10% concentration. It was discovered that this enables a significantly higher level of solubility.

[0249] By definition, according to the present invention, the degree of polymerization (DP) is less than 20 and approximately 3900 Da less Chitosan derivatives with an average molecular weight of ____ are called chitosan oligomers, chito oligomers, oligo It is called chitose or chito-oligosaccharide (COS). These terms are used synonymously. The definition of whether a chitosan oligomer has fewer than 10 monomer units is defined above. It is permissible to deviate from the classical definition of oligomeric structure as defined above. However, this development According to Akira, chitosan oligomers are defined as having fewer than 20 monomer units. So, "oligoamino sugar" or "oligomer amino sugar" or, instead, "short-chain amino polysaccharide" It is also called "".

[0250] Low molecular weight chitosan oligomer (MW < 3900 g / mol, preferably < 3000 g / mol) The uniqueness of (also called chito-oligosaccharide or oligochitose) is 30,000g / m Compared to general chitosan with a molecular weight of ~5,000,000 g / mol or more, it is acidic and It enables high solubility in both alkaline and alkaline media. In addition, chito-oligosaccharides have short Due to its chain length, and therefore depending on its degree of polymerization (DP), it is readily soluble in water. 3000g / mol Chitosan oligomers with a molecular weight of 10-15 monomer glucosamine units (D- Based on glucosamine monomer units or N-acetyl-D-glucosamine monomer units This amino sugar efficiently polymerizes with the crosslinking agent, i.e., polyisocyanate, forming the shell wall. Since it can form structural units, it increases the reaction with isocyanate components, In contrast to ting, the core-shell microcapsule is directly incorporated as a segment into its shell. It can be packed in. Moreover, even smaller components allow for even denser bridging. Therefore, these compounds are sugar-based or bio-based core-shell micro It is suitable for capsule preparation. As a result, chitosan in oligosaccharide form is within the scope of the present invention. It is preferred to use it. For example, glucosamine and various oligochitoses By using a mixture formulation, the crosslinking density and properties in the shell wall can be adjusted. can.

[0251] Preferably, the chito-oligosaccharides and their derivatives that are suitably used in the context of the present invention are 30 It has a molecular weight of less than 00 g / mol or 3000 Da.

[0252] In a more preferred variation, the chito-oligosaccharide has fewer than 20 monomer units, preferably 15. The following monomer units, more preferably 10 or fewer monomer units, are included.

[0253] In addition, even smaller molecules include isocyanate components and bio-based crosslinking agents. That is, less than 20 monomer units, preferably 15 monomer units or less, and further Preferably, sugars and / or amino sugars having 10 or fewer monomer units independently. Isosyl is surrounded by a capsule-forming aid that enables efficient cross-linking between them. This allows for the promotion of diffusion toward the oily core containing the anate linker. Bio-based or (amino) sugar-based high-molecular-weight compounds as reaction products that form cell shells. Sub-materials are formed.

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

[0255] Furthermore, small alkaline or neutral chitosan oligomers as described above —In other words, compared to long-chain chitosan, chito-oligosaccharides are isocyanates dissolved in the oil phase. This enables improved interfacial reactions with crosslinking agents. Polyisocyanates are more basic under acidic conditions. That is, under alkaline conditions, amino sugars, such as glucosamine and short It was further discovered that it reacts with the amino group of the chitosan oligomer chain. Therefore, Furthermore, the pH value is maintained above 8 during the preparation process described herein. Therefore, preferably the pH of the first and / or second aqueous phases is in the alkaline range. Mashiku is greater than 8.

[0256] Therefore, in preferred modifications of the present invention, (Ami) is preferably used within the scope of the present invention. (n) The sugar has fewer than 20 monomer units, preferably 15 or fewer monomer units, even more preferably or (amino) sugars having 10 or fewer monomer units independently. According to this, at least one such sugar and / or at least one amino sugar is poly It reacts with socianates (plural possible).

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

[0258] Preferably, the core-shell microcapsule of the present invention contains at least two isocyanates At least one polyisocyanate having a t group, and the following group: glucosamine, maltodextrin Less than 20 monomer units selected from dextrin and / or chito-oligosaccharides Reaction products with at least one sugar and at least one amino sugar, each independently present. A polymer material comprising or consisting thereof, wherein the core is at least one effective component It includes or consists of minutes.

[0259] These (amino) components, alone or in mixtures, are used in consumer product formulations for extended periods (small amounts). It is stable (for at least 4 weeks) and exhibits high biodegradability; highly stable, but at the same time This enables the formation of microcapsules with superior properties. Chito-oligosaccharide-based capsules For further information, please refer to Examples 2 and 3, and for maltodextrin-based capsules. See Examples 6-8 and 10.

[0260] However, in a more even more preferred embodiment, a small number of monomer units having fewer than 20 At the very least, one (amino) sugar component is a monomer (i.e., a monosaccharide or amino monosaccharide). A sugar is a sugar, and an even more preferred (amino) sugar-based component is glucosamine. (See Example 1 or 5).

[0261] Glucosamine can be used as an (amino) sugar component only, or as specified herein. Other (amino) sugar components as defined in, e.g., maltodextrin and / Alternatively, it can be suitably combined with chito-oligosaccharides. Glucosamine is monomeric amino acids. It is a nosaccharide compound and one of the most common monosaccharides, further used as a dietary supplement. Core-shell microcapsules, formulated based on glucosamine, offer superior performance within the product formulation. It exhibits stability, high release performance, and improved biodegradability.

[0262] Within the scope of the present invention, generally, small molecules such as glucosamine or glucose have a structure Due to the similarity in structure, even larger (amino) disaccharides, as defined herein, (A It can be freely mixed with oligosaccharides or short-chain (amino) sugars.

[0263] Therefore, in a preferred embodiment, the shell has at least two isocyanate groups. At least one polyisocyanate and less than 20 monomer units are independently formed. The reaction product of a substance having at least one sugar and / or at least one amino sugar. A core-shell microcapsule containing or consisting of a polymer material is disclosed, In this case, at least one sugar and / or at least one amino sugar is glucosamine. The core contains, or consists of, at least one active ingredient.

[0264] Polyisocyanates formed by crosslinking urea-based and / or urethane-based The monomer units of the t are less than 20, preferably 15 or fewer monomer units, even more preferably The benefits of sugars (or amino sugars) having 10 or fewer monomer units The reactions with usable amino groups and / or hydroxyl groups are as follows for the amino sugar components: An example is shown below. [ka]

[0265] As a result, polyisocyanates as defined herein and as defined herein Based on the reaction of (amino) sugars, it is possible to obtain core-shell microcapsules. And in that case, the shell material has at least two isocyanate groups One polyisocyanate, preferably at least one aliphatic polyisocyanate, In other words, a polyisocyanate having more than 1 isocyanate group, preferably at least A mixture of two polyisocyanates (preferably the polyisocyanates in the mixture) At least one of the components is aliphatic, or the polyisocyanate in the mixture (All are virtually aliphatic) and less than 20 monomer units, preferably 15 or fewer monomers - A unit, more preferably 10 or fewer monomer units, each independently having such units Each contains less than 20 monomer units, 15 or less, or 10 or less monomer units, or It is a reaction product of at least one sugar and / or at least one amino sugar. The core contains or is composed of a bio-based polymer material, and the core has at least one active ingredient For example, a product containing or consisting of a fragrance compound.

[0266] In that regard, preferably, at least one polyisocyanate is aliphatic. More preferably, a mixture of two or more polyisocyanates is used, in which case preferably The polyisocyanates are, at least one or all of which are aliphatic. or at least one or all of the polyisocyanates in the polyisocyanate mixture It is aromatic. Further alternatives include using a mixture of two or more polyisocyanates. In that case, at least one of the polyisocyanates is aliphatic, and the polyisocyanates are small At least one of them is aromatic. Preferably, a mixture of two or more polyisocyanates is used. If so, the mixture contains more than 80 mol% of aliphatic components / polyisocyanates. Preferably, or consisting of the same. In the latter case, preferably, aliphatic polyisocyanates. The molar or weight ratio of 'te' (multiple) to aromatic polyisocyanates (multiple) is 8 The range is 5 to 15, and more preferably 90 to 10 to 99:1.

[0267] The isocyanate component is preferably selected independently from the (amino) sugar component. This leads to a significant difference in reactivity between aromatic isocyanates and aliphatic isocyanates. As a result, aliphatic / aromatic isocyanates are sheared independently of amine / alcohol components. It forms a hierarchical structure within the region.

[0268] Therefore, in a further embodiment, the present invention relates to a shell having at least two isocyanates A polyisocyanate having at least one group and less than 20 monomer units Reactions with at least one sugar and / or at least one amino sugar that are independently present The product comprises or consists of a polymer material, and the core contains at least one active ingredient This relates to core-shell microcapsules, including or consisting of such capsules.

[0269] In that regard, one or more methods that allow adjustment of the crosslinking density and, consequently, the resulting capsule properties. A combination of sugars (or more) and / or amino sugars (or more) is particularly preferred. This is crosslinking. This results in varying lengths of bridges between components that affect density, and different connections between components. Due to its functional properties, it enables different functionalities for the capsules. Furthermore, it allows for various degrees of polymerization and crosslinking. This is achieved, providing a more flexible capsule wall composition and positively impacting the overall capsule properties. It has an effect.

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

[0271] A primary hydroxyl group is a primary carbon atom, that is, one carbon atom is directly bonded to it. A hydroxyl group (-OH) bonded to a carbon atom is a secondary hydroxyl group This refers to a secondary carbon atom, that is, two carbon atoms directly bonded to the carbon atom connected to it. Yes, they are.

[0272] On the other hand, primary amines replace one of the three hydrogen atoms with a non-hydrogen group. Therefore, it can be derived from ammonia, that is, the nitrogen atom is a non-hydrogen atom, for example, carbon Since it bonds with the elementary component group, two hydrogen atoms remain. When referring to secondary amines, three water atoms remain. In these secondary substituted amines, two of the elementary atoms are replaced by non-hydrogen groups, i.e., nitrogen The element is bonded to two non-hydrogen atoms, with only one hydrogen atom remaining bonded to nitrogen.

[0273] Preferably, at least one sugar has at least two hydroxyl groups, At least one amino sugar is selected from at least two glycerides identified above. It has functional groups, and in this case, these functional groups have enhanced stability and are more tightly crosslinked. While providing a cell shell, it also enhances capsule release performance, i.e., release behavior. To enable this, at least one of these functional groups is polyurethane-based and / or The amine group is for the formation of polyurea-based bonds.

[0274] In a more preferred variation, the present invention relates to core-shell microcapsules according to the present invention. It is a substance having at least one sugar and / or monomer unit having less than 20 monomer units. At least one amino sugar is a monosaccharide, such as glucose, galactose, or fructose. xylose, mannose, arabinose, erythrose, threose, ribose, arabinose Rabinose, lyxose, allose, altrose, thalose, fucose, rhamnose, Amino monosaccharides, for example, glucosamine, galactosamine, N-acetylglucosamine, disaccharides Examples include sucrose, lactose, maltose, isomaltulose, trehalose, Lactulose, cellobiose, chitobiose, isomaltose, isomaltulose, mal Tulose, amino disaccharides, linear and / or branched oligosaccharides, e.g., malto-oligosaccharides For example, maltodextrin, raffinose, stachyose, fructo-oligosaccharides, Lysitose, umbelliferose, cyclodextrin, oligoamino sugar (oligomer) Selected from the group consisting of mino sugars, for example, chito-oligosaccharides, or mixtures thereof. .

[0275] Alternatively, or in combination with the (amino) sugars identified above, less than 20 monomers - Units, preferably 15 or fewer monomer units, and even more preferably 10 or fewer monomer units per layer. From primary and secondary hydroxyl groups (-OH) and thiol groups (-SH) that have units A thiosaccharide having at least two functional groups independently selected from the group is preferably used. This is possible. Preferably, these thiosaccharides enable the formation of polythiourethane structures / bonds. It has one or more functional thiol groups (-SH). Preferably, at least one thiol group Polythiourethane base and poly This enables the formation of both polyurethane-based structures.

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

[0277] In another preferred variation of the present invention, the shell is therefore at least two isocyanates At least one polyisocyanate having a t group, preferably two or more polyisocyanates A mixture of ions and at least one sugar having less than 20 monomer units each independently and / or reaction with at least one amino sugar and / or at least one thio sugar The product comprises or consists of a polymer material, and the core contains at least one active ingredient Core-shell microcapsules containing or consisting of such capsules are described.

[0278] Further alternatives include one hydroxyl group (-OH) linked to each carbon atom. Sugar alcohols, such as sorbitol or mannitol, also have isocyanate components. It can be used as a component for a reaction.

[0279] at least one sugar and / or at least one amino sugar and / or at least one The ratio of one thiosaccharide, i.e., (amino) sugar and / or thiosaccharide component, to the total oil phase The ratio is at least 0.2% by weight of the total weight of the oil phase, preferably at least 0.5% by weight, It is particularly preferably at least 1% by weight. The upper limit is in the range of 5 to 10% by weight. However Meanwhile, to ensure that all polyisocyanate molecules react, the aqueous phase is peroxide. Excess (amino) sugar and / or thiosugar components, i.e., unreacted components, are generally present. It is a wish.

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

[0281] As shown above, the second aqueous phase is optional and may include one or more additional formation aids, for example, It comprises colloidal protective agents and / or surfactants as identified above, and it is second It can be added in an amount of approximately 0.1 to 5% by weight, preferably 0.2 to 2% by weight, based on the aqueous phase. ru.

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

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

[0284] Preferably, the bio-based core-shell microcapsule or the core according to the present invention. The first and / or second water in the process of preparing a slurry containing shell microcapsules One or more capsule-forming agents used in the phase are therefore surfactants and / or or colloidal protective agent, preferably a colloidal protective agent as specified above. It is a compounding agent. Furthermore, preferably, the forming aid(s) used are based on biopolymers.

[0285] Therefore, the microcapsules according to the present invention contain capsule-forming aids (or more). It may thus be produced using at least one aqueous phase. The amount of active substance(s) is For example, it is in the range of 0.1 to 5% by weight based on each phase.

[0286] Alternatively, these substances improve the stability of microcapsules that are finely dispersed in the aqueous phase. It can be added to the final microcapsule slurry to enhance its properties.

[0287] To improve the spreadability of the composition on skin or hair, or to improve the water resistance and / or Or to improve sweat resistance and / or peeling resistance, and to modify the protective factors of the composition To improve performance, it may be added instead to or in addition to the second aqueous phase or the final capsule slurry. A suitable polymer is, for example, International Speciality P Sold by products under the trade name Antaron (trademark) V-220 VP / Eicosene copolymer, International Speciali The product names Antaron (trademark) V-216 and Anta are sold by ty Products. VP / hexadecene copolymer, sold under ron(trademark)V-516, In Product name An Tricontanyl PVP, sold under the taron(trademark) WP-660, Pen Sold by reco under the product names Versagel (registered trademark) MC and MD. isohexadecane and ethylene / propylene / styrene copolymer and butylene / Chilen copolymer, manufactured by Penreco under the trade name Versagel® ME. Hydrogenated polyisobutene and ethylene / propylene / styrene copolymer sold under the original packaging Mer and butylene / styrene copolymer, traded as Derma by AkzoNobel cryl(registered trademark)79, Dermacryl(registered trademark)AQF and Dermacr Acrylate / octylacrylamide sold under yl(registered trademark)LT Polymer, Lubrizol, trade name Avalure (trademark) UR 450 & Polyurethane sold under 525, for example, PPG-17 / IPDI / DMP A copolymer, Lubrizol, trade name Avalure (trademark) UR-405, Polyurea sold under -410, -425, -430 and -445, -525 Tan-2 and -4, traded under the name Avalure(trademark)UR-5 by Lubrizol. Polyurethane 5 and butyl acetate and isopropyl are sold under 10 and -525. Alcohol, manufactured by BASF under the brand name Luviset (registered trademark) PUR Polyurethane-1 and -6, sold by Cognis under the brand name Cosmed Hydrogenated dimer dilinoleyl / dimethic acid sold under ia(registered trademark)DC It is a rucopolymer.

[0288] Furthermore, the pH value of the second aqueous phase is preferably in the range of 8 to 11, for example, hydroxide By using an alkaline solution such as a potassium or sodium hydroxide solution It can be adjusted. More preferably, the pH of the second aqueous phase is greater than 9 and less than 11. Therefore, if the pH value is within this range, the crosslinking agent (or multiple agent) in the organic phase, i. The reaction of socianates with amino sugars is promoted. In the case of minutes, high pH values, i.e., pH values ​​above 8 to 9, indicate the release of amine hydrochloride. It causes a conversion to mine (-NH2, NH-). The amine hydrochloride base is from the free amine group. Since it reacts slowly with isocyanates, a high pH value is generally preferable. Sugar-based composition If the element is used, similarly, a pH value higher than 8 is advantageous. A pH value is alkaline. By adding a water-soluble hydroxyl and / or a basic catalyst such as DABCO(registered trademark) It can be adjusted accordingly.

[0289] Next, in step (d), the oil phase and the first aqueous phase are mixed together to create a finely dispersed and stabilized mixture. A provisional oil-in-water emulsion with individual droplets is obtained. In this step, the oil phase (isotherapy) (containing an anate component, an active ingredient, and optionally additional oil components) and a first aqueous phase (capsule formation) The mixture (including auxiliary agents) is 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: oil-in-water ( In an O / W emulsion, oil droplets are dispersed in water. This is the most common type of emulsion. This is the type. Conversely, a water-in-oil (W / O) emulsion contains finely dispersed water droplets in the oil. In the context of this invention, an emulsion is an oil-in-water (O / W) emulsion in which the oil phase is dispersed in the aqueous phase. The core-shell microcapsule of the present invention is preferably hydrophobic, as the active ingredient is hydrophobic. It is included as a core material in cells.

[0291] Alternatively, prepare a corresponding water-in-oil emulsion for encapsulating hydrophilic active substances. It is possible.

[0292] Interfacial reaction between isocyanate components (multiple possible) and (amino) sugar components (multiple possible) To achieve this, the isocyanate components (multiple may be) are mainly water-insoluble, while (A The sugar components (multiple components are acceptable) must be water-soluble.

[0293] Core-shell capsules are typically formed by the fine dispersion of core material(s) in the aqueous phase. It is manufactured. Isocyanate components and sugars in the oil phase near the interface between the aqueous and oil phases. Alternatively, based on the reaction with amino sugar components, the polymer wall material is finely dispersed / individually in oil droplets. It is formed around the shell wall and the oil core. A suspension containing oil is produced. Therefore, the size of the oil droplets remains the same, and the following is formed. Determine the size of the capsule core. High rotational speed is necessary for the finely dispersed, individual, homogeneous oil droplets. This enables the formation of homogeneous core-shell microcapsules, resulting in a uniform size.

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

[0295] Formation of emulsion in the case of a liquid active ingredient according to the present invention or in the case of a solid active ingredient Formation of a suspension, i.e., the internal non-aqueous or oily phase being separated by the external aqueous or hydrophilic phase. The emulsification or suspension is carried out under high turbulence or strong shear, thereby turbulence or Determine the diameter of the microcapsules that will provide the required shear strength. Microcapsule manufacturing is ongoing. It can be continuous or discontinuous. As the viscosity of the aqueous phase increases, Alternatively, as the viscosity of the oil phase decreases, the size of the resulting capsules usually decreases.

[0296] Preferably, emulsification, i.e., the formation of a provisional oil-in-water emulsion, is preferably performed individually. To achieve a homogeneous provisional oil-in-water emulsion in which the particle size is uniform, for example, , Ultra-Turrax (registered trademark) from IKA (registered trademark)Works 300 The mixture is subjected to high-speed shearing by using it at 0 rpm to 5000 rpm for approximately 20 seconds to approximately 120 seconds. This is done by doing so. Subsequently, in order to prevent particle aggregation, for example, overhead milling Using a shearing machine, set the shearing speed to 300 rpm to 800 rpm, preferably 600 rpm to 6 I reduced the engine speed to 50 rpm.

[0297] In that regard, the temperature is preferably in the range of 0°C to 50°C, preferably 20°C to 40°C. It is maintained during this period.

[0298] Once a provisional oil-in-water emulsion is prepared, the isocyanate component isocyanate At least two functional groups with the anneate functional group, namely a hydroxyl group and / or an a Reaction of mine groups and / or thiol groups results in polyurethane-based and / or polyurea To form a bond between the base and / or the polythiourethane base, as defined above There are fewer than 20 monomer units, preferably 15 or fewer monomer units, even more preferably Mashiku is at least one sugar and / or each having 10 or fewer monomer units independently. or a second water containing at least one amino sugar and / or at least one thio sugar The phases and then mix them together.

[0299] The second aqueous phase is preferably 300 rpm to 800 rpm, preferably 600 rpm to 6 It is added at a stirring speed of 50 rpm. Preferably, the second aqueous phase is 0°C to 50°C, preferably It is added at a temperature between 20°C and 40°C.

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

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

[0302] Preferably, core-shell microcapsules or core-shell microcapsules according to the first embodiment. In the process of preparing a slurry or microcapsules containing capsules, at least 2 A polyisocyanate having at least one isocyanate group, less than 20 mono A hydroxyl group (-OH) having a Mer unit, preferably a primary and secondary hydroxyl group, as well as a primary and secondary hydroxyl group (-OH). From the group consisting of a secondary amine group (-NH2, -NH-) or a thiol (-SH) group, At least one sugar having at least two functional reactive groups selected for standing and / or The molar ratio or weight ratio to amino sugars and / or at least one thio sugar, preferably The molar ratio 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, then efficient A microphone exhibiting excellent emission characteristics, resulting in high stability and a high degree of cross-linking. It is possible to achieve the goal of a capsule.

[0304] Finally, the microcapsules obtained in step (e) in the form of a microcapsule slurry The material needs to be hardened.

[0305] Once the provisional oil-in-water emulsion is mixed with the second aqueous phase, the polyaddition occurs. This process is carried out, and crude microcapsules containing the active substance are formed. Forming aids(s) are incorporated into the capsule shell or bind to the capsule surface. It is understood. At the same time, microcapsules exhibit insufficient stability in dispersed systems, so A final curing step is required: After the cross-linking process is complete, the prepared microcapsules are used. It is in the form of an aqueous dispersion, and the capsule shell or capsule wall is soft and flexible in its raw state. It exists as microcapsules. Therefore, it is still soft and flexible, which is worrying. It hardens, i.e., rigidifies, the shell or wall of a fixed single-layer microcapsule, so By consuming cyanate and thereby growing the polymer, sufficient stability is provided. Therefore, it is necessary to subject the microcapsules to an additional curing process. Normally, curing This was obtained by using a high temperature of approximately 50°C to approximately 90°C for a period of approximately 1 to 12 hours. This is done by processing the dispersed system. Aggregation of crude microcapsules, and consequently, agglomeration. To avoid this, use a non-high-speed shear blade during the curing process at 300 rpm to 1000 rpm. It is advantageous to continuously stir the dispersion system at pm. Preferably, the stirring speed is such that the curing process During operation, the speed is approximately 650 rpm.

[0306] If desired, the solvent can be removed to obtain a "pure" capsule, which is usually, It shows an average diameter of approximately 5 microns to 50 microns.

[0307] As a result, by preparing a slurry, bio-based core-shell microcapsules The process for preparing the slurry is optional, and preferably from the slurry / dispersion system (step (g)) to the dry form This includes an additional step of isolating the microcapsules themselves in their natural state.

[0308] This can be achieved, for example, by filtration. Further general methods suitable for this purpose The technique involves removing the solvent(s) and obtaining isolated microcapsules. These include, for example, filtration or spray drying, freeze-drying or vacuum drying. Also, centrifugal separation. And subsequent drying may also be an option.

[0309] Optionally, the process may include an additional step (f) instead of isolating the microcapsules after step (f). 2) Contains natural gum (e.g., xanthan gum, gellan gum, diutan gum). Add one or more suspension aids or structuring aids selected from cellulose gum as a thickening agent. It provides high suspension stability.

[0310] In that regard, the thickener(s) are preferably applied at approximately 1200 rpm to 1500 rpm. It is added while stirring for 1 to 5 minutes, and then the stirring speed is reduced to less than 1000 rpm, if preferred. Alternatively, reduce the speed to approximately 850 rpm. This will allow the addition of a thickening agent or structuring agent to break down the particles. It provides stability to the slurry against "creaming" or precipitation.

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

[0312] In addition, preferably, in particular with respect to the formation of polyurethane-based structures, (amino) sugar structures Adding a catalyst(s) to accelerate the reaction between the component and the isocyanate crosslinking agent This can be done. Suitable catalysts include, for example, tin, zinc, bismuth, or, for example, DABCO (Registered Trademark) (1,4-Diazabicyclo[2.2.2]Octane; Air Product ts & Chemicals, Inc; Supplier: Sigma-Aldrich Co Metal ligands based on tertiary amines, such as those found in rp. St. Louis, MO, USA. It is a catalyst.

[0313] Preferably, the catalyst(s) are in the oil phase and / or in one or both of the aqueous phases and / Alternatively, it can be added directly to a (provisional) oil-in-water emulsion. Preferably, the synergistic effect of the catalyst. For the effect, approximately 0.03-0.1% by weight of a metal-based catalyst (bismuth neodecanoate) is used. ) is added to the organic / oil phase, and then approximately 0.03-0.1% by weight of a tertiary amine (for example) If DABCO(registered trademark) is added to one of the aqueous phases, or to the (provisional) oil-in-water emulsion... It is added directly. Preferably, this compound has a lower reaction rate compared to other metal-ligand catalysts. Bismuth neodecanoate is used as a catalyst because its toxicity is desirable.

[0314] Overall, the processes described herein are for more efficient crosslinking. This allows for significant savings in shell material, thus avoiding adverse effects on capsule stability or performance. Without compromising quality, it further reduces the required isocyanate content compared to state-of-the-art capsules. To enable stable and high-performing bio-based or sugar-based core shell microsulfates. This enables the preparation of chlorocapsules. In addition, capsules manufactured in this way are of very high quality. Because it has excellent base compatibility and high biodegradability, it is particularly suitable for today's society where health awareness continues to grow. and environmental awareness It is particularly suitable for use in various consumer goods.

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

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

[0317] Therefore, the present invention relates to a core-shell micro for preparing consumer products. This also relates to the use of capsules. The core-shell microcapsules of the present invention are not limited to the following: Uses: Cosmetics, personal care products, especially skin cleansing products 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 detergents and cleaning agents, fabric softeners, fragrances It is suitable for use in adhesives, fragrance enhancers, and pharmaceuticals.

[0318] Finally, the present invention also relates to core-shell microcapsules according to the present invention or to the present invention This also relates to consumer products, preferably scented, which include a slurry of microcapsules. In this regard, consumer products in particular include cosmetics, personal care products, and especially skin cleansers. Products and skincare products, shampoos, rinse-off conditioners, deodorants, antiperspirants, and more. Deodorizing lotions, fabric care products and home care / household products, especially liquid detergents and all-purpose cleaners. Laundry and cleaning agents, fabric softeners, fragrance enhancers, and the same group including pharmaceuticals, or are selected from the group consisting of them.

[0319] Examples of personal care products include shampoo, conditioner, hair conditioner, soap, and Body wash, body soap, such as cream, shower salt or bath salt, Generally solid and liquid soaps, body liquids, mousses, oils or gels, hygiene products, Generally, cosmetics, body lotions; hair fragrances and personal care products including lotions that are left on the skin. For personal care use, personal cleansers or disinfectants, pre-shaving products, splash colognes and Scented refreshing wipes, shower gel, shaving soap, shaving foam, bath oil Ill, cosmetic emulsion, for example, skin cream and skin lotion, facial cream and Facial lotion, sunscreen cream and lotion, after-sun cream and lotion Hand cream and hand lotion, foot cream and foot lotion, Hair removal creams and lotions, after-shaving creams and lotions, sunscreens and lotions, hair care products, such as hair spray, hair gel, hair lotion, Hair conditioners, permanent and semi-permanent hair dyes, hair modifiers, e.g., kohl Perms and straightening agents, hair tonics, hair creams and lotions, deodorants and Antiperspirants, such as underarm sprays, roll-ons, deodorant sticks, deodorant creams, or decorative products. Cosmetics for use are examples. Rinse-off products are liquids, solids, pastes or any other physical form. Gel is also acceptable.

[0320] Examples of home care products include solid or liquid detergents, all-purpose cleaners, fabric softeners, and cooling agents. Examples include water and detergent for ironing, fabric softener and desiccant sheets, among which liquid and powder are preferred. Detergents, fragrances, and fabric softeners in powder and tablet form are preferred. Further examples include floor cleaners and window cleaners. Glass cleaner, dishwashing detergent, bathroom and sanitary cleaner, rinse lotion, solid and liquid toilet cleaners, powder and foam carpet cleaners, dishwashing products or various other products. Liquid and powder detergents for washing surfaces, pre-treatment agents for laundry, such as bleach, soaking agents and Stain removers, fabric softeners, fabric coolants, cleaning soaps, cleaning tablets, disinfectants, liquids, gels , or surface disinfectants and air purifiers in the form of applying a solid carrier, 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-based preparations, for example, Examples include powdered and liquid detergents and fabric softeners.

[0322] This core-shell microcapsule allows for the efficient encapsulation of a wide range of active ingredients, such as fragrances. This makes it possible to reduce interactions between scented products and other ingredients in the product formulation. This completely prevents, as well as reduces or completely prevents the evaporation of potentially slightly volatile components. The use of microcapsules offers the possibility of controlling the components under precisely defined conditions. It enables the target release of (multiple) substances. Therefore, for example, a substance containing fragrance. In the case of Kurocapsules, environmental conditions (oxidation effects caused by air or other components in the product formulation) may be a factor. Since fragrances that are generally sensitive can be encapsulated, the fragrance substances remain stable during storage. Only when the desired fragrance is to be released, a specific signal or trigger (e.g., mechanical stress) By applying (S), the microcapsules are broken, and the fragrance is released efficiently. The capsule of the present invention exhibits good sensory performance as defined in the specification. During the destruction of the device (without loss during storage), it enables the controlled release of the active ingredient. At the same time, it provides sufficient stability for the capsule over a long period, while also offering higher performance compared to state-of-the-art capsules. It is biodegradable.

[0323] [Examples]

[0324] Preparation of core-shell microcapsules

[0325] The following encapsulated particles (core-shell microcapsules) are described below. It was prepared as follows. Based on the preparation described below, a completely synthesized state-of-the-art (ba Compared to microcapsules (non-iobase), it exhibits high biodegradability and superior release characteristics. It contains multiple bio-based materials dispersed in an aqueous phase, which maintain capsule stability even during long-term storage. / (amino) sugar-based core-shell microcapsules are included in the corresponding microcapsules. A slurry was obtained.

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

[0327] [Table 1]

[0328] Table 2 shows the relative weights of isocyanate compounds used in the context of the present invention and examples. Summarize the volume ratios and molar ratios.

[0329] [Table 2]

[0330] Example 1: Glucosamine-based microcapsules I

[0331] Glucosamine is used as a polyfunctional nucleophile, and polyvinyl alcohol is used as a capsule-forming aid. Ru (PVA, Selvol (trademark) 523, Sekisui Specialty Ch Microcapsules according to the present invention were prepared using emicals (Japan).

[0332] More specifically, 210g of flavoring ingredients, here TomCap (registered trademark) (Sym Measure out rise (Teterboro, NJ) into a 250ml beaker, and add both to C 6.29g of Desmodur (registered trademark) from Ovestro Corporation (Standard) N-3400 Isocyanate Monomer (Hexamethylene diisocyanate uretidi) N, HDI-urethidione, aliphatic polyisocyanate; equivalent weight: 193g and 1.57g Mondur® M Flakes (Monomer Diphenylmethane-4,4'-Diiso Cyanate; aromatic polyisocyanate; equivalent weight: 125.2) and together, the relative weights of each are... Aliphatic and aromatic polyisothea in a molar ratio of 80:20 or relative molar ratio of 72.3:27.7 An oil phase containing nate was formed. Subsequently, 0.3 g of oil-soluble catalyst (bismuth neodecanoate) was added. Aldrich Chemical Corporation,St. Louis, MO Add (US). In a separate 800 ml beaker, add 32.2 g of polyvinyl alcohol to water. Selvol (PVA, Selvol (trademark) 523, Sekisui Specialty C) Prepare a solution (322g) containing chemicals (Japan), and form the first aqueous phase. It was done. Next, 0.3g of DABCO(registered trademark)(1,4-diazabicyclo[2.2 .2] Octane, Aldrich Chemical Corporation, St. Stir at 3500 rpm for approximately 20-60 seconds in the presence of Louis, MO, USA. Shear force (IKA (registered trademark) Werke, Staufen, Germany) We decided to apply the commercially available Ultra Turrax (registered trademark), T-50. Furthermore, the oil phase is emulsified into the aqueous phase, resulting in an oil-in-water fragrance emulsion with an average particle size of 5-50 microns. The catalyst is obtained, that is, after emulsification, it is added to a provisional oil-in-water emulsion. The particle size of the dispersed oil particles was measured using the Mastersizer® 3000 particle size analyzer. -(Malvern Instruments,117 Flanders Road, Measurements were taken using Westborough (MA, USA). Preferably, in the aqueous phase. The median particle size of the finely dispersed oil droplets is in the range of 20 μm to 30 μm.

[0333] Place the resulting provisional oil-in-water emulsion into an overhead mixer and add 60g Gradually add the 10% glucosamine solution (second aqueous phase) while stirring at 600 rpm. Mixed. The glucosamine solution used was 54g of deionized water mixed with 6g of glucosamine HCl. Biosynth Carbosynth®, United Kingdom It was prepared by dissolving ). The pH was adjusted by adding potassium hydroxide to approximately The value was adjusted to 9.5-10.5. The resulting capsule slurry was heated to 70°C. At the very least, it was allowed to cure for 3 hours. The microcapsules in the suspension are in the aqueous phase (water) and microcapsules The difference in density between the capsules will cause them to separate over time. To avoid this, a structuring agent is added to provide the solution viscosity. Therefore, the obtained in the aqueous phase To stabilize the microcapsules, the slurry is heated at 1200 rpm for approximately 2-4 minutes. While stirring, finally add 0.60g of Kelco-vis(trademark) DG (diutan gum, Add CP Kelco Inc., then reduce the stirring speed to 850 rpm, and continue I left it there and let it harden for another hour.

[0334] The resulting microcapsules have a fairly narrow particle size distribution range within the aqueous phase. This indicates that the bio-based core-shell microcapsules have a uniform particle size. It exists. Core-shell microcapsules have a median volume-based particle size of 25.3 μm (Dv(50 It has (see Figure 16A).

[0335] Furthermore, the resulting microcapsules can be used, for example, in product formulations (fabric softeners) with high mechanical properties. Demonstrating both physical and chemical stability, it reveals a cutting-edge, non-biobased microcapsule. It exhibits superior emission characteristics that surpass [another method] (see Figures 1A and 1B). Furthermore, the obtained product can be used as is. Microcapsules have significantly increased compared to state-of-the-art microcapsules that are not biodegradable at all. It exhibits enhanced biodegradability.

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

[0337] As a polyfunctional nucleophile, chitosan oligosaccharide (chito-oligosaccharide) and a capsule-forming aid are used. Polyvinyl alcohol (PVA, Selvol (trademark) 523, Sekisui S Using the micro (specialty chemicals, Japan) according to the present invention Capsules were prepared.

[0338] More specifically, 210g of flavoring ingredients, here TomCap (registered trademark) (Sym Measure out rise (Teterboro, NJ) into a 250ml beaker, and add both to C 6.29g of Desmodur (registered trademark) from Ovestro Corporation (Standard) N-3400 Isocyanate Monomer (Hexamethylene diisocyanate uretidi) N, HDI-urethidione, aliphatic polyisocyanate; equivalent weight: 193g and 1.57g Mondur® M Flakes (Monomer Diphenylmethane-4,4'-Diiso Cyanate; aromatic polyisocyanate; equivalent weight: 125.2) and together, the relative weights of each are... Aliphatic and aromatic polyisothea in a molar ratio of 80:20 or relative molar ratio of 72.3:27.7 An oil phase containing nate was formed. Subsequently, 0.3 g of oil-soluble catalyst (bismuth neodecanoate) was added. Aldrich Chemical Corporation,St. Louis, MO Add (US). In a separate 800 ml beaker, add 3.02 g of polyvinyl alcohol to water. Selvol (PVA, Selvol (trademark) 523, Sekisui Specialty C) Prepare a solution (302g) containing chemicals (Japan), and form the first aqueous phase. It was done. Next, 0.3g of DABCO(registered trademark)(1,4-diazabicyclo[2.2 .2] Octane, Aldrich Chemical Corporation, St. Stir at 3500 rpm for approximately 20-60 seconds in the presence of Louis, MO, USA. Shear force (IKA (registered trademark) Werke, Staufen, Germany) We decided to apply the commercially available Ultra Turrax (registered trademark), T-50. Furthermore, the oil phase is emulsified into the aqueous phase, and an oil-in-water fragrance with an average particle size in the range of 5 to 50 microns is produced. A emulsion was obtained. The particle size of the finely dispersed oil particles is Mastersizer®. 3000 particle size analyzer (Malvern Instruments, 117 Fla) Measurements were taken using Westers Road (Westborough, MA, USA).

[0339] The resulting provisional oil-in-water emulsion is placed in an overhead mixer, and 10% Add 80g of chitosan oligosaccharide solution (second aqueous phase) gradually while maintaining a constant flow rate of 600 rpm. It was stirred. The chitosan oligosaccharide solution was made by mixing 8g of chitosan oligosaccharide HCl (molecular weight < 3000) Da, Biosynth Carbosynth (registered trademark), United King It was prepared by dissolving dom) in 72 g of deionized water. The pH value was determined by potassium hydroxide. The concentration was adjusted to approximately 10-11 by adding mu. The resulting capsule slurry was 7 It was cured at 0°C for at least 3 hours. Finally, the slurry was heated at 1200 rpm. While stirring for approximately 2-4 minutes, add 0.60g of Kelco-vis(trademark) DG (dilutant). Add (CP Kelco Inc.), then reduce the stirring speed to 850 rpm. Next, it was allowed to harden for another hour.

[0340] The final core-shell microcapsules are located within a volume-based particle size of 22.9 μm in the slurry. It has a median value (Dv(50)) (see Figure 16B), and is dryer-dried with fabric softener. It exhibits good stability and release characteristics even after aging (see Figures 2A and 2B). and).

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

[0342] As a polyfunctional nucleophile, chitosan oligosaccharide (chito-oligosaccharide) and a capsule-forming aid are used. Polyvinyl alcohol (PVA, Selvol (trademark) 523, Sekisui S Using the micro (specialty chemicals, Japan) according to the present invention Capsules were prepared.

[0343] More specifically, 210g of flavoring ingredients, here TomCap (registered trademark) (Sym Measure out rise (Teterboro, NJ) into a 250ml beaker, and add both to M 1.57g of STABIO (commercial product) derived from itsui Chemicals (Japan) (Standard) D-370N (Bio-based 1,5-pentamethylene diisocyanate (PDI)) Aliphatic polyisocyanurate based on; equivalent weight: 168.24) and 1.57 g Take nate(trademark)600(1,3-bis(isocyanatomethyl)cyclohexane; aliphatic) Polyisocyanate (equivalent weight: 97.14) is combined with the other, with a relative weight ratio of 50:50. This formed an oil phase containing aliphatic polyisocyanates with a relative molar ratio of 36.6:63.4. And 0.3g of oil-soluble catalyst (bismuth neodecanoate, Aldrich Chemica (I Corporation) was added. In another 800 ml beaker, 3.02 ml was added to the water. g of polyvinyl alcohol (PVA, Selvol (trademark) 523, Sekisui S Prepare a solution (302g) containing Specialty Chemicals (Japan). Prepared to form the first aqueous phase. Then, 0.3g of DABCO(registered trademark)(1,4-di Azabicyclo[2.2.2]octane, Aldrich Chemical Corp. 3500rpm (IKA(registered trademark) Werke, Stauf) Ultra Turrax (registered trademark), T- 50) By stirring for approximately 20-60 seconds, shear force is applied to the oil phase, which is then converted to water. The mixture was emulsified into a phase to obtain an oil-in-water fragrance emulsion having an average particle size in the range of 5 to 50 microns. The particle size of the finely dispersed oil particles is Mastersizer (registered trademark) 3000 particle size analog. Riser (Malvern Instruments, 117 Flanders Ro Measurements were taken using (ad, Westborough, MA, USA).

[0344] The resulting provisional oil-in-water emulsion is placed in an overhead mixer, and 10% 80g of chitosan oligosaccharide solution was gradually added while stirring at 600 rpm. Tosan oligosaccharide solution is 8g of chitosan oligosaccharide HCl (molecular weight <3000 Da, Bios ynth Carbosynth (registered trademark, United Kingdom) 72 It was prepared by dissolving g in deionized water. The pH value was determined by adding potassium hydroxide. The concentration was adjusted to approximately 9.5-10.5. The resulting capsule slurry was heated to 70°C. It was cured for at least 3 hours. Finally, the slurry was heated at 1200 rpm for approximately 2 hours. Stir for 4 minutes while adding 0.60g of Kelco-vis(trademark) DG (diutan gum, CP) Add Kelco Inc., then reduce the stirring speed to 850 rpm, and then It was allowed to harden for another hour.

[0345] The final core-shell microcapsules are located in the center of a 25.9 μm volume-based particle size distribution within the slurry. It has a value (Dv(50)) (see Figure 16C) and was treated with a fabric softener solution for one week. Although testing was performed, the rope exhibited excellent release characteristics, especially after drying (see Figures 3A and 3B). (This refers to...). In this particular case, increasing the amount of aliphatic isocyanate is preferable to Example 2 in terms of stability. It appears to have an effect.

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

[0347] Glucosamine and chitosan oligosaccharide are used as polyfunctional nucleophiles, and capsule-forming aids are also used. Polyvinyl alcohol (PVA) (Selvol (trademark) 523, Sekisui Using the microphone according to the present invention (Specialty Chemicals, Japan) A capsule was prepared.

[0348] More specifically, 210g of flavoring ingredients, here TomCap (registered trademark) (Sym Measure out rise (Teterboro, NJ) into a 250ml beaker, and add both to M 3.93g of STABIO (commercial product) derived from itsui Chemicals (Japan) (Standard) D-370N (Bio-based 1,5-pentamethylene diisocyanate (PDI)) Aliphatic polyisocyanurate based on; equivalent weight: 168.24g and 3.93g Take nate(trademark)600(1,3-bis(isocyanatomethyl)cyclohexane; aliphatic) Polyisocyanate (equivalent weight: 97.14) is combined with the other, with a relative weight ratio of 50:50. This formed an oil phase containing aliphatic polyisocyanates with a relative molar ratio of 36.6:63.4. And 0.3g of oil-soluble catalyst (bismuth neodecanoate, Aldrich Chemica (I Corporation) was added. In another 800 ml beaker, 3.02 ml was added to the water. g of polyvinyl alcohol (PVA, Selvol (trademark) 523, Sekisui S Prepare a solution (302g) containing Specialty Chemicals (Japan). Prepared to form the first aqueous phase. Then, 0.3g of DABCO(registered trademark)(1,4-di Azabicyclo[2.2.2]octane, Aldrich Chemical Corp. By stirring at 3500 rpm for approximately 20-60 seconds in the presence of rations, the shearing process is performed. Breaking force (commercially available from IKA (registered trademark) Werke, Staufen, Germany) By applying Ultra Turrax (registered trademark, T-50), the oil phase is converted to water. The mixture was emulsified into a phase to obtain an oil-in-water fragrance emulsion having an average particle size in the range of 5 to 50 microns. The particle size of the finely dispersed oil particles is Mastersizer (registered trademark) 3000 particle size analog. Riser (Malvern Instruments, 117 Flanders Ro Measurements were taken using (ad, Westborough, MA, USA).

[0349] The resulting provisional oil-in-water emulsion is placed in an overhead mixer, and 5% ki Tosan oligosaccharide solution (molecular weight < 3000 Da; equivalent to approximately 12-15 monomer units) ) and 5% glucosamine (both are registered trademarks of Biosynth Carbosynth). Gradually add 80g of the solution mixture (from the United Kingdom) Then, it was stirred at 600 rpm. The mixed chitosan oligosaccharide / glucosamine solution was added to 4 g of chitosan oligosaccharide. By dissolving tosan oligosaccharide and 4g of glucosamine HCl in 72g of deionized water... It was prepared by adding potassium hydroxide to adjust the pH value to 10-11. The slurry of the capsules was cured at 70°C for at least 3 hours. Finally, the slurry was... Stir at 1200 rpm for approximately 2-4 minutes while adding 0.60g of Kelco-vis (trademark) Add DG (Diutan Gum, CP Kelco Inc.), then stir at a speed of 85 The rotation speed was reduced to 0 rpm, and then it was allowed to cure for another hour.

[0350] The final core-shell microcapsules are located in the center of the 22.6 μm volume-based particle size range within the slurry. It has a value (Dv(50)) (see Figure 16D) and exhibits excellent performance (release characteristics) after drying. It demonstrates high stability within the formulation and during the drying process.

[0351] Example 5: Glucosamine-based microcapsules II

[0352] Glucosamine (Biosynth Carbosynth (Registered) as a polyfunctional nucleophile (Registered trademark), United Kingdom) and Capsul (as a capsule-forming aid) This product uses starch (a registered trademark) (commercially available from Ingredion Inc.). Microcapsules according to the invention were prepared.

[0353] More specifically, 210g of flavoring ingredients, here TomCap (registered trademark) (Sym Measure out rise (Teterboro, NJ) into a 250ml beaker, and add both to C 6.29g of Desmodur (registered trademark) from Ovestro Corporation (Standard) N-3400 Isocyanate Monomer (Hexamethylene diisocyanate uretidi) N, HDI-urethidione, aliphatic polyisocyanate; equivalent weight: 193g and 1.57g Mondur® M Flakes (Monomer Diphenylmethane-4,4'-Diiso Cyanate; aromatic polyisocyanate; equivalent weight: 125.2) and together, the relative weights of each are... Aliphatic and aromatic polyisothea in a molar ratio of 80:20 or relative molar ratio of 72.3:27.7 An oil phase containing nate was formed. Subsequently, 0.6 g of oil-soluble catalyst (bismuth neodecanoate) was added. Aldrich Chemical Corporation added another 800m In a 1-liter beaker, add 6.44 g of octenyl succinate (OSA) starch (Ca) to water. A solution (322g) containing psul (registered trademark), Ingredion Inc. Prepared and formed the first aqueous phase. Then, 0.6 g of DABCO(registered trademark) (1,4 - Diazabicyclo[2.2.2]octane, Aldrich Chemical Cor Under the presence of poration, 3500rpm (IKA(registered trademark) Werke,Sta Ultra Turrax (registered trademark), sold commercially in ufen, Germany. By applying shear force by stirring for approximately 20-60 seconds in T-50, the oil An oil-in-water fragrance emulsion in which the phase is emulsified in the aqueous phase, having an average particle size in the range of 5 to 50 microns. The particle size of the finely dispersed oil particles was obtained as follows: Mastersizer (registered trademark) 3000 particles Degree analyzer (Malvern Instruments, 117 Flanders) Measurements were taken using Road, Westborough, MA, USA.

[0354] Place the resulting provisional oil-in-water emulsion into an overhead mixer and add 60g The 10% glucosamine solution was gradually added while stirring at 600 rpm. The samin solution is made by adding 6g of glucosamine HCl (Biosynth Ca) to 54g of deionized water. By dissolving rbosynth (registered trademark, United Kingdom) It was prepared by adding potassium hydroxide to adjust the pH to 10-11. The capsule slurry was cured at 70°C for at least 3 hours. Finally, the slurry was 1 Stir at 200 rpm for approximately 2-4 minutes while adding 1.8g of Keltrol(registered trademark) Add xanthan gum (CP Kelco Inc.), then stir at a speed of 850 rp. The temperature was reduced to m, and then cured for another hour.

[0355] The final core-shell microcapsules are located in the center of a volume-based particle size distribution of 32.1 μm within the slurry. It has a value (Dv(50)) (see Figure 16E), and is particularly outstanding after rope drying. It exhibits capsule properties as well as mechanical and chemical stability. Starch is used as a capsule-forming aid. In other words, using a bio-based capsule-forming aid is the core shell of the present invention. This is thought to have a positive effect on the capsule stability and release characteristics of microcapsules.

[0356] Example 6: Maltodextrin-based microcapsules I

[0357] Maltodextrin DE8 is used as a polyfunctional nucleophile, and polyvinyl acetate is used as a capsule-forming aid. Nyl alcohol (PVA, Selvol (trademark) 523, Sekisui Special Using lty Chemicals, Japan, the microcapsules according to the present invention Prepared.

[0358] More specifically, 210g of flavoring ingredients, here TomCap (registered trademark) (Sym Measure out rise (Teterboro, NJ) into a 250ml beaker, and add both to C 6.29g of Desmodur (registered trademark) from Ovestro Corporation (Standard) N-3400 Isocyanate Monomer (Hexamethylene diisocyanate uretidi) N, HDI-urethidione, aliphatic polyisocyanate; equivalent weight: 193g and 1.57g Mondur® M Flakes (Monomer Diphenylmethane-4,4'-Diiso Cyanate; aromatic polyisocyanate; equivalent weight: 125.2) and together, the relative weights of each are... Aliphatic and aromatic polyisothea in a molar ratio of 80:20 or relative molar ratio of 72.3:27.7 An oil phase containing nate was formed. Subsequently, 0.7 g of oil-soluble catalyst (bismuth neodecanoate) was added. Aldrich Chemical Corporation added another 800m In a 1 liter beaker, add a 1% PVA solution (approximately 241 g) (i.e., a 1% concentration). PVA solution) (Selvol(TM) 523, Sekisui Specialty C A solution was prepared (chemicals, Japan) to form the first aqueous phase. The solution was 6.5 g 235.2% PVA solution (therefore equivalent to 0.65g of pure PVA) It was prepared by mixing with g of deionized water. The as-prepared solution was used during the execution of the experiment. This corresponds to 0.25% of the total PVA addition (i.e., one-quarter of the total PVA addition). And, 3500rpm (IKA (registered trademark) Werke, Staufen, Germany With the commercially available Ultra Turrax (registered trademark, T-50), approximately 20-6 By applying shear force through stirring for 0 seconds, the oil phase is emulsified into the aqueous phase, 4 An oil-in-water fragrance emulsion with an average particle size in the range of ~50 microns was obtained. It was finely dispersed. The particle size of the oil particles was measured using the Mastersizer(registered trademark) 3000 particle size analyzer (Ma lvern Instruments,117 Flanders Road,West Measurements were taken using a Borough (MA, USA) device.

[0359] Place the resulting provisional oil-in-water emulsion into an overhead mixer and mix at 650°C. While stirring at rpm, the remaining 0.75% PVA solution (i.e., deionized water) (The remaining three-quarters of the total addition of 1% PVA containing 1.96g of PVA) (Trademark) 523, Sekisui Specialty Chemicals, Japan n) is added, and similarly 0.7 g of oil-soluble catalyst (bismuth neodecanoate, Aldrich C Chemical Corporation) and 60g of 10% Maltodextrin DE8 The solution was added. A total of 2.61 g of PVA was added. The maltodextrin DE8 solution was 8 Dissolve 6 g of maltodextrin containing the equivalent amount of dextrose in 54 g of deionized water. The capsules were prepared by the following method. The resulting capsule slurry was cured at 70°C for at least 30 minutes. Then, 10% maltodextrin DE prepared in the same manner as previously described was used. An additional 60g of ingredient 8 was added. The slurry was cured again at 70°C for another 30 minutes. Finally While stirring the slurry at 1200 rpm for approximately 2-4 minutes, add 0.60 g of Kelco- Add vis(trademark)DG (diutan gum, CP Kelco Inc.), then stir. The mixing speed was reduced to 850 rpm, and the temperature was raised to 80°C for another hour.

[0360] The fact that the resulting microcapsules have a narrow particle size distribution range in the aqueous phase means This demonstrates that the bio-based core-shell microcapsules have a uniform particle size. Core-shell microcapsules have a median volume-based particle size (Dv(50)) of 27.6 μm. (See Figure 16F). The core-shell microcapsule according to Example 6 is comparative Compared to the non-biobased, state-of-the-art microcapsules in Example 13, this represents a significant improvement in safety. It exhibits emission characteristics similar to those of the qualitative method (see Examples 6A and 6B). Furthermore, the complete Compared to state-of-the-art synthetic microcapsules, biodegradability is improved (see Example 17). (Regarding the subject).

[0361] Example 7: Maltodextrin-based microcapsules II

[0362] Maltodextrin DE8 is used as a polyfunctional nucleophile, and polyvinyl acetate is used as a capsule-forming aid. Nyl alcohol (PVA, Selvol (trademark) 523, Sekisui Special Using lty Chemicals, Japan, the microcapsules according to the present invention Prepared.

[0363] More specifically, 210g of flavoring ingredients, here TomCap (registered trademark) (Sym Measure out 7.07g of rise (Teterboro, NJ) into a 250ml beaker. Bayhydur® 305 isocyanate monomer (hexamethylene diiso) Hydrophilic aliphatic polyisocyanates based on cyanate (HDI), Covestro Corporation; equivalent weight: 259.6) and 0.785g Takenate ( Trademark) 600 (1,3-bis(isocyanatomethyl)cyclohexane; aliphatic polyisomethyl Anate, Mitsui Chemicals (equivalent weight: 97.14), together, Aliphatic polyisocyanates at a relative weight ratio of 90:10 or a relative molar ratio of 77.1:22.9 An oil phase containing was formed. Subsequently, 0.7 g of oil-soluble catalyst (bismuth neodecanoate, Ald Rich Chemical Corporation added another 800ml bottle. In the maker, a 1% PVA aqueous solution (241g) was prepared to form the first aqueous phase, but it was 1%PVA(Selvol(trademark)523, Sekisui Specialty Ch This corresponds to 0.25% of the total additions (emicals, Japan) (see Example 6). ). Next, 3500rpm (IKA(registered trademark) Werke,Staufen,Ger The Ultra Turrax (registered trademark, T-50) sold by many is approximately By applying shear force through stirring for 20-60 seconds, the oil phase is emulsified into the aqueous phase. A fragrance emulsion with an average particle size in the range of 4 to 50 microns was obtained. The particle size of the scattered oil particles was measured using the Mastersizer(registered trademark) 3000 particle size analyzer. Malvern Instruments,117 Flanders Road,We Measurements were taken using Stborough, MA, USA.

[0364] Place the resulting provisional oil-in-water emulsion into an overhead mixer and mix at 650°C. While stirring at rpm, the remaining 0.75 of the PVA (1% PVA solution in deionized water) was added. %(Selvol(trademark)523, Sekisui Specialty Chemical Add als (Japan), and similarly add 0.7g of oil-soluble catalyst (bismuth neodecanoate, A ldrich Chemical Corporation) and 60g of 10% maltodextrin Maltodextrin DE8 solution was added. Maltodextrin DE8 solution contains 8 dextrose By dissolving 6 g of maltodextrin having an equivalent (DE) in 54 g of deionized water, The mixture was then prepared. The resulting capsule slurry was cured at 70°C for at least 30 minutes. Subsequently, a 10% maltodextrin DE8 solution prepared by the same method as previously described was used. An additional 60g was added. The slurry was cured again at 70°C for another 30 minutes. Finally, While stirring the rally at 1200 rpm for approximately 2-4 minutes, add 0.60g of Kelco-vi Add s(trademark)DG (Diutan Gum, CP Kelco Inc.), then stir rapidly. The rotation speed was reduced to 850 rpm, and the temperature was then raised to 80°C for another hour.

[0365] The fact that the resulting microcapsules have a sharp particle size distribution range in the aqueous phase means This demonstrates that the bio-based core-shell microcapsules have a uniform particle size. Core-shell microcapsules have a median volume-based particle size (Dv(50)) of 51.5 μm. It possesses (see Figure 16G). Furthermore, it is compared to state-of-the-art, completely synthetic microcapsules. All materials exhibit improved biodegradability (see Figure 18).

[0366] Example 8: Maltodextrin-based microcapsules III

[0367] Maltodextrin DE8 is used as a polyfunctional nucleophile, and polyvinyl acetate is used as a capsule-forming aid. Nyl alcohol (PVA, Selvol (trademark) 523, Sekisui Special Using lty Chemicals, Japan, the microcapsules according to the present invention Prepared.

[0368] More specifically, 210g of flavoring ingredients, here TomCap (registered trademark) (Sym Measure out rise (Teterboro, NJ) into a 250ml beaker, and add both to C 6.29g of Desmodur (registered trademark) from Ovestro Corporation (Standard) N-3400 Isocyanate Monomer (Hexamethylene diisocyanate uretidi) N, HDI-urethidione, aliphatic polyisocyanate; equivalent weight: 193g and 1.57g Mondur® M Flakes (Monomer Diphenylmethane-4,4'-Diiso Cyanate; aromatic polyisocyanate; equivalent weight: 125.2) and together, the relative weights of each are... Aliphatic and aromatic polyisothea in a molar ratio of 80:20 or relative molar ratio of 72.3:27.7 An oil phase containing nate was formed. Subsequently, 0.7 g of oil-soluble catalyst (bismuth neodecanoate) was added. Aldrich Chemical Corporation added another 800m In a 1-liter beaker, a 1% PVA aqueous solution (241 g) was prepared to form the first aqueous phase. It is 1% PVA (Selvol (trademark) 523, Sekisui Specialty This corresponds to 0.25% of the total additions (Chemicals, Japan) (as in previous examples) (See reference). Next, 3500rpm (IKA(registered trademark) Werke, Staufe n, Ultra Turrax (registered trademark), T-5, which is commercially available from Germany. By applying shear force by stirring for approximately 20-60 seconds in step 0), the oil phase is converted into water. The mixture was emulsified into a phase to obtain an oil-in-water fragrance emulsion having an average particle size in the range of 4 to 50 microns. The particle size of the finely dispersed oil particles is Mastersizer (registered trademark) 3000 particle size analog. Riser (Malvern Instruments, 117 Flanders Ro Measurements were taken using (ad, Westborough, MA, USA).

[0369] Place the resulting provisional oil-in-water emulsion into an overhead mixer and mix at 650°C. While stirring at rpm, the remaining 0.75 of the PVA (1% PVA solution in deionized water) was added. %(Selvol(trademark)523, Sekisui Specialty Chemical Add als (Japan) and similarly add 0.7g of catalyst DABCO(registered trademark) (1,4- Diazabicyclo[2.2.2]octane, Aldrich Chemical Corp. (oration) and 60g of 10% maltodextrin DE8 solution were added. A chistrin DE8 solution contains maltodextrin 6 with 8 dextrose equivalents (DE). The capsule slurry was prepared by dissolving g in 54 g of deionized water. It was cured at 70°C for at least 30 minutes. Then it was prepared in the same manner as previously described. An additional 60g of 10% maltodextrin DE8 solution was added. The slurry was then mixed again. The mixture was cured for another 30 minutes at °C. Finally, the slurry was heated at 1200 rpm for approximately 2-4 minutes. While stirring, add 0.60g of Kelco-vis(trademark) DG (diutan gum, CP Ke Add (lco Inc.), then reduce the stirring speed to 850 rpm and continue for another hour. The temperature was raised to 80°C.

[0370] The fact that the resulting microcapsules have a sharp particle size distribution range in the aqueous phase means This demonstrates that the bio-based core-shell microcapsules have a uniform particle size. Core-shell microcapsules have a median volume-based particle size (Dv(50)) of 26.4 μm. It possesses (see Figure 16H) and exhibits improved biodegradability (see Figure 19). Furthermore, even after drying the capsules of the present invention in the product formulation and aging them for 4 weeks, they still exhibit high quality. It exhibits high stability and performance (see Figures 6A-6D and 8A-8D). Examples 6 and 8 are The selected catalyst is different.

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

[0372] Maltodextrin DE8 and glucosamine are used as polyfunctional nucleophiles, and capsule formation is also performed. As an auxiliary agent, polyvinyl alcohol (PVA, Selvol(trademark) 523, Sekisu Using i Specialty Chemicals, Japan) the present invention Microcapsules were prepared.

[0373] More specifically, 210g of flavoring ingredients, here TomCap (registered trademark) (Sym Measure out rise (Teterboro, NJ) into a 250ml beaker, and add both to C 6.29g of Desmodur (registered trademark) from Ovestro Corporation (Standard) N-3400 Isocyanate Monomer (Hexamethylene diisocyanate uretidi) N, HDI-urethidione, aliphatic polyisocyanate; equivalent weight: 193g and 1.57g Mondur® M Flakes (Monomer Diphenylmethane-4,4'-Diiso Cyanate; aromatic polyisocyanate; equivalent weight: 125.2) and together, the relative weights of each are... Aliphatic and aromatic polyisothea in a molar ratio of 80:20 or relative molar ratio of 72.3:27.7 An oil phase containing nate was formed. Subsequently, 0.5 g of oil-soluble catalyst (bismuth neodecanoate) was added. Aldrich Chemical Corporation added another 800m In a 1-liter beaker, a 1% PVA aqueous solution (241 g) was prepared to form the first aqueous phase. It is 1% PVA (Selvol (trademark) 523, Sekisui Specialty This corresponds to 0.25% of the total additions (Chemicals, Japan) (as in previous examples) (See reference). Next, 3500rpm (IKA(registered trademark) Werke, Staufe n, Ultra Turrax (registered trademark), T-5, which is commercially available from Germany. By applying shear force by stirring for approximately 20-60 seconds in step 0), the oil phase is converted into water. The mixture was emulsified into a phase to obtain an oil-in-water fragrance emulsion having an average particle size in the range of 4 to 50 microns. The particle size of the finely dispersed oil particles is Mastersizer (registered trademark) 3000 particle size analog. Riser (Malvern Instruments, 117 Flanders Ro Measurements were taken using (ad, Westborough, MA, USA).

[0374] Place the resulting provisional oil-in-water emulsion into an overhead mixer and mix at 650°C. While stirring at rpm, PVA was added (1% PVA solution in deionized water) to the remaining 0.75% Add the following, followed by 0.5g of catalyst DABCO(registered trademark) (1,4-diazabicycline). [2.2.2] Octane, Aldrich Chemical Corporation n) was added along with 60g of 10% glucosamine solution. The glucosamine solution contained 6g of glucosamine MinHCL (Biosynth Carbosynth(registered trademark), United K It is prepared by dissolving (ingdom) in 54 g of deionized water, and then KOH The pH value was adjusted to 7-8 by adding the substance. The resulting capsule slurry was heated at 70°C for 30 minutes. After curing, an additional 60g of 10% maltodextrin DE8 solution was added. Todextrin DE8 solution contains maltodextrin with 8 dextrose equivalents (DE). It was prepared by dissolving 6 g of ion in 54 g of deionized water. The resulting capsule was then processed. The Lee was cured at 70°C for another 30 minutes. Finally, the slurry was heated at approximately 1200 rpm. Stir for 2-4 minutes while adding 0.60g of Kelco-vis(trademark) DG (diutan gum, Add CP Kelco Inc., then reduce the stirring speed to 850 rpm, The temperature was then raised to 80°C for one hour. This procedure corresponds to Example 9B.

[0375] In parallel, prepare a microcapsule slurry according to the process described above. However, 30g of the corresponding glucosamine solution and 30g of the corresponding maltodextrin solution The liquid is added simultaneously before the first curing step, and then 30g of glucosamine solution and 30g of ma There was a difference in that the rutodextrin solution was added after the first curing step (as in Example 9A). handle).

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

[0377] Example 10: Maltodextrin-based microcapsules IV

[0378] Maltodextrin DE8 is used as a polyfunctional nucleophile, and polyvinyl acetate is used as a capsule-forming aid. Nyl alcohol (PVA, Selvol (trademark) 523, Sekisui Special Using lty Chemicals, Japan, the microcapsules according to the present invention Prepared.

[0379] More specifically, 210g of flavoring ingredients, here TomCap (registered trademark) (Sym Measure out 3.93g of rise (Teterboro, NJ) into a 250ml beaker. Bayhydur® 305 isocyanate monomer (hexamethylene diiso) Hydrophilic aliphatic polyisocyanates based on cyanate (HDI), Covestro Corporation; equivalent weight: 259.6) and 1.57g Takenate (commercial Standard) 600 (1,3-bis(isocyanatomethyl)cyclohexane; aliphatic polyisocyan Nate (Mitsui Chemicals; equivalent weight: 97.14g) and 2.36g of ST ABiO(trademark)370-N(based on 1,5-pentamethylene diisocyanate (PDI)) Polyisocyanates; aliphatic polyisocyanates, Mitsui Chemical (s; equivalent: 168.24) are combined with a relative weight ratio of 50:20:30 or relative mass It forms an oil phase containing three aliphatic polyisocyanates with a ratio of 33.4:35.7:30.9. Next, 0.7g of oil-soluble catalyst (bismuth neodecanoate, Aldrich Che (Added Mical Corporation, St. Louis, MO, US). Prepare a 1% PVA aqueous solution (241g) in an 800ml beaker to form the first aqueous phase. However, it is 1% PVA (Selvol (trademark) 523, Sekisui Speci This corresponds to 0.2% of the total additives (alty Chemicals, Japan) (previous actual (See the example). Next, 3500rpm (IKA(registered trademark) Werke,Sta Ultra Turrax (registered trademark), sold commercially in ufen, Germany. By applying shear force by stirring for approximately 20-60 seconds in T-50, the oil The phase is emulsified in the aqueous phase to create an oil-in-water fragrance emulsion with an average particle size in the range of 4 to 50 microns. We obtained the following. The particle size of the finely dispersed oil particles is Mastersizer(registered trademark)3000 Particle size analyzer (Malvern Instruments, 117 Flander) Measurements were taken using s Road (Westborough, MA, USA).

[0380] Place the resulting provisional oil-in-water emulsion into an overhead mixer and mix at 650°C. While stirring at rpm, the remaining 0.75 of the PVA (1% PVA solution in deionized water) was added. %(Selvol(trademark)523, Sekisui Specialty Chemical Add als (Japan) and similarly add 0.7g of catalyst DABCO(registered trademark) (1,4- Diazabicyclo[2.2.2]octane, Aldrich Chemical Corp. (A) and 60g of 10% maltodextrin DE8 solution were added. Torin DE8 solution contains 6 g of maltodextrin with 8 dextrose equivalents and 54 g of maltodextrin. It was prepared by dissolving in deionized water. The resulting capsule slurry was heated at 70°C. Allow to cure for at least 30 minutes. Then, 10% molten metal prepared in the same manner as previously described. An additional 60g of rutodextrin DE8 solution was added. The slurry was then heated again at 70°C for 3 minutes. Allow to cure for 0 minutes. Finally, stir the slurry at 1200 rpm for approximately 2-4 minutes. 0.60g Kelco-vis(trademark) DG (Diutan Gum, CP Kelco In Add c.), then reduce the stirring speed to 850 rpm and leave the temperature at 80°C for another hour. I raised the temperature to ℃.

[0381] The fact that the resulting microcapsules have a sharp particle size distribution range in the aqueous phase means This demonstrates that the bio-based core-shell microcapsules have a uniform particle size. Core-shell microcapsules have a median volume-based particle size (Dv(50)) of 13.7 μm. It possesses (see Figure 16J). Furthermore, core-shell microcapsules are used in product formulations. Excellent even after long-term storage, or even after mechanical stress from washing machines or heat. It exhibits release characteristics and shows good performance and stability (see Figures 10A-10D). 3 The combination of different aliphatic polyisocyanates is thought to have a positive effect on stability and performance. It breaks.

[0382] Example 11: Microcapsules II (90 / 1) based on chito-oligosaccharide and glucosamine 0HDI / MDI (Shell wall reduction)

[0383] Furthermore, bio-based microcapsules exhibiting shell wall reduction have been prepared. The amount of shell wall is calculated based on the equivalent. In Examples 1-10, the amount / thickness of the shell wall is currently It is equivalent to the most advanced microcapsules. In Examples 11 and 12, the amount of the shell wall It reduces weight and thickness by almost half compared to the most advanced models. It also reduces the isocyanate content. By doing so, the thickness of the capsule can be significantly reduced, and the shape of the shell wall can be made even thinner. I was able to achieve my goal.

[0384] As a polyfunctional nucleophile, chitosan oligosaccharide and glucosamine, and as a capsule-forming aid, Polyvinyl alcohol (PVA, Selvol (trademark) 523, Sekisui Sp Using the microcatheterization method according to the present invention (using Ecialty Chemicals, Japan) A capsule was prepared.

[0385] More specifically, 210g of flavoring ingredients, here TomCap (registered trademark) (Sym Measure out rise (Teterboro, NJ) into a 250ml beaker, and add both to C 4.27g of Desmodur (registered trademark) from Ovestro Corporation (Standard) N-3400 Isocyanate Monomer (Hexamethylene diisocyanate uretidi) N, HDI-urethidione, aliphatic polyisocyanate; equivalent weight: 193g and 0.48g Mondur® M Flakes (Monomer Diphenylmethane-4,4'-Diiso Cyanate; aromatic polyisocyanate; equivalent weight: 125.2) and together, the relative weights of each are... Aliphatic and aromatic polyisotheas in a molar ratio of 90:10 or a relative molar ratio of 85.4:14.6 An oil phase containing nate was formed. Subsequently, 0.6 g of oil-soluble catalyst (bismuth neodecanoate) was added. Aldrich Chemical Corporation added another 800m In a 1 liter beaker, add 3.02 g of polyvinyl alcohol (PVA, Selvol(commercial)) to water. Mark) 523, Sekisui Specialty Chemicals, Japan) A solution (302 g) containing was prepared, and an aqueous phase was formed. Then, 0.3 g of DABCO was added. (Registered Trademark) (1,4-Diazabicyclo[2.2.2]Octane, Aldrich Ch Under the existence of Emical Corporation (St. Louis, MO, USA) By stirring at 3500 rpm for approximately 20-60 seconds, shear force (IKA (registered trademark) Ultra Turr, which is sold commercially in Werke, Staufen, Germany. By applying ax(registered trademark), T-50), the oil phase is emulsified into the aqueous phase, and 5-50 An oil-in-water fragrance emulsion with an average particle size in the micron range was obtained. Finely dispersed oil particles The particle size of this child is measured using the Mastersizer(registered trademark) 3000 particle size analyzer (Malve rn Instruments,117 Flanders Road,Westbor Measurements were taken using (ough, MA, USA).

[0386] Place the resulting oil-in-water emulsion into an overhead mixer and mix at 600 rpm. While stirring, 5% chitosan oligosaccharide (molecular weight <3000 Da) and 5% glucosamine were added. (Both are registered trademarks of Biosynth Carbosynth®, United Ki 80g of the solution mixture (derived from ngdom) was immediately added. Mixed chitosan oligosaccharide / glucose The Cosamine solution consists of 4g of chitosan oligosaccharide and 4g of glucosamine HCl mixed with 72g of iodine. It was prepared by dissolving it in water. The pH value was determined by adding potassium hydroxide. The ratio was adjusted to approximately 10-11. The resulting capsule slurry was then heated at 70°C to reduce its volume. It was allowed to harden for at least 3 hours. Finally, the slurry was stirred at 1200 rpm for approximately 2-4 minutes. While 0.60g of Kelco-vis(trademark) DG (diutan gum, CP Kelco Add (Inc.), then reduce the stirring speed to 850 rpm, followed by another hour. It hardened.

[0387] The final core-shell microcapsules have a volume-based particle size of 22.6 μm within the slurry. The median value (Dv(50)) is present (see Figure 16K). The capsule shell is significantly smaller. Although they are reduced in size, the microcapsules according to the present invention are particularly effective in delivering products even after 4 weeks of aging. It exhibits excellent release characteristics and stability within the mixture, which is a completely synthetic conventional technique compared to Comparative Example 13. Comparable to that of the microcapsules used in the procedure (see Figures 11A and 11B). The capsule as is exhibits a shell wall that is considerably thinner compared to a standard capsule shell, but in the example... The microcapsules of the present invention according to 11 (and Example 12) are used in the corresponding product formulations. Even four weeks after use, it exhibits excellent release properties and stability. The capsule properties are almost double. Capsules relating to state-of-the-art technology having a capsule shell of a certain thickness (for example, the one in Comparative Example 13) It is comparable to the characteristics of ).

[0388] Example 12: Microcapsules III (86 / ) based on chito-oligosaccharide and glucosamine 14. HDI / MDI (Shell wall reduction)

[0389] As a polyfunctional nucleophile, chitosan oligosaccharide and glucosamine, and as a capsule-forming aid, Polyvinyl alcohol (PVA, Selvol (trademark) 523, Sekisui Sp Using the microcatheterization method according to the present invention (using Ecialty Chemicals, Japan) Capsules were prepared. These capsules are microcapsules related to cutting-edge technology (e.g.) For example, according to Example 13, the shell is approximately twice as large as in Examples 11 and 12. This shows the final capsule shell, composed of reduced shell walls, all of which represent a considerable reduction in size. vinegar.

[0390] More specifically, 210g of flavoring ingredients, here TomCap (registered trademark) (Sym Measure out rise (Teterboro, NJ) into a 250ml beaker, and add both to C 4.09g of Desmodur (registered trademark) from Ovestro Corporation (Standard) N-3400 Isocyanate Monomer (Hexamethylene diisocyanate uretidi) N, HDI-urethidione, aliphatic polyisocyanate; equivalent weight: 193g and 0.66g Mondur® M Flakes (Monomer Diphenylmethane-4,4'-Diiso Cyanate; aromatic polyisocyanate; equivalent weight: 125.2) and together, the relative weights of each are... Aliphatic and aromatic polyisothea in a molar ratio of 86:14 or relative molar ratio of 80.1:19.9 An oil phase containing nate was formed. Subsequently, 0.6 g of oil-soluble catalyst (bismuth neodecanoate) was added. Aldrich Chemical Corporation added another 800m In a 1 liter beaker, add 3.02 g of polyvinyl alcohol (PVA, Selvol(commercial)) to water. Mark) 523, Sekisui Specialty Chemicals, Japan) A solution (302 g) containing was prepared, and an aqueous phase was formed. Then, 0.3 g of DABCO was added. (Registered Trademark) (1,4-Diazabicyclo[2.2.2]Octane, Aldrich Ch Under the existence of Emical Corporation (St. Louis, MO, USA) By stirring at 3500 rpm for approximately 20-60 seconds, shear force (IKA (registered trademark) Ultra Turr, which is sold commercially in Werke, Staufen, Germany. By applying ax(registered trademark), T-50), the oil phase is emulsified into the aqueous phase, 5-50 ml An oil-in-water fragrance emulsion with an average particle size within the range of clones was obtained. Finely dispersed oil particles The granularity is measured by Mastersizer(registered trademark) 3000 granularity analyzer (Malver n Instruments,117 Flanders Road,Westboro Measurements were taken using (ugh, MA, USA).

[0391] Place the resulting oil-in-water emulsion into an overhead mixer and mix at 600 rpm. While stirring, 5% chitosan oligosaccharide (molecular weight <3000 Da) and 5% glucosamine were added. (Both are registered trademarks of Biosynth Carbosynth®, United Ki 80g of the solution mixture (derived from ngdom) was immediately added. Mixed chitosan oligosaccharide / glucose The Cosamine solution consists of 4g of chitosan oligosaccharide and 4g of glucosamine HCl mixed with 72g of iodine. It was prepared by dissolving it in water. The pH value was determined by adding potassium hydroxide. The mixture was adjusted to approximately 10-11. The resulting capsule slurry was heated at 70°C for at least 3 hours. It was cured. Finally, the slurry was stirred at 1200 rpm for approximately 2-4 minutes while adding 0.6 0g Kelco-vis(trademark) DG (Diutan Gum, CP Kelco Inc.) The mixture was then added, the stirring speed was reduced to 850 rpm, and it was cured for another hour.

[0392] The final core-shell microcapsules have a volume-based particle size of 22.8 μm within the slurry. The median value (Dv(50)) is present (see Figure 16L). The capsule shell is significantly reduced. Although small, the microcapsules according to the present invention are particularly effective even after 4 weeks of aging. The product formulation exhibited excellent release characteristics and mechanical and chemical stability, as seen in Comparative Example 1. 3. Comparable to those of conventionally synthesized microcapsules (Figure 11A and 1) (See 1B).

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

[0394] In the comparative example, guanidine carbonate was used as the polyfunctional nucleophile and poly was used as the capsule-forming aid. Vinyl alcohol (PVA, Selvol (trademark) 523, Sekisui Speci Microcapsules were prepared using alty Chemicals (Japan).

[0395] More specifically, 210g of flavoring ingredients, here TomCap (registered trademark) (Sym Measure out rise (Teterboro, NJ) into a 250ml beaker, and add both to C 6.29g of Desmodur (registered trademark) from Ovestro Corporation (Standard) N-3400 Isocyanate Monomer (Hexamethylene diisocyanate uretidi) N, HDI-urethidione, aliphatic polyisocyanate; equivalent weight: 193g and 1.57g Mondur® M Flakes (Monomer Diphenylmethane-4,4'-Diiso Cyanate; aromatic polyisocyanate; equivalent weight: 125.2) and together, the relative weights of each are... Aliphatic and aromatic polyisothea in a molar ratio of 80:20 or relative molar ratio of 72.3:27.7 An oil phase containing phosphate was formed. In another 800 ml beaker, 1% polyvinyl alcohol was added to water. Call (PVA, Selvol (trademark) 523, Sekisui Specialty) Prepare a solution (322g) containing Chemicals (Japan) and prepare the first aqueous phase. Formed. Then, by stirring at 3500 rpm for about 20-60 seconds, shear force is applied. U, a registered trademark of IKA, is sold commercially by Werke, Staufen, Germany. By applying Itra Turrax (registered trademark), T-50), the oil phase is converted to the aqueous phase. The mixture was emulsified to obtain an oil-in-water fragrance emulsion with an average particle size of 5 to 50 microns. The particle size of the scattered oil particles was measured using the Mastersizer(registered trademark) 3000 particle size analyzer. Malvern Instruments,117 Flanders Road,We Measurements were taken using Stborough, MA, USA.

[0396] Add the resulting oil-in-water emulsion to an overhead mixer and add 15% gua vitreous carbonate. 28g of nidin solution was gradually added while stirring at 600rpm. The solution was prepared by dissolving 3.2 g of guanidine carbonate in 24 g of deionized water. The obtained capsule slurry was cured at 70°C for at least 2 hours. Finally, the slurry While stirring the Lee at 1200 rpm for approximately 2-4 minutes, add 0.60 g of Kelco-vis. Add (trademark) DG (Diutan Gum, CP Kelco Inc.), then stir at a certain speed. The rotation speed was reduced to 850 rpm, and then the machine was cured at 80°C for another hour.

[0397] The final core-shell microcapsules are within a volume-based particle size of 20.6 μm in the slurry. It has a median value (Dv(50)) (see Figure 16M) and does not exhibit biodegradability (see Figure 15). (See reference).

[0398] Sensory evaluation of fragrance core-shell microcapsules

[0399] For sensory evaluation, the microcapsules according to the present invention are used in cutting-edge microcapsule technology. Compared to the cell (Comparative Example 13), that is, the microphone manufactured as described above. We compared the slurries of the Rocapsules.

[0400] 0.3g of the obtained core-shell microcapsules were mixed with 30g of commercially available fabric softener. Downy® Ultra Free & Gentle® Liquid Fabric Condenser Disperse in a conditioner (Proctor & Gamble) and leave for at least one week, preferably. These represent the ages of 1 week, 2 weeks, and 4 weeks, respectively (shown as 1-week sample, 2-week sample, etc. in the diagram). A test was conducted. To evaluate the sensory characteristics, different fabric softener samples (each with a different mineral content) were used. Each of the following (containing chlorophyll particles) comes in a pack of 10 cotton-based face towels (small towels). It was added to 10 cotton-based hand towels (large towels). For reference, 0.1 g of aromatic oil (TomCap®, Symrise, Teterboro, NJ) I dispersed it directly into 30g of fabric softener.

[0401] Washing instructions are as follows: Place the towel (cotton cloth) in the washing machine and wash the corresponding core cloth. Fabric softener containing microcapsules or pure, unencapsulated fragrance oil (see reference) After aging the agent for the time indicated above, add it to the fabric softener dispenser and the washing program Started (device: automatic washer-dryer: Whirlpool(registered trademark)(USA); washing Washing cycle: Normal wash; Washing temperature: Warm (32-44℃); Wash load: Normal.

[0402] After washing, the towels were divided into two groups and hung on a clothesline to air dry (as shown in the diagram). (shown as "rope drying") or mechanically dried in a dryer (shown as "dryer drying" in the diagram) (Then, I labeled the towels and stored them in a large plastic bag until the test.) .

[0403] The fragrance was released in three steps, and the intensity of the released fragrance was evaluated by 10 trained panelists. The evaluation was conducted blindly based on a scale ranging from 1 (odorless) to 6 (very strong). The decision was made. The first step is to smell the untreated, prepared towels. The second step is to smell the towel after lightly crumpling it; for this purpose, By rubbing it, it was subjected to slight mechanical stress. The third step was to move the towel back and forth between the hands. By moving it vigorously several times, you rub the towel hard, which mechanically damages the capsule, and the capsule After releasing the liquefied aromatic oil, explain how to smell it. After each step, check the intensity of the fragrance. Nelist praised it.

[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] Composition of microcapsules prepared according to Examples 1-6 (Figures 1A / B and 6A / 6B) was compared with standard polyurea microcapsules prepared according to Comparative Example 13.

[0407] A sugar and / or amino sugar having fewer than 20 monomer units is used as a component. The performance of Iobase (amino) sugar-based microcapsules is completely after mechanical drying. Regarding the performance of guanidine-crosslinked polyurea-based microcapsules related to cutting-edge synthesis technology It is comparable, and even slightly better. However, for rope-dried samples... Furthermore, the present invention provides fabric softeners containing bio-based (amino) sugar-based microcapsules. Samples treated with the agent showed significantly higher fragrance intensity. Mechanical stress and heat It was thought that this would increase the release of volatile substances from the fabric treated with the emulsion. Drying in a dryer The low fragrance intensity of the towel samples was due to the rupture of microcapsules caused by mechanical shock inside the dryer. This can be explained by the increase in decay and the increase in evaporation due to heat.

[0408] However, the bio-based microcapsules of the present invention are completely synthetic and state-of-the-art. It appears to be even more stable than microcapsules, and the evaporation of volatile fragrance components is even more efficient. It can be effectively suppressed. The strength after crumpling and / or rubbing The significant increase (considerably larger than the capsule in the comparative example) indicates efficient encapsulation of the fragrance substance. This is particularly evident from Figures 6A and 6B. The experiment demonstrated the encapsulation of the present invention. While exhibiting high mechanical and thermal stability (washing machines, dryers), the target of the active ingredient remains. This enables the release of such substances. Furthermore, the microcapsules of the present invention can be used, for example, in consumer product distribution. When incorporated into a compound and subjected to aging, it exhibits high chemical stability, and the active ingredients This enables efficient encapsulation and effectively maintains long-term product quality. Akira's capsules enable efficient encapsulation and superior, targeted release of active ingredients. Furthermore, the microcapsules of this invention are compared to the most advanced, fully synthetic microcapsules. Therefore, it is not significantly affected by the drying process inside the dryer. As a result, the bio-based These core-shell microcapsules are highly suitable for incorporation into various consumer product formulations.

[0409] Furthermore, 33% by weight of active aromatic oil (equivalent to 0.1% by weight of pure aromatic oil) The slurry of each fragrance microcapsule of the present invention, containing 0.3% by weight of the components of Examples 1 to 12. A sample of fabric softener containing - was directly incorporated into the fabric softener as a reference, at 0.1% by weight. The fragrance oil was compared to both machine-dried and rope-dried towels. Figures 1-12). The free, unencapsulated aromatic oils evaporate rapidly, and the drying process and While the bio-based microcapsules according to the present invention were not detected after storage, the fragrance It enables stable encapsulation of the material, exhibits excellent and targeted release behavior, and as a result This enabled a highly perceptible fragrance intensity (i.e., high sensory performance).

[0410] Even after four weeks of aging in the fabric softener, efficient encapsulation of fragrance substances was observed. The fact that this could be done means that the core shell of the present invention could be incorporated into fabric softeners, and by extension into consumer product formulations. The microcapsules demonstrate high stability (for example, Figures 8A-8D; Figures 10A-10D; See Figures 11A and 11B; and Figures 12A to 12D.

[0411] Furthermore, the present invention provides microcapsules having a shell with reduced thickness (Examples 11 and 11) (See 12) This is comparable to state-of-the-art microcapsules with considerably thick shell walls. It exhibits excellent performance and stability.

[0412] As a result, the bio-based core-shell microcapsules according to the present invention are mechanically impacted and While remaining even more stable in the face of heat, it simultaneously achieves the target release of encapsulated active substances. It can be concluded that this makes possible (see mechanically dried sample). Furthermore, this The invented bio-based microcapsules allow active substances to be contained in consumer products for more than four weeks. While encapsulation is efficient, state-of-the-art capsules lose a considerable amount of active material over time. (See rope-dried sample). Therefore, the bio-based micro according to the present invention. The capsule offers an improved balance of efficient encapsulation, stability, and target release characteristics / performance. We can conclude that this demonstrates good.

[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] Biodegradation of microcapsule slurry in the environment is the biodegradation of polymer shells according to the present invention. This includes biological degradation. The measurement of the biological activity or degradation of shell materials is particularly in accordance with the OECD guidelines. Under the line, it can be determined in different environments such as soil, ocean, water, or sludge.

[0416] OECD tests that can be used to determine the biodegradability of organic chemicals include O The six test methods described in ECD Testing Guidelines No. 301AF: DOC D ie-Away test (TG301A), CO2 evaluation test (TG301B), modified MITI Test (I) (TG301C), sealed bottle test (TG301D), modified OECD screen This includes the nervous ventricular test (TG301E) and the pressure breathing measurement test (TG301F). 28th The following acceptable levels of biodegradation obtained within the specified timeframe: 70% DOC removal (TG301A and TG 301E); 60% theoretical carbon dioxide (ThCO2) (TG301B); 60% theoretical The oxygen requirement (ThOD) (TG301C, TG301D, and TG301F) is easily biodegradable. This may be considered evidence. Further details can be found in the official OECD guidelines for testing chemical substances. Introduction to: OECD (2006), Revised Introduction to the OECD Guidelines for Testing of Chem icals,Section 3,OECD Guidelines for the Testing of Chemicals,Section 3,OECD Publ It can be found in Ishing, Paris.

[0417] Testing System

[0418] Test method and test system used for analyzing the biodegradability of microcapsules according to the present invention (contact The test materials (species materials) followed standard test guidelines and procedures in accordance with the OECD 301F biodegradability test. They match.

[0419] Isolation of shell material (sample preparation)

[0420] The shell makes up 1-10% by weight of the entire core-shell microcapsule (after subtracting water). The wall is protected by water-soluble reagents (protective coating) obtained by extraction and washing of the payload (i.e., core). It was obtained by removing unreacted (amino) sugars and salts.

[0421] Shell isolation involves the following steps: 1) Wash with water to remove any soluble materials, and then separate the shell by centrifugation. The process of separating; 2) A hydrophobic "core" solvent using an organic solvent, such as a lower alcohol or acetone. The extraction process; 3) The resulting shell material is heat-dried to remove any remaining solvent and water, followed by grinding. A multi-step process that includes the step of obtaining shell powder, that is, shell material in powder form. Therefore, it was achieved.

[0422] Shell wall isolation can be achieved through other processes, such as freeze-drying, vacuum drying, or spray drying. , or it can also be achieved using more complex processes, such as supercritical CO2 extraction.

[0423] Biodegradation tests were performed on the isolated microcapsule shell powder obtained as is, and standardization was performed. The samples were subjected to testing according to the OECD 301F procedure. In the first biodegradability test, The shell material of the microcapsules in Example 1 is OE for Chemical Test No. 301F. In accordance with the CD guidelines (1992), its biodegradability was assessed using pressure breathing measurement tests. The analysis was performed according to the standardized OECD 301F procedure (Sample #1). Test Guide According to the line, the biodegradation curve for the test item showed that biodegradation had begun, but by day 28 of exposure, plastic had not yet been found. Since it did not reach the target, the test was extended to day 45. Sample #1 is unique. It was found to exhibit secondary biodegradability. In addition, the test items were concentrated at 100 mg / L. It did not have an inhibitory effect on the activity of sludge microorganisms activated at a certain degree. However, The second sample (sample #2) of the microcapsule shell material related to Example 1 exhibits nearly complete biodegradability. This demonstrated that it can be achieved (see Figures 13 and 14).

[0424] The capsule shells prepared according to Comparative Example 13 and US6,586,107B Analysis of comparative test samples corresponding to the capsules disclosed in section 2 is performed on these fully synthetic guani. This shows that the gin-based capsule material is not biodegradable at all (see Figure 15). (and). Therefore, based on the decomposition curve, the core-shell microcapsule according to the present invention is currently Because it is more biodegradable than the most advanced microcapsules currently available, it is an even more ecologically friendly consumption method. It can be concluded that it is even more preferable in terms of being a consumer product.

[0425] consumer product formulation

[0426] The following describes the present invention, which enables efficient encapsulation and excellent release of active ingredients. This document shows various suitable consumer product formulations according to the present invention, including cellulose microcapsules.

[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 at least two isocyanates A polyisocyanate having at least one group and less than 20 monomer units A polymer that is a reaction product of at least one sugar and / or at least one amino sugar. A material comprising or consisting thereof, wherein the core comprises at least one active ingredient, The core-shell microcapsule comprising the same.

2. The sugar(s) and / or amino sugar(s)(s) are of biological origin, as described in claim 1. Core-shell microcapsules.

3. At least one of the one or more polyisocyanates having at least two isocyanate groups The core-shell microcapsule according to claim 1 or 2, wherein one of the components includes an aliphatic structure.

4. The monomer in which at least one sugar and / or at least one amino sugar is 15 or less The present invention relates to any one of claims 1 to 3, having units, preferably 10 or fewer monomer units. Core-shell microcapsules.

5. The at least one sugar and / or at least one having fewer than 20 monomer units The amino sugars are monosaccharides, such as glucose, galactose, fructose, and xylose. , mannose, arabinose, erythrose, threose, ribose, arabinose, ri Xose, allose, altrose, talose, fucose, rhamnose, amino monosaccharides, e.g. For example, glucosamine, galactosamine, N-acetylglucosamine, disaccharides, for instance, Cloth, lactose, maltose, isomaltulose, trehalose, lactulose, Cellobiose, Chitobiose, Isomaltose, Isomaltulose, Maltulose, Am nonosodium bisaccharides, linear and / or branched oligosaccharides, e.g., malto-oligosaccharides, e.g., malto-oligosaccharides Todextrin, raffinose, stachyose, fructooligosaccharide, merisitose, u Ampeliferose, cyclodextrin, linear and / or branched oligomeric amino sugars For example, selected from the group consisting of chito-oligosaccharides or mixtures thereof, claim A core-shell microcapsule as described in any one of items 1 to 4.

6. The above at least one sugar and / or at least one amino sugar is primary and secondary Similar to the rhoxyl group (-OH), primary and secondary amine groups (-NH ２ It consists of , -NH-) Having at least two functional groups independently selected from the group, any one of claims 1 to 5 Core-shell microcapsules as described in the section.

7. The at least one active ingredient is a cosmetic active ingredient, for example, an active skin product ingredient. pesticides, perfume substances, fragrance oils, aromatic substances, aromas, active pharmaceutical ingredients, dyes, UV agents Vibrant substances, optical glossing agents, thickeners, drape and foam control agents, smoothing agents, electrostatic charge Anti-wrinkle agent, anti-wrinkle agent, disinfectant, antibacterial agent, antifungal agent, mold stain preventative, antiviral agent Deodorizers, antibacterial agents, desiccants, stain-resistant agents, antifouling agents, odor inhibitors, fabric deodorizers, dye fixatives, colorants - Maintenance agents, color restorers / recovery agents, fade inhibitors, abrasion inhibitors, wear-resistant agents, fabric preservatives, abrasion Inhibitors, rinsing aids, UV protectants, sun-fading inhibitors, insect repellents, anti-allergic agents, fire resistant agents Waterproofing agents, fabric softeners, shrinkage-resistant agents and / or stretch-resistant agents, fluorescent paints, solvents, waxes, etc. It consists of ricone oil, lubricants, coolants, TRPV preparations, and a mixture of the above-mentioned active ingredients. A core-shell microcapsule selected from the group according to any one of claims 1 to 6. 。

8. The microcapsules are 1 μm to 100 μm, preferably 5 μm to 55 μm, most preferably The median volume-based particle size (Dv(50)) is 5 μm to 50 μm, as per claim 1 to A core-shell microcapsule as described in any one of item 7.

9. The shell of the aforementioned microcapsule meets the OECD 301F biodegradability standard (pressure breathing measurement test). In accordance with any of claims 1 to 8, it is essentially biodegradable, preferably readily biodegradable. Core-shell microcapsules as described in item 1.

10. A microcapsule slurry, dispersed in an aqueous phase, any one of claims 1 to 9 The material comprises a plurality of core-shell microcapsules as described above, preferably the microcapsules in the aqueous phase The concentration of the chlorocapsule is greater than 5% by weight but less than 70% by weight, preferably greater than 20% by weight. The microphone is less than 60% by weight, most preferably more than 30% by weight and less than 50% by weight. Slurry of locapsules.

11. A process for preparing a microcapsule slurry, comprising the following steps: (a) at least one polyisocyanate having at least two isocyanate groups The process of providing an oil phase containing one or more active ingredients; (b) a step of providing a first aqueous phase comprising at least one forming aid; (c) at least one sugar having less than 20 monomer units and / or at least one A second aqueous phase is provided containing amino sugars, and optionally, the aqueous phase further provides one or more additional forming aids. Processes involving the agent; (d) Mixing the oil phase and the first aqueous phase to obtain a provisional oil-in-water emulsion. To the extent; (e) Mix the second aqueous phase with the provisional emulsion obtained in step (d). The process of obtaining a slurry of microcapsules; (f) a step of curing the microcapsules obtained in step (e), vinegar.

12. By preparing the microcapsule slurry according to claim 11, the core shell A process for preparing microcapsules, followed by (g) The process includes the step of isolating the core-shell microcapsules from the slurry. Rothes.

13. The aforementioned forming aids (multiple) may be surfactants (multiple) and / or colloidal protective agents (multiple) The core-shell microcapsule or core-shell microcapsule according to claim 11 or 12, which is acceptable. A process for preparing a slurry containing microcapsules.

14. The at least one polyisocyanate having at least two isocyanate groups at least one sugar having less than 20 monomer units and / or at least one Any one of claims 11 to 13, wherein the molar ratio to amino sugars is in the range of 1:3 to 1:

1. Core-shell microcapsules or slurry containing core-shell microcapsules as described in section - The process of preparing.

15. Claims 11 to 14, wherein the forming aid(s) are biopolymer derivatives(s). Either the core-shell microcapsule described in item 1 or the core-shell microcapsule containing The process of preparing a slurry.

16. Core-shell microphone obtained by the process described in any one of claims 11 to 15 A slurry containing locapsules.

17. Core-shell microphone obtained by the process described in any one of claims 12 to 15 Locapsule.

18. A core-shell microcapsule according to any one of claims 1 to 9 or 17, The consumer product comprising a slurry of microcapsules according to claim 10 or 16 hand, The aforementioned products are cosmetics, personal care products, especially skin cleansing products, shampoos, rinse-off cosmetics. Conditioners, deodorants, antiperspirants, body lotions, fabric care products and home care products. Garden products, especially liquid detergents, all-purpose cleaners, laundry detergents and cleaning agents, fabric softeners, fragrances, and aromatics. The consumer product.

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