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    • 专利摘要:
    POLYUREA MICROCAPSULA PREPARATION PROCESS. The present invention relates to an aminoplast central shell microcapsule of a shell stabilized by a polyisocyanate. It also provides a method to stabilize aminoplast microcapsules in consumer products rich in liquid aqueous surfactant.
    公开号:BR112014015148B1
    申请号:R112014015148-2
    申请日:2012-12-13
    公开日:2021-05-18
    发明作者:Nicolas Pichon；Sonia Godefroy；Arnaud Struillou
    申请人:Firmenich Sa；
    IPC主号:
    专利说明:

    Technical Field
    [001] The present invention relates to aminoplast microcapsules stabilized by a polyisocyanate and consumer products rich in liquid aqueous surfactant comprising such capsules. It also provides a method to stabilize aminoplast microcapsules in consumer products rich in liquid aqueous surfactant. Invention History and Problem to be Solved
    [002] One of the problems faced by the perfume industry is the relatively rapid loss of the olfactory benefit provided by odorous compounds due to their volatility, particularly that of "higher notes". This problem is usually solved by using a delivery system, eg capsules containing a perfume, to release the fragrance in a controlled manner. Aminoplast microcapsules formed from a melamine-formaldehyde resin are often used to encapsulate hydrophobic actives, thus protecting said actives and providing their controlled release.
    [003] However, capsules such as aminoplast suffer from stability problems when used in consumer products comprising surfactants, such as consumer perfumery products, especially after prolonged storage at elevated temperatures. In these products, the encapsulated active tends to leak from the capsule, even if the capsule wall remains intact, by diffusion through the wall due to the presence of surfactants capable of solubilizing the encapsulated active in the base of the product. The leakage phenomenon reduces the efficiency of the capsules to protect the asset and provide its controlled release. This is especially disadvantageous when the active is a volatile ingredient such as perfume.
    [004] Several technologies have been developed to improve the stability of aminoplast capsules in consumer perfumery products. In one approach, the composition of the encapsulated material is specifically designed to prevent leakage (see, for example, US 2005/0112152, EP 1894603 and US 2005/0153135). The disadvantage of this solution is that it imposes a restriction on the active to be encapsulated, thus reducing the perfumer's freedom to create perfumes based on their organoleptic characteristics.
    [005] Alternatively, some prior art documents disclose coating the capsules (see WO 2004/016234) with an additional layer or shell (two shell systems). The disadvantage of this approach is that during manufacturing, additional steps are required compared to the classic method of preparing aminoplast capsules, resulting in additional chemical steps and costs.
    [006] Thus, prior art methods to reduce perfume leakage from capsules when incorporated into consumer products comprising surfactants often have the disadvantage of reducing the olfactory performance of capsules.
    [007] Therefore, it would be of specific interest to provide a method to improve the stability of aminoplast capsules, for example, in applications such as consumer products that contain liquid aqueous surfactant as perfume products. It would be even more advantageous to provide capsules that have good stability in products containing surfactants and at the same time have good olfactory performance. Capsules must therefore be in the right balance between retaining the perfume during storage and the proper release of the perfume through use of the product. The present invention addresses these problems. Furthermore, it would still be preferable to offer a solution to these problems that does not involve high temperatures and very acidic conditions during the encapsulation process, nor does it require additional processing steps after encapsulation.
    [008] No prior art document describes the stabilization of aminoplast capsules using an additive combined with the active to be encapsulated prior to encapsulation. In particular, the use of a polyisocyanate as such an additive has never been mentioned or even suggested in the prior art.
    [009] US 4,353,809 discloses the combination of an aminoplast resin with a polyisocyanate compound to form microcapsules. However, the present document refers to the totally different technical field of applying capsules to paper. Capsules are therefore used in dry conditions or in organic solvents rather than in consumer products based on liquid aqueous surfactant. It is well known to those skilled in the encapsulation art that the stability of capsules is totally different when used in dry conditions, in an organic solvent or in a medium containing aqueous surfactant. Furthermore, the olfactory performance of the capsules is by no means mentioned in this prior art document. Therefore, the present document does not offer any assistance for the problems addressed in the present invention. Detailed Description of the Invention
    [0010] In order to solve the problems mentioned above, the present invention relates to a microcapsule of an aminoplast shell, or a wall, with a central capsule that can be obtained by a process comprising the steps of: 1) mixing a perfume oil with at least one polyisocyanate having at least two isocyanate functional groups to form an oil phase 2) dispersing or dissolving in water an aminoplast resin and optionally a stabilizer to form an aqueous phase; 3) preparing an oil-in-water dispersion, in which the average droplet size is comprised between 1 and 100 µm, mixing the oil phase and the aqueous phase; 4) performing a curing step to form the wall of said microcapsule; and 5) optionally drying the final dispersion to obtain the dry central shell microcapsule.
    [0011] For the sake of clarity, by the terms "a shell, or a wall" it is here understood that said microcapsule has a wall that is not coated, neither internally nor externally, by a different material or film-forming polymers. In any case, the capsules of the invention are devoid of polysiloxane and/or PVP (polyvinyl pyrrolidone) and their copolymers. Said microcapsules may have material deposited on their surface, such as colloidal stabilizers or a cationic polymer, but in an amount which is in any case insufficient to form a continuous phase, film, wall, coating made of other polymers or resin.
    [0012] For purposes of clarity, it is understood by the expression "central shell microcapsule" or similar, in the present invention, that the capsule has a size within the micron range (e.g., an average diameter between approximately 1 and 100 μm ) and comprises an outer shell or wall based on solid oligomers and a continuous inner oil phase surrounded by the outer shell. In other words, bodies such as coacervates or extrudates (eg, porous solid phases containing droplets of a liquid) are not part of the invention. According to an embodiment of the invention, the size of said microcapsules, and hence the droplet size in step 1), is comprised between approximately 5 and 50 µm, or even between approximately 5 and 25 µm.
    [0013] For purposes of clarity, the expression "dispersion" in the present invention is understood to mean a system in which the particles are dispersed in a continuous phase of a different composition and specifically includes a suspension or an emulsion.
    [0014] By "perfume oil" (or also "perfume") is meant herein a perfume which is a liquid at approximately 20°C and which will be in the center of the central shell capsules. According to any of the above configurations, said perfume oil in which the polyisocyanate is dissolved in step 1) may be a single perfumery ingredient or a mixture of ingredients in the form of a perfumery composition. By "perfumery ingredient" herein is meant a compound, which is used in the preparation of perfumery or composition to impart a hedonic effect. In other words, this ingredient, in order to be considered perfumery, must be recognized by a person with knowledge in the art as capable of positively or pleasantly conferring or modifying the odor of a composition, and not just with an odor. For purposes of the present invention, ingredients that neutralize bad odor are also encompassed by the definition of "fragrance ingredient".
    [0015] The nature and type of perfumery ingredients present in the base do not deserve a more detailed description in this instrument, which, in any case, would not be exhaustive, being the person with knowledge in the art able to select them based on your general knowledge and in accordance with the intended use or application and the desired organoleptic effect. In general terms, these perfumery ingredients belong to chemical classes as varied as alcohols, aldehydes, ketones, esters, ethers, acetates, nitriles, terpenoids, heterocyclic nitrogen or sulfur compounds and essential oils, and the aforementioned perfumery coingredients may be of origin natural or synthetic. Many of these co-ingredients are, in any case, listed in reference texts such as S. Arctander's book Perfume and Flavor Chemicals, 1969, Montclair, New Jersey, USA, or its later versions, and in other works similar in nature as well. as in the abundant patent literature in the field of perfumery. It is understood that said ingredients may also be compounds known to release in a controlled manner various types of perfumery compounds.
    [0016] Perfumery ingredients can be dissolved in a solvent currently in use in the perfume industry. The solvent is preferably not an alcohol. Examples of such solvents are diethylphthalate, isopropyl myristate, Abalyn® (pitch resins available from Eastman), benzyl benzoate, ethyl citrate, limonene or other terpenes, or isoparaffins. Preferably, the solvent is very hydrophilic and highly sterically hindered, eg Abalyn®. Preferably, the perfume comprises less than 30% solvent. More preferably, the perfume comprises less than 20%, and even more preferably, less than 10% solvent, all such percentages being defined by weight relative to the total weight of the perfume. Most preferably, the perfume is essentially solvent free.
    [0017] According to a specific embodiment of the invention, the perfume contains less than 10% of its own weight of primary alcohols, less than 15% of its own weight of secondary alcohols and less than 20% of its own weight of tertiary alcohols . Preferably, the perfume does not contain any primary alcohol and contains less than 15% secondary and tertiary alcohols. These limited amounts of alcohols have the advantage of reducing the amount of isocyanate functional groups that react with the perfume.
    [0018] According to any of the configurations of the invention, the perfume oil represents between approximately 10% and 60% w/w, or even between 20% and 45% w/w, by weight, with respect to the total weight of the dispersion as obtained after step 3).
    [0019] The oil phase of step 1) also comprises at least one polyisocyanate, each having at least two isocyanate functional groups.
    [0020] For purposes of the present invention, each polyisocyanate comprises at least two isocyanate functional groups. Said polyisocyanate can comprise up to 6, or even only 4, isocyanate functional groups. According to any of the above configurations, said polyisocyanate contains at least three isocyanate functional groups. After these numbers of functional groups, the ideal reaction of the polyisocyanate with the aminoplast resin is obtained, with a greater number of isocyanate groups per polyisocyanate compound leading to an increase in cross-linking.
    [0021] Low volatility polyisocyanates are preferred due to their low toxicity.
    [0022] The polyisocyanate can be aliphatic, aromatic or a mixture of aromatic and aliphatic polyisocyanates. In the case of polyisocyanate mixtures, each member of the mixture has at least two isocyanate functional groups.
    [0023] According to any of the embodiments of the invention, said polyisocyanate is an aromatic polyisocyanate.
    [0024] The term "aromatic polyisocyanate" is understood herein as any polyisocyanate comprising an aromatic medium. Preferably, it comprises a phenyl, a toluyl, a xylyl, a naphthyl or diphenyl moiety, and more preferably a toluyl or xylyl moiety. Preferred aromatic polyisocyanates are biurets and polyisocyanurates, and more preferably comprise one of the above specific aromatic media. Most preferably, the aromatic polyisocyanate is a polyisocyanurate of toluene diisocyanate (commercially available from Bayer under the tradename Desmodur® RC), a trimethylol propane adduct of toluene diisocyanate (commercially available from Bayer under the tradename Desmodur® L75 ), a trimethylol propane adduct of xylylene diisocyanate (commercially available from Mitsui Chemicals under the tradename Takenate® D-110N). In a more preferred embodiment, the aromatic polyisocyanate is a trimethylol propane adduct of xylylene diisocyanate.
    [0025] According to any of the embodiments of the invention, said polyisocyanate is an aliphatic polyisocyanate.
    [0026] The term "aliphatic polyisocyanate" is defined as a polyisocyanate that does not comprise any aromatic medium. Preferred aliphatic polyisocyanates are a hexamethylene diisocyanate trimer, an isophorone diisocyanate trimer, a hexamethylene diisocyanate trimethylol propranolol adduct trimer (available from Mitsui Chemicals) or a hexamethylene diisocyanate biuret (commercially available from Bay ® N 100), among which a hexamethylene diisocyanate biuret is even more preferred.
    [0027] According to any of the embodiments of the invention, said at least one polyisocyanate is in the form of a mixture of at least one polyisocyanate and at least one aromatic polyisocyanate, both comprising at least two or three isocyanate functional groups, such as a mixture of a hexamethylene diisocyanate biuret with a trimethylol propane adduct of xylylene diisocyanate, or a mixture of a hexamethylene diisocyanate biuret with a polyisocyanurate of toluene diisocyanate and a mixture of a biuret with a polyisocyanurate of toluene diisocyanate and a mixture of a biuret of hexamethylene diisocyanate with a trimethylol propane adduct of toluene diisocyanate. More preferably, it is a mixture of a hexamethylene diisocyanate biuret with a trimethylol propane adduct of xylylene diisocyanate.
    [0028] In a preferred configuration, at least one aliphatic polyisocyanate and at least one aromatic polyisocyanate are used in a respective molar ratio of between 80:20 and 10:90, preferably between 75:25 and 20:80, more preferably between 60:40 and 20:80, and even more preferably between 60:40 and 30:70, more preferably between 45:55 and 30:70.
    [0029] Preferably, the polyisocyanate is added in an amount of between 0.01% and 20% w/w, more preferably between 0.1% and 10% w/w, more preferably between 0.5% and 5 % w/w by weight with respect to the total weight of the perfume oil.
    [0030] In step 2), for the formation of the aqueous phase, requires an aminoplast resin. These aminoplast resins are the reaction products of the polycondensation of one or more amines with one or more aldehydes, preferably formaldehyde. Examples of suitable amines include urea, melamine and derivatives thereof. Preferably, the aminoplast resin is selected from melamine-formaldehyde and urea-formaldehyde condensates and more preferably from melamine-formaldehyde condensates. Such melamine-formaldehyde and urea-formaldehyde condensates are well known to the person skilled in the encapsulation art and are described in detail in the abundant available literature disclosing such condensates. Various materials and process steps are suitable for forming these capsules. These encapsulating polymers, therefore, do not warrant a detailed description in this instrument, which in any case would not be exhaustive.
    [0031] In a preferred configuration, the aminoplast resin is added in amounts ranging from approximately 0.5% and 15% w/w, or even between 1.0% and 10% w/w, by weight with respect to total weight of the dispersion as obtained after step 3).
    Suitable methods for forming aminoplast resins and microcapsules are, for example, described in detail in Dietrich K., Bonatz E., Nastke H., Herma H., Walter M. and Teige W.; Acta Polymerica 41 (1990), pp. 91-95, in Bonatz E., Dietrich K., Herma, H., Walter M. and Teige W.; Acta polymerica 40 (1989), pp. 683-690, in Dietrich K., Bonatz E., Geistlinger H., Herma H., Nastke R., Purz H.-J., Schlawne M., and Teige W.; Acta Polymerica 40 (1989), pp. 325-331, in Dietrich K., Herma H., Nastke R., Bonatz E. and Teige W.; Acta Polymerica 40 (1989), pp. 243251, in Lee H.Y., Lee S.J., Cheong I.W., and Kim J.H.; J. Microencapsulation 19 (2002), pp. 5,59569. US 4,353,809 also discloses the fundamental steps and details of aminoplast capsule formation. This method can be applied in the present invention (eg the action required to carry out step 4).
    [0033] The aqueous phase may also optionally comprise a stabilizer. According to any of the above configurations of the present invention, the dispersion comprises between approximately 0% and 5% w/w of at least one stabilizer, the percentage being expressed in w/w regime with respect to the total weight of the dispersion as obtained after step 3). In yet another aspect of the invention, the dispersion comprises between approximately 0% and 2% w/w of at least one stabilizer. In yet another aspect of the invention, the dispersion comprises between approximately 0% and 1% w/w of at least one stabilizer.
    [0034] For clarity, in the present context, by the term "stabilizer" or similar, it is understood that the normal meaning understood by a person skilled in the art, for example, a compound that is capable of, or added to, stabilize the system, for example, to prevent aggregation or agglomeration of microcapsules, for example, during application or during preparation. The use of said stabilizer is standard knowledge of the person skilled in the art.
    [0035] For the purposes of the present invention, said stabilizer may be an ionic or non-ionic surfactant or a colloidal stabilizer. The exact nature of these stabilizers is well known to a person skilled in the art. As non-limiting examples, the following stabilizers can be mentioned: nonionic polymers such as cellulose derivatives such as hydroxyethyl cellulose, polyethylene oxide, copolymers of polyethylene oxide and polypropylene oxide or polyethylene and polypropylene or polyethylene oxide, alkyl acrylate copolymers and N-vinylpyrrolidone ; ionic polymers such as acrylamide and acrylic acid copolymers (such as Alcapsol® 144 from Ciba), eg acid/acrylamide copolymers produced from a monomer blend of acrylic acid and acrylamide where the acrylic acid content is in the range of 30 at 70%, acid anionic surfactant (such as sodium dodecyl sulfate), acrylic copolymers with a sulfonate group (such as sodium poly(sulfonated styrene) and copolymers of vinyl ethers and maleic anhydride.
    [0036] According to any of the configurations of the present invention above, said stabilizer is an ionic surfactant such as copolymers of acrylamide and acrylic acid.
    [0037] Step 3) is a mixing step, which is well known and a person skilled in the art knows how to carry it out. However, it should be mentioned that according to any of the embodiments of the invention, in said step, the pH of said aqueous phase can typically be adjusted, and not limiting, between 4 and 7, preferably between 4.5 and 6.
    [0038] In step 4), the microcapsules of the invention are formed. The means of carrying out this step are also well known and a person skilled in the art knows how to carry it out. As examples, and not by way of limitation, curing can be carried out by heating the dispersion to approximately 60° to 95°C, until completion of the wall formation. Then, step 4) is completed by cooling the obtained dispersion to room temperature. The resulting product obtained after step 4) is called sludge.
    [0039] According to a specific configuration of the invention, at the end of step 4), some cationic polymers can also be added to the sludge of the invention. Said cationic polymers are well known to a person skilled in the art, e.g. they are described in WO 08/098387 page 5, lines 10 to 30.
    [0040] Preferred cationic polymers will have cationic charge densities of at least 0.5 meq/g, more preferably at least approximately 1.5 meq/g, but also preferably less than approximately 7 meq/g, more preferably less than that approximately 6.2 meq/g. The cationic charge density of cationic polymers can be determined by the Kjeldahl method as described in the North American Pharmacopoeia under chemical tests for the determination of nitrogen.
    [0041] The preferred cationic polymers are chosen among those that contain units that comprise primary, secondary, tertiary and/or quaternary amine groups that can be part of the main polymer chain or be carried by a directly connected side substitute. The weight average molecular weight (Mw) of the cationic polymer is preferably between 10,000 and 2M Dalton, more preferably between 50,000 and 1.5M Dalton. As specific examples, one can mention Salcare® SC60 (cationic copolymer of acrylamidopropyltrimonium chloride and acrylamide, origin: BASF) or Luviquat®, such as PQ 11N, FC 550 or Supreme (polyquaternium-11 to 68 or quaternized copolymers of vinylpyrrolidone origin : BASF), or also Jaguar® (C13S or C17, Rhodia origin).
    [0042] According to any of the configurations of the invention above, an amount of cationic polymers comprised between 0% and 10% w/w is added, or even between approximately 1% and 5% w/w, the percentage being expressed in w/w regime with respect to the total weight of the sludge as obtained after step 4). It is clearly understood by a person skilled in the art that only part of said added cationic polymers will be incorporated into/deposited in the microcapsule shell.
    [0043] According to a specific embodiment of the invention, at the end of step 4) one can optionally add to the sludge, just before or after cooling to room temperature, compounds that are known as residual free aldehyde scavengers such as formaldehyde. Such compounds are well known in the art and can, for example, be urea or ethylene urea.
    [0044] Said aqueous sludge obtained at the end of step 4) can be used directly as a perfume ingredient, in particular for applications that are water-based, such as fabric softener or liquid soap. Therefore, another object of the present invention is an aqueous sludge comprising the microcapsules of the invention, for example a sludge as obtained directly for the process of preparing the microcapsules. Said sludge may also comprise some formulation aids, such as stabilizers or viscosity control agents, or even biocides or bactericides.
    [0045] Alternatively, in optional step 5), the sludge obtained by the process described above may be subjected to drying, such as spray drying, to provide the microcapsules as such, eg in powder form. It is understood that any standard method known to a person skilled in the art for carrying out such drying also applies.
    [0046] The present invention also relates to a perfumed liquid consumer product comprising: a) from 2 to 65% by weight, with respect to the total weight of the consumer product, of at least one surfactant; b) water; and c) the above aminoplast microcapsules. The above aminoplast microcapsules can also be described as obtained by a process comprising the steps of: i. preparing an oil phase by mixing at least one polyisocyanate with at least two isocyanate functional groups with a perfume; and ii. encapsulate the oil phase obtained in step a) in an aminoplast resin. The microcapsules as obtained after step 4), or the sludge as obtained after step 5), can, for example, be incorporated into the consumer product from 0.01 to 10% w/w, more preferably from 0.05 at 2% w/w, more preferably from 0.1 to 1% w/w, these percentages being defined by weight with respect to the total weight of the consumer product. Logically, the above concentrations can be adapted according to the desired olfactory effect in each product.
    [0047] The consumer product may be in the form of a personal or home care product or in the form of a finely fragrant aqueous product. Examples of personal care products include a shampoo, a cream with or without a rinse, a body bath or shower, gel, oil or mousse, a hygiene product, body or hair spray, a cosmetic preparation, a body lotion, a deodorant or an antiperspirant such as deodorant or roll-on antiperspirant. Examples of fine-fragranced aqueous products include a perfume, aftershave, or cologne. Examples of home care products include liquid detergent, all-purpose cleaner, fabric softener or coolant, ironing water, detergent, fabric softener or towelette. As detergents, we include here products such as detergent compositions or cleaning products for washing or cleaning various surfaces, for example, intended for the treatment of textiles or hard surfaces (floors, tiles, stone floors, etc.). Preferably, the surface will be textile.
    [0048] Consumer product base formulations can be found in the abundant literature relating to these products. These formulations do not justify a detailed description in this instrument, which, in any case, would not be exhaustive. The person skilled in the art of formulating these consumer products is perfectly capable of selecting the appropriate components based on his general knowledge and available literature. In particular, examples of such formulations can be found in patents and patent applications relating to these products, for example, in WO 2008/016684 (pages 10 to 14), in US 2007/0202063 (paragraphs [0044] to [0099]) in WO 2007/062833 (pages 26 to 44), in WO 2007/062733 (pages 22 to 40), in WO 2005/054422 (pages 4 to 9), in EP 1741775, in GB 2432843, in GB 2432850, in GB 2432851 or in GB 2432852.
    [0049] The desired stability is achieved in consumer products that comprise several types of surfactants, including cationic, anionic, nonionic, zwitterionic and nonionic semipolar surfactants, in amounts ranging up to 65% by weight, more preferably between 2 and 50% by weight, based on the total weight of the consumer product. For purposes of the present invention, surfactants are preferably intended as those commonly used in consumer goods products. They are well known to a person skilled in the art and do not warrant further description. Non-exhaustive examples of such surfactants comprise sodium alkylbenzene sulfonate, sodium alkyl sulfate, sodium alkyl ether sulfate and fatty acid salts for anionic surfactants; ethoxylated alcohols, alkyl N-methyl glucamide and alkyl polyglucoside for nonionic surfactants; quaternary ammonium salts such as alkyltrimethylammonium chloride or methylsulfate, di-(tallowoxy-ethyl)dimethylammonium, ditallowdimethyl ammonium for cationic surfactants; alkyl betaines, alkyl starch betaines, amino oxides for zwitterionic and amphoteric surfactants. For purposes of the present invention, surfactants are preferably intended as excluding polymeric stabilizer emulsifiers such as acrylic copolymers and gum arabic which are typically used to stabilize emulsions in encapsulation processes.
    [0050] In a preferred embodiment of the invention, the capsules are stable in the consumer liquid aqueous perfume product such that less than 60% of the initial perfume charge leaks from the capsules when stored in that product. The storage time and temperature at which this stability is preferably achieved depends on the type of consumer product. Preferably, these stability results are achieved after 2 or even 4 weeks of storage at 43°C for products such as liquid detergents and fabric softeners.
    [0051] In another embodiment, the present invention provides a method for stabilizing aminoplast microcapsules in a liquid consumer product comprising water and 2 to 65% by weight of surfactant, with respect to the consumer product, comprising the mixture of a polyisocyanate to the perfume to be encapsulated to form an oil phase prior to the encapsulation process. Examples
    [0052] The following examples are even more illustrative of the embodiments of the present invention, and further demonstrate the advantages of the capsules of the invention with respect to prior art teachings. Example 1 Preparation of aminoplast microcapsules for use in the invention Aminoplast microcapsules for use in the invention (Capsules B) were prepared with the following ingredients: Table 1: Composition of Capsules B


    [0053] The oil phase was prepared by mixing a polyisocyanate (trimethylol propane adduct of xylylene diisocyanate, Takenate® D-110N, origin: Mitsui Chemicals) with a perfume oil comprising the ingredients listed in Table 2. oil phase consists of 0.1% Takenate® D-110N and 99.9% perfume oil. Table 2: Composition of perfumery composition
    1) Origin: Firmenich SA, Geneva, Switzerland 2) 2-Tert-butyl-1-cyclohexyl acetate, origin: International Flavors & Fragrances, USA
    [0054] To make the slime of the capsules, the copolymer of acrylamide and acrylic acid and the melamine-formaldehyde resin were dissolved in water to form the aqueous phase. Then, the perfume premix oil was added to the solution and the pH was adjusted to 5 with acetic acid. The temperature was raised to 90 °C for 2 hours to allow the capsules to cure. At that point, the capsules are formed, cross-linked and stabilized. A 3% Salcare solution was then added to the mixture at 90°C and allowed to react for 1 hour at 90°C. Then, an ethylene urea solution (approximately 3% w/w ethylene urea to sludge weight) was added as is commonly done with aminoplast capsules as an agent to sweep away residual free formaldehyde and the mixture was left. cool to room temperature. The final pH was adjusted to 7 with sodium hydroxide.
    [0055] Posterior capsules (Capsules C to E) were prepared according to the above protocol, except that the amounts of Takenate® D-110N and perfume varied as indicated in the table below. Table 3: Amount of polyisocyanate and perfume in the oil phase used to prepare Capsules from C to E
    1) Trimethylol propane adduct of xylylene diisocyanate (origin: Mitsui Chemicals) 2) Perfume composition with the ingredients in Table 2 Example 2 Preparation of aminoplast microcapsules for use in the invention
    [0056] Capsules F to H were prepared using the method described in Example 1, except that, in the oil phase, Takenate® D-110N was replaced by the aliphatic polyisocyanate Desmodur® N 100 (Hexamethylene diisocyanate biuret (origin) Bayer)). The respective amounts of polyisocyanate and perfume oil in the oil phase used in Capsules F to H are summarized in the table below. Table 4: Amount of polyisocyanate and perfume oil in the oil phase in Capsules from C to E
    1) Hexamethylene diisocyanate biuret (Bayer origin) 2) Perfume composition with the ingredients in Table 2 Example 3 Preparation of aminoplast microcapsules for use in the invention
    [0057] Capsules I to K were prepared using the method described in Example 1, except that, in the oil phase, Takenate® D-110N was replaced by a 50/50 % blend weight of the polyisocyanate Aromatic Takenate® D-110N and Aliphatic Polyisocyanate Desmodur® N 100. The respective amounts of the polyisocyanates and perfume oil in the oil phase used in Capsules I to K are summarized in the table below. Table 5: Amount of polyisocyanates and perfume oil in the premix oil used in Capsules I to K
    1) Hexamethylene diisocyanate biuret (Bayer origin) 2) Trimethylol propane adduct of xylylene diisocyanate (origin: Mitsui Chemicals) 3) Perfume composition with the ingredients in Table 2 Example 4 (comparative) Preparation of polyisocyanate-free aminoplast microcapsules
    [0058] Control Capsules A were prepared using the method described in Example 1, except that polyisocyanate was not added. The perfume composition as such was used in place of the oil phase. Example 5 Average diameter of the capsules of the invention
    [0059] The size distribution of Control Capsules A and Capsules B to K was controlled by Optical Microscopy and Light Scattering (Mastersizer S, Malvern) and the mean diameter was calculated (arithmetic mean) for each type of capsules. The results are summarized in the table below. Table 6: Average Diameter of Capsules from A to K
    Example 6 Preparation of a fabric softener of the invention
    A concentrated unscented fabric softener base was prepared by mixing the ingredients listed in Table 7 in the indicated amounts. Percentages are defined by weight relative to the total weight of the unscented fabric softener base. Table 7: Concentrated unscented fabric softener base formulation (pH ~2.85)
    1) Origin: Stepan 2) Origin: Avecia
    [0061] Softeners from B to K were prepared by adding Capsules from B to K at 0.45% by weight, with respect to the total weight of the softener in the unscented softener base of Table 7 under gentle agitation. Preparation of a fabric softener comprising Control Capsules A:
    [0062] The Control A Softener was prepared by adding the Control A Capsules at 0.45% by weight, with respect to the total weight of the softener in the base of unscented softener in Table 7 under gentle agitation. Stability of aminoplast microcapsules in the fabric softener of the invention
    [0063] The storage stability of the capsules in Control Softener A and Softeners B to K was evaluated. Softeners were stored for up to one month at 43 °C or two weeks at 50 °C. The amount of perfume leaked from the capsules was then measured by solvent extraction and GC-MS analysis. The results are summarized in the table below. Table 8: Storage stability of capsules in Softeners B to K in Control Softener A


    [0064] It was apparent from these results that each of Capsules B to K of the present invention was more stable in the softener base than in the corresponding Control Capsules A, as less perfume leaked from the capsules after the storage period. This shows that the addition of a polyisocyanate to the perfume prior to encapsulation increases the storage stability of aminoplast microcapsules in the fabric softener base. The improvement in stability is evident even after adding only small amounts of these additives (of 0.1% by weight, based on the perfume premix oil). Even better results are obtained when isocyanate is used in an amount of at least 0.5% or even at least 1%. Olfactory performance of aminoplast microcapsules in the fabric softener of the invention
    [0065] The olfactory performance of Control Capsules A and Capsules B to K was evaluated in Control Softener A and Softeners B to K, both fresh and after storage for up to 4 weeks at 43 °C.
    [0066] Crimped cotton towels (20 pieces, 18 cm * 18 cm, approximately 30 g each) were washed with 30 g of unscented detergent in a washing machine (Miele Novotronic W300-33CH) at 40 °C using the cycle program I enjoy. Washing was followed by rinsing at 900 rpm with 12.7 g of Softeners B to K or Control Softener A. Crimped towels were then dried in-line for 24 hours before being evaluated.
    [0067] Perfume perception intensity in dry towels treated with Softeners B to K and Control Softener A was assessed by a panel of 20 trained panelists. They were asked to rub the towels over their hands and then rate the perceived intensity of the scent on a scale of 1 to 7, where 1 meant no odor and 7 meant very strong odor. The results are summarized in the table below. Table 9: Olfactory performance of Capsules B to K compared to Control Softener A both fresh and after storage for one month at 43 °C

    [0068] These results make it clear that, after storing the fabric softener, the intensity of the perfume odor was perceived with greater intensity in the fabric treated with the fabric softener of the present invention than with the control softener. This demonstrates that the persistence of the capsules' olfactory performance over time when the fabric softener is stored is better when a polyisocyanate is added to the perfume prior to aminoplast capsule formation than when the capsules are made without isocyanate. Example 7 Preparation of a concentrated liquid detergent of the invention
    [0069] Detergents D and E were prepared by adding Capsules D and E at 0.4% by weight, with respect to the total weight of the detergent, in a commercially available concentrated liquid detergent base Persil® 3X Small and Mighty (trademark from Unilever, UK). This base (pH ~8) contains 5% to 15% nonionic surfactants (such as alcohol ethoxylates) and anionic surfactants (such as sodium alkylbenzene sulphonate and sodium alkyl ether sulphate), also with less than 5% fat soap . Preparation of a concentrated liquid detergent comprising Control Capsules A
    [0070] Control Detergent A was prepared by adding Control Capsules A at 0.40% by weight, relative to the total weight of the detergent, in a commercially available concentrated liquid detergent base Persil® Small and Mighty (trademark of Unilever, UK). Stability of aminoplast microcapsules in the commercially available liquid detergent of the invention
    [0071] The storage stability of the capsules in Detergents D and E and in Detergent Control A was evaluated. Detergents comprising the capsules were stored for up to four weeks at 43°C or 2 weeks at 50°C and the amount of perfume having leaked from the capsules was measured by solvent extraction and GC-MS analysis. The results are summarized in the table below. Table 10: Storage stability of capsules in Detergents D and E and Control Detergent A

    [0072] It is apparent from these results that Capsules D and E were more stable in the concentrated liquid detergent base than the corresponding Control Capsules A, in which no polyisocyanate was used, thus demonstrating that the addition of a poly -isocyanate to the perfume prior to encapsulation enhances the storage stability of aminoplast microcapsules in a concentrated liquid detergent base. Olfactory performance of aminoplast microcapsules in a concentrated liquid detergent of the invention
    [0073] The olfactory performance of Capsules D and E and Control Capsules A was then evaluated in Detergents D and E and Control Detergent A, fresh and after four weeks of storage at 43 °C.
    [0074] The fabrics (2.5 kg of cotton crimped towels) were washed at 40 °C in a European standard horizontal axis machine. 80 g of freshly prepared detergent was placed at the start of the wash through the detergent drawer. After washing, the fabrics were line dried and the odor intensity of the cotton towels was assessed by a 20-member trained board after 1 day of drying. Board members were asked to rate the odor intensity of the towels after lightly rubbing the tissues on their hands on a scale of 1 to 7, with 1 corresponding to no odor and 7 to very strong odor. The results are shown in Table 11. Table 11: Olfactory performance of Capsules D and E and Control Capsules A in concentrated liquid detergent

    [0075] It is clear from these results that after storing the detergent, the perfume intensity was greater in fabrics washed with Detergents D and E, than in fabrics washed with Control Detergent A. This demonstrates that the persistence of olfactory performance of capsules over time when detergent is stored is better when the perfume is mixed with a polyisocyanate prior to encapsulation than when capsules are made without it. Example 8 Stability of aminoplast microcapsules in the fabric softener of the invention
    [0076] The storage stability of Control Capsules A and Capsules D and E of the invention, and capsules according to WO2004/016234, was evaluated in Control Softener A and Softeners D to E and from the softener WO2004 respectively. Softeners were stored for two weeks at 40 °C and 45 °C. The amount of perfume having leaked from the capsules was then measured by solvent extraction and GC-MS analysis. The results are summarized in the table below.
    [0077] Capsules according to WO2004/016234 were obtained by repeating examples 1 and 3 of said document, using integrated PVP of Takenate® D-110 N and in quantities according to WO2004/016234.
    [0078] In other words, capsules according to WO2004/016234 were made using the following amounts with the same experimental procedure as in Example 1: Table 12: Composition of capsules according to WO2004/016234 Examples 1 and 3

    [0079] Posterior capsules (D and E) were prepared according to the protocol of Example 1, except that the amounts of Takenate® D-110N and perfume varied as indicated in table 3. Table 13: Storage stability of capsules in Softeners D and E from WO2004/016234 and in Control Softener A


    [0080] It is apparent from these results that the two capsules WO 2004/016234 Examples 1 and 3 are less stable on the softener base than the corresponding Control Capsules A, which are themselves less stable than Capsules D and E of the present invention, as more perfume leaked from the capsules after the storage period. This shows that the formation of a second layer or shell (two shell systems) of PvP (WO 2004/016234 Example 1 or 3) is detrimental to stability even if a cross-linking agent such as toluene diisocyanate is added ( WO 2004/016234 Example 3). In fact, a second layer does not help to solve the storage stability problem of capsules in fabric softener, on the contrary, it worsens perfume leakage. This is in stark contrast to the present invention, which clearly helps to reduce perfume leakage. Olfactory performance of aminoplast microcapsules in fabric softener of the invention
    [0081] The olfactory performance of Control Capsules A and Capsules D and E and capsules of WO2004/016234 was evaluated in the Control Softener A and Softeners D and E, both fresh and after storage for up to 2 weeks at 40 ° Ç.
    [0082] Crimped cotton towels (20 pieces, 18 cm * 18 cm, approximately 30 g each) were washed with 30 g of unscented detergent in a washing machine (Miele Novotronic W300-33CH) at 40 °C using the program short cycle. Washing was followed by rinsing at 900 rpm with 12.7 g of Softeners D and E or Control Softener A. Crimped towels were then dried in-line for 24 hours before being evaluated.
    [0083] Perfume perception intensity on dry towels treated with Softeners D and E and WO2004/016234 and Control Softener A was evaluated by a board of 20 trained members. They were asked to rub the towels over their hands and then rate the perceived intensity of the scent on a scale of 1 to 7, where 1 meant no odor and 7 meant very strong odor. The results are summarized in the table below. Table 14: Olfactory performance of Capsules D and E and of WO2004/016234 compared to Softener Control A both fresh and after storage for 2 weeks at 40 °C

    [0084] In fresh samples, the formation of an additional second layer or shell (two shell systems) of PvP (WO 2004/016234 Example 1) or PvP with toluene diisocyanate (WO 2004/016234 Example 3) led to a loss of olfactory performance of the capsules compared to Control A Softener, as opposed to that obtained with Softeners D and E (which are like the Performance Control Softener A).
    [0085] After storage for 2 weeks at 40 °C, perfume odor intensity was perceived more strongly in fabric treated with a softener of the present invention (D and E) than with control softener A or both examples of WO2004/016234.
    权利要求:
    Claims (9)
    [0001]
    1. Perfumed liquid consumer product, characterized in that it comprises: a) from 2 to 65% by weight, in relation to the total weight of the consumer product, of at least one surfactant; b) water; and c) single-layer aminoplast core-shell microcapsules obtainable by a process comprising the steps of: 1) mixing a perfume oil with at least one polyisocyanate having at least two isocyanate functional groups to form an oil phase; 2) dispersing or dissolving in water an aminoplast resin and, optionally, a stabilizer to form an aqueous phase; 3) preparation of an oil-in-water dispersion, in which the average droplet size is comprised between 1 and 100 µm, by mixing the oil phase and the aqueous phase; 4) performing a curing step to form the wall of said microcapsules; and 5) optionally drying the final dispersion to obtain dry core-shell microcapsules.
    [0002]
    Product according to claim 1, characterized in that said perfume oil contains less than 10% of its own weight of primary alcohols, less than 15% of its own weight of secondary alcohols and less than 20% of its own weight of tertiary alcohols.
    [0003]
    Product according to claim 1 or 2, characterized in that said perfume oil represents between about 10% and 60% w/w, by weight, with respect to the total weight of the dispersion obtained after step 3).
    [0004]
    4. Product according to any one of claims 1 to 3, characterized in that said at least one polyisocyanate is a mixture of at least one aliphatic polyisocyanate and at least one aromatic polyisocyanate, the aliphatic polyisocyanate and the aromatic polyisocyanate being in a respective molar ratio ranging from 80:20 to 10:90.
    [0005]
    Product according to any one of claims 1 to 3, characterized in that said at least one polyisocyanate is an aromatic polyisocyanate.
    [0006]
    6. Product according to any one of claims 1 to 5, characterized in that said at least one polyisocyanate is added in an amount comprised between 0.01% and 20% w/w by weight, in relation to the total weight of perfume oil, preferably between 0.1% and 10%, more preferably between 0.5% and 5%.
    [0007]
    Product according to any one of claims 1 to 6, characterized in that said aminoplast resin is a condensate of melamine-formaldehyde or urea-formaldehyde.
    [0008]
    8. Product according to any one of claims 1 to 7, characterized in that said aminoplast resin is added in an amount comprised between 0.5% and 15% w/w, in weight in relation to the total weight of the dispersion obtained after step 3).
    [0009]
    Product according to any one of the preceding claims, characterized in that said product is a personal or household care product.
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    法律状态:
    2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-08-20| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2021-03-02| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|
    2021-03-30| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-05-18| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 13/12/2012, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    EP11195110.9|2011-12-22|
    EP11195110|2011-12-22|
    PCT/EP2012/075393|WO2013092375A1|2011-12-22|2012-12-13|Process for preparing polyurea microcapsules|
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