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    • 专利摘要:
    process for preparing polyurea microcapsules. The present invention relates to a process for producing perfume-containing microcapsules with a polyurea wall that can be used in household or personal care products, as well as to the microcapsules themselves and consumer products including such microcapsules. The process of the invention utilizes a combination of aromatic and aliphatic polyisociates at specific relative concentrations.
    公开号:BR112012029551B1
    申请号:R112012029551-9
    申请日:2011-06-07
    公开日:2019-01-29
    发明作者:Arnaud Struillou；Nicolas Pichon；Sonia Godefroy；Claudie Bellouard Drevet
    申请人:Firmenich Sa；
    IPC主号:
    专利说明:

    PROCESS FOR PREPARATION OF POLYUREA MICROCapsules Technical Field The present invention relates to a process for producing perfume capsules containing a polyurea wall that can be used in personal and household care products as well as the microcapsules themselves and consumer products themselves. comprising these microcapsules. The process of the invention utilizes a combination of aromatic and aliphatic polyisocyanates at specific relative concentrations.
    Background of the Invention and Problem to Be Solved One of the problems faced by the perfumery industry is the relatively rapid loss of olfactory benefit of odorous compounds due to their volatility, particularly the "top notes". This problem is generally addressed by using an application system, e.g., perfume-containing capsules, to release the fragrance in a controlled manner. Polyurea capsules, formed by polymerization between a polyisocyanate and a polyamine, are well known capsules used in a wide variety of technical fields, including perfumery. However, such application systems may suffer stability problems when incorporated into surfactant-based products, such as detergents or fabric softeners, which are strongly aggressive to said application systems. It is especially difficult to prepare capsules with both good stability and good olfactory performance. The retention capacity of the perfume, and hence the ability of the capsules to prevent loss of volatile ingredients, is in particular dependent upon the stability of the capsules at the base of the product. On the other hand, the hedonic effect perceived by consumers using a fragrant product and, therefore, their perception of the quality of this product depends on the olfactory performance of the capsules. In particular, capsules that have good stability on a product basis do not automatically have good olfactory performance. It is therefore desirable to provide capsules with both good stability and good olfactory performance.
    Several prior art documents address the problem of stability of polyurea microcapsules.
    This is for example the case of US 3,886,085, which discloses a process for the preparation of thin oil droplet microcapsules employing a polyisocyanate adduct with a free isocyanate group and a polyamine or polyamine adduct with a free amino group. Among the polyisocyanate adducts that may be used, aromatics are mentioned. This process allegedly produces capsules that encapsulate a perfume, where the perfume can be stored for a long time without being released through the capsule walls or shells (ie stable capsules). However, the capsules are specifically designed to be applied on paper. It is well known that the presence of surfactants in fragrant products such as household and personal care products makes the bases of these products very aggressive to the capsules incorporated therein, thus having a very negative impact on the storage capacity of the capsules. Such aggressive conditions do not exist when the capsules are applied to paper, so the stability of the capsules applied to paper cannot be compared to the stability of microcapsules in media containing surfactants such as perfumed products. In addition, the problem of capsule olfactory performance is not addressed in this document. US 4,668,580 discloses a process for producing polyurea microcapsules in which a wide variety of polyisocyanates may be used, including aliphatic and aromatic. Example 3 of this document uses a polyisocyanate mixture consisting of 90% biuretized hexamethylene diisocyanate and 10% carbodiimide modified polymethylene polyphenyl diisocyanate. This paper addresses the problem of providing capsules with an "inhomogeneous" organic phase having an organic liquid and an insoluble polyisocyanate within it. The application of this technology in the field of perfumery is not glimpsed or even suggested in this document. Therefore, the problem of combining the storage stability of perfume capsules and good olfactory performance is not addressed in this document. The present invention offers a novel process for preparing polyurea microcapsules. Advantageously, it solves the problem of providing highly stable capsules while having good olfactory performance. The present solution to this problem is not described or even suggested in any previous document.
    Summary of the Invention The present invention relates to a process for preparing polyurea microcapsules encapsulating a perfume. The invention relates to the capsules themselves as well as the fragrant compositions and fragrant articles containing them. Detailed Description of the Invention An object of the present invention is a process for the preparation of polyurea microcapsules comprising a) dissolving a mixture of at least one aliphatic polyisocyanate and at least one aromatic polyisocyanate, both comprising at least two isocyanate functional groups, in a perfume to form a solution; b) adding to the mixture obtained in step a) an aqueous solution of an emulsifier or colloidal stabilizer; c) adding to the mixture obtained in step b) a polyamine to form a polyurea wall with the polyisocyanate to form a thick suspension of microcapsules; characterized in that aliphatic polyisocyanate and aromatic polyisocyanate are used in a respective molar ratio ranging from 80:20 to 10:90. The perfume in which the polyisocyanate is dissolved in step a) may be a perfuming ingredient alone or a mixture of ingredients in the form of a perfuming composition. Any fragrant ingredient or composition may be used. Specific examples of such fragrance ingredients can be found in the current literature, for example, in Perfume and Flavor Chemicals, 1969 (and later editions), by S. Arctander, Montclair NJ (USA), as well as in the extensive patent literature and other texts. related to the perfume industry. They are well known to the person skilled in the art of perfuming consumer products, that is, in the art of giving a pleasant odor to a consumer product.
    Perfuming ingredients can be dissolved in a solvent commonly used in the perfume industry. The solvent preferably is not an alcohol. Examples of such solvents are diethyl phthalate, isopropyl myristate, Abalyn® (rosin resins available from Eastman), benzyl benzoate, ethyl citrate, limonene or other terpenes or isoparaffins. Preferably, the solvent is highly hydrophobic and quite sterically hindered, such as, for example, Abalyn®.
    Preferably, the perfume includes less than 30% of the solvent. More preferably, the perfume comprises less than 20% and even more preferably less than 10% of the solvent, all such percentages being defined by weight relative to the total weight of the perfume. Most preferably, the perfume is essentially solvent free.
    According to the preferred embodiment of the invention, the perfume used in the process of the invention contains less than 10% primary alcohol by its own weight, less than 15% secondary alcohol by its own weight and less than 20% tertiary alcohol. in its own weight. Preferably, the perfume used in the process of the invention does not contain primary alcohols and contains less than 15% secondary and tertiary alcohols.
    According to another preferred embodiment of the invention, an amount of between 25 and 60% of perfume is used in the process of the invention, these percentages being defined by weight relative to the total weight of the obtained microcapsule slurry.
    Polyisocyanates used in the process of the invention comprise at least two isocyanate groups. Preferably, they contain at least three isocyanate groups. By following these numbers of functional groups, optimal capsule wall crosslinking or meshing is achieved, thereby providing microcapsules that exhibit slow and prolonged fragrance release as well as good stability in the consumer product.
    Low volatility polyisocyanates are preferred because of their low toxicity. The term "aromatic polyisocyanate" is intended herein to include any polyisocyanate that includes an aromatic moiety. Preferably, it includes a phenyl, toluyl, xylyl, naphthyl or diphenyl component, more preferably a toluyl or xylyl component. Preferred aromatic polyisocyanates are biurides and polyisocyanurates, more preferably comprising one of the specific aromatic components cited above. More preferably, the aromatic polyisocyanate is a toluene diisocyanate polyisocyanurate (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 xylene diisocyanate (commercially available from Mitsui Chemicals under the tradename Takenate® D-110N). The chemical structures of these preferred aromatic polyisocyanates are shown in Figure 1. In the most preferred embodiment, the aromatic polyisocyanate is a trimethylol propane adduct of xylene diisocyanate. The term "aliphatic polyisocyanate" is defined as a polyisocyanate that does not include an aromatic moiety. Preferred aliphatic polyisocyanates are a hexamethylene diisocyanate trimer, an isophorone diisocyanate trimer, a hexamethylene diisocyanate trimethyl adduct (available from Mitsui Chemicals) or a hexamethylene diisocyanate biuride (commercially available from Bayer Desmodur® N 100), among which hexamethylene diisocyanate biuride is even more preferred. The chemical structure of this preferred aliphatic polyisocyanate is shown in Figure 1. Examples of preferred specific mixtures of at least one aliphatic polyisocyanate and at least one aromatic polyisocyanate are a mixture of a hexamethylene diisocyanate biuride adduct with xylene diisocyanate trimethyl propane a mixture of hexamethylene diisocyanate biuride with a toluene diisocyanate polyisocyanurate and a mixture of a hexamethylene diisocyanate biuride with a toluene diisocyanate trimethylol propane adduct. More preferably, it is a mixture of a hexamethylene diisocyanate biuride with a xylene diisocyanate trimethylol propane adduct.
    In a preferred embodiment, at least one aliphatic polyisocyanate and at least one aromatic polyisocyanate are used in a respective molar ratio between 75:25 and 20:80, more preferably between 60:40 and 20:80, even more preferably between 60:40. and 30:70, the most preferable being between 45:55 and 30:70. Preferably, the polyisocyanate mixture is added in an amount between 2 and 20% by weight, relative to the total weight of the solution obtained in step a). In step b) of the process of the present invention, an aqueous solution of an emulsifier or colloidal stabilizer is added to the mixture of step a). In a preferred embodiment, a dispersion or emulsion is formed where droplets of the mixture obtained in step a) are dispersed throughout the aqueous solution of the colloidal emulsifier or stabilizer. For the purpose of the present invention, an emulsion is characterized by stabilization of oil droplets by emulsifiers, whereas in a dispersion the droplets are stabilized by a colloidal stabilizer. The dispersion or emulsion may be prepared by high shear mixing and adjusted to the desired droplet size. Droplet size can be verified by light scattering measurements or microscopy. Preferably, an aqueous solution of a colloidal stabilizer is used and therefore a dispersion is formed.
    Examples of colloidal stabilizers are polyvinyl alcohol, cellulose derivatives such as hydroxyethyl cellulose, polyethylene oxide, polyethylene and polyethylene oxide copolymers or polypropylene oxide, acrylamide and acrylic acid copolymers or cationic polymers such as a cationic copolymer. vinylpyrrolidone and a quaternized vinylimidazole such as those sold under the tradename Luviquat® (commercially available from BASF). Preferably, the colloidal stabilizer is a polyvinyl alcohol or cationic polymer which is a vinylpyrrolidone and quaternized vinylimidazole copolymer, or a mixture thereof.
    Examples of emulsifiers are anionic surfactant such as sodium dodecyl sulfate or Stepantex® (commercially available from Stepan), nonionic surfactant such as polyethylene oxide diblock copolymers or polypropylene oxide.
    In step c) of the process of the invention, a polyamine is added. The polyurea wall of the microcapsules is the result of interfacial polymerization between the polyisocyanate dissolved in step a) and the polyamine added in step c).
    For the purpose of the present invention, the polyamine may be used alone or may be mixed with glycerine.
    Preferably said polyamine is selected from the group consisting of 1,2-diaminopropane, 1,2-diaminoethane, diethylenetriamine, water soluble guanidine salts and guanidine, tris- (2-aminoethyl) amine, N, N'-bis (3-Aminopropyl) ethylenediamine and N, N, N ', N'-tetrakis (3-aminopropyl) -1,4-butanediamine. The chemical structures of these preferred polyamines are shown in Figure 1.
    More preferably, the polyamine is selected from the group consisting of water soluble guanidine salts and guanidine, tri- (2-aminoethyl) amine, N, N'-bis (3-aminopropyl) ethylenediamine and N, N, N ' N'-tetrakis (3-aminopropyl) -1,4-butanediamine. The main preference is that water soluble guanidine salts and N, N'-bis (3-aminopropyl) ethylenediamine are selected from guanidine. "Water soluble guanidine salt" means a water soluble salt resulting from the reaction of guanidine with an acid. An example of such salts is guanidine carbonate. The amount of polyamine used is generally adjusted so that for each mol of the isocyanate group dissolved in the perfume of step a), from 0.5 to 3 moles of amino groups in step c) is added. Preferably, for each mol of the isocyanate group dissolved in the perfume in step a), from 1 to 3, more preferably 1 to 2 moles of amino groups are added in step c). No specific action is required to induce polymerization between polyisocyanates and polyamine. The reaction begins immediately after the polyamine is added. Preferably, the reaction is maintained for 2 to 15 hours, more preferably for 2 to 10 hours. The specific composition of the polyurea wall is essential in obtaining microcapsules that are in an optimal balance between release and retention in order to achieve satisfactory release of fragrances when the capsules are placed in tissues or hair while show the desired stability at the base of the product (e.g., by effectively opposing the extraction of the perfume by the surfactants of the consumer product). Therefore, the selection of polyamine and polyisocyanate, among those mentioned above, allows a fine tuning of the properties and stability of the capsules.
    In an optional step of the process of the invention, the microcapsules may be isolated from the suspension. In another optional step, the thick suspension of the microcapsules may be dried in a generally known manner to form a powder of the polyurea microcapsules. Any drying method known to a person skilled in the art may be used and, in particular, the suspension may be atomized to provide a powder from the microcapsules.
    Microcapsules obtained by the process of any of the above embodiments are also an object of the present invention. Therefore, the present invention provides microcapsules comprising a polyurea wall which comprises the polymerization reaction product between at least one polyisocyanate and at least one polyamine; a colloidal stabilizer or emulsifier; and an encapsulated perfume; characterized in that the polyisocyanate is in the form of a mixture of at least one aliphatic polyisocyanate and at least one aromatic polyisocyanate in a respective molar ratio between 80:20 and 10:90, both aromatic and aliphatic polyisocyanate comprising at least two isocyanate functional groups.
    According to the preferred embodiment, the polyurea wall is the product of the polymerization reaction between at least one polyisocyanate and at least one polyamine.
    The obtained microcapsules have an average diameter (d (v, 0.5)) of between 1 and 50 pm and preferably between 5 and 35 pm, more preferably between 5 and 20 pm. In the present context, "mean diameter" refers to the arithmetic mean. The present inventors have found that with microcapsules of this size optimum deposition and / or adhesion of the microcapsules to the target surface, for example tissue, hair or skin, is achieved. The polyisocyanate mixture, the perfume, the colloidal stabilizer or emulsifier and the polyamine, as well as the respective amounts thereof, are as defined above in any embodiment related to the microcapsule preparation process.
    The microcapsules of the invention may be advantageously used for the controlled release of the encapsulated perfume. Therefore, it is particularly appreciated to include such microcapsules as fragrant ingredients in a fragrant consumer product. This result is highly surprising as such consumer products may contain high amounts (typically more than 10% of their own weight) of specific surfactant / surfactant / solvent types which are known to significantly reduce the stability and performance of the products. said capsules. In other words, the use of the microcapsules of the invention in the consumer product offers unexpected advantages over the same use as other prior art capsules.
    As shown in the examples below, polyurea microcapsules obtained by the process of the invention offer good perfume retention while presenting good olfactory performance. They offer a controlled release of the encapsulated perfume, said perfume being slowly released from the microcapsules, greatly improving the duration and intensity of the perfume.
    The capsules of the present invention have the advantage of being stable. More preferably, microcapsules are considered stable when no more than 50% of the initial perfume charge leaks from the capsules when stored for one month at 38 ° C when incorporated into a consumer product, for example, one of the consumer products. listed below.
    A perfumed consumer product comprising the microcapsules of the invention is therefore also an object of the present invention. In particular, the consumer product may be in the form of a household or personal care product or in the form of a fine fragrance. Examples of personal care products include shampoos, hair conditioners, soaps, bath salts, mousses, oils or gels, toiletries, cosmetic preparations, body lotions, deodorants and antiperspirants. Examples of fine fragrances include perfumes, aftershave and colognes. Examples of household care products include solid or liquid detergents, multipurpose toiletries, fabric softeners and softeners, ironing and detergent products, fabric softeners, including liquid, powder and tablet detergents and fabric softeners. are preferred. As detergents we include products such as detergent compositions or cleaners for washing or sanitizing various surfaces, for example for the treatment of fabrics or hard surfaces (floors, slabs, stone floors, etc.). Preferably, the surface is a fabric.
    Most preferred consumer products include powder and liquid detergents, fabric softeners, liquid soaps, deodorants and antiperspirants, more preferably roll-on deodorants and antiperspirants, hair shampoo, hair conditioners and body lotions. The thick suspension of capsules obtained in the process of the invention may be used as such to perfume the consumer products. For example, the reaction mixture may be added directly to a liquid tissue softener. Alternatively, microcapsules obtained in the process of the invention may be isolated from the reaction mixture before being incorporated into a consumer product. Similarly, the reaction mixture containing the inventive microcapsules may be sprayed onto a dry powder product such as a detergent powder or the microcapsules may be dried and added to such products in solid form. Microcapsules may, for example, be atomized.
    Preferably, the consumer product comprises 0.01 to 10%, more preferably 0.05 to 2% of the microcapsules of the present invention, such percentages being defined by weight relative to the total weight of the consumer product. Of course, the above concentrations may be adapted according to the desired olfactory effect in each product.
    Formulations of the consumer product bases in which the microcapsules of the invention may be incorporated may be found in the abundant literature regarding such products. These formulations do not need a detailed description here, which would not be complete in any way. One skilled in formulating such consumer products is perfectly capable of selecting the appropriate components based on their general knowledge and available literature. In particular, examples of such formulations may be found in patents and patent applications relating to such products, for example, WO 2008/016684 (pages 10 to 14), US 2007/0202063 (paragraphs [0044] to [0099]). WO 2007/062833 (pages 26 to 44), WO 2007/062733 (pages 22 to 40), WO 2005/054422 (pages 4 to 9), EP 1741775, GB 2432843, GB 2432850, GB 2432851 or GB 2432852.
    Description of the drawings Figure 1: Chemical structures of some polyamines and polyisocyanates which may be used in the present invention.
    Figure 2; Graph representing the stability of the capsules of the invention in Softeners A to G and Control A Softener as a function of the proportion (moi%) of aliphatic polyisocyanate (Desmodur® N 100) in the Desmodur® N 100 / Takenate® D-110N mixture used to prepare capsules.
    Examples The following examples further illustrate the embodiments of the present invention and also demonstrate the advantages of the devices of the invention over the prior art teachings.
    Example 1 Preparation of the Polyurea Microcapsules of the Invention Polyurea microcapsules according to the invention (Capsules A) were prepared with the following ingredients: Table 1: Composition of Capsules A Ϊ) Hexamethylene Diisocyanate Biuride, Origin: Bayer 2) xylene diisocyanate trimethylol propane, origin: Mitsui Chemicals 3) Fragrant composition with tabular ingredients Table 1a) Perfume composition a) Origin: Dragoco, Holzminden, Germany b) Origin: Firmenich SA, Geneva, Switzerland c) Methyl dihydrojasmonate, Origin: Firmenich SA, Geneva, Switzerland d) Origin: International Flavors & Fragrances, USA
    e) 1,2,3,5,6,7-Hexahidro-1,2,3,3-pentamethyl-4h-inden-4-one, origin: International Flavors & Fragrances, USA f) 3- (4-Terc -butylphenyl) -2-methylpropanal, origin: Givaudan SA, Vernier, Switzerland g) 1- (5,5-Dimethyl-1-cyclohexen-1-yl) -4-penten-1-one, origin: Firmenich SA, Geneva , Switzerland h) 1- (Octahidro-2,3,8,8-tetramethyl-2-naphthalenyl) -1-ethanone, origin: International Flavors & Fragrances, USA i) Dodecahydro-3a, 6,6,9a-tetramethyl naphtho [2,1-b] furan, origin: Firmenich SA, Geneva, Switzerland j) 3-Methyl-4- (2,6,6-trimethyl-2-cyclohexen-1-yl) -3-buten-2-one, Origin: Givaudan SA, Vernier, Switzerland k) Pentadecenolide, Origin: Firmenich SA, Geneva, Switzerland l) 1-Methyl-4- (4-methyl-3-pentenyl) cyclohex-3-ene-1-carboxaldehyde, origin: International Flavors & Fragrances, USA 4) Mowiol® 18-88, origin: Fluka 5) Tetraethyl ammonium chloride (50% aqueous solution), origin: Fluka 6) Origin: Acros Organics Desmodur® N 100 and Takenate D-110N were dissolved in the perfume. The oil phase was introduced into a one-liter double-walled glass reactor equipped with a scraper stirrer and an Ika rotor-stator system (6500-24000 rpm). The oil phase was stirred at 50 rpm with the scraper shaker for 5 minutes.
    A 1% by weight aqueous stabilizing solution relative to the total weight of the stabilizing solution was prepared by dissolving the polyvinyl alcohol in 543.5 g of deionized water.
    This solution was introduced into the reactor at room temperature and the scraper shaker was turned off.
    A preemulsion was then prepared by dispersing the perfume phase into the aqueous phase with the Ika rotor / stator system for 10 minutes at 13500 rpm.
    After the emulsion was prepared, stirring was continued with the scraper shaker at 200 rpm until the end of the process. Tetraethyl ammonium chloride solution was added to the emulsion. Then a solution of guanidine carbonate in 19 g of deionized water was added to the reactor for one hour. The temperature of the reaction mixture was then slowly raised for one hour from room temperature to 70 ° C. The temperature was then kept at 70 ° C for 2 hours. The stirring speed was then reduced to 100 rpm and the capsule suspension was cooled to room temperature. The perfume content of the capsule suspension was approximately 40% of the total weight of the suspension.
    Example 2 Preparation of the Polyurea Microcapsules of the Invention Capsules B to G were prepared using the method described in Example 1. The same amounts of perfume, polyvinyl alcohol, tetraethyl ammonium chloride, guanidine carbonate and water were used as in Table 1. Only the amounts of Desmodur® N 100 and Takenate® D-110N varied as indicated in the table below.
    Table 2: Quantities of Polyisocyanates in Capsules B to G 1) Hexamethylene Diisocyanate Biuride, Origin: Bayer 2) Addylate with Xylene Diisocyanate Trimethylol Propane, Origin: Mitsui Chemicals Example 3 Preparation of the Polyurea Microcapsules of the Invention Capsules H and I were prepared using the method described in Example 1. The same amounts of perfume, polyvinyl alcohol, tetraethyl ammonium chloride, guanidine carbonate and water were used as shown in Table 1. Only the nature and amount of the polyisocyanate varied. Takenate® D-110N was replaced by Desmodur® RC in capsules H and Desmodur® L75 in capsules I. The respective amounts of polyisocyanate used in capsules H and I are summarized in the two tables below.
    Table 3: Amount of Polyisocyanates in Capsules H 1) Hexamethylene Diisocyanate Biuride, Origin: Bayer 2) Toluene Diisocyanate Polyisocyanurate, Origin: Bayer Table 4: Amount of Hexamethylene Diisocyanate Biuride, Origin: Bayer 2) Toluene Diisocyanate Trimethylol Propane, Origin: Bayer Example 4 Preparation of the Polyurea Microcapsules of the Invention Polyurea microcapsules according to the invention (Capsules J) were prepared with the following ingredients.
    Table 5: Capsule Composition J Ϊ) Hexamethylene BiüretõdA diisocyanate, origin: Bayer 2) Adduct with xylene diisocyanate trimethylol propane, origin: Mitsui Chemicals 3) Fragrant composition of Table 1a (as in Example 1) 4) Mowiol® 18- 88, origin: Fluka 5) Tetraethyl ammonium chloride (50% aqueous solution), origin: Fluka 6) Origin: Acros Organics Desmodur® N 100 and Takenate D-110N were dissolved in the perfume. This oil phase was introduced into a one-liter double-walled glass reactor equipped with a scraper stirrer and an Ika rotor-stator system (6500-24000 rpm). The oil phase was stirred at 50 rpm with the scraper shaker for 5 minutes. A 1% by weight aqueous stabilizing solution relative to the total weight of the stabilizing solution was prepared by dissolving the polyvinyl alcohol in 543.5 g of deionized water.
    This solution was introduced into the reactor at room temperature and the scraper shaker was turned off.
    A preemulsion was then prepared by dispersing the perfume phase into the aqueous phase with the Ika rotor / stator system for 10 minutes at 13500 rpm.
    After the emulsion was prepared, stirring was continued with the scraper shaker at 200 rpm until the end of the process. Tetraethyl ammonium chloride solution was added to the emulsion. Then a solution of guanidine carbonate in 19 g of deionized water was added to the reactor for one hour. The temperature of the reaction mixture was then kept at room temperature for two hours. The perfume content of the capsule suspension was approximately 40% of the total weight of the suspension.
    Example 5 Preparation of the Polyurea Microcapsules of the Invention Capsules K, L and M were prepared using the method described in Example 4. The same amounts of perfume, polyvinyl alcohol, tetraethyl ammonium chloride, Desmodur® N 100, Takenate® D were used. -110N and water, as in Table 5. Only the nature and amount of the polyamine used varied, as summarized in the following table.
    Table 6: Polyamines used in Capsules K, L and M 1) Origin: Fluka Example 6 Preparation of the Polyurea Microcapsules of the Invention Capsules N to P were prepared using the method described in Example 4, except that 6.8 g of tris (2- aminoethyl) amine (origin: Fluka) was used as polyamine. The respective amount of Desmodur® N 100 and Takenate® D-110N varied for each of these capsules as summarized in the table below.
    Table 7: Amounts of Polyisocyanates in Capsules N to P 1) Hexamethylene Diisocyanate Biuride, Origin: Bayer 2) Addylate with Xylene Diisocyanate Trimethylol Propane, Origin: Mitsui Chemicals Example 7 Preparation of Polyurea Microcapsules of the Invention Capsules Q a S were prepared using the method described in Example 4, except that 11.1 g of N, N, N ', N'-tetrakis (3-aminopropyl) -1,4-butanediamine (DAB-Am-4, origin: Sigma-Aldrich ) were used as polyamine. The respective amount of Desmodur® N 100 and Takenate® D-110N varied for each of these capsules as summarized in the table below.
    Table 8: Quantities of Polyisocyanates in Capsules Q to S "Tj Hexamethylene Diisocyanate Biuride, Origin: Bayer -2) Adduct with Xylene Diisocyanate Trimethylol Propane Origin: Mitsui Chemicals Example 8 Preparation of Polyurea Microcapsules of the Invention T Capsules and U were prepared using the method described in Example 4, except that 12.2 g of N, N'-bis (3-aminopropyl) ethylenediamine (origin: Acros Organics) were used as polyamine.The respective amount of Desmodur® N 100 and Takenate ® D-110N varied for each of these capsules as summarized in the table below.
    Table 9: Quantities of Polyisocyanates in Capsules T and U 1) Hexamethylene Diisocyanate Biide, Origin: Bayer 2) Addylate with Xylene Diisocyanate Trimethylol Propane Origin: Mitsui Chemicals Example 9 (Comparative) Preparation of Polyurea Microcapsules Containing Only One Polyisocyanate Aliphatic Comparative capsules (Control A) were prepared using only an aliphatic polyisocyanate. The capsules have the following ingredients: Table 10: Control Composition A 1) Hexamethylene Diisocyanate Biuride, Origin: Bayer 2) Origin: Acros Organics 3) Fragrant Composition of Table 1a (as in Example 1) 4) Mowiol® 18- 88, origin: Fluka 5) Tetraethyl ammonium chloride (50% aqueous solution), origin: Fluka These capsules were prepared using the method described in Example 1.
    Example 10 (Comparative) Preparation of Polyurea Microcapsules Containing Only an Aliphatic Polyisocyanate Controls B to G and L were prepared according to the method of Example 4. The amounts of Desmodur® N 100, perfume, polyvinyl alcohol, tetraethyl ammonium chloride and water used were as shown in Table 10. Only the nature and amount of polyamine used varied as indicated in the following table.
    Table 11: Composition of Controls B to G and L 1) Origin: Acros Organics 2) Origin: Fluka 3) DAB-Am-4, Origin: Sigma-Aldrich 4) Origin: Acros Organics Example 11 (comparative) Preparation of polyurea containing only one aromatic polyisocyanate Comparative capsules (Control H) were prepared using only an aromatic polyisocyanate. These capsules have the following ingredients: Table 12: Control Composition H 1) Xylene Diisocyanate Trimethylol Propane Adduct, Origin: Mitsui Chemicals 2) Fragrant Composition of Table 1a (as in Example 1) 3) Mowiol® 18-88, origin: Fluka 4) Tetraethyl ammonium chloride (50% aqueous solution), origin: Fluka 5) Origin: Acros Organics These capsules were prepared using the method described in Example 1. Example 12 (comparative) Preparation of polyurea microcapsules containing only an aromatic polyisocyanate Controls I to K and M were prepared according to the method of Example 4. The amounts of Takenate® D-110N, perfume, polyvinyl alcohol, tetraethyl ammonium chloride and water used were as shown in Table 12. Only The nature and amount of the polyamine used varied in Controls I to K and M, as summarized in the following table.
    Table 13: Composition of Controls I to K and M 1) Origin: Fluka 2) DAB-Am-4, Origin: Sigma-Aldrich 3) Origin: Acros Organics Example 13 Average Diameter of Capsules of the Invention The Size Distribution of Capsules A U was controlled by light microscopy and light diffusion (Mastersizer S, Malvern) and mean diameter was calculated (arithmetic mean) for each type of capsule. The results are summarized in the following table.
    Table 14: Average Capsule A to U Diameters
    Example 14 Preparation of a Fabric Softener Containing the Polyurea Microcapsules of the Invention A concentrated, non-fragrant fabric softener base was prepared by mixing the related ingredients in Table 15 in the amounts indicated. Percentages are defined by weight relative to the total weight of the non-fragrant fabric softener base.
    Table 15: Formulation of concentrated, non-scented fabric softener base 1) Origin: Stepan 2) Origin: Avecia Softeners A to U were prepared by adding Capsules A to U at 1.26% by weight by weight softener, under gentle agitation, based on unscented fabric softener of Table 15.
    Example 15 (Comparative) Preparation of a Fabric Softener Containing the Polyurea Microcapsules of Examples 9 to 12 Control Softeners A to M were prepared by adding Controls A to M at 1.25% by weight relative to the total weight of the softener, under gentle agitation, in the fragrance-free softener base prepared in Example 14.
    Example 16 Stability of the Polyurea Microcapsules of the Invention on Tissue Softener Stability during storage of the capsules in Softeners A to U and Control Softeners A to G and L was evaluated. The softeners containing the capsules were stored for one month at 38 ° C and the amount of perfume that leaked from the capsules was measured by solvent extraction and GC-MS analysis. The results are summarized in the following table.
    Table 16: Stability during capsule storage in Softeners A to U and Control Softeners A to G and L From these results it can be seen that each of the capsules of the present invention was more stable in the softener base than in the corresponding control. where only aliphatic polyisocyanate was used, thus showing that the combination of an aromatic polyisocyanate with an aliphatic polyisocyanate in the claimed ratios improves the storage stability of polyurea microcapsules in a fabric softener base. In order to further illustrate these results, the stability of the capsules in Softeners A to G and Control Softener A is shown in Figure 2. It is clear from this graph that the stability of the capsules is clearly enhanced by blending an aromatic polyisocyanate such as Takenate® D-110N with aliphatic polyisocyanate in all claimed reasons.
    Example 17 Olfactory Performance of the Polyurea Microcapsules of the Invention in a Tissue Softener The olfactory performance of Capsules B, C, E, G, T, and U as well as Controls A, H, L, and M was then evaluated in the corresponding tissue softeners. Examples 14 and 15. Cotton terry towels (20 pieces, 18 cm x 18 cm, about 30 g each) were washed with 30 g of non-fragrant detergent in a washing machine (Miele Novotronic W300-33CH) at 40 °. C using the short cycle program. Washing was followed by rinsing at 900 rpm with 12.7 g of Softeners or Control Softeners. Terry towels were then dried on the clothesline for 24 hours before being evaluated. The intensity of perfume perception on dry towels treated with Softeners B, C, E and G and Control Softeners A and H was assessed by a panel of 20 trained panelists. They were asked to rub the towels on their hands and then rate the intensity of perfume perception on a scale from 1 to 7, where 1 means no odor and 7 means a very strong odor. The intensity of perfume perception in dry towels treated with T and U Softeners and Control L and M Softeners was evaluated according to the same method by a panel of 10 trained panelists using the same scale. The results are summarized in the following table.
    Table7: Olfactory Performance of Capsules B, C, E, G, Controls A, Η, M, and L Content in a Fabric Softener Evaluation of the Scent Perception Intensity on Dry Towels Treated with M to S Softeners and Control Softeners E to G and I to K were performed as described above, except that panelists were asked to rate the intensity of perfume perception on a scale from 0 to 10, where 0 means no odor and 10 means very strong odor. . The results are summarized in the following table.
    Table 18: Olfactory Performance of Capsules M to S and Controls E to G and I to K in a Fabric Softener These results show that the intensity of perfume odor was more strongly perceived in fabric treated with a softener containing the present capsules. invention than with both controls. Therefore, the perfume is perceived more intensely when the capsules are made with a combination of an aromatic and aliphatic polyisocyanate in the claimed ratios than when the capsules are made with an exclusively aromatic polyisocyanate or an exclusively aliphatic polyisocyanate.
    Example 18 Preparation of a concentrated liquid detergent containing the polyurea microcapsules of the invention Liquid Detergents E, G, T and U were prepared by mixing 0.275% by weight Capsules E, G, T and U with respect to the total weight. detergent, with commercially available non-fragrant concentrated liquid detergent based Tide® 2X HE without perfume and color (trademark of Procter and Gamble, USA).
    Example 19 (comparative) Preparation of a concentrated liquid detergent containing the polyurea microcapsules of Examples 9 to 12 Control A, H, L and M Liquid Detergents were prepared by mixing 0.275% Controls A, H, L and M by weight, in relation to the total weight of the detergent, with the commercially available non-perfumed Tide® 2X HE concentrated non-scented liquid detergent base (trademark of Procter and Gamble, USA).
    Example 20 Olfactory performance of the polyurea microcapsules of the invention in the concentrated liquid detergent The olfactory performance of Capsules E, G, Te U as well as Controls A, H, L and M was then evaluated on the corresponding concentrated liquid detergents of Examples 18 and 19.
    Fabrics (2.5 kg Terry cotton towels) were washed at 40 ° C in a common European horizontal axis machine. 80 g of freshly prepared detergent was dispensed at the beginning of the wash through the detergent drawer. After washing, the fabrics were dried on clothesline and the odor intensity of the cotton towels was evaluated by a panel of 20 trained panelists after 1 day of drying. Panelists were asked to rate the intensity of the odor of the towels after gently rubbing the fabrics by hand on a scale of 1 to 7, 1 corresponding to the absence of odor and 7 corresponding to a very strong odor. Results are shown in Table 19.
    Table 19: Olfactory Performance of Capsules E, G, T and U and Controls A, H, LeM in Concentrated Liquid Detergent It is clear from these results that after friction, perfume intensity was higher in detergent-washed fabrics. liquid containing the capsules of the invention than in fabrics washed with the liquid detergent containing the control capsules.
    Therefore, the perfume is perceived more intensely when the capsules are made with a combination of an aromatic and aliphatic polyisocyanate in the claimed ratios than when the capsules are made with an exclusively aromatic polyisocyanate or with an exclusively aliphatic polyisocyanate.
    Example 21 Stability of the polyurea microcapsules of the invention in a concentrated liquid detergent Stability during storage of the capsules in Liquid Detergents E, G, T and U and Control Liquid Detergents A and L was evaluated. Detergents containing the capsules were stored for four weeks at 38 ° C and the amount of perfume leaking from the capsules was measured by solvent extraction and GC-MS analysis. The results are summarized in the following table.
    Table 20: Storage stability of the capsules of the invention in Liquid Detergents E, G, Te U and Control Liquid Detergents A and L. From these results it can be seen that each of the capsules of the present invention was more stable on detergent basis. concentrated liquid than in the corresponding control, where only aliphatic polyisocyanate was used, thus showing that the combination of an aromatic polyisocyanate with an aliphatic polyisocyanate in the claimed ratios improves the stability during storage of polyurea microcapsules in a concentrated liquid detergent base. .
    Example 22 Preparation of a concentrated detergent powder containing the polyurea microcapsules of the invention. Powder Detergents E, G, T and U were prepared by mixing 0.275% by weight Capsules E, G, T and U Total detergent based on commercially available non-fragrant concentrated detergent powder Ultra Tide® Free and Gentle (registered trademark of Procter and Gamble, USA).
    Example 23 (Comparative) Preparation of a concentrated detergent powder containing the polyurea microcapsules of Examples 9 to 12. Powder Detergents A, H, L and M were prepared by adding Controls A, H, L and M to 0.275. % by weight relative to the total weight of detergent in the commercially available non-fragrant concentrated detergent powder Ultra Tide® Free and Gentle (trademark of Procter and Gamble, USA).
    Example 24 Olfactory Performance of Polyurea Microcapsules of the Invention in Concentrated Detergent The olfactory performance of Capsules E, G, T, and U as well as Controls A, H, L, and M was then evaluated on the corresponding concentrated detergent powders of Examples 22. it's 23
    Fabrics (2.5 kg Terry cotton towels) were washed at 40 ° C in a common European horizontal axis machine. 50 g of freshly prepared detergent was dispensed at the beginning of the wash through the detergent drawer. After washing, the fabrics were dried on clothesline and the odor intensity of the cotton towels was evaluated by a panel of 20 trained panelists after 1 day of drying. Panelists were asked to rate the intensity of the odor of the towels after gently rubbing the fabrics by hand on a scale of 1 to 7, 1 corresponding to the absence of odor and 7 corresponding to a very strong odor. Results are shown in Table 21.
    Table 21: Olfactory Performance of Capsules E, G. T and U and Controls A, H, L and M in Concentrated Detergent It is clear from these results that after friction, perfume intensity was higher in the washed fabrics. with the concentrated detergent powder containing the capsules of the invention than in fabrics washed with the concentrated detergent powder containing the control capsules.
    Therefore, the perfume is perceived more intensely when the capsules are made with a combination of an aromatic and aliphatic polyisocyanate in the claimed ratios than when the capsules are made with an exclusively aromatic polyisocyanate or an aliphatic polyisocyanate alone.
    Example 25 Preparation of a Liquid Soap Containing the Polyurea Microcapsules of the Invention A liquid soap formulation was prepared by mixing the ingredients listed in Table 22 in the amounts indicated. Percentages are defined by weight relative to the total weight of the liquid soap formulation.
    Table 22: Composition of Liquid Soap Formulation 1) Polyacrylate-1 Crospolymer, Origin: Noveon 2) Pareth C12 -C15 Sodium Sulphate) Origin: Zschimmer & Schwarz 3) Cocoamidopropyl Betaine, Origin: Goldschmidt AG 4) DMDM Hydantoin and Iodopropinyl butylcarbamate, origin: Lonza Liquid Soaps E, G, Te U were prepared by mixing 0.5% by weight Capsules E, G, T and U with respect to the total weight of liquid soap in the liquid soap formulation prepared above.
    Example 26 / Comparative) Preparation of a Liquid Soap Containing the Polyurea Microcapsules of Examples 9 to 12 Control A, H, L and M Liquid Soaps were prepared by adding 0.5% by weight Controls A, H, L and M to the total weight of the liquid soap in the liquid soap formulation prepared in Example 25.
    Example 27 Olfactory Performance of Polyurea Microcapsules of the Invention in Liquid Soap The olfactory performance of Capsules E, G, T and U as well as Controls A, H, L and M was then evaluated on the corresponding liquid soaps of Examples 25 and 26.
    Liquid Soaps were applied to wool samples intended to mimic human skin. The wool samples were moistened for 30 s under running water at 38 ° C. The Liquid Soaps were then respectively applied in an amount of 0.5 g with a micropipette and then foamed for 10 s by rubbing a finger over the entire surface. The samples were then rinsed for 20 s under running water at 38 ° C and finally allowed to dry on a heating table at 32 ° C. The intensity of the perfume was then blindly assessed by an expert panel consisting of 4 trained panelists who were asked to rate the perceived intensity of the perfume on the wool samples after hand rubbing, on a scale from 1 to 7, where 1 means no odor and 7 means very strong odor. The results are summarized in Table 23. Table 23: Olfactory Performance of Capsules E, G, T and U and Controls A. H, Le M in Liquid Soap It is clear from these results that after friction, perfume intensity It was higher in wool samples washed with the liquid soap containing the capsules of the invention than in wool samples washed with the liquid soap containing the control capsules.
    Therefore, the perfume is perceived more intensely when the capsules are made with a combination of an aromatic and aliphatic polyisocyanate in the claimed ratios than when the capsules are made with an exclusively aromatic polyisocyanate or with an exclusively aliphatic polyisocyanate.
    Example 28 Stability of the polyurea microcapsules of the invention in a liquid soap Storage stability of the capsules in Liquid Soaps E, G, T and U and Control Liquid Soaps A and L was evaluated. The liquid soap products containing the capsules were stored for four weeks at 40 ° C and the amount of perfume leaking from the capsules was measured by SPME and GC-MS analysis. The results are summarized in the following table.
    Table 24: Stability during storage of the capsules of the invention in the EG T and U Liquid Soaps and Control A and L Liquid Soaps From these results it can be seen that each of the capsules of the present invention was more stable in the liquid soap base than that in the corresponding control, in which only aliphatic polyisocyanate was used, thus showing that the combination of an aromatic polyisocyanate with an aliphatic polyisocyanate in the claimed ratios improves the storage stability of polyurea microcapsules in a liquid soap base.
    Example 29 Preparation of a roli-on antiperspirant deodorant product containing the polyurea microcapsules of the invention A roll-on antiperspirant deodorant emulsion formulation was prepared by mixing the related ingredients in Table 25 in the amounts indicated. Percentages are defined by weight relative to the total weight of the roll-on antiperspirant deodorant formulation.
    Table 25: Composition of the roll-on antiperspirant deodorant formulation 1) Origin: Croda 2) Origin: Croda 3) Origin: Croda 4) Origin: Clariant Deodorants E, G, T and U were prepared by mixing Capsules E, G, T and U at 1.26% by weight relative to the total weight of the roll-on antiperspirant deodorant in the roll-on antiperspirant deodorant emulsion formulation prepared above.
    Example 30 (comparative) Preparation of a roll-on antiperspirant deodorant containing the polyurea microcapsules of Examples 9 to 12 Control A, H, L and M Deodorants were prepared by adding Controls A, H, L and M to 1, 26% by weight relative to the total weight of the roll-on antiperspirant deodorant in the roll-on antiperspirant deodorant emulsion formulation prepared in Example 29.
    Example 31 Olfactory Performance of the Roll-On Antiperspirant Deodorant Polyurea Microcapsules of the Invention The olfactory performance of Capsules E and G as well as Controls A and H was evaluated in the corresponding deodorants of Examples 29 and 30.
    0.15 g of the deodorant was spread on absorbent paper (4.5 cm x 12 cm) and allowed to dry for 1 hour at room temperature before evaluation. The intensity of perfume perception on absorbent papers treated with deodorants was assessed by a panel of 10 trained panelists. They were asked to gently rub the absorbent papers with one finger and then rate the intensity of perfume perception on a scale from 0 to 10, where 0 means no odor and 10 means very strong odor. The results are summarized in the following table.
    Table 26: Olfactory Performance of Capsules E and G and Controls A and H in Roll-on Antiperspirant Deodorant It is clear from these results that, after friction, perfume intensity was slightly higher in absorbent papers treated with roll antiperspirant deodorant. containing the capsules of the invention than on absorbent papers treated with the antiperspirant roll-on deodorant containing the control capsules. Therefore, the perfume is perceived more intensely when the capsules are made with a combination of an aromatic and aliphatic polyisocyanate in the claimed ratios than when the capsules are made with an exclusively aromatic polyisocyanate or with an exclusively aliphatic polyisocyanate.
    Example 32 Stability of the polyurea microcapsules of the invention in a roll-on antiperspirant deodorant The storage stability of the capsules in Deodorants E, G, T and U and Control Deodorants A and L was evaluated. The deodorants were stored for 4 weeks at 45 ° C and the amount of perfume leaking from the capsules was measured by SPME and GC-MS analysis. The results are summarized in the following table.
    Table 27: Storage Stability of Capsules of the Invention in Deodorants E, G, T and U and Deodorants Controls A and L. From these results it can be seen that each of the capsules of the present invention was more stable on a deodorant basis. roll-on antiperspirant than in the corresponding control, where only aliphatic polyisocyanate was used, thus showing that the combination of an aromatic polyisocyanate with an aliphatic polyisocyanate in the claimed ratios improves the storage stability of polyurea microcapsules on a roll-on antiperspirant deodorant.
    Example 33 Preparation of a Hair Shampoo Containing the Polyurea Microcapsules of the Invention A hair shampoo formulation was prepared by mixing the ingredients listed in Table 28 in the amounts indicated. Percentages are defined by weight relative to the total weight of the hair shampoo formulation.
    Table 28: Hair shampoo formulation composition 1) Origin: Rhodia 2) Origin: Cognis 3) Origin: Cognis 4) Origin: Cognis 5) Origin: Degussa 6) Origin: Lonza Shampoos E, G, T and U were prepared by mixing Capsules E, G, T and U at 0.5% by weight with respect to the total weight of the shampoo in the hair shampoo formulation prepared above.
    Example 34 (Comparative) Preparation of a Hair Shampoo Containing the Polyurea Microcapsules of Examples 9 to 12 Control A, H, L and M Shampoos were prepared by adding Controls A, H, L and M 0.5% by weight relative to the total weight of the shampoo in the hair shampoo formulation prepared in Example 33.
    Example 35 Olfactory Performance of Polyurea Microcapsules of the Invention in Hair Shampoo The olfactory performance of Capsules E, G, T and U as well as Controls A, H, L and M was then evaluated in the corresponding hair shampoo of Examples 33 and 34. .
    A 10 g hair sample was first washed with 2.5 g of shampoo, rinsed for 30 seconds under 37 ° C tap water before repeating the same wash / rinse operation a second time. The hair sample was then dried for 6 hours at room temperature prior to evaluation. The intensity of perfume perception in shampooed hair samples was assessed by a panel of 10 trained panelists. They were asked to gently brush the hair samples 3 times and then rate the intensity of perfume perception on a scale from 1 to 7, where 1 means no odor and 7 very strong odor. The olfactory performance of T and U Capsules as well as L and M Controls was also evaluated using the same method after a 24 hour drying time. The results are summarized in the following table.
    Table 29: Olfactory Performance of EG T and U Capsules and Controls A, H, L and M in Hair Shampoo It is clear from these results that perfume intensity was slightly higher after combing hair samples washed with shampoo for hair containing the capsules of the invention than hair samples washed with the shampoo containing the control capsules. Therefore, the perfume is perceived more intensely when the capsules are made with a combination of an aromatic and aliphatic polyisocyanate in the claimed ratios than when the capsules are made with an exclusively aromatic polyisocyanate or an aliphatic polyisocyanate alone.
    Example 36 Stability of the Polyurea Microcapsules of the Invention in a Hair Shampoo Stability during storage of the capsules in Shampoos E, G, T and U and Control Shampoos A and L was evaluated. Hair shampoos were stored for 2 weeks at 40 ° C and the amount of perfume leaking from the capsules was measured by SPME and GC-MS analysis. The results are summarized in the following table.
    Table 30: Stability during storage of the capsules of the invention in E. G, T and U Shampoos and Control A and L Shampoos. From these results it can be seen that each of the capsules of the present invention was more stable on the basis of shampoo for than in the corresponding control where only aliphatic polyisocyanate was used, thus showing that the combination of an aromatic polyisocyanate with an aliphatic polyisocyanate in the claimed ratios improves the storage stability of polyurea microcapsules in a hair shampoo base. .
    Example 37 Preparation of the Rinse Capillary Conditioner Containing the Polyurea Microcapsules of the Invention Rinse capillary conditioners (hereinafter called the rinse conditioner) E, G, T and U were prepared by mixing the Capsules E, G, T and U to 0.5 % by weight relative to the total weight of the rinse conditioner in the Pantene® commercially available rinse conditioner formulation (trademark of Procter and Gamble, USA).
    Example 38 (Comparative) Preparation of the Rinse Capillary Conditioner Containing the Polyurea Microcapsules of Examples 9 to 12 The Rinse Control (hereinafter called Rinse Conditioner) capillary conditioners A, H, L and M were prepared by mixing Capsules A, H, L and M 0.5% by weight relative to the total weight of the rinse conditioner in the commercially available Pantene® rinse conditioner formulation (Trademark of Procter and Gamble, USA).
    Example 39 Olfactory performance of the polyurea microcapsules of the invention in the rinse conditioner The olfactory performance of Capsules E, G, T and U as well as Controls A, H, L and M was then evaluated in the corresponding rinse conditioner of Examples 37 and 38.
    Hair samples (10 g) were first washed with 2.5 g of the shampoo formulation prepared in Example 33 (without perfume and without capsules) and rinsed for 30 seconds under tap water at 37 ° C before spreading 1 g rinse conditioner. The hair samples were then rinsed for 30 seconds under 37 ° C tap water and allowed to dry at room temperature prior to evaluation. Rinse conditioners E and G and rinse conditioners control A and H remained dry for 24 hours, while rinse conditioners T and U and rinse conditioners control L and M remained dry for 6 hours before evaluation. The intensity of perfume perception on hair samples treated with the above rinse hair conditioners was assessed by a panel of 10 trained panelists. They were asked to gently comb the hair samples 3 times and then rate the intensity of perfume perception on a scale from 1 to 7, where 1 means no odor and 7 means a very strong odor. The results are summarized in the following table.
    Table 31: Olfactory Performance of E.G.TeUe Capsules of A.H.L. and M. Controls in Rinse Capillary Conditioner I
    It is clear from these results that perfume intensity was greater after combing hair samples treated with the rinse hair conditioner containing the capsules of the invention than in hair samples treated with the rinse hair conditioner containing the control capsules. Therefore, perfume is perceived more intensely when the capsules are made with a combination of an aromatic and aliphatic polyisocyanate in the claimed ratios than when the capsules are made with an exclusively aromatic polyisocyanate or an aliphatic polyisocyanate alone.
    Example 40 Stability of the polyurea microcapsules of the invention in a rinse capillary conditioner The storage stability of the capsules in the Rinse Capillary Conditioner E, G, T and U and the Rinse Capillary Conditioner Control A and L was evaluated. Rinsable hair conditioners were stored for 2 weeks at 40 ° C and the amount of perfume that was leaked from the capsules was measured by SPME and GC-MS analysis. The results are summarized in the following table.
    Table 32: Storage stability of the capsules of the invention in EG T and U Rinse Capillary Conditioner and Control A and L Rinse Capillary Conditioner It can be seen from these results that each of the capsules of the present invention was more stable on the capillary conditioner base. than the corresponding control, in which only aliphatic polyisocyanate was used, thus showing that the combination of an aromatic polyisocyanate with an aliphatic polyisocyanate in the claimed ratios improves the storage stability of the polyurea microcapsules in a rinse capillary conditioner base.
    Example 41 Preparation of a Non-Rinse Hair Conditioner Containing the Polyurea Microcapsules of the Invention A non-rinse hair conditioner formulation was prepared by mixing the ingredients listed in Table 33 in the amounts indicated. Percentages are defined by weight relative to the total weight of the non-rinse hair conditioner formulation.
    Table 33: Non-Rinse Hair Conditioner Formulation Composition 1) Origin: Rhodia 2) Origin: Ciba 3) Origin: Rohm & Haas 4) Origin: Wacker 5) Origin: Clariant Non-Rinse Hair Conditioners E, G, T and U were prepared by mixing the 0.26% by weight Capsules E, G, Te U relative to the total weight of the non-rinse capillary conditioner in the non-rinse capillary conditioner formulation prepared above.
    Example 42 (Comparative) Preparation of the Non-Rinse Capillary Conditioner Including the Polyurea Microcapsules of Examples 9 to 12 Non-Rinse Control Capillary Conditioners (hereinafter called Control Capillary Conditioners) A, H, L and M were prepared by adding Controls A, 0.26% by weight H, L and M relative to the total weight of the conditioner in the non-rinse hair conditioner formulation prepared in Example 42.
    Example 43 Olfactory Performance of Polyurea Microcapsules of the Invention in Non-Rinsed Capillary Conditioner The olfactory performance of Capsules E, G, T, and U, as well as Controls A, H, L, and M, was then evaluated in the corresponding capillary conditioner of Examples 41. e42.
    Hair samples (10 g) were first washed with 2.5 g of the shampoo formulation prepared in Example 33 (unscented and without capsules) and rinsed for 30 seconds under tap water at 37 ° C before 0.5 g of the conditioner was spread. non-rinsing capillary. Hair samples treated with conditioner E and G and control conditioner A and H were then allowed to dry for 24 h at room temperature prior to evaluation. Hair samples treated with the T and U conditioner and the L and M control conditioner were allowed to dry for 6 hours at room temperature prior to evaluation. The intensity of perfume perception in hair samples treated with non-rinse hair conditioners was assessed by a panel of 10 trained panelists. They were asked to gently brush the hair samples 3 times and then rate the intensity of perfume perception on a scale from 1 to 7, where 1 means no odor and 7 means a very strong odor. The results are summarized in the following table.
    Table 34: Olfactory performance of E. G, T and U Capsules and Controls A, H, L and M in non-rinse hair conditioner It is clear from the results that perfume intensity was higher after combing treated hair samples with the non-rinse capillary conditioner formulation containing the capsules of the invention than in hair samples treated with the non-rinse capillary conditioner formulation containing the control capsules. Therefore, perfume is perceived more intensely when the capsules are made with a combination of aromatic and aliphatic polyisocyanate in the claimed ratios than when capsules are made with exclusively aromatic polyisocyanate or exclusively aliphatic polyisocyanate.
    Example 44 Stability of the polyurea microcapsules of the invention in a non-rinse capillary conditioner Stability during storage of the capsules in capillary conditioner E, G, T and U and control capillary conditioner A and L was evaluated. Non-rinse hair conditioners were stored for 2 weeks at 45 ° C and the amount of perfume that was leaked from the capsules was measured by SPME and GC-MS analysis. The results are summarized in the following table.
    Table 35: Storage stability of the capsules of the invention in EG T and Ü Capillary Conditioners and Capillary Conditioner A and L From these results it can be seen that each of the capsules of the present invention was more stable in the non-rinse capillary conditioner base of that in the corresponding control, in which only aliphatic polyisocyanate was used, thus showing that the combination of an aromatic polyisocyanate and an aliphatic polyisocyanate in the claimed ratios improves stability during storage of polyurea microcapsules in a non-rinse capillary conditioning base.
    Example 45 Preparation of a Body Lotion Comprising the Polyurea Microcapsules of the Invention Body Lotions E, G, T and U were prepared by dispersing Capsules E, G, T and U at 1.25% by weight relative to the total weight of the body lotion into a commercially available body lotion formulation (Bath & Body Work, USA).
    Example 46 (Comparative) Preparation of a body lotion comprising the polyurea microcapsules of Examples 9 to 12 Control A, H, L and M Body Lotions were prepared by dispersing the 1.25% by weight Capsules A, H, L and M , in relation to the total body lotion weight in a commercially available body lotion formulation (source: Bath & Body Work, USA).
    Example 47 Olfactory Performance of the Polyurea Microcapsules of the Invention on Body Lotion The olfactory performance of Capsules E, G, T and U as well as Controls A, H, L and M was evaluated in the corresponding body lotions of Examples 45 and 46. An amount 0.15 g of each body lotion was spread on absorbent paper 1 (4.5cm * 12cm) and allowed to dry for 1 hour at room temperature prior to evaluation. The intensity of perfume perception on absorbent papers treated with the above body lotions was assessed by a panel of 10 trained panelists. They were asked to lightly rub the absorbent papers with one finger and then rate the intensity of perfume perception on a scale from 0 to 10, where 0 means no odor and 10 means a very strong odor. The results are summarized in the following table.
    Table 36: Olfactory Performance of Capsules E. G, T and U and Controls A, H, L and M on Body Lotion It is clear from the results that perfume intensity was higher after rubbing the absorbent papers treated with body lotion. containing the capsules of the invention than after rubbing the absorbent papers treated with the body lotion containing the control capsules. Therefore, the perfume is perceived more intensely when the capsules are made with a combination of an aliphatic and aromatic polyisocyanate for the claimed reasons than when the capsules are made with an exclusively aromatic polyisocyanate or with an exclusively aliphatic polyisocyanate.
    Example 48 Stability of the polyurea microcapsules of the invention in a body lotion Storage stability of the capsules in Body Lotions E, G, T and U and Body Lotions Control A and L was evaluated. Body lotions were stored for 2 days at 25 ° C and the amount of perfume that leaked from the capsules was measured by SPME and GC-MS analysis. The results are summarized in the following table.
    Table 37: Stability during storage of capsules of the invention in Body Lotions E, G, T and U and Control Body Lotions A and L From these results it can be seen that each of the capsules of the present invention was more stable on the basis of body lotion than in the corresponding control, in which only aliphatic polyisocyanate was used, thus showing that the combination of an aromatic polyisocyanate with an aliphatic polyisocyanate in the claimed ratios improves stability during storage of polyurea microcapsules in a body lotion base.
    权利要求:
    Claims (13)
    [1]
    A process for preparing polyurea microcapsules comprising a) dissolving a mixture of at least one aliphatic polyisocyanate and at least one aromatic polyisocyanate, both containing at least two isocyanate functional groups in a perfume to form a solution; b) adding to the solution obtained in step a) an aqueous solution of emulsifier or colloidal stabilizer; c) adding to the mixture obtained in step (b) of a polyamine to form a polyurea wall with the polyisocyanate to form a microcapsule suspension; characterized in that aliphatic polyisocyanate and aromatic polyisocyanate are used in a respective molar ratio ranging from 80:20 to 10:90.
    [2]
    Process according to Claim 1, characterized in that the microcapsule suspension is dehydrated in a generally known manner to form a polyurea microcapsule powder.
    [3]
    Process according to Claim 1 or 2, characterized in that a volume of between 25 and 60% of the perfume is used, such percentages being defined by weight in relation to the total weight of the obtained microcapsule suspension.
    [4]
    Process according to any one of Claims 1 to 3, characterized in that the aromatic polyisocyanate contains a phenyl, toluyl, xylyl, naphthyl or diphenyl component.
    [5]
    Process according to any one of Claims 1 to 4, characterized in that the aromatic polyisocyanate is selected from the group consisting of a toluene diisocyanate polyisocyanurate, a toluene diisocyanate trimethylol propane adduct and a trimethylol adduct. xylene diisocyanate propane.
    [6]
    Process according to any one of claims 1 to 5, characterized in that the aliphatic polyisocyanate is selected from the group consisting of a hexamethylene diisocyanate trimer, an isophorone diisocyanate trimer and a hexamethylene diisocyanate biuride.
    [7]
    Process according to any one of Claims 1 to 6, characterized in that the mixture of an aliphatic polyisocyanate and an aromatic polyisocyanate is a mixture of a hexamethylene diisocyanate biuride and a xylene diisocyanate trimethyl propane adduct.
    [8]
    Process according to any one of claims 1 to 7, characterized in that the aliphatic polyisocyanate and aromatic polyisocyanate are used in a respective molar ratio between 60:40 and 20:80.
    [9]
    Process according to any one of Claims 1 to 8, characterized in that the polyisocyanate mixture is used in an amount of 2 to 20% by weight, based on the total weight of the solution obtained in step a).
    [10]
    Process according to any one of claims 1 to 9, characterized in that the colloidal stabilizer is a polyvinyl alcohol, a cellulose derivative, polyethylene oxide, a polyethylene oxide copolymer and a polyethylene oxide or a polypropylene copolymer, a copolymer acrylamide and acrylic acid, a cationic polymer or a mixture thereof.
    [11]
    Process according to any one of claims 1 to 10, characterized in that the polyamine is selected from the group consisting of water-soluble guanidine salts, guanidine, tris- (2-aminoethyl) amine, Ν, Ν, Ν ' , N'-tetrakis (3-aminopropyl) -1,4-butanediamine and N, N'-bis (3-aminopropyl) ethylenediamine.
    [12]
    A polyurea microcapsule according to claim 11, comprising a polyurea wall which includes the polymerization reaction product between at least one polyisocyanate and at least one polyamine; and a colloidal stabilizer or emulsifier; and an encapsulated perfume; characterized in that the polyisocyanate is in the form of a mixture of at least one aliphatic polyisocyanate and at least one aromatic polyisocyanate in a respective molar ratio between 80:20 and 10:90, both aromatic and aliphatic polyisocyanate containing at least two isocyanate functional groups.
    [13]
    Consumer product, characterized in that it contains the microcapsules as defined in claim 11 or 12.
    类似技术:
    公开号 | 公开日 | 专利标题
    BR112012029551B1|2019-01-29|process for preparing polyurea microcapsules
    CN108367264B|2021-07-27|Process for preparing polyurea microcapsules with improved deposition
    JP6861629B2|2021-04-21|Method for manufacturing polyurea microcapsules with improved adhesion
    JP5868431B2|2016-02-24|Polyurea microcapsule
    US9498411B2|2016-11-22|Microcapsules and uses thereof
    JP6012724B2|2016-10-25|Method for producing polyurea microcapsules
    JP6214553B2|2017-10-18|Method for producing polyurea microcapsules
    EP3559193A1|2019-10-30|Density balanced high impact perfume microcapsules
    JP2018506420A|2018-03-08|Method for producing microcapsules without melamine formaldehyde
    EP3774016A1|2021-02-17|Process for preparing microcapsules with improved deposition
    同族专利:
    公开号 | 公开日
    US9271905B2|2016-03-01|
    MX2012013587A|2012-12-17|
    US20130230574A1|2013-09-05|
    JP2013530825A|2013-08-01|
    JP6012598B2|2016-10-25|
    MX339276B|2016-05-19|
    EP2579976B1|2017-08-09|
    BR112012029551A2|2016-12-13|
    WO2011154893A1|2011-12-15|
    ZA201208422B|2013-07-31|
    EP2579976A1|2013-04-17|
    CN102939151B|2015-05-20|
    CN102939151A|2013-02-20|
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    法律状态:
    2018-08-21| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application according art. 36 industrial patent law|
    2018-12-11| B09A| Decision: intention to grant|
    2019-01-29| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 07/06/2011, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US35378710P| true| 2010-06-11|2010-06-11|
    EP10165700|2010-06-11|
    EP10165700.5|2010-06-11|
    US61/353,787|2010-06-11|
    EP11166533|2011-05-18|
    EP11166533.7|2011-05-18|
    EP11166717|2011-05-19|
    EP11166717.6|2011-05-19|
    PCT/IB2011/052471|WO2011154893A1|2010-06-11|2011-06-07|Process for preparing polyurea microcapsules|
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