• 专利附录
  • 专利说明
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    • 专利摘要:
    summary stable formaldehyde free microcapsules. The present invention relates to essentially formaldehyde free water-dispersible core-coating microcapsules. in particular, they refer to core-coating microcapsules with a coating obtained by reaction of cross-linking polyisocyanates or polyoxyranes and oligomeric compositions, which are the reaction products between a polyamine component and a particular mixture of glyoxal and a 2, C4-6 2-dialkoxyetanal The present invention also comprises core-coating microcapsules of the invention as part of a fragrant composition or a fragrant consumer product.
    公开号:BR112014011165B1
    申请号:R112014011165-0
    申请日:2012-10-29
    公开日:2019-09-17
    发明作者:Damien Berthier；Géraldine Leon；Nicolas Paret；Lahoussine Ouali
    申请人:Firmenich Sa；
    IPC主号:
    专利说明:

    001 The present invention relates to the field of perfumery. More particularly, it concerns water-dispersible core-coating microcapsules, essentially free of formaldehyde.
    The present invention also comprises the core-coating microcapsules of the invention as part of a perfumed composition or a perfumed consumer product.
    TECHNICAL STATUS
    003 Microcapsules are a widely known type of product, generally used as a liquid phase vehicle.
    004 A specific type of said microcapsules is called aminoplastic microcapsules, which comprise an external wall obtained by reacting a polyamine (in general, melamine, that is, 2,4,6-triamino-1,3,5-triazine) and an aldehyde (almost always, in fact, formaldehyde). These microcapsules are very useful in the case where the liquid core is a volatile compound or composition, such as perfumes, since they are able to break under certain conditions, releasing the volatile material in a controlled manner.
    However, said capsules, which are essentially based on formaldehyde, always contain residual amounts of free formaldehyde due to unreacted precursors or a slow decomposition of thermoset oligomers. Formaldehyde-free capsules are nowadays desirable due to regulatory concerns, therefore there is a need on the part of the industry for formaldehyde-free core-coating microcapsules that perform similarly to those based on formaldehyde, which perform better in terms of product stability and release.
    006 Some attempts to obtain formaldehyde-free microcapsules have been published in the state of the art. Mention may be made of those described in WO 2009/100553, which describes aminoplastic capsules obtained by reacting at least one polyamine and imprecisely defined as “substituted methylene moieties”, which are exemplified by glyoxal esters hemiacetal or by 2.2 -dimethoxy-ethanal (DME) or 2,2-diphenoxyethane. In fact, all the capsules specifically described are obtained by reaction of melamine (as the original polyamine) and DME or methyl 2-hydroxy-2-methoxy-acetate, as "substituted methylene portions". However, we have found that the performance and stability of such capsules are not satisfactory for an industrial application, as shown later in the Examples.
    Therefore, there is still a need for formaldehyde-free core-coating microcapsules that have superior stability performance.
    DESCRIPTION OF THE INVENTION
    Surprisingly, a new type of formaldehyde-free microcapsules, of similar constitution, has now been discovered that has superior stability compared to the prior art formaldehyde-free core-coating microcapsules.
    Therefore, a first object of the present invention is a process for obtaining the above microcapsules. In other words, a process for the preparation of a core-coating microcapsule, said process comprising the steps of:
    1) preparation of an oligomeric composition, comprising the reaction product of, or which can be obtained by the joint reaction of:
    a) a polyamine component in the form of melamine or a mixture of melamine and at least one C1-4 compound comprising two NH2 functional groups;
    b) an aldehyde component in the form of a mixture of glyoxal, a 2,2-diaoxyciethyl C4-6 and, optionally, a glyoxalate, said mixture having a molar ratio glyoxal / 2,2-dialcoxietanal C4-6 comprised between about 1 / 1 and 10/1; and
    c) a protic acid catalyst;
    2) preparation of an oil-in-water dispersion, in which the droplet size is between 1 and 600 pm, and comprising:
    i) an oil;
    ii) an aqueous medium;
    iii) at least one oligomeric composition, as obtained in step 1);
    iv) at least one crosslinking agent chosen from:
    A) aromatic or aliphatic C4-C12 di or triisocyanates and their biurides, triurides, trimers and trimethylolpropane adduct; and / or
    B) a compound of di or trioxirane, of the formula
    A- (oxiran-2-ylmethyl) n where n represents 2 or 3 and A represents a C2-C6 group, optionally comprising from 2 to 6 nitrogen and / or oxygen atoms;
    / 35
    v) optionally, a C1-4 compound, which comprises two NH2 functional groups;
    3) heating said dispersion;
    4) cooling said dispersion; and
    5) optionally, adding at least one cationic polymer and / or urea or ethylene urea to the dispersion of step 4); and
    6) optionally, drying the final dispersion, to obtain the dry core-coating microcapsule.
    For the sake of clarity, by the term “core-coating microcapsule”, or the like, in the present invention, it is intended that the capsule has a micrometric proportion size (for example, an average diameter between about 1 and 600 pm) and comprises an oligomer-based coating or solid external wall and an internal continuous oil phase surrounded by the external coating. In other words, bodies such as coacervates or extrudates (that is, 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, consequently, the size of the drops in step 1), is between about 5 and 200 pm.
    For the sake of clarity, by the term "dispersion" in the present invention, a system is intended in which the particles are dispersed in a continuous phase of a different composition and, specifically, includes a suspension or an emulsion.
    According to any of the previous embodiments of the present invention, the dispersion comprises between about 10% and 50% of oil, the percentage being expressed in w / w, in relation to the total weight of the dispersion. In yet another aspect of the invention, the dispersion comprises between about 20% and 45% of oil.
    By "oil" is meant here an organic phase, which is a liquid, at about 20 ° C, and which will be in the core of the core-coating capsules. According to any of the previous embodiments of the present invention, said oil can be selected from a perfume, insecticide, substance for neutralizing bad odor, fungicide, insect repellent and mixtures thereof.
    According to any of the previous embodiments of the present invention, said oil is a perfume. Said perfume can be in the form of a pure perfuming ingredient or a perfuming composition.
    By "perfuming composition" is meant here the normal sense of the technique, that is, a composition comprising several perfuming ingredients and, optionally, at least one suitable solvent and / or at least one perfumery adjuvant.
    0033 The term “perfuming ingredient” or “perfuming co-ingredient” means a compound that is used in a perfuming preparation or composition to impart a hedonic effect. In other words, such a co-ingredient, which must be considered to be perfuming, must be recognized by a person skilled in the art as being able to confer or modify in a positive or pleasant way the odor of a composition, and not just as having an odor.
    0034 The nature and type of the perfuming co-ingredients present in the base do not justify a more detailed description here, which, in any case, would not be exhaustive, the expert being able to select them based on their general knowledge, and according to the intended use or application and the desired organoleptic effect. In general terms, these perfuming co-ingredients belong to chemical classes as varied as alcohols, lactones, aldehydes, ketones, esters, ethers, acetates, nitriles, terpenoids, nitrogenous or sulfurized heterocyclic compounds and essential oils, and the said perfuming co-ingredients can 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 their more recent versions, or in other works of a similar nature , as well as in the abundant patent literature, in the field of perfumery. It is also intended that said co-ingredients can also be compounds known to release, in a controlled manner, various types of perfuming compounds.
    0035 By “suitable solvent”, we are looking for a material that is practically neutral from the point of view of perfumery, that is, that does not significantly alter the organoleptic properties of the perfuming ingredients, and is generally not miscible in water, that is, it has a solubility in water less than 10%, or even less than 5%. Said solvent is, in general, a solvent commonly used in perfumery, such as, for example, dipropylene glycol, diethyl phthalate, isopropyl myristate, benzyl benzoate, 2- (2-ethoxyethoxy) -1-ethanol or ethyl citrate , limonene or other terpenes, isoparaffins, such as those known under the trademark Isopar® (manufacturer: Exxon Chemical) or glycol ethers and glycol ether esters, such as those known under the trademark Dowanol® (manufacturer: Dow Chemical Company).
    0036 By "perfumery adjuvant" we mean here an ingredient capable of giving an additional advantage, such as a color, a resistance to light in particular, chemical stability, etc. A detailed description of the nature and type of adjuvant commonly used in perfumed bases cannot be exhaustive, but it has to be mentioned that said ingredients are well known to a person skilled in the art.
    According to any of the previous embodiments of the present invention, the aqueous medium comprises, or is essentially, water, as a diluent of the dispersion, and, optionally, can comprise at least one polyol and / or at least one stabilizing agent.
    According to any of the previous embodiments of the present invention, the dispersion comprises between about 0% and 5% of at least one stabilizing agent, the percentage being expressed in w / w, relative to the total weight of the dispersion. In yet another aspect of the invention, the dispersion comprises between about 0% and 2% of at least one stabilizing agent. In yet another aspect of the invention, the dispersion comprises between about 0% and 1% of at least one stabilizing agent. In the case where the aldehyde component also comprises a glyoxalate, and, in particular, when the diamino compound is 1H-1,2,4-triazole-3,5-diamine, the amount of said stabilizer in the dispersion can be 0% (without adding stabilizing agent).
    0039 For the sake of clarity, in the present context, the expression “stabilizing agent”, or similar, means the normal meaning understood by one skilled in the art, that is, a compound that is capable of stabilizing, or is added to the system , for example, to prevent aggregation or agglomeration of microcapsules, for example, during application or during preparation. The use of said stabilizing agent is standard knowledge of the person skilled in the art.
    For the purpose of the present invention, said stabilizing agent can be an ionic or non-ionic surfactant, or a colloidal stabilizing agent. The exact nature of such stabilizing agents is well known to a person skilled in the art. Non-limiting examples include stabilizing agents: nonionic polymers such as polyvinyl alcohol, cellulose derivatives, such as hydroxyethyl cellulose, polyethylene oxide, polyethylene oxide copolymers and polyethylene or polypropylene oxide, copolymers of acrylates of alkyl and N-vinylpyrrolidone;
    0041 ionic polymers, such as acrylamide and acrylic acid copolymers (such as Alcapsol® 144, from Ciba), for example, acid / acrylamide copolymers produced from the mixture of acrylic acid and acrylamide monomers, in which the content acrylic acid is in the range of 30 to 70%, acid anionic surfactant (such as sodium dodecyl sulfate), acrylic copolymers containing a sulfonate group (such as sodium / 35 poly (styrene) sulfonate and vinyl ether and anhydride copolymers maleic.
    According to any of the previous embodiments of the present invention, said stabilizing agent is an ionic surfactant.
    According to any of the previous embodiments of the present invention, the dispersion also comprises between about 0% and 10% of at least one polyol, the percentage being expressed in w / w, in relation to the total weight of the dispersion, or still comprised between about 0% and 2% of at least one polyol. In yet another aspect of the invention, when the diamino compound is urea, said amount can be comprised between about 0.1% and 2% of at least one polyol. In yet another aspect of the invention, when the diamino compound is 1H-1,2,4-triazole-3,5-diamine, said amount can be comprised between about 0% and 1.5%, or 0.5% of at least one polyol.
    0044 For the sake of clarity, the term "polyol" or the like is intended to mean the normal meaning understood by one skilled in the art, that is, a compound comprising one or more alcohol functional groups, and is generally used to aid in crosslinking / curing / deposition of the microcapsule coating. The use of said polyol is standard knowledge of the person skilled in the art.
    0045 Said polyol can be selected from aromatic, aliphatic and polymeric polyols. As non-limiting examples, aromatic polyols such as 3,5-dihydroxy toluene, resorcinol, xylenol, bisphenol, polyhydroxy naphthalene, polyphenol obtained by cellulose degradation can be mentioned; aliphatic polyols, such as humic acids, 2,2, dimethyl-1,3-propanediol, 1,1,1-tris- (hydroxymethyl) -propane, pentaerythritol, sorbitol or sugar derivatives and the like; polymeric polyols, such as celluloses or carboxymethylcellulose derivatives, such as alkaline salts of carboxymethylcellulose (for example, and in particular a sodium salt such as Ambergum® 1221 (from Hercules Aqualon) or Blanose ™ 12M8P (from Ashland Inc.).
    According to any of the previous embodiments of the present invention, said polyol is an aliphatic polymeric polyol, such as a derivative of carboxymethylcellulose ether (such as, and in particular, Ambergum® 1221 or Blanose ™ 12M8P).
    According to any of the previous embodiments of the present invention, the dispersion comprises between about 1% and 20% of the oligomeric composition, the percentage being expressed in w / w, in relation to the total weight of the dispersion. In yet another aspect of the invention, the dispersion comprises between about 1% and 8% of the oligomeric / composition. In general, the amount of oligomeric composition present in the dispersion can also be defined as being between 4% and 15% of the oligomeric composition in w / w, relative to the total weight of oil added to the dispersion.
    0048 Said oligomeric compositions are described in patent application WO 2011/161618. However, to be exhaustive, said oligomeric composition can be, in particular, as described here below.
    0049 The term "glyoxal" means both the free form of dialdehyde (ie, OHC-CHO) and the hydrated form (for example, (HO) 2HC-CHO).
    0050 The term "glyoxalate" means glyoxylic acid or an alkaline salt of glyoxylic acid (such as OHC-COONa or OHC-COOK) or a mixture thereof. The term "glyoxalate" is also understood to mean both the free form of aldehyde (i.e., OHCCOOH) and the hydrated form (for example, (HO) 2HC-COOH or (HO) 2HC-COONa).
    0051 For the sake of clarity, the expression “an oligomeric composition”, or similar, means the normal meaning understood by one skilled in the art, that is, a mixture of oligomers, as a reaction product, and other optional components. In the simplest embodiment of the invention, said optional embodiment can be, as a non-limiting example, water and / or unreacted process reagent (e.g., the acid catalyst). By "oligomer" is meant a compound that is not in itself a macropolymer, as it is a resin, but rather a molecule of small size, comprising between about 4 to 100, or even, preferably, 30 units, derived of monomeric constituents.
    According to any of the previous embodiments of the present invention, the oligomers of the present invention have a molar mass (M) comprised between about 200 g / mol and 2,500 g / mol. In yet another aspect of the invention, said M is between about 220 g / mol and 1,200 g / mol.
    According to any of the previous embodiments of the present invention, as a polyamine component, a mixture of melamine and at least one C1-4 compound comprising two NH2 functional groups is used. According to any of the previous embodiments of the present invention, said compound is a C1-2 compound comprising two NH2 functional groups. For the sake of clarity, the term "C1-4 compound comprising two NH2 functional groups" or the like is intended for a C1-4 hydrocarbon compound comprising two NH2 functional groups, and, in addition, said compound may optionally , include one to three nitrogen and / or oxygen atoms. In particular, said compound is a C1-2 compound comprising two NH2 functional groups and a carbonyl group or a 1,2,4-triazole functional group. Non-limiting examples of said C1-4 compound comprising two NH2 functional groups (diamino compounds) can be urea, 1H-1,2,4-triazole-3,5-diamine and mixtures thereof.
    In accordance with any of the previous embodiments of the present invention, mixtures with a molar ratio of melamine / diamino compound comprised between about 4/1 and 1/4, or between 3.5 / 1 and 1 / 3.5, or alternatively between about 2/1 and 1/3, or alternatively between about 1.3 / 1 and 1/3. In the case where the diamino compound is 1H- 1,2,4-triazole-3,5diamine, one can also mention the molar ratio melamine / 1H-1,2,4-triazole-3,5diamine between about 1.5 / 1 and 1 / 1.5 .
    0055 For the sake of clarity, the expression “2,2-dialcoxietanal C4-6” means a 2,2-dialcoxietanal with, in total, between 4 to 6 carbon atoms. According to an embodiment of the present invention, said 2,2-dialcoxyethanal C4-6 can be 2,2dimethoxyethanal, 2,2-diethoxyethanal and mixtures thereof.
    According to any of the previous embodiments of the present invention, said aldehyde component has a molar ratio of glyoxal / 2,2-dialcoxietanal between about 1.1 / 1 and 7/1, or even between about 1, 4/1 and 6.5 / 1. It can also be mentioned that, in the case where the diamino compound is urea, then said glyoxal / 2,2-dialcoxietanal may advantageously be between about 1.5 / 1 and 6.1 / 1. It can also be mentioned that, in the case where the diamino compound is 1H-1,2,4-triazole-3,5-diamine, then said glyoxal / 2,2-dialcoxietanal may be advantageously between about 1.4 / 1 and 2.2 / 1.
    The aldehyde component can also include (as an optional constituent) a glyoxalate. According to any of the previous embodiments of the present invention, when present, said glyoxalate is present in amounts such that the molar ratio of glyoxal / glyoxalate is between about 4/1 and 1/1, or even between about 3 , 5/1 and 2 / 1. According to any of the previous embodiments of the present invention, said glyoxalate is present and within values as stated in the above mentioned ratio, in particular when the diamino compound is 1H-1,2, 4-triazole-3,5-diamine.
    According to any of the previous embodiments of the present invention, the polyamine component and said aldehyde component are mixed in a ratio such that the molar ratio of the total amine functional group / total aldehyde-free functional group (also referred to as (NH 2 ) tot / (CHO) tot) is between about 4/1 and 1/2, or between about 1.9 / 1 and 1 / 1.9, or alternatively between about 1.7 / 1 and 1 / 1.7. For the sake of clarity, a melamine represents three functional groups amine and the diamino compound, for example, urea, represents 2. Likewise, glyoxal represents two functional groups free of aldehydes and the 2,2dialcoxietanal C4-6 or glyoxalate represents an aldehyde-free functional group.
    As a person skilled in the art understands and knows, said protic acid is a catalyst or initiator of the oligomerization reaction, and therefore said protic acid can also react with the other components and become, at least partially, part of the formed oligomers. According to any of the previous embodiments of the present invention, said protic acid catalyst is selected from mineral acids, C1-6 mono or dicarboxylic acids and mixtures thereof. Non-limiting examples of such acids are phosphoric, nitric, sulfuric or hydrochloric acids, or acetic, formic, oxalic or glyoxylic acids. More specifically, said acid catalyst is selected from formic, acetic, glyoxylic and nitric acids and their mixtures.
    0060 According to any of the previous embodiments of the present invention, the oligomeric composition is obtained by reacting the various components in water and the oligomeric composition is obtained by a single step process, in which all the reagents are mixed together or by means of a multi-step process, in which the reagents are subsequently reacted together.
    According to any of the previous embodiments of the present invention, the oligomer is obtained by a process in which all the different components are reacted together, in water, and the pH of the final reaction medium is preferably between 6 and 9.5.
    According to any of the previous embodiments of the present invention, the oligomer is obtained by a two-step process. In a first step, the polyamine component reacts with the aldehyde component in an aqueous medium, at an alkaline pH. Then, in a second step, the acid catalyst is added to the reaction medium in order to act at an acidic pH.
    According to any of the previous embodiments of the present invention, the pH of said first step can be between about 7 and 10, or still between about 8.5 and 10. In yet another aspect of the invention, the reaction temperature the first stage can be between about 20 ° C and 80 ° C, or between / 35 about 40 ° C and 80 ° C.
    In yet another aspect of the invention, said first step can be carried out for about 0.1 hour to about 4 hours (reaction time). However, more specifically, the reaction time of said first step depends on the reaction temperature and its pH, and can be comprised, for example, between about 1 hour to about 4 hours, for a temperature between about 40 ° C to about 80 ° C, and a pH between about 8 and about 10. Alternatively, said reaction time can be comprised, for example, between about 0.5 hour to about 2 hours, for a temperature between about 50 ° C and about 80 ° C, and a pH between about 7 and about 9.5.
    The pH of said first step can generally be defined by adding an appropriate amount of potassium or sodium hydroxide to the reaction medium.
    According to any of the previous embodiments of the present invention, said acid catalyst is added to the reaction mixture of the first step, in an amount sufficient to acidify the latter. The pH of said second step can be between about 4.0 and 6, or between about 4.5 and 5.5. In yet another aspect of the invention, the reaction temperature of the first step can be between about 40 ° C and 100 ° C, or between about 50 ° C and 90 ° C.
    In yet another aspect of the invention, said second step can be carried out for about 0.5 hour to about 4 hours (reaction time). However, more specifically, the reaction time of said first step depends on the reaction temperature and its pH and can be, for example, between about 1 hour to about 2.5 hours, for a temperature between about 50 ° C and about 80 ° C, and a pH between about 4.5 and about 5.5. Alternatively, said reaction time can be, for example, between about 0.5 hour to about 4 hours, for a temperature between about 50 ° C and about 80 ° C, and a pH between about 4.5 and about 5.5.
    As can be seen, the result of this process is an aqueous solution comprising the oligomeric composition of the present invention. Typically, the aqueous solution comprises between about 30% and 70% of the oligomeric composition (solids content), the percentage being expressed in w / w, in relation to the total weight of the solution.
    Said aqueous solution can be used directly for the microcapsule preparation process, as described below, or can be dried, to provide the oligomeric composition.
    11/35
    The dispersion of step 2) also comprises at least one cross-linking agent which can be a di or triisocyanates (hereinafter also referred to as a polyisocyanate) and / or an oxirane-based compound (hereinafter also referred to as a polyoxirane).
    0071 According to any of the previous embodiments of the present invention, the dispersion comprises between about 0.5% and 15% of at least one cross-linking agent, the percentage being expressed in w / w, in relation to the total weight of the dispersion, or even between about 1% and 12% of at least one crosslinking agent.
    0072 For the sake of clarity, the term "aromatic or aliphatic di or triisocyanates" is intended here as a hydrocarbon compound, which can be totally aliphatic or also comprise an aromatic group, and which also has two or three isocyanate groups.
    0073 For the sake of clarity, by "biuret, triuret" is intended here a product of self-addition of such aromatic or aliphatic di or triisocyanates and which comprise the triple radical HN-CO-N-CO-NH (biuret functional group) or the tetra radical HN-CO-NCO-N-CO-NH (triuride functional group). Said biurets or triurides are generally the products of water reaction with a di or triisocyanate. Similarly, by "trimer" is intended here an isocyanurate derivative of said di or triisocyanates (i.e., a compound comprising the 1,3,5-triazinane2,4,6-trione moiety). By "trimethylolpropane adduct" is meant here an isocyanate, which is a reaction product between di or triisocyanate and trimethylolpropane.
    0074 According to any of the previous embodiments of the present invention, the following di or triisocyanates can be mentioned: hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, toluene diisocyanate, a toluene diisocyanate trimethylolpropane adduct (commercially available from Bayer, under the trade name Desmodur® L75), a xylylene diisocyanate trimethylolpropane (commercially available from Mitsui Chemicals, under the trade name Takenate® D-110N), a hexamethylene diisocyanate trimer, an isophorone diisocyanate trimer, hexamethylene diisocyanate trimethylolpropane adduct (available from Mitsui Chemicals) or hexamethylene diisocyanate biuret (commercially available from Bayer under the trade name Desmodur® N 100).
    0075 According to any of the previous embodiments of the present invention, the following oxiran-2-ylmethyl derivatives may be mentioned: 1,3,5-tris (oxiran-2-ylmethyl) -
    1,3,5-triazinane-2,4,6-trione, 4- (oxiran-2-ylmethoxy) -N, N-bis (oxiran-2-ylmethyl) -aniline, 1,3bis (oxiran-2-ylmethoxy ) benzene (also known as resorcinol diglycidyl ether), 1,2-bis (oxiran-2-ylmethoxy) ethane (also known as ethylene glycol diglycidyl ether) and 2,2 '- (2-ethyl-2- ( (oxiran-2-ylmethoxy) methyl) propane-1,3-diyl) bis (oxy) bis (methylene) dioxirane (also known as trimethylolpropane diglycidyl ether).
    According to any of the previous embodiments of the present invention, the cross-linking agent is a di or triisocyanate.
    According to the process of the invention, the dispersion may also comprise a C1-4 compound, which comprises two NH2 functional groups (diamino compound), as defined above. The said compound is believed to help harden the microcapsule lining. The addition of said compound can be attractive, in particular, when an oligomer is used in which the NHWCHOtot ratio is close to the minimum range specified above.
    According to any of the previous embodiments of the process of the invention, the dispersion of step 2) comprises said compound C1-4 which comprises two functional groups NH2. Said compound comprising two NH2 functional groups (diamino compound) can be urea, 1H-1,2,4-triazole-3,5-diamine and mixtures thereof.
    According to any of the previous embodiments of the invention, an amount of diamino compound comprised between about 5% and 100%, or between about 10% and 80%, or alternatively between about 15% and 75%, the percentage being expressed in w / w, in relation to the total weight of the resin. It is clearly understood by one skilled in the art that only a part of said aggregated diamino compound will be incorporated into the microcapsule coating.
    0080 Typical ways to form the dispersions of step 2) are known to a person skilled in the art, and are also described here below, or in the Examples below. Typically, the dispersion can be obtained by stirring the components, up to 24,000 rpm, to disperse the oil in water (with an Ultra-Turrax mechanical stirrer or microwave).
    According to any of the previous embodiments of the present invention, the pH of said dispersion can be adjusted between 4 and 9.5, before step 3), for example, by adding an appropriate amount of a base, such as hydroxide sodium.
    According to any of the previous embodiments of the invention, in step 3) the dispersion is heated to a temperature comprised between 35 ° C and 100 ° C. In yet another aspect of the invention, the temperature of said dispersion emulsion is
    13/35 between 50 ° C and 90 ° C. Said heat treatment can be carried out for about 0.5 hour to 6 hours. More specifically, the heating time depends on the temperature and pH of said emulsion or dispersion, and, for example, it can be between about 1 hour to about 5 hours, for a temperature between about 60 ° C and about 80 ° C, and a pH between about 4.5 and about 9.5.
    Step 4) of the process of the invention is intended to interrupt the hardening process of the coating of the core-coating microcapsule thus obtained, and can be carried out by any known method. Typically, the dispersion can be cooled to temperatures between about 10 and 30 ° C, in general, to room temperature. Said step 4) can optionally include a neutralization of the dispersion thus obtained, at a pH comprised between pH between 6.5 and 7.5, for example, by adding an appropriate amount of a base, such as sodium hydroxide .
    0084 According to optional step 5), some cationic polymers can also be added to the dispersion of the invention. Preferred cationic polymers will have cationic charge densities of at least 0.5 meq / g, more preferably at least about 1.5 meq / g, but also preferably less than about 7 meq / g, more preferably , less than about 6.2 meq / g. The density of the cationic charge of cationic polymers can be determined by the Kjeldahl method, as described in the US Pharmacopoeia, under chemical tests for the determination of nitrogen.
    0085 Preferred cationic polymers are chosen from those containing units comprising primary, secondary, tertiary and / or quaternary amine groups, which may form part of the main polymer chain or may be supported by an additional substituent, directly attached to it. The average molecular weight (Mw) of the cationic polymer is preferably between 10,000 and 2 M Dalton, more preferably between 50,000 and 1.5 M Dalton. Specific examples include Salcare® SC60 (cationic copolymer of acrylamide and acrylamidopropyltrimony chloride, manufacturer: BASF) or Luviquat®, such as PQ 11N, FC 550 or Supreme (polyquaternium-11 to 68 or quaternized vinylpyrrolidone copolymers, manufacturer: BASF) or also Jaguar® (C13S or C17, manufacturer Rhodia).
    0086 According to any of the previous embodiments of the invention, in step 5) an amount of cationic polymers between about 0% and 60% or between about 5% and 40% is added, the percentage being expressed in p / p, in / 35 in relation to the total weight of the resin. It is clearly understood by one skilled in the art that only part of said added cationic polymers will be incorporated into / deposited on the microcapsule coating.
    According to optional step 5), an amount of urea or ethylene urea can also be added to the dispersion of the invention, which can be useful to eliminate possible free glyoxal in the suspension. According to any of the previous embodiments of the invention, in step 5) an amount of urea or ethylene urea is added between about 0% and 10%, or between about 1% and 5%, the percentage being expressed in w / w, in relation to the total weight of the dispersion. It is clearly understood by a person skilled in the art that only a part of said added cationic polymers will be incorporated into / deposited on the microcapsule coating.
    As noted above, the result of this process is an aqueous dispersion (or suspension) comprising core-coating microcapsules of the invention. Typically, the aqueous suspension comprises between 10% and 60% of capsules, the percentage being expressed in w / w in relation to the total weight of the suspension. According to any of the previous embodiments of the invention, the aqueous suspension comprises between 20% and 55% of the capsules.
    Said aqueous suspension can be used directly as a perfuming ingredient, in particular for applications that are aqueous based, for example, a softener or a liquid soap. Therefore, another object of the present invention is an aqueous suspension comprising the microcapsules of the invention, for example a suspension as obtained directly for the process of preparing the microcapsules. Said suspension may comprise some formulation auxiliary agents, such as stabilizing or viscosity control agents, or biocides or bactericides.
    Alternatively, the suspension obtained by the process described above can be subjected to drying, such as spray drying, to provide the microcapsules as such, that is, in powder form. It is intended that any standard method known to a person skilled in the art is also applicable to carry out such drying.
    For the reasons explained above, another object of the present invention is a composition of matter according to that obtained or that can be obtained by the process described above. One skilled in the art understands that said composition of matter comprises the core-coating microcapsules, in dry form or as an aqueous suspension.
    0092 According to any of the above embodiments, of said core-coating microcapsules, the oil content of the core normally represents between 40% and 98% of the total weight of the microcapsules (ie the weight of the dispersion minus the weight of the Water). In yet another aspect of the invention, said oil core represents between 70% and 95%, or even between 80% and 90%, of the total weight of the microcapsules.
    According to any of the above embodiments, of said core-coating microcapsules, the amount of the coating normally represents between 2% and 60% of the total weight of the capsules. In yet another aspect of the invention, said oligomer based coating represents between 5% and 30%, or even between 10% and 20%, of the total weight of the microcapsules.
    0094 According to any of the previous embodiments of the invention, said core-coating microcapsules are those obtained by using, in the process of the invention, an oil-in-water dispersion, in which the oil is a perfume oil and comprising
    0095 - at least one oligomeric composition, as defined above, and which comprises a glyoxalate;
    0096 - a cross-linking agent, as defined above;
    0097 - optionally, at least one polyol, as defined above;
    0098 and in which at least one C1-4 compound is also added during the process, comprising two NH2 functional groups, as defined above (step 2 of the process of the invention), that is, a process that provides microcapsule capsules , which comprise glyoxalate and do not comprise a stabilizing agent.
    As mentioned above, the invention relates to the use of a microcapsule of the invention as a perfuming ingredient. In other words, it is a method of checking, increasing, improving or modifying the odor properties of a perfuming composition or a perfumed article, which method includes the addition of an effective amount to said composition or article. of at least one microcapsule of the invention. By "use of a microcapsule of the invention" it is to be understood here also the use of any composition that contains a microcapsule of the invention, and that can be advantageously employed in the perfumery industry.
    Said compositions, which can in fact be advantageously employed as perfuming ingredients, are also an object of the present invention.
    00101 Therefore, another object of the present invention is a perfuming composition comprising:
    I) as a perfuming ingredient, at least one microcapsule of the invention, or a suspension containing said microcapsule of the invention, as defined above;
    Ii) at least one ingredient selected from the group consisting of a liquid perfumery vehicle and a perfumery base; and
    00104 iii) optionally, at least one perfumery adjuvant.
    00105 By “perfumery vehicle”, we intend here a liquid material that is practically neutral from the point of view of perfumery, that is, that does not significantly alter the organoleptic properties of the perfuming ingredients.
    00106 As a perfumery vehicle we can mention, as non-limiting examples, an emulsifying system, that is, a solvent and surfactant system, or a solvent generally used in perfumery. A detailed description of the nature and type of solvents normally used in perfumery cannot be exhaustive. However, we can mention, as a non-limiting example, solvents such as dipropylene glycol, diethyl phthalate, isopropyl myristate, benzyl benzoate, 2- (2-ethoxyethoxy) -1-ethanol or ethyl citrate, which are the most commonly used. For compositions comprising both a perfumery vehicle and a perfumery base, other suitable perfumery vehicles, in addition to those previously specified, may also be ethanol, water / ethanol mixtures, limonene or other terpenes, isoparaffins, such as those known under the trademark Isopar® (manufacturer: Exxon Chemical) or glycol ethers and glycol ether esters, such as those known under the trademark Dowanol® (manufacturer: Dow Chemical Company).
    00107 By "perfumery base" we mean here a composition that comprises at least one perfuming co-ingredient, as defined above. The term “perfumery adjuvant” is as defined above.
    A composition of the invention consisting of at least one microcapsule of the invention and at least one perfumery vehicle represents a particular embodiment of the invention, as well as a perfuming composition comprising at least one microcapsule of the invention, at least one perfumery vehicle, at least at least one perfumery base and, optionally, at least one perfumery adjuvant.
    00109 It is worth mentioning here that the possibility of having, in the above mentioned compositions / 35, more than one microcapsule of the invention is important, as it allows the perfumer to prepare chords, perfumes that have the odorous tone of several compounds of the invention, thus creating new tools for your work.
    00110 Furthermore, the core-coating microcapsules of the invention can also be advantageously used in all fields of modern perfumery, that is, functional or fine perfumery, to positively transmit or modify the smell of a consumer product when to which said microcapsules of the invention are added. Consequently, a fragrant consumer product comprising:
    I) as a perfuming ingredient, at least one microcapsule of the invention, as defined above; and
    00112 ii) a consumer perfumery base;
    00113 is also an object of the present invention.
    The compound of the invention can be added as such or as part of the perfuming composition of the invention.
    00115 For the sake of clarity, it should be mentioned that, by "perfuming consumer product" is intended a consumer product that is expected to provide at least a perfuming effect, in other words, it is a perfumed consumer product. For the sake of clarity, it should be mentioned that, as a “consumer perfumery base” we intend the functional formulation, as well as, optionally, additional benefit agents, which correspond to a consumer product that is compatible with the perfuming ingredients and is expected to transfer a pleasant odor to the surface to which it is applied (eg skin, hair, fabric or home surface). In other words, a perfumed consumer product according to the invention comprises the functional formulation as well as, optionally, additional benefit agents, which correspond to the desired consumer product, for example, a detergent or an air purifier, and an effective olfactory amount of at least one microcapsule of the invention.
    00116 The nature and type of the constituents of the consumer perfumery base do not justify a more detailed description here, which, in any case, would not be exhaustive, the expert being able to select them based on their general knowledge, and of according to the nature and desired effect of said product.
    00117 Non-limiting examples of suitable perfumery base can be a perfume, such as a fine perfume, a cologne or an aftershave lotion; a fabric care product, such as a liquid or solid detergent, a fabric softener, / 35 a fabric deodorizer, ironing water, paper or bleach; a body care product, such as a hair care product (for example, a shampoo, coloring preparation or hair spray), a cosmetic preparation (for example, a moisturizer or deodorant or antiperspirant), or a skin care product (for example, a scented soap, mousse, bath or shower oil or gel, or a hygiene product); an air deodorizing product, such as a “ready to use” air freshener or powder air freshener; or a product for home use, such as a cleaning cloth, dishwasher detergent or detergent for hard surfaces.
    00118 According to one embodiment of the invention, the fine or functional perfumery base is in the form of a fabric, household or hair product, such as a fabric softener, a detergent or a shampoo.
    The proportions in which the microcapsules, according to the invention, can be incorporated into the various articles or compositions mentioned above, vary within a wide range of values. These values depend on the nature of the article to be perfumed and the desired organoleptic effect, as well as on the nature of the co-ingredients on a given basis, when the microcapsules, according to the invention, are mixed with perfuming co-ingredients, solvents or additives commonly used in the art.
    00120 For example, in the case of perfuming compositions, the usual concentrations are in the order of 0.1% to 50%, by weight, or even more, of the microcapsules of the invention, based on the weight of the composition in which they are incorporated. Concentrations below these, such as on the order of 0.01% to 5%, by weight, can be used when these microcapsules are incorporated in perfumed articles, the percentage being in relation to the weight of the article.
    EXAMPLES
    00121 The invention will now be described in greater detail by means of the following examples, where the abbreviations have the usual meaning in the art, with temperatures being indicated in degrees Celsius (° C).
    00122 TGA (Thermogravimetric Analysis): The resin solids content was measured with a thermogravimetric analyzer (Mettler-Toledo TGA / SDTA851 e ) equipped with a microbalance (precision: 1 pg) and a precision oven with an internal volume of 35 ml , under a constant flow of hydrogen of 20 ml / min. The resin (10 mg) was introduced into the 40 μΙ / 35 aluminum container. The measurement started at 25 ° C to 100 ° C, at 5 ° C / min intervals, remained at 100 ° C, for 1 h, and finally at 200 ° C, at 10 ° C / min intervals. The solids content was determined by calculating the ratio between the weight of the sample (plateau) and the initial weight in the crucible.
    00123 The performance of the capsule was evaluated at 50 ° C (Figures 1a-6a) and 280 ° C (Figures 6b10b) or 300 ° C (Figures 9a-10b) with a similar thermogravimetric analyzer. Perfume evaporation was measured as a function of time. The dispersion microcapsules (10 mg) were introduced into the 70 μι alumina container. Measurement at 50 ° C started from 25 ° C to 50 ° C, at 5 ° C / min intervals, and then remained at 50 ° C for 4 h. Temperature measurement at 280 ° C started from 25 ° C to 280 ° C, at 5 ° C / min intervals, and then remained at 280 ° C for 1 hour and 5 minutes. The measurement at 300 ° C started from 25 ° C to 300 ° C, at 5 ° C / min intervals, and then remained at 300 ° C for 1 h. The slower evaporation of essential oil with a long-lasting profile has been linked to a more stable capsule.
    00124 TOF-MS (Flight Time Mass Spectrometry): The analysis of resin compositions was performed by liquid chromatography, with a TOF-MS detector (TOF high resolution> 10000, Agilent 1200 HPLC system Agilent G1969A MS TOF system compound by an APCI multimode source (Atmospheric Pressure Chemical Lonning) + ESI (Electrospray Lonning)) composed of a binary solvent manager (or G1312b pump) and an automatic sampler (g1329a). This TOF detector can analyze the product with a molecular mass greater than 3,000 g / mol. The analyzes were carried out in 0.1% by weight aqueous formic acid solution at room temperature, without columns. Standard Method: water premix: 0.1% formic acid (Biosolve n ° 23244125 ULC / MSD batch 550361). HPLC: 0.5 ml / min, injection volume: 1 μl with sampler with well plate (without column), thermostat temperature: 60 ° C (± 0.1 ° C). A blank measurement was performed between each sample.
    00125 MSD (Mass Spectrometric Detector): Lonization by multimode Electrospray (ESI) + APCI Pos LCMSD TOF High Resolution 3 ppm acq. Source: Positive mode, supply voltage 2,000 V, cap V 2,500 V, Corona 4 μA, drying gas N 2 , 5 l / min, at 325 ° C, nebulizer 30 psig, at 200 ° C. Fragmentor: 140 to 320 V. Scan limits: 103 to 3,000, online standard for mass adjustment.
    00126 SEC (Molecular Exclusion Chromatography): Resin solutions (0.5% by weight) / 35 were analyzed by molecular exclusion chromatography in 0.1% formic acid by weight and aqueous ammonium acetate solution at 0.05 M (mobile phase, pH = 4.70). The analyzes were performed at 30 ° C, with a flow rate of 0.45 ml / min, using a ThermoFinnigan Surveyor LC-Pump and automatic sampler (20 pl injected). The column used was supplied by TOSOH BIOSCIENCE (TSKgel Super AW2500, 6.0 mm ID, 15.0 cm long, polyvinyl resin). Molecular weights were measured using the ThermoFinnigan Surveyor UV / VIS detector and a SpectraSystem RI-150 (35 ° C) refractive index detector. The detectors were calibrated with standard poly (ethylene glycol) from 106 to 1,982 g / mol.
    00127 Materials: 2,2-dimethoxyethanal (DME), oxalaldehyde (glyoxal, GY) and 2-oxoacetic acid (glyoxylic acid, AGY) were used as 60%, 40% and 50% w / w aqueous solutions, respectively. 1,3,5-triazine-2,4,6-triamine (melamine, M), urea and 1H-1,2,4-triazole-3,5-diamine (guanazole, T, purity = 88.6 %), as received. Ambergum® 1221 was used as a 2% w / w solution in water. Alcapsol 144 to 20% w / w was dissolved in water. Sodium hydroxide (NaOH) 30% w / w was dissolved in water. Nitric acid was used as a 30% w / w solution in water. Formic acid (Aldrich, Switzerland) was used, as received.
    Example 1
    00128 Preparation of oligomers according to the invention
    00129 Oligomeric composition n ° 1: In a 50 ml round bottom flask, urea (2.66 g),
    1,3,5-triazine-2,4,6-triamine (1.86 g), 2,2-dimethoxyacetaldehyde (60% w / w in water, 2.54 g) and oxalaldehyde (40% w / w in water, 8.58 g) were added in demineralized water (20.00 g). The pH, between 5.80 and 6.00, was adjusted with sodium hydroxide (30% w / w in water, 0.36 g) between pH = 9 and 10. The mixture was heated at 60 ° C for 20 minutes, to result in a solution (pH = 6.70 to 7.00). Then, nitric acid (30% w / w in water, 2.00 g) was added to correct the pH to 4.50 to 4.70.
    Compound Amount(g) n (mol) eq. ReasonM / U ReasonGY / DME ReasonNH2tot / CHOtot Melamine 1.86 14.7 1 d / Q Urea 2.66 44.3 3 1/3 DME 2.54 14.7 1 1/1 GY 8.58 59.1 44/1
    00130 Oligomeric composition n ° 2: In a 50 ml round-bottom flask, oxalaldehyde (40% w / w in water, 2.11 g), 2,2-dimethoxyacetaldehyde (60% w / w in water, 1.68 g ), 2/35 oxoacetic acid (50% w / w in water, 0.72 g) and 1,3,5-triazine-2,4,6-triamine (1.11 g) were added in demineralized water (1 , 90 g). The pH was adjusted with sodium hydroxide (30% w / w in water, 1.04 g) between 2.47 to 9.56. The mixture was heated at 45 ° C for 25 minutes, to result in a solution (pH = 9.10). Then, demineralized water (8.35 g) was added, and the resin was stirred for 5 minutes (pH = 9.09).
    Compound Amount(g) n (mol) ReasonGY / DME / AGY NH 2 tot / CHOtot ratio DME 1.68 9.69 2/3/1 1 / 1.65 GY 2.11 14.55 AGY 0.72 4.85 Melamine 1.11 8.78
    00131 Oligomeric composition no. 3: In a 50 ml round bottom flask, urea (2.66 g),
    1,3,5-triazine-2,4,6-triamine (1.86 g), 2,2-dimethoxyacetaldehyde (60% w / w in water, 2.54 g) and oxalaldehyde (40% w / w in water, 3.76 g) were added in demineralized water (20.00 g). The pH of 5.50 was adjusted with sodium hydroxide (30% w / w in water, 0.10 g) to a pH = 9.20. The mixture was heated at 60 ° C for 20 minutes to result in a solution (pH = 6.70 to 7.00). Then, nitric acid (30% w / w in water, 2.00 g) was added to correct the pH to 4.50.
    Compound Amount n eq. Reason ReasonGY / DME ReasonNH2tot / CHOtot (g) (mmol) M / U Melamine 1.86 14.7 1 1/3 Urea 2.66 44.3 32/1 DME 2.54 14.7 11.77 / 1 GY 3.76 25.9 1.77
    00132 Oligomeric composition n ° 4: In a 50 ml round-bottom flask, oxalaldehyde (40% w / w in water, 0.87 g), 2,2-dimethoxyacetaldehyde (60% w / w in water, 1.38 g), 2-oxoacetic acid (50% w / w in water, 0.59 g) and glutaraldehyde (25% w / w in water,
    2.37 g) and 1,3,5-triazine-2,4,6-triamine (0.91 g) were added in demineralized water (1.60 g). The pH was adjusted with sodium hydroxide (30% w / w in water, 0.89 g) from 2.21 to 9.45. The mixture was heated at 45 ° C for 25 minutes, to result in a solution (pH = 8.73). Then, demineralized water (6.80 g) was added, and the resin was stirred for 5 min.
    Compound Quantity (g) n (mmol) NH 2 tot / CHOtot ratio DME 1.38 7.96 1 / 1.65
    / 35
    GY 0.87 6.00Glutaraldehyde 2.37 5.93 AGY 0.59 3.99 Melamine 0.91 7.22
    00133 Oligomeric composition No. 5 '. In a 50 ml round-bottom flask, oxalaldehyde (40% w / w in water, 1.90 g), 2,2-dimethoxyacetaldehyde (60% w / w in water, 1.68 g), 2-oxoacetic acid (50% w / w in water, 0.72 g) and glutaraldehyde (25% w / w in water, 0.58 g) and 1,3,5-triazine-2,4,6-triamine (1,11 g) were added in demineralized water (1.90 g). The pH was adjusted with sodium hydroxide (30% w / w in water, 0.87 g) from 2.21 to 9.45. The mixture was heated at 45 ° C for 25 minutes, to result in a solution (pH = 8.73). Then, demineralized water (8.40 g) was added, and the resin was stirred for 5 min.
    Compound Quantity (g) n (mmol) NH2tot / CHOtot ratio DME 1.68 9.69 1 / 1.65 GY 1.90 13.10 Glutaraldehyde 0.58 1.45 AGY 0.72 4.86 Melamine 1.11 8.80
    Example 2
    00134 Preparation of microcapsules with polyisocyanates
    00135 Composition of perfume oil.
    Feedstock Quantity (g) Romascone® 1) 4.0 Verdox® 2) 4.0 Lorysia® 3) 4.0 Lilial® 4) 4.0 Hexyl salicylate 4.0
    00136 1) 2,2-dimethyl-6-methylene-1-cyclohexanecarboxylate; manufacturer. Firmenich SA, Geneva,
    Switzerland
    2) 2-tert-butyl-1-cyclohexyl acetate; manufacturer. International Flavors & Fragrances, USA
    00138 3) 4- (1,1-dimethylethyl) -1-cyclohexyl acetate; manufacturer. Firmenich SA, Geneva, Switzerland
    00139 4) 3- (4-tert-butylphenyl) -2-methylpropanal; manufacturer. Givaudan SA, Vernier, Switzerland
    00140 A: Preparation of microcapsules with oligomeric composition No. 1
    00141 General protocol. The solution of oligomeric composition no. 1 (38 g) was dissolved in a solution of Ambergum® 1221 (a "polyol") and guanazole (a C1-4 diamino compound).
    / 35
    A solution of perfume oil and polyisocyanate was added and emulsified with Ultra-Turrax, at 24,000 rpm, for 2 minutes (pH = 5.00 to 5.60). The reaction mixture was heated to 60 ° C or 80 ° C for 4 hours, then cooled to room temperature (pH = 5.00 to 5.50). The suspension of microcapsules was neutralized with a sodium hydroxide solution (30% by weight in water).
    00142 Microcapsules 1: microcapsules prepared in the presence of Desmodur® N100, as a polyisocyanate and Ambergum® 1221, as a polyol
    Feedstock Quantity (g) % (w / w) Oligomeric composition No. 1 (26.8% by weight in water) 38 6.8 Polyol (Ambergum® 1221.2%, by weight, in water) 60 0.8 Guanazola 4 2.7 Perfume oil 40 26.6 Desmodur® N100 (a polyisocyanate) 7.45 5.0 Water to balance 58.1 Total 150.17 100
    00143 Microcapsules 2: microcapsules prepared in the presence of Desmodur® N100, as a polyisocyanate, and Blanose ™ 12M8P, as a polyol
    Feedstock Quantity (g) % (w / w) Oligomeric composition No. 1 (26.9% by weight in water) 28.5 6.8 Polyol (Blanose ™ 12M8P, 2% by weight in water) 45 0.8 Guanazola 3 2.7 Perfume oil 30 26.6 Desmodur® N100 (a polyisocyanate) 5.6 5.0 Water to balance 58.1 Total 112.7 100
    00144 Microcapsules 3: microcapsules prepared in the presence of hexamethylene diisocyanate
    Feedstock Quantity (g) % (w / w) Oligomeric composition No. 1 (26.9% by weight in water) 28.5 6.9 Polyol (Ambergum® 1221.2%, by weight, in water) 45 0.8 Guanazola 3 2.7 Perfume oil 30 27.1 Hexamethylene diisocyanate 3.93 3.5 Water to balance 59.0 Total 110.74 100
    00145 Microcapsules 4: microcapsules prepared in the presence of Takenate® D-110N
    Feedstock Quantity (g) % (w / w) Oligomeric composition No. 1 (26.9% by weight in water) 28.5 6.5 Polyol (Ambergum 1221, 2% by weight in water) 45 0.8
    / 35
    Guanazola 3 2.5 Perfume oil 30 25.4 Takenate® D-110N 10.9 9.2 Water to balance 55.6 Total 118.1 100
    00146 Microcapsules 5 '. microcapsules prepared in the presence of isophorone diisocyanate
    Feedstock Quantity (g) % (w / w) Oligomeric composition No. 1 (26.9% by weight in water) 28.5 6.6 Polyol (Ambergum® 1221.2%, by weight, in water) 45 0.8 Guanazola 3 2.5 Perfume oil 30 25.8 Isophorone diisocyanate 9 7.7 Water to balance 56.6 Total 116.2 100
    00147 B: Preparation of microcapsules with oligomeric composition No. 2
    00148 General protocol. A solution of oligomeric composition no. 2 (16.9 g) was placed in a 200 ml reactor, in the presence of guanazole (a C1-4 diamino compound, 0.98 g) and demineralized water (32.5 g, pH = 9.00 to 9.50). A solution of perfume oil and polyisocyanate (21.00 g) was added and emulsified with Ultra-Turrax, between 21,500 and 24,000 rpm, for 2 minutes (pH = 8.50 to 9.00). The pH was adjusted to 5.00 to 5.50 with formic acid (30% w / w, in water). The reaction mixture was heated to 60 ° C for 4 h, cooled to room temperature (pH = 5.50 to 6.00). The suspension of microcapsules was neutralized with a sodium hydroxide solution (30% by weight in water).
    00149 Microcapsules 6. microcapsules prepared in the presence of Desmodur® N100
    Feedstock Quantity (g) % (w / w) Oligomeric composition no. 2 (19.6% by weight in water) 16.9 4.5 Guanazola 0.98 1.3 Perfume oil 21.0 28.6 Desmodur® N100 (a polyisocyanate) 1.81 2.5 Formic acid (30% by weight in water) 0.14 0.06 Water to balance 63.04 Total 73.44 100
    00150 Microcapsules 7: microcapsules prepared in the presence of isophorone diisocyanate
    Feedstock Quantity (g) % (w / w) Oligomeric composition no. 2 (19.6% by weight in water) 16.9 4.5 Guanazola 0.98 1.3 Perfume oil 21.0 28.4
    / 35
    Isophorone diisocyanate 2.17 2.9 Formic acid (30% by weight in water) 0.18 0.07 Water to balance 62.83 Total 73.86 100
    00151 Microcapsules 8: microcapsules prepared in the presence of hexamethylene diisocyanate
    Feedstock Quantity (g) % (w / w) Oligomeric composition no. 2 (19.6% by weight in water) 17.0 4.5 Guanazola 0.98 1.3 Perfume oil 21.0 28.6 Hexamethylene diisocyanate 1.64 2.2 Formic acid (30% by weight in water) 0.19 0.08 Water to balance 63.32 Total 73.46 100
    00152 Microcapsules 9: microcapsules prepared in the presence of Takenate® D-110N
    Feedstock Quantity (g) % (w / w) Oligomeric composition no. 2 (19.6% by weight in water) 16.9 4.5 Guanazola 0.98 1.3 Perfume oil 21.0 28.3 Takenate® D-110N 2.64 3.6 Formic acid (30% by weight in water) 0.16 0.06 Water to balance 62.24 Total 74.33 100
    00153 Microcapsules 10: microcapsules prepared in the presence of Takenate® D-110N, as a polyisocyanate, and Ambergum® 1221, as a polyol
    Feedstock Quantity (g) % (w / w) Oligomeric composition no. 2 (19.6% by weight in water) 33.97 4.4 Guanazola 1.96 1.3 Perfume oil 42.0 28.0 Takenate® D-110N (a polyisocyanate) 5.28 3.5 Formic acid (30% by weight in water) 0.42 0.08 Polyol (Ambergum® 1221.2%, by weight, in water) 66.38 0.89 Water to balance 61.83 Total 150.01 100
    00154 Microcapsules 11: microcapsules prepared in the presence of Takenate® D-110N, as a polyisocyanate, Ambergum® 1221, as a polyol, and guanidine carbonate, as a diamino compound
    Feedstock Quantity (g) % (w / w) Oligomeric composition no. 2 (19.6% by weight in water) 16.63 4.37
    / 35
    Guanidine carbonate 0.89 1.19 Perfume oil 21.00 28.1 Takenate® D-110N (a polyisocyanate) 2.64 3.54 Formic acid (30% by weight in water) 0.21 0.08 Polyol (Ambergum® 1221.2%, by weight, in water) 33.19 0.89 Water to balance 61.83 Total 74.56 100
    00155 C: Preparation of microcapsules with oligomeric composition No. 3
    00156 General protocol: The solution of oligomeric composition no. 3 (32.9 g) was dissolved in a solution of Ambergum® 1221 (a "polyol") and guanazola (a C1-4 diamino compound). A solution of perfume oil and polyisocyanate was added and emulsified with Ultra-Turrax, at 24,000 rpm, for 2 minutes (pH = 5.00 to 5.60). The reaction mixture was heated at 60 ° C for 4 hours, then cooled to room temperature (pH = 5.00 to 5.50).
    00157 Microcapsules 12: microcapsules prepared in the presence of Takenate® D-110N, as a polyisocyanate, and Ambergum® 1221, as a polyol
    Feedstock Quantity (g) % (w / w) Oligomeric composition No. 3 (24.8% by weight in water) 32.9 5.4 Polyol (Ambergum® 1221.2%, by weight, in water) 60 0.8 Guanazola 4 2.6 Perfume oil 40 26.4 Takenate® D-110N (a polyisocyanate) 14.54 9.6 Water to balance 55.2 Total 151.44 100
    00158 D: Preparation of microcapsules 13 with oligomeric composition No. 4
    00159 General protocol: The solution of oligomeric composition No. 4 (15.41 g) was dissolved in a solution of Ambergum® 1221 (a “polyol”) and guanazola (a C14 diamino compound). A solution of perfume oil and polyisocyanate was added and emulsified with Ultra-Turrax, at 24,000 rpm, for 2 minutes (pH = 5.22). The reaction mixture was heated at 45 ° C for 1 h, 60 ° C for 1 h, 80 ° C for 3 h, and finally cooled to room temperature (pH = 5.00 to 5, 50).
    00160 Microcapsules 13: microcapsules prepared in the presence of Takenate® D-110N, as a polyisocyanate, and Ambergum® 1221, as a polyol
    Feedstock Quantity (g) % (w / w) Oligomeric composition No. 4 (21.0% by weight in water) 15.41 4.62 Polyol (Ambergum® 1221.2%, by weight, in water) 27.22 0.78 Guanazola 0.80 1.14
    / 35
    Perfume oil 25.83 36.87 Takenate® D-110N (a polyisocyanate) 2.17 3.10 Water to balance 53.49 Total 70.06 100
    00161 E: Preparation of microcapsules 14 with oligomeric composition No. 5
    00162 General protocol: Solution of oligomeric composition no. 5 (xxx g) was dissolved in a solution of Ambergum® 1221 (a “polyol”) and guanazola (a C1-4 diamino compound). A solution of perfume oil and polyisocyanate was added and emulsified with Ultra-Turrax, at xxx rpm, for xxx min (pH = 5.00-5.60). The reaction mixture was heated at 45 ° C for 1 h, 60 ° C for 1 h, 80 ° C for 3 h, and finally cooled to room temperature (pH = 5.00 to 5, 50).
    00163 Microcapsules 14: microcapsules prepared in the presence of Takenate® D-110N, as a polyisocyanate, and Ambergum® 1221, as a polyol
    Feedstock Quantity (g) % (w / w) Oligomeric composition No. 5 (21.2% by weight in water) 17.16 4.84 Polyol (Ambergum® 1221.2%, by weight, in water) 33.19 0.88 Guanazola 0.98 1.30 Perfume oil 21.00 27.93 Takenate® D-110N (a polyisocyanate) 2.64 3.51 Water to balance 61.54 Total 75.18 100
    Example 3
    00164 Preparation of microcapsules with polyoxirane
    00165 A: Preparation of microcapsules with oligomeric composition No. 1
    00166 General protocol: The solution of oligomeric composition no. 1 (38 g) was dissolved in a solution of Ambergum® 1221 (a “polyol”) and guanazola (a “C1-4 diamino compound”). A solution of perfume oil and polyoxyrane was added and emulsified with Ultra-Turrax, at 24,000 rpm, for 2 minutes (pH = 5.00 to 5.60). The reaction mixture was heated to 60 ° C or 80 ° C for 4 hours, then cooled to room temperature (pH = 5.00 to 5.50). The suspension of microcapsules was neutralized with a sodium hydroxide solution (30% by weight in water).
    00167 Microcapsules 15: microcapsules prepared in the presence of ethylene glycol diglycidyl ether (a polyoxyrane)
    Feedstock Quantity (g) % (w / w) Oligomeric composition No. 1 (26.9% by weight in water) 28.5 6.7 Polyol (Ambergum® 1221.2%, by weight, in water) 45 0.8 Guanazola 3 2.6
    / 35
    00168 Perfume oil 30 26.4 Diglycidyl ether of ethylene glycol (a polyoxyrane) 7 6.2 Water to balance 57.3 Total 113.6 100 00168 Microcapsules 16: the reaction mixture was heated to 80 ° C for 4 hours 00169 Feedstock Quantity (g) % (w / w) Oligomeric composition No. 1 (26.9% by weight in water) 28.5 6.7 Polyol (Ambergum® 1221.2%, by weight, in water) 45 0.8 Guanazola 3.0 2.6 Perfume oil 30.0 26.4 Diglycidyl ether of ethylene glycol (a polyoxyrane) 7.0 6.2 Water to balance 57.3 Total 113.6 100 00169 Microcapsules 17: microcapsules prepared in the presence of resorcinol diglycidyl ether 00170 Feedstock Quantity (g) % (w / w) Oligomeric composition No. 1 (26.9% by weight in water) 28.5 6.6 Polyol (Ambergum® 1221.2%, by weight, in water) 45 0.8 Guanazola 3.0 2.6 Perfume oil 30.0 25.9 Resorcinol diglycidyl ether (a polyoxyrane) 9.0 7.8 Water to balance 56.3 Total 115.9 100 00170 Microcapsules 18: microcapsules prepared in the presence of resorcinol diglycidyl ether at 80 ° C for 4 h 00171 Feedstock Quantity (g) % (w / w) Oligomeric composition No. 1 (26.9% by weight in water) 28.5 6.6 Polyol (Ambergum® 1221.2%, by weight, in water) 45 0.8 Guanazola 3.0 2.6 Perfume oil 30 25.9 Resorcinol diglycidyl ether (a polyoxyrane) 9.0 7.8 Water to balance 56.3 Total 115.8 100 00171 Microcapsules 19: microcapsules prepared in the presence of trimethylolpropane diglycidyl etherFeedstock Quantity (g) % (w / w) Oligomeric composition No. 1 (26.9% by weight in water) 28.5 6.7 Polyol (Ambergum® 1221.2%, by weight, in water) 45 0.8 Guanazola 3 2.6
    / 35
    Perfume oil 30 26.1 Trimethylolpropane diglycidyl ether (a polyoxyrane) 8.1 7.0 Water to balance 56.8 Total 115.1 100
    00172 Microcapsules 20: microcapsules prepared in the presence of trimethylolpropane diglycidyl ether at 80 ° C for 4 h
    Feedstock Quantity (g) % (w / w) Oligomeric composition No. 1 (26.9% by weight in water) 28.5 6.7 Polyol (Ambergum® 1221.2%, by weight, in water) 45 0.8 Guanazola 3 2.6 Perfume oil 30 26.1 Trimethylolpropane diglycidyl ether (a polyoxyrane) 8.1 7.0 Water to balance 56.8 Total 115.0 100
    00173 B: Preparation of microcapsules with oligomeric composition No. 2
    00174 Microcapsules 21: Oligomeric composition No. 2 (16.9 g) was placed in a 200 ml reactor, in the presence of guanazole (a “C1-4 diamino compound”, 0.98 g) and demineralized water (32.5 g, pH = 8.33). A solution of perfume oil (21.00 g) and trimethylolpropane diglycidyl ether (1.97 g) was added and emulsified with UltraTurrax, at 24,000 rpm, for 2 minutes (pH = 7.75). The pH was adjusted with formic acid (30%, w / w, in water, 0.16 g, pH = 5.34). The reaction mixture was heated to 80 ° C for 4 h, and finally cooled to room temperature (pH = 5.67). The suspension of microcapsules was neutralized with a sodium hydroxide solution (30% by weight in water).
    Feedstock Quantity (g) % (w / w) Oligomeric composition no. 2 (19.6% by weight in water) 16.9 4.5 Guanazola 0.98 1.3 Perfume oil 21.0 28.5 Trimethylolpropane diglycidyl ether (a polyoxyrane) 1.97 2.7 Formic acid (30% by weight in water) 0.14 0.06 Water to balance 62.94 Total 73.61 100
    Example 4
    00175 Microcapsules, according to the state of the art (comparison)
    00176 A: microcapsules obtained using the oligomeric composition and the inventive process of the state of the art PCT / IB2011 / 052700
    00177 Comparative Microcapsule 1: preparation with oligomeric composition n ° 1/35
    Feedstock Quantity (g) % (w / w) Oligomeric composition No. 1 (26.9% by weight in water) 38 7.1 Polyol (Ambergum® 1221.2%, by weight, in water) 60 0.8 Guanazola 4 2.8 Perfume oil 40 28 Water to balance 61.3 Total 142.68 100
    00178 Comparative Microcapsule 2: preparation with oligomeric composition No. 1 and
    Blanose ™ 12M8P (a “polyol”, 2% w / w, in water, 45.00 g), used instead of
    Ambergum® 1221
    Feedstock Quantity (g) % (w / w) Oligomeric composition No. 1 (26.9% by weight in water) 28.5 7.2 Polyol (Blanose ™ 12M8P, 2% by weight in water) 45 0.8 Guanazola 3 2.8 Perfume oil 30 28.0 Water to balance 61.2 Total 107.1 100
    00179 Comparative Microcapsule 3: preparation with oligomeric composition No. 2
    Feedstock Quantity (g) % (w / w) Oligomeric composition no. 2 (19.6% by weight in water) 16.9 4.6 Guanazola 0.98 1.4 Perfume oil 21.0 29.3 Formic acid 0.24 0.1 Water to balance 64.6 Total 71.73 100
    00180 B: microcapsules obtained using the oligomeric composition and the inventive process WO 2009/100553
    00181 Oligomeric composition: according to the state of the art WO 2009/100553
    00182 In a 250 ml round bottom flask, melamine (11.2 g, 89 mmol) and DME (30.8 g,
    178 mmol) were dissolved in water (3.7 g, 205 mmol). The pH was adjusted with 0.27 g of sodium hydroxide (pH = 9.53). The mixture was heated at 60 ° C for 2 h to result in a solution. Then, formic acid (1.02 g, 22 mmol) was added to correct the pH at 4.50.The mixture was heated to 60 ° C for 4h. The solution was stored in the refrigerator (pH = 4.23). M = 350 g / mol (measured by SEC).
    00183 Table: Reason for the various starting materials
    Compound Quantity (g) n (mol) eq. NH 2 tot / CHOtot ratio Melamine 11.2 89 1 3/2 DME 30.8 178 2
    / 35
    00184 Comparative capsules 4: In a 200 ml reactor, dissolved in water (25.00 g) and added to the oligomeric composition (5.51 g), colloidal stabilizing agent (Gantrez AN-119BF, 0.81 g) and polyol (2 g, resorcinol, 30%, in water). Perfume oil (20.00 g) was added and the reaction mixture was sheared with Ultra-Turrax at 21,000 rpm for 2 minutes. The reaction mixture was then stirred at 300 rpm and heated at 45 ° C for 1 h, then at 60 ° C for 1 hour, and finally at 75 ° C for 3 h. The resulting suspension was cooled (pH = 5.39) and neutralized with a solution of sodium hydroxide (30%, in water, 0.35 g, pH = 6.70).
    Feedstock Quantity (g) % (w / w) Colloidal stabilizing agent (Gantrez® AN-119BF) 0.81 1.5 Polyol (Resorcinol, 30%, in water) 2.00 1.1 Demineralized water to balance 56.4 Oligomeric composition (~ 53.9%, in water) 5.51 4.2 Perfume oil 20.00 36.8 Total 53.67 100
    Example 5
    00185 Aqueous solutions of cationic copolymers were added to the anionic capsules at the end of the synthesis. Copolymers are listed below.
    Code Copolymers Provider Solution in water(% by weight) M(g / mol) Cationic activity (meq / g) THE Salcare SC 60 BASF 3 1,000,000 1.9 B Luviquat PQ 11 BASF 20 1,000,000 0.8 Ç Luviquat Excellence BASF 40 40,000 6.1 D Luviquat FC 550 BASF 40 80,000 3.3 AND Luviquat FC 370 BASF 40 100,000 2.0 F Luviquat Style BASF 20 400,000 3.0 G Sensomer CI 50 Lubrizol 32 2,000,000 unknown H Sensomer CT 400 Lubrizol 1.2 unknown 3.0 I Sensomer CT 250 Lubrizol 1.2 unknown 1.9 J Jaguar C17 Rhodia 1 unknown unknown K Jaguar C162 Rhodia 1 unknown unknown L Jaguar Excel Rhodia 1 unknown unknown M Jaguar C14 S Rhodia 1 unknown unknown
    / 35
    00186 Different amounts of copolymer solutions were added to 5 g of microcapsule dispersions, and the zeta potential of the dispersions was measured. The lowest concentration of each copolymer that results in a positive potential difference was recorded below.
    00187 In the presence of 10 microcapsules:
    Copolymer Amount of copolymer solution (g) Concentration (%, by weight) Zeta Potential(mV) none -37 Salcare SC 60 4.660 1.45 +26 Luviquat PQ 11 0.700 2.46 -1 Luviquat Excellence 0.175 1.35 +31 Luviquat FC 550 0.175 1.35 +20 Luviquat FC 370 0.350 2.62 +21 Luviquat Style 0.700 2.46 +44 Sensomer CI 50 0.872 4.75 +14 Sensomer CT 400 11,660 0.84 +38 Sensomer CT 250 11,660 0.84 +31 Jaguar C17 20,970 0.81 +11 Jaguar C162 34,950 0.87 +7 Jaguar Excel 27,960 0.85 +7 Jaguar C14 S 27,960 0.85 +3
    00188 In the presence of microcapsule 12:
    Copolymer Amount of copolymer solution (g) Concentration (%, by weight) Zeta Potential(mV) none -49 Salcare SC 60 2,330 0.95 +17 Luviquat PQ 11 0.700 2.46 +16 Luviquat Excellence 0.175 1.35 +48 Luviquat FC 550 0.175 1.35 +36 Luviquat FC 370 0.175 1.35 +26 Luviquat Style 0.350 1.31 +37 Sensomer CI 50 0.654 3.70 +18 Sensomer CT 400 5.83 0.65 +19 Sensomer CT 250 5.83 0.65 +16 Jaguar C17 13.98 0.74 +7 Jaguar C162 20.97 0.81 +2 Jaguar Excel 20.97 0.81 +6 Jaguar C14 S 20.97 0.81 +4
    / 35
    Example 6 00189 Use in application of microcapsules of the invention 00190 • Application for washing the body 00191 Table: Formulation for washing the body
    Ingredients % w / w 1. Deionized water 58.40 2. Carbopol® Aqua CC PolymerCross-linked polyacrylate polymer-1 (Noveon) 8.00 3. Citric acid (40% aqueous solution) 0.50 4. Zetesol AO 328 UPareth Sodium Sulfate C12-C15 (Zschimmer & Schwarz) 25.00 5. Tego® Betain F 50 Cocoamidopropyl betaine (Goldschmidt AG) 4.00 6. Glydant ™ Plus LiquidDMDM hydantoin and iodopropynyl Butylcarbamate (Lonza) 0.10 7. Sodium Chloride (20% aqueous solution) 4.00
    00192 The capsules were added to the body wash formulation to obtain a perfume concentration of 0.2% w / w. The dispersions were stored at room temperature for 24 hours. The body wash formulation (1 ml) was diluted with water (4 ml) and then extracted with isooctane containing 1,4dibromobenzene as an internal standard (5 ml). The organic solutions are then analyzed by GC to measure the leakage of perfume. The results on the leakage of oil from the microcapsules (%) are obtained from equation 1:
    00193 Oil leak (%) = 100 x (oil mass detected in the aqueous phase) / (oil mass introduced into the dispersion) (1)
    00194 The corresponding values are shown in the following table, with a margin of error of 5%:
    / 35
    25 ° C 40 ° C Example Microcapsule s t0 1 to s 2nd 4th 8th 12th 1 to s 2nd 4th 8th 12th 2A 1 2 2 0.5 1 2 1 2 0.4 2 1 1 2 2 0 2 2 1 2 0 1 2 1 2 3 1 2 3 3 5 7 9 9 7 11 13 4 2 1 2 1 1 2 1 1 1 1 2 5 2 3 3 6 720 17 17 242B 6 2 2 2 2 1 1 2 2 3 2 1 7 2 16 16 24 - - 54 62 - - - 8 2 5 7 7 10 10 15 25 24 30 - 9 1 1 1 2 2 1 1 2 2 2 1 10 0 011 0 02E 14 0 03A 18 2 27 31 - - - 34 40 - - - 4 Microcapsulecomparative 1 4 90 100 Microcapsulecomparative 2 2 75 44 Microcapsulecomparative 3 2 76 95 Microcapsulecomparative 4 42100
    00195 s = week / - = measurement stopped
    00196 As can be seen, all microcapsules of the invention are more stable in relation to oil leakage during storage, when compared to the state of the art microcapsules, which are CH2O free.
    00197 • Softener application
    00198 The microcapsules were diluted in a fabric softener (composition: 16.5% Stepantex® VK90 (Stepan), 0.2% calcium chloride, 83.3% water) to obtain a perfume concentration of 0 , 8% w / w. The dispersions were stored at room temperature for 24 hours. A portion of the softener (1 ml) was diluted with water (4 ml) and then extracted with isooctane (5 ml) containing 1,4dibromobenzene as an internal standard (150 mg / l). The organic solutions were then analyzed by GC to measure the leakage of perfume. The results on the leakage of oil from the microcapsules (%) are obtained from equation 1. The corresponding / 35 values are presented in the table below.
    25 ° C 40 ° C Microcapsule s t0 1 to s 2nd 4th 8th 12th 1 to s 2nd 4th 8th 12th 1 0 2 0 0 1 0 1 1 0 2 3 6 0 0 0 0 0 0 3 3 4 5 9 10 0 0 - - - - 0 - - - - 11 0 0 - - - - 0 - - - - 14 0 0 - - - - 0 - - - - Microcapsulecomparative 1 4 100 - - - - 100 - - - - Microcapsulecomparative 2 4 100 - - - - 100 - - - - Microcapsulecomparative 3 2 100 - - - - 100 - - - - Microcapsulecomparative 4 94 100 - - - - 100 - - - -
    00199 s = week / - = measurement stopped
    00200 As can be seen from Table 3B, all microcapsules of the invention are more stable in relation to oil leakage, during storage, when compared to the state of the art microcapsules, which are CH2O free.
    权利要求:
    Claims (14)
    [1]
    1) preparation of an oligomeric composition which comprises the reaction product of, or which can be obtained by a joint reaction of:
    a) a polyamine component in the form of melamine or a mixture of melamine and at least one C1-4 compound comprising two NH2 functional groups;
    b) an aldehyde component in the form of a mixture of glyoxal, a 2,2-diaoxyciethyl C4-6 and, optionally, a glyoxalate, said mixture having a molar ratio of glyoxal / 2,2-dialcoxietanal C4-6 comprised between 1/1 and 10/1; and
    c) a protic acid catalyst;
    1. Process for the preparation of a core-coating microcapsule, said process comprising the steps of:
    [2]
    2/3 between 0.5% and 15% of at least one cross-linking agent, the percentage being expressed in w / w, in relation to the total weight of the dispersion.
    2. Process, according to claim 1, characterized by the fact that the dispersion comprises:
    between 10% and 50% of oil;
    between 1% and 20% of the oligomeric composition;
    Petition 870190066088, of 7/12/2019, p. 5/7
    2) preparation of an oil-in-water dispersion, in which the droplet size is between 1 and 600 pm, and comprising:
    i) an oil;
    ii) an aqueous medium;
    iii) at least one oligomeric composition, as obtained in step 1);
    iv) at least one crosslinking agent chosen from:
    A) aromatic or aliphatic C4-C12 di or triisocyanates and their biurides, triurides, trimers and trimethylolpropane adduct; and / or
    B) a di or trioxirane compound of formula
    A- (oxiran-2-ylmethyl) n characterized by n representing 2 or 3 and A representing a C2-C6 group, optionally, comprising from 2 to 6 nitrogen and / or oxygen atoms;
    v) optionally, a C1-4 compound, which comprises two NH2 functional groups;
    [3]
    3/3 ylmethyl) -aniline, 1,3-bis (oxiran-2-ylmethoxy) benzene, 1,2-bis (oxiran-2-ylmethoxy) ethane and 2,2 '(2-ethyl-2 - ((oxiran -2-ylmethoxy) methyl) propane-1,3-diyl) bis (oxy) bis (methylene) dioxirane.
    3. Process according to claim 1 or 2, characterized by the fact that the aqueous medium comprises between 0% and 5% of at least one stabilizing agent and between 0% and 10% of at least one polyol, the percentage being expressed in w / w, in relation to the total weight of the dispersion.
    3) heating said dispersion;
    [4]
    4. Process according to claim 3, characterized in that said stabilizing agent is an ionic surfactant and said polyol is an aliphatic polymeric polyol.
    4) cooling said dispersion; and
    [5]
    Process according to any of claims 1 to 4, characterized in that said polyamine component is a mixture of melamine and at least one compound chosen from urea, 1H-1,2,4-triazole-3, 5-diamine and mixtures thereof, and the molar ratio of melamine / compound C1-4 comprising two NH2 functional groups between 2/1 and 1/3.
    5) optionally, drying of the final dispersion, to obtain the dried core-coating microcapsule.
    [6]
    Process according to any one of claims 1 to 5, characterized in that said aldehyde component is a mixture of glyoxal and at least one glyoxalate, 2,2-dimethoxy-ethanal and mixtures thereof, and has a molar ratio of glyoxal / 2,2-dialcoxietanal between 2.2 / 1 and 6.5 / 1 and the molar ratio of glyoxal / glyoxalate is between 4/1 and 1/1.
    [7]
    7. Process according to any of claims 1 to 6, characterized by the fact that an amount of at least one cationic polymer between 0% and 60% is added, the percentage being expressed in w / w, in relation to weight total resin.
    [8]
    8. Process according to any of claims 1 to 7, characterized in that said di or triisocyanate is selected from hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, toluene diisocyanate, a toluene diisocyanate trimethylolpropane adduct , a trimethylolpropane xylylene diisocyanate adduct, a hexamethylene diisocyanate trimer, an isophorone diisocyanate trimer, a hexamethylene diisocyanate trimethylolpropane or a hexamethylene diisocyanate biuret.
    [9]
    9. Process according to any of claims 1 to 7, characterized by the fact that said di or trioxirane compound is selected from among 1,3,5tris (oxiran-2-ylmethyl) -1,3,5-triazinane-2 , 4,6-trione, 4- (oxiran-2-ylmethoxy) -N, N-bis (oxiran-2
    Petition 870190066088, of 7/12/2019, p. 6/7
    [10]
    10. Dispersion of core-coating microcapsule or dry core-coating microcapsule, characterized in that it can be obtained by a process as defined in any of claims 1 to 9.
    [11]
    11. Perfuming composition characterized by the fact that it comprises:
    i) as a perfuming ingredient, at least one microcapsule of the invention, or a suspension containing said microcapsule of the invention, as defined in claim 10;
    ii) at least one ingredient selected from the group consisting of a liquid perfumery vehicle and a perfumery base; and iii) optionally, at least one fragrance adjuvant.
    [12]
    12. Perfumed consumer product, characterized by the fact that it comprises:
    i) as a perfuming ingredient, at least one core-coating microcapsule, as defined in claim 10; and ii) a perfumery base.
    [13]
    13. Perfumed consumer product according to claim 12, characterized by the fact that the perfumery base is a perfume, a fabric care product, a body care product, an air care product or a home care product.
    [14]
    14. Perfumed consumer product, according to claim 13, characterized by the fact that the aforementioned:
    perfume is a fine perfume, a cologne or an aftershave;
    fabric care product is a liquid or solid detergent, a fabric softener, a fabric deodorizer, an iron, a paper or a bleach; body care product is a hair care product, a cosmetic preparation or a skin care product;
    air treatment product is a “ready to use” air purifier or powder air purifier;
    home care product is a handkerchief, dishwasher detergent or hard surface detergent.
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    法律状态:
    2018-12-04| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|
    2019-06-04| B06T| Formal requirements before examination|
    2019-09-03| B09A| Decision: intention to grant|
    2019-09-03| B15K| Others concerning applications: alteration of classification|Free format text: AS CLASSIFICACOES ANTERIORES ERAM: B01J 13/14 , A01N 25/28 , C11D 3/50 Ipc: A61K 8/06 (2006.01), A61K 8/11 (2006.01), A61K 8/4 |
    2019-09-17| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 29/10/2012, OBSERVADAS AS CONDICOES LEGAIS. (CO) 20 (VINTE) ANOS CONTADOS A PARTIR DE 29/10/2012, OBSERVADAS AS CONDICOES LEGAIS |
    优先权:
    申请号 | 申请日 | 专利标题
    EP111886008|2011-11-10|
    EP11188600|2011-11-10|
    EP121563878|2012-02-21|
    EP12156387|2012-02-21|
    PCT/EP2012/071340|WO2013068255A1|2011-11-10|2012-10-29|Stable formaldehyde-free microcapsules|
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