• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    Perfume microcapsules of bilayer structure. The present invention relates to microcapsules formed by an oily core containing at least one perfume, surrounded by a first membrane containing at least one synthetic polymer and whose outer surface is coated with a second membrane. The second membrane comprises at least one non-silicone compound, non-polymeric, insoluble in water, having a melting point comprised between 20 and 120ºC. These microcapsules can be found in aqueous suspension. The invention also relates to the method of manufacturing said microcapsules by in situ polymerization, as well as to their uses, in particular in detergent compositions. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2707754A2
    申请号:ES201830727
    申请日:2018-07-18
    公开日:2019-04-04
    发明作者:Pierre Moreno；Yves Ortais；Thibault Hunault；Antoine Gouteyron；Chloé Charier；Thomas Delmas；Guilhem Billuart
    申请人:Jafer Entpr R&d；GEM INNOV；
    IPC主号:
    专利说明:

    [0001] Bicapa structure perfume microcapsules
    [0002] Object of the invention
    [0003] The present invention relates to microcapsules that contain an interior oily phase containing a perfume, surrounded by a double envelope. It also relates to the method of manufacturing said microcapsules, as well as to their uses, in particular in detergent compositions.
    [0004] BACKGROUND OF THE INVENTION
    [0005] It is known that the microencapsulation of perfumes, constituted in particular by essential oils, makes it possible to protect them, to avoid the loss of volatile aromatic ingredients, to control the release profile of the perfume and to improve its stability (IT Carvalho et al., International Journal of Cosmetic Science, 2015, 1-11). In this way it is possible to formulate these perfumes in different compositions, in particular detergents (WO 2015/104469). EP 2 684 600 and WO 01/73188 therefore describe bilayer microcapsules comprising an oily core containing a perfume, coated with a first layer of natural polymer and then with a hydrophobic layer based in particular on fatty acid esters or magnesium stearate. Most often, however, the encapsulation is performed by the copolymerization of aldehyde-based and polyamine-based compounds. In particular, aminoplast resins obtained by polycondensation of a polyamine (in which they generate melanin, which is a triazine derivative) with an aldehyde (most often formaldehyde) are used (US Pat. No. 5,137,646). WO 2005/018795 therefore describes double-walled microcapsules containing a phase change material (or optionally a perfume) comprising an inner membrane of aminoplast resin and an outer membrane of thermoplastic material.
    [0006] Although these resins are effective for the encapsulation of perfumes and their cost remains advantageous, their use remains controversial, since these resins are a source of free formaldehyde that remains in the continuous aqueous phase at the end of the capsule-forming process. In fact, certain monomers do not react during the polymerization around the oil phase droplets containing the perfume. Alternatively or additionally, formaldehyde can be released in the continuous aqueous phase due to the chemical equilibria that take place in the material. However, formaldehyde is a volatile, irritant compound and considered a major carcinogen for health organisms. For this reason, its concentration in compositions is subject to regulation for numerous applications.
    [0007] Controlling and minimizing the presence of free formaldehyde in the compositions represents a real challenge for the industry. This problem is usually solved by adding to these compositions formaldehyde inhibitors (US Pat. No. 7,807,076; US Pat. No. 4,409,156), such as urea or arginine, but this solution does not always sufficiently preserve the degradation of the membrane and therefore presents, in certain cases, limited effectiveness.
    [0008] In addition, it remains necessary to improve the encapsulation efficiency, the protection of the perfume and the physico-chemical stability of the microcapsules in time and temperature.
    [0009] To solve one or more of the problems mentioned above, different solutions have been proposed, including the use of one or more silicone membranes instead of or in addition to the aminoplast membrane (US Pat. No. 7,799,752; EP 2 618 927; WO 2015/104469). Although these solutions have made it possible to achieve more stable perfume microcapsules, particularly in the presence of detergents, the use of silicones in everyday products is increasingly questioned due, on the one hand, to their bioaccumulation, in particular in aquatic systems and , on the other hand, an indication of endocrine disrupting effect that weighs on certain silicones. Therefore, it would be desirable to provide microcapsules that did not contain silicone compounds.
    [0010] In this context, the inventors have shown that the presence of a second particular hydrophobic membrane, crystallized on the first polymeric resin membrane, could improve the physicochemical stability of the microcapsules with time and temperature and could contribute to better preserve the olfactory intensity of the encapsulated perfume, in particular when used in detergent compositions. In the case where the microcapsules are based on aminoplast resin, the present invention also makes it possible to limit the formaldehyde formation in the course of time.
    [0011] Summary of the invention
    [0012] The invention relates to microcapsules formed by a core constituted by an oil phase containing at least one perfume, said core being covered with a first membrane containing at least one polymer and whose outer surface is covered with a second membrane essentially constituted by less a non-silicone compound, non-polymeric, insoluble in water, having a melting point comprised between 20 and 120 ° C, characterized in that the polymer of the first membrane is chosen from: phenol-formaldehyde resins; optionally etherified aminoplast resins, in particular urea-formaldehyde, melaninformaldehyde, melanin-urea-formaldehyde, glycoluril-formaldehyde, acetoguanamine-formaldehyde or benzoguanamine-formaldehyde, in which the urea may be substituted by an alkyleneurea or a thiourea and / or the formaldehyde may be substituted by glyoxal, as well as its methylated derivatives; polyureas; epoxy resins; polyimides; polyamides; polyurethanes, alkyl poly (meth) acrylates; as well as their mixtures.
    [0013]
    [0014] It also has as an object a suspension of these microcapsules in an aqueous medium.
    [0015]
    [0016] The invention also has as its objective the method of manufacturing these microcapsules or their suspension, which comprises the following successive steps:
    [0017]
    [0018] a) an emulsion of an oil phase containing at least one perfume in an aqueous phase is formed in the presence of at least one surfactant and of at least one monomer or prepolymer,
    [0019] b) said emulsion is heated with stirring in order to polymerize said monomers or prepolymers and to thereby form a first membrane around the oil phase,
    [0020] c) at least one hydrophobic compound in the molten state is introduced with agitation, in said aqueous phase, said hydrophobic compound being a non-silicone, non-polymeric, water-insoluble compound, having a melting point comprised between 20 and 120 ° C ,
    [0021] d) the suspension thus obtained is cooled with agitation, in order to crystallize said hydrophobic compound and thereby form a second membrane on the first membrane,
    [0022] e) optionally, said microcapsules are isolated and dried.
    [0023]
    [0024] It even aims to use these microcapsules as a perfuming additive in a detergent, cosmetic or pharmaceutical composition or in textile materials, preferably cardboard, preferably in a detergent composition.
    [0025] Finally, the present invention has as its object a detergent composition comprising these microcapsules.
    [0026]
    [0027] Detailed description
    [0028]
    [0029] The present invention relates to microcapsules containing at least one perfume. In the context of the present description, "perfume" refers to a single compound or a mixture of volatile and odoriferous compounds. These compounds have a vapor tension higher than atmospheric pressure at room temperature. They are listed in particular in the Merck Index, 8th Edition, Merck & Co., Inc. Rahway, N.J. These compounds can be of synthetic or natural origin. It can be, for example, one or several plant essential oils, chosen for example between Asteraceae, Myrtaceae, Lauraceae, Lamiaceae, Rutaceae and Zingiberaceae, which are usually extracted from any part of these plants by extraction with the aid of a supercritical fluid. , hydrodistillation, extraction by maturation, steam drag or any other method that allows the extraction of perfumed molecules from a plant.
    [0030]
    [0031] Whether they are of synthetic or natural origin, perfumes generally comprise compounds, optionally terpenic, chosen from alcohols, aldehydes and esters.
    [0032]
    [0033] The following perfuming compounds can be used in particular as perfume in the present invention, alone or in combination: methyl 2-methyl butyrate; 2-methyl isopropyl butyrate; Ethyl 2-methyl butyrate; Ethyl 2-methyl pentanoate; ethyl heptanoate; ethyl octanoate; isobutyl hexanoate; amyl butyrate; amyl heptanoate; isoamyl isobutyrate; hexyl acetate; hexyl butyrate; hexyl isobutyrate; hexyl isovalerate; hexyl propionate; Ethyl 2-cyclohexyl propanoate; Ethyl 3,5,5-trimethyl hexanoate; Glyceryl-5-hydroxydecanoate; prenyl acetate; Methyl 2-butenyl acetate; Methyl 3-nonenoate; ethyl decenoate; ethyl octenoate; ethyl decadienoate; ethyl octenoate; Citronellyl acetate; 2-hex-1-enyl isovalerate; 2-hexen-1-yl propionate; 2-hexenen-1-yl valerate; (E) -2-hexeno-3-hexen-1-yl; 3-Hexen-1-yl 2-methylbutyrate; 3-hexen-1-yl acetate; 3-hexen-1-yl benzoate; 3-hexen-1-yl formate; 3-hexen-1-yl tiglato; 2-methyl butyl 2-methyl butyrate; butyl isovalerate; allyl cyclohexane; allyl cyclohexyl propionate; allyl cyclohexyl valerate; benzyl octanoate; gamma-decalactone; gamma-dodecalactone; Jasmine lactone; jasmolactone; nonalactone; 6-acetoxydihydroteaspyran; phenoxyethyl isobutyrate; pivacicleno; dimethyl anthranilate; methyl anthranilate; octanal; nonanal; channel; dodecanal; methyl nonyl acetaldehyde; methyl octyl acetaldehyde; 2,4-hexadienal; intreleveno; decen-1-al; nonen-1-al; aldoxal geraldehyde; citral isociclo; d-limonene; ligustral; tridecenal; triplal; vertoliff; ciclal C; heliotropin; neocaspireno; beta naphthol ethyl ether; beta naphthol methyl ether; hyacinth ether; 2-heptyl cyclopentanone; undecavertol; frutonyl; and its mixtures.
    [0034]
    [0035] In the present invention, the perfume is included in an oil phase that forms the core of the microcapsule. This oily phase can consist exclusively of perfume, that is, one or more perfuming compounds. As an alternative, it may comprise one or more volatile and / or nonvolatile oils, of vegetable and / or synthetic origin, in addition to the perfume. In the context of the present description, by "oil" reference is made to a liquid compound at room temperature (25 ° C) and atmospheric pressure (105 Pa) which, when introduced to ratio of at least 1% by weight in water at 25 ° C, is not completely soluble in water, or is soluble up to a maximum of at least 10% by weight, based on the weight of oil introduced into the water. These oils can be used in particular to increase the hydrophobic character of the oily core when the perfume is not sufficiently, particularly in the case where the perfume comprises, or is constituted by, one or more essential oils. Examples of oils of that type include hydrocarbon oils, in particular fatty acid esters, such as ethyl myristate and methyl stearate. In this way, the perfume can represent from 1 to 100%, preferably from 50 to 100% by weight, for example from 80 to 100% by weight or alternatively from 50 to 80% by weight, with with respect to the total weight of the oil phase.
    [0036] Furthermore, it is preferred that the perfume and the hydrocarbon oil present optionally represent from 70 to 100%, preferably from 80 to 100%, even from 90 to 100%, better, from 95 to 100% , of the weight the oil phase. The latter may optionally contain one or more antioxidant agents, viscosity agents, UV absorbers, density rectifiers, photostabilizers or any other stabilizing compound that must be readily identified by the person skilled in the art in addition to the components mentioned above. To form a microcapsule according to the invention, each gothic of this oil phase is covered by an envelope, said "first membrane", containing at least one synthetic polymer that is capable of polymerizing in aqueous phase, chosen from: the resins of phenol-formaldehyde (or phenolic resins); the optionally etherified aminoplast resins, in particular urea-formaldehyde, melanin-formaldehyde, melanin-urea-formaldehyde, glycoluril-formaldehyde, acetoguanamine-formaldehyde or benzoguanamine-formaldehyde, in which the urea may be substituted by an alkyleneurea or a thiourea and / or formaldehyde may be substituted by glyoxal, as well as its methylated derivatives; polyureas; epoxy resins; polyimides; polyamides; polyurethanes, alkyl poly (meth) acrylates, without this listing being limiting; as well as their mixtures.
    [0037] It is preferred to use an aminoplast resin, preferably a urea-formaldehyde resin or melaninformaldehyde or melanin-urea-formaldehyde, having for example a melanin / formaldehyde ratio of 1: 1.5 to 1: 6, preferably 1. : 3 to 1: 6, or a polyurea.
    [0038] According to a preferred embodiment of the invention, the first membrane further comprises at least one surfactant, such with an amphiphilic polymer. Examples of amphiphilic polymers which are suitable for this use are in particular: the copolymers of acrylic acid and of acrylamide; the copolymers of maleic anhydride and ethylenic monomer, in particular the copolymers of alkyl vinyl ether and maleic anhydride; the homo- and copolymers of styrenesulfonic acid, the homo- and copolymers diacid acrylamido-2-methylpropane sulfonic acid, the cellulose derivatives such as sodium carboxymethyl cellulose; and its mixtures.
    [0039] The microcapsules according to the invention are such that the first membrane mentioned above is coated, on its outer surface, ie on its surface opposite that which is in contact with the oil core, with a second membrane consisting essentially of a particular hydrophobic compound. By "essentially constituted", reference is made to the second membrane containing from 60 to 100% by weight, preferably from 70 to 100% by weight, more preferably from 80 to 100% by weight and , better, from 90 to 100% by weight of hydrophobic compound, with respect to the total weight of the second membrane. This hydrophobic compound is a non-polymeric, water-insoluble silicone compound which has a melting point of between 20 and 120 ° C, preferably of 35 to 95 ° C, more preferably of 48 to 95 ° C and, better, from 55 to 95 ° C.
    [0040] Examples of hydrophobic compounds of that type are:
    [0041] - linear or branched alkanes, for example waxes whose net formula is CnH2n + 2 with n between 20 and 50 such as paraffins of type 6003, 5603, 4110 marketed by Parafluid ™
    [0042] - linear fatty alcohols containing advantageously from 12 to 22, preferably from 18 to 22, carbon atoms, such as stearyl alcohol, behenyl alcohol and mixtures thereof,
    [0043] fatty acids advantageously containing 12 to 22, and preferably 18 to 22, carbon atoms, which may be saturated or unsaturated, linear or branched (such as lauric stearic acids), optionally hydroxylated (such as acid) hydroxystearic), esterified (such as ethyl palmitate and pentaerythritol tetrabehenate), salified and / or oligomerized (in particular the dimer of linoleic acid),
    [0044] - and their mixtures.
    [0045] In the context of the present invention, it is preferred to use the fatty acid salts in particular the salts of stearic acid and ricinoleic acid, preferably magnesium stearate or zinc ricinoleate, more preferably magnesium stearate.
    [0046] The microcapsules according to the invention have, for example, an oil phase / first membrane weight ratio ranging from 3: 1 to 9: 1, preferably from 4: 1 to 8: 1, and a first membrane / weight ratio. second membrane from 4: 1 to 50: 1 and preferably from 5: 1 to 20: 1.
    [0047] Advantageously they are slightly spherical and have, for example, a mean diameter D50 between 1 and 50 | jm, preferably from 1 to 30 jm, more preferably from 1 to 10 jm, as measured by laser diffraction with the aid of a Mastersizer® 3000 Granulometer from Malvern.
    [0048] These microcapsules can be present in particular in the form of an aqueous suspension.
    [0049] Method of preparation of the microcapsules
    [0050] The microcapsules according to the invention can be prepared in particular following a coacervation (or phase separation) method, by interfacial or in situ polymerization or even by atomization or extrusion.
    [0051] In the coacervation method, the oil phase is dispersed a polymer solution, then the polymer is transformed into a coacervate, in such a way that it forms a continuous layer around the droplets of oil phase. In the in situ polymerization method , which is preferred for the manufacture of the microcapsules according to the invention, the polymerization of the monomers or prepolymers is carried out directly on the surface of the oil phase droplets.
    [0052] More particularly, the method used comprises a first step consisting of forming an emulsion of an oil phase containing at least one perfume in an aqueous phase of generally acidic pH, in the presence of at least one surfactant and of at least one monomer or prepolymer. The emulsion can be formed by mixing, generally between 10 and 95 ° C, preferably between 20 and 50 ° C and most preferably between 20 and 35 ° C, of the oil phase with an aqueous phase containing the monomer or prepolymer and the surfactant. Alternatively, the monomer or prepolymer and / or the surfactant can be included in the oil phase. The weight ratio of the aqueous phase to the oil phase can vary from 1: 1 to 5: 1, preferably from 1: 1 to 3: 1 and more preferably from 1: 1 to 2: 1. In the case where the first membrane is formed by a melanin-formaldehyde resin, melanin and formaldehyde monomers or a condensate (methyolmelanin) or polycondensate (prepolymers) of these two monomers are used. However, it is evident that several different monomers and / or prepolymers can be combined, in the case where it is desired that the first membrane of the microcapsules comprises a copolymer, a polymer mixture or an interpenetrated network of polymers. The monomers or prepolymers can represent from 1 to 25% by weight, more preferably from 1 to 15%, and preferably from 3 to 10% by weight, based on the weight of the reaction mixture. The surfactant can be chosen from those described above. It can be used in an amount representing from 0.5 to 10%, preferably from 1 to 5% and more preferably from 1 to 3% by weight, based on the total weight of the reaction mixture. .
    [0053] The emulsification step is carried out with stirring, in particular with the aid of a paddle or propeller stirrer or homogenizer, for example at a speed of 2,000 to 15,000 rpm, preferably 4,000 to 12,000 rpm. more preferably from 5,000 to 10,000 rpm. Agitation is continued throughout the emulsification, which may last from several minutes to several hours, for example from 1 to 75 minutes and preferably from 5 to 30 minutes, better, from 10 to 15 minutes. This step is generally carried out between 10 and 95 ° C, preferably between 20 and 50 ° C and more preferably between 20 and 35 ° C.
    [0054] The pH of the aqueous phase is preferably adjusted in the range from 3 to 7, more preferably from 3.5 to 6.5 and, better, from 4 to 6.5, in particular by the addition of an organic or inorganic acid. such as citric or acetic acid. The adjustment of the pH can be carried out after or before the mixing of the aqueous and oily phases and before or after the introduction of the monomers or prepolymers and / or of the surfactant into the aqueous phase, if appropriate.
    [0055] In the second step of the method according to the invention, the polymerization of the monomer or prepolymer is carried out by heating at a temperature ranging, for example, from 40 to 95 ° C, preferably from 85 to 95 ° C. This step is usually carried out under weaker agitation than the emulsification step, for example at 500 -1,000 turns / min, and for a period of time of one to several hours, for example 2 to 4 hours. In this way a first membrane is formed around each of the droplets of the oil phase.
    [0056] Then, one or more hydrophobic compounds, such as those described above, are introduced into the aqueous phase. The introduction of this compound is carried out with stirring, for a period of time varying, for example, from several minutes to one hour, in particular from 20 to 40 minutes, at a temperature above the melting point of this hydrophobic compound or of the group of the hydrophobic compounds, in the case where they are used in admixture, for example at a temperature of 40 to 100 ° C, preferably of 50 to 100 ° C, more preferably of 60 to 100 ° C even of 90 to 100 ° C C. This hydrophobic compound can represent from 0.1 to 2% by weight, preferably from 0.3 to 1.2% by weight and, better still, from 0.4 to 1% by weight, based on the total weight of the suspension thus formed.
    [0057] The suspension obtained is then cooled by maintaining the stirring, usually up to room temperature, in order to crystallize said compound and thereby form a second membrane on the first membrane. In the course of cooling or immediately afterwards, it is possible to adjust the pH of the aqueous phase with the aid of any suitable base, to a value compatible with the application that is foreseen later.
    [0058] Alternatively or in addition, an additional surfactant may be added to the aqueous phase. In particular, an HLB surfactant greater than 8 is used which allows the suspension of microcapsules to be stabilized. This surfactant may represent from 0.5 to 5% and preferably from 1 to 3% of the total weight of the suspension.
    [0059]
    [0060] In a preferred embodiment of the invention, in the case where an aminoplast resin is used for the preparation of the first membrane, a formaldehyde neutralizing agent can be added to the aqueous phase, either during the manufacture of the microcapsules, or subsequently, in the microcapsule suspension obtained. Examples of formaldehyde neutralizing agents are urea; ethylene urea; imidazolidin-2-one; tetrahydro-2-pyrimidone; melanin; diethanolamine; arginine; ammonia; acetylacetone; the compounds comprising at least one acetoacetate functional group, such as methyl, tert-butyl or ethyl acetoacetate; dimethyl or methyl tert-butyl malonate; sodium sulfite; hydroxylamine hydrochloride; compounds containing from 1 to 16 carbon atoms and comprising at least one, advantageously several, group or functional groups hydrazide, such as adipic acid dihydrazide, isophthalic acid dihydrazide and carbodihydrazide; and its mixtures.
    [0061]
    [0062] The suspension of microcapsules according to the invention therefore advantageously contains in this case one of several formaldehyde neutralizing agents (s) such as those mentioned above, which may represent, for example, from 0.1 to 10% by weight and preferably from 0.4 to 5%, more preferably from 0.4 to 2% by weight, based on the total weight of the suspension, and advantageously decreasing the concentration of dissolved formaldehyde in the aqueous phase.
    [0063]
    [0064] At the end of this method, a suspension of microcapsules is obtained which can be used as such, optionally after concentration. Alternatively, the microcapsules are expected to be collected by centrifugation or filtration, optionally washed with an appropriate solvent, and then dried. Therefore they can be used in dry form.
    [0065]
    [0066] Brief description of the figures
    [0067]
    [0068] Figure 1 schematically illustrates the method of preparing the microcapsules according to the invention.
    [0069] Figure 2 represents the variation of the perfume encapsulation rate in different microcapsules containing varying amounts of magnesium stearate, stored at 70 ° C, as a function of time.
    [0070] Figures 3A and 3B depict the alteration of the odor as a function of time (respectively before and after the rubbing of a perfume encapsulated in the microcapsules according to the invention and comparative microcapsules, impregnated on cardboards which are then kept at 70 ° C, by comparison with a control sample which is a perfume solution preserved at 4 ° C.
    [0071] Figure 4 represents the alteration of the odor of a perfume encapsulated in the microparticles according to the invention and comparative microcapsules, preserved at 70 ° C, then impregnated after washing on towels. Figure 5 represents the olfactory intensity of a perfume encapsulated in the microcapsules according to the invention and comparative microcapsules, after two months of storage in a softening base at room temperature, then internalization after washing on hand washed towels at 30 ° C. ° C.
    [0072] Figure 6 illustrates the olfactory intensity, determined by a panel of experts, of a perfume encapsulated in the microparticles according to the invention and comparative microcapsules, then impregnated on towels machine washed and dried under different conditions.
    [0073] Figure 7 illustrates the evolution of the formaldehyde concentration [F] (final concentration / initial concentration of formaldehyde) as a function of time in microcapsule suspensions according to the invention and comparatives treated with the aid of two different formaldehyde neutralizing agents (urea and tertbutyl acetoacetate).
    [0074]
    [0075] Examples
    [0076]
    [0077] The invention will be better understood in view of the examples that follow, which are provided purely by way of illustration and are not intended to limit the scope of the invention, which is defined by the appended claims.
    [0078]
    [0079] Example 1: Preparation of a suspension of perfumed microcapsules
    [0080]
    [0081] An oil-in-water emulsion was prepared in a mixture, in the order of 60 g of water, 45 g of surfactant (10% solution) constituted by a copolymer of poly (methyl vinyl ether-co-maleic anhydride) marketed by ASHLAND INC. with the trade name Gantrez® at N-1 1 9 BF, 100 g of perfume and 12.5 g of melaninformaldehyde prepolymer provided by SYRIATOS SA under the trade name WF-70®. Mixing was performed with vigorous agitation (7,500 rpm) for 10 minutes at 70-80 ° C. Stirring was decreased to 600 rpm and continued for 3 h at 90 ° C to form the microcapsule wall. Always with stirring, 1.2 g of magnesium stearate in the molten state (at 95-100 ° C) was then added to the suspension. Stirring was continued for 30 min, then the suspension was cooled to room temperature to crystallize the stearate magnesium around the microcapsules. 5 g of a second surfactant (Polysorbate 85 marketed by the company ERCA SpA under the trade name Ercasorb® TOE V / FD) was added to the suspension, which was neutralized with the aid of a solution of triethanolamine.
    [0082] In this way, a suspension of perfume microparticles of bilayer structure was obtained.
    [0083] Example 2: Stability test at 70 ° C
    [0084] Suspensions similar to that described in Example 1, of pH comprised between 5 and 6.5 and containing variable amounts of magnesium stearate, were conditioned in flasks stored at 70 ° C. The test samples obtained are then tested at different time intervals to evaluate the rate of perfume encapsulation.
    [0085] The perfume encapsulation rate corresponds to the percentage of encapsulated perfume mass with respect to the percentage of total perfume mass. It is determined by a thermogravimetric analysis device (Mettler's TGA 2). The method consists of determining the different mass losses after heating the test samples following a temperature gradient of 25 to 500 ° C at a speed of 10 ° C / min and with a volume of N2 = 20 ml / min. The loss of encapsulated perfume occurs from 240 ° C. The residual rate at 240 ° C corresponds therefore to the sum of the encapsulated perfume mass and the mass of the membranes (which is 7 g).
    [0086] The results obtained are illustrated in the attached Figure 2, in which:
    [0087] C7b refers to microcapsules that do not contain a second membrane
    [0088] C8 refers to microcapsules containing 0.1% magnesium stearate
    [0089] C9 refers to microcapsules containing 0.2% magnesium stearate
    [0090] C10 refers to microcapsules containing 0.3% magnesium stearate
    [0091] C11 refers to microcapsules containing 0.4% magnesium stearate
    [0092] C12b refers to microcapsules containing 0.5% magnesium stearate
    [0093] C13 refers to microcapsules containing 1% magnesium stearate
    [0094] C14 refers to microcapsules containing 1.5% magnesium stearate
    [0095] As highlighted from this Figure, the microcapsules that do not comprise the second membrane (C7b) have an initial encapsulation rate of perfume lower than most of the microcapsules according to the invention. In addition, this rate decreases greatly from the first days of storage at 70 ° C and remains clearly lower than that obtained with all the microcapsules according to the invention. It is further observed that the microcapsules containing from 0.4 to 1% by weight, and in particular 0.5% by weight (C7b), of magnesium stearate are the most stable in time. The tests that follow are therefore carried out on these microcapsules.
    [0096] Example 3:. Olfactory alteration test
    [0097] Example 3A: Cardboard test
    [0098] The microcapsule suspension prepared in Example 1 was diluted to 20% in distilled water. Next, 70 mg of this solution was applied on a paperboard (or "cardboard") that was allowed to dry for 30 min. Then the cards were placed in the oven at 70 ° C. Under the same conditions, comparative scented cards were prepared, impregnated with microcapsules devoid of a second membrane but otherwise identical to those previously used.
    [0099] Two expert panelists performed a sensory evaluation. Four test samples were evaluated at the most in the course of each trial, without exceeding 5 tests per day, in order not to saturate the nose of the panelists. The latter evaluated the olfactory intensity of the perfume and its possible alteration by attributing to each test sample a note on a scale of 0 to 10. The perfume is considered altered and its smell is different to that perceived by a control formed by a solution of the same perfume preserved at 4 ° C. The further away from the control perfume note, the more altered the odor is (for example: burning, hot, soap, acid, chlorine, sour, etc.). For each evaluation, the test samples were smeared with concealment, randomly and at least twice to confirm the attributed score.
    [0100] The evaluation was repeated after manual treatment of the cardboards (the cardboard is folded in 2 in its center, the two sides are rubbed together with a constant pressure by an experienced technician).
    [0101] Figures 3A and 3B illustrate the results obtained on the stored test samples from 14 to 28 days. As shown in Figure 3A, the perfume contained in the microcapsules according to the invention, containing 0.5% by weight of magnesium stearate (C12b), is altered less in time than the content in the comparative microcapsules. , devoid of second membrane (C7b). The same happens after the treatment (Figure 3B).
    [0102] Example 3B: Test on towels
    [0103] A solution containing 1% microcapsule suspension according to Example 1, stored at 70 ° C for 30 days, was prepared in a non-scented softener base (commercially available) to be used for machine washing. The towels were placed knotted in the drum of a washing machine. 25 g of this softening base solution was added to the softener compartment of the machine, which was regulated with a "softening" program for a period of approximately 15 min. The towels were then dried for 24 h at room temperature. Comparative perfumed towels, impregnated with microcapsules devoid of second membrane but otherwise identical to those previously used, were washed and dried under the same conditions.
    [0104] The smell alteration of the perfume was evaluated in the same way as before, using as a control sample a towel washed with the same program, with the help of a softening base solution containing 1% perfume in free form, stored at 4 ° C (perfume identical to the encapsulated), and dried as mentioned above.
    [0105] The results of this evaluation are presented in Figure 4. As shown in the Figure, the odor present in the towels treated with the aid of the microparticles according to the invention (C12b) is less altered than that present in the treated towels with the help of comparative microcapsules, which do not comprise the second membrane (C7b).
    [0106] These tests make it possible to conclude that the perfume microparticles according to the invention are more stable at temperature than identical microcapsules but do not contain a second membrane. Example 4: Olfactory properties
    [0107] Example 4A: Hand wash
    [0108] A solution comprising 0.2% suspension according to Example 1 was prepared in a softening base on the market. This solution was stored for 2 months at room temperature, then 5 g of this solution was added to 1 l of tap water at 30 ° C. A small towel was immersed in the solution and stirred for 2 min before leaving it submerged for 15 min. The towel was then drained and then dried for 24 h at room temperature. Comparative towels impregnated with microcapsules devoid of second membrane but otherwise identical to those previously used, were washed and dried under the same conditions.
    [0109] Two expert panelists performed a sensory evaluation. Four test samples were evaluated at the most in the course of each trial, without exceeding 5 tests per day, in order not to saturate the nose of the panelists. The latter evaluated the olfactory intensity of the perfume by attributing to each test sample a note on a scale of 0 to 10. For each evaluation, the test samples were smeared with concealment, randomly and at least twice to confirm the attributed score. .
    [0110] The results of this evaluation are presented in Figure 5. As seen from this Figure, the odor present in the towels treated with the aid of the microparticles according to the invention (C12b) is more intense than that present in the towels treated with the help of comparative microcapsules, which do not comprise the second membrane (C7b), after washing by hand at 30 ° C
    [0111] Example 4B: Machine washing
    [0112] A solution was prepared by diluting a 1% suspension according to Example 1 in a non-perfumed softening base. The towels were placed knotted in the drum of a washing machine. 25 g of this softening base solution was added to the softener compartment of the machine, which was regulated with a "softening" program for a period of approximately 15 min. The towels were then dried well at room temperature for 24 h, either in the dryer for 2 h at 70 ° C or for 1 h at 80 ° C. An additional test sample was prepared using a 2% microcapsule suspension, which was dried for 3 h at 80 ° C. Comparative perfumed towels, impregnated with microcapsules devoid of second membrane but otherwise identical to those previously used, were washed and dried under the same conditions.
    [0113] The pain intensity of the perfume was evaluated in the same manner as mentioned above.
    [0114] The results of this evaluation are presented in Figure 6. As shown in this Figure, the odor present in the towels treated with the aid of the microparticles according to the invention (C12b) is more intense than that present in the towels treated with the aid of comparative microcapsules, which do not comprise the second membrane (C7b), regardless of the drying mode used.
    [0115] These tests make it possible to conclude that the perfume microparticles according to the invention they are more effective, in a laundry treatment plant, than identical microcapsules but do not contain a second membrane.
    [0116] Example 5: Measurement of the free formaldehyde rate
    [0117] The microcapsule suspension of Example 1 was divided into two test samples treated respectively with two different formaldehyde neutralizing agents: urea (U) (1.2% by weight) or tert-butyl acetoacetate (TBAA) (5.3 % in weigh). Two suspension test samples of comparative microcapsules, which contained microcapsules identical to those of Example 1 but devoid of second membrane, were prepared and mixed with the same formaldehyde neutralizing agents in the same proportions.
    [0118] The rate of free formaldehyde in each of the test samples was measured at different time intervals, with the aid of MQuant® analytical test kits provided by MERCK KGa. The results of this test are presented in Figure 7. As shown in this Figure, the microcapsules according to the invention release less formaldehyde than the comparative microcapsules after 15 days of storage at room temperature.
    [0119] Example 6: Detergent compositions
    [0120] Expert in the subject prepared the following compositions in a classical manner, mixing their components, named here by their INCI names, in the proportions indicated.
    [0121] 6A - Softening composition
    [0122]
    [0123]
    [0124]
    [0125] 6B- liquid detergent
    [0126]
    [0127]
    权利要求:
    Claims (9)
    [1]
    Microcapsules formed by a core constituted by an oil phase containing at least one perfume, said core being coated with a first membrane containing at least one polymer and whose outer surface is covered with a second membrane essentially constituted by at least one compound non-silicone, non-polymeric, insoluble in water, having a melting point comprised between 20 and 120 ° C, characterized in that the polymer of the first membrane is chosen from: phenol-formaldehyde resins; optionally etherified aminoplast resins, in particular urea-formaldehyde, melanin-formaldehyde, melanin-urea-formaldehyde, glycoluril-formaldehyde, acetoguanamine-formaldehyde or benzoguanamine-formaldehyde, in which the urea may be substituted by an alkyleneurea or a thiourea and / or the formaldehyde may be substituted by glyoxal, as well as its methylated derivatives; polyureas; epoxy resins; polyimides; polyamides; polyurethanes, alkyl poly (meth) acrylates; as well as their mixtures.
    [2]
    2. Microcapsules according to claim 1, characterized in that the non-silicone compound is selected from linear or branched alkanes, linear fatty alcohols and saturated or unsaturated fatty acids, linear or branched, optionally hydroxylated, esterified, salified and / or oligomerized, and its mixtures.
    [3]
    3. Microcapsules according to claim 1 or 2, characterized in that the fatty acid salt is chosen from the salts of stearic acid and ricinoleic acid, preferably magnesium stearate or zinc ricinoleate, more preferably magnesium stearate.
    [4]
    4. Microcapsules according to any one of claims 1 to 3, characterized in that the polymer of the first membrane is chosen from aminoplast resins, preferably urea-formaldehyde resins or melanin-formaldehyde or melanin-urea-formaldehyde, and polyureas.
    [5]
    5. Suspension of microcapsules, characterized in that it comprises microcapsules according to any one of claims 1 to 4 in an aqueous medium.
    [6]
    6. Suspension of microcapsules according to claim 5, characterized in that it also contains at least one formaldehyde neutralizing agent selected from: urea; ethyleneurea; imidazolidin-2-one; tetrahydro-2-pyrimidone; melanin; diethanolamine; arginine; ammonia; acetylacetone; the compounds comprising at least one acetoacetate functional group, such as methyl, tert-butyl or ethyl acetoacetate; dimethyl or methyl tert-butyl malonate; sodium sulfite; Hydroxylamin hydrochloride; compounds containing from 1 to 16 carbon atoms and comprising at least one, advantageously several, functional group (s) hydrazide, such as adipic acid dihydrazide, isophthalic acid dihydrazide and carbodihydrazide; and its mixtures.
    [7]
    Method for preparing the microcapsules according to any one of claims 1 to 4 or of the suspension according to claims 5 or 6, characterized in that it comprises the following successive steps:
    a) an emulsion of an oil phase containing at least one perfume in an aqueous phase is formed in the presence of at least one surfactant and of at least one monomer or prepolymer,
    b) said emulsion is heated with agitation in order to polymerize said monomers or prepolymers and to thereby form a first membrane around the oil phase,
    c) at least one hydrophobic compound in the molten state is introduced with agitation in said aqueous phase, said hydrophobic compound being a non-silicone compound insoluble in water, having a melting point comprised between 20 and 120 ° C,
    d) the suspension thus obtained is cooled with agitation, in order to crystallize said hydrophobic compound and thereby form a second membrane on the first membrane,
    e) eventually, said microcapsules are isolated and dried.
    [8]
    8. Use of the microcapsules according to any one of claims 1 to 4 or of the suspension according to claim 5 or 6 as perfuming additive in a detergent, cosmetic or pharmaceutical composition or in textile, paper or cardboard, of preference in a detergent composition.
    [9]
    9. Detergent composition comprising microcapsules according to any one of claims 1 to 4 or suspension according to claims 5 or 6.
    类似技术:
    公开号 | 公开日 | 专利标题
    CN105828927B|2018-10-30|Mixing microcapsule
    JP5202831B2|2013-06-05|Core shell type capsule
    JP2019500210A|2019-01-10|Process for producing polyurea microcapsules with improved adhesion
    US10188593B2|2019-01-29|Polysaccharide delivery particle
    WO2017001385A1|2017-01-05|Delivery system with improved deposition
    ES2707754B2|2020-03-16|Bilayer structure perfume microcapsules
    JP6762950B2|2020-09-30|Microcapsules that emit strong vanilla aroma notes
    WO2015091877A1|2015-06-25|Particle-stabilized microcapsules
    BR112016020321B1|2021-03-30|COMPOSITION IN MICROCapsule AND PROCESS FOR ITS FORMATION
    US20180116918A1|2018-05-03|Benefit delivery particle and composition comprising the particle
    JP2020523289A|2020-08-06|Rinse-off conditioner composition containing microcapsules
    WO2018215351A1|2018-11-29|Microcapsule system for polysensory olfactory effects i
    JP2010001417A|2010-01-07|Fragrance-lasting microcapsule
    JP6570628B2|2019-09-04|Method for producing antibacterial microcapsules
    JP2017538815A|2017-12-28|Microcapsules containing photosensitive polymer that generates gas and use thereof
    EP3532025A1|2019-09-04|Personal care compositions comrising surface-modified particles and non-volatile functionalised silicone
    JP2011130986A|2011-07-07|Deodorant composition
    JP4266982B2|2009-05-27|Method for forming a gel containing ingredients therein
    WO2018077570A1|2018-05-03|A personal care composition comprising particles
    BR112014011713B1|2019-03-06|COMPOSITION IN THE FORM OF AN OIL-IN-WATER EMULSION AND COSMETIC PROCESS TO TREAT HUMAN BODY ODOR, PARTICULARLY ODOR IN AXYLES
    JP2019523128A|2019-08-22|Method for producing microcapsules
    BR112016010646B1|2021-12-28|CAPSULE DISPENSING SYSTEM, AND, CONSUMPTION PRODUCT
    同族专利:
    公开号 | 公开日
    ES2707754B2|2020-03-16|
    FR3069252A1|2019-01-25|
    ES2707754R1|2019-04-17|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    WO2001073188A1|2000-03-27|2001-10-04|Givaudan Sa|Disposable cleaning cloth|
    AU2003253526A1|2003-08-26|2005-03-10|Universidade Do Minho|Double walled microcapsules with an outer thermoplastic wall and application process thereof|
    GB0803124D0|2008-02-21|2008-03-26|Unilever Plc|Improvements relating to benefit particles|
    KR20110130416A|2009-03-12|2011-12-05|라이온 가부시키가이샤|Flavor particles and granular detergent composition comprising same|
    EP2684600A1|2012-07-10|2014-01-15|Laboratoires Meiners Sarl|Core-shell capsules and methods for encapsulation of reactive ingredients by diffusional exchange through spherical capsule membranes|
    CN102899168B|2012-10-24|2013-10-16|湖南以翔科技有限公司|Double-layer coated essence microcapsule and preparation method thereof|
    WO2016023145A1|2014-08-11|2016-02-18|The Procter & Gamble Company|Laundry detergent|
    KR20160034015A|2014-09-19|2016-03-29|강원대학교산학협력단|Method for manufacturing crosslinked microcapsule having excellent stability and sustained-release of core substance, and microcapsule manufactured thereby|FR3106980B1|2020-02-10|2022-02-18|Jafer Entpr R&D Sl|Deodorant composition containing 1,8-para-menthenethiol, 3-mercaptohexyl acetate and undecylenic acid or its derivatives|
    法律状态:
    2019-04-04| BA2A| Patent application published|Ref document number: 2707754 Country of ref document: ES Kind code of ref document: A2 Effective date: 20190404 |
    2019-04-17| EC2A| Search report published|Ref document number: 2707754 Country of ref document: ES Kind code of ref document: R1 Effective date: 20190410 |
    2020-03-16| FG2A| Definitive protection|Ref document number: 2707754 Country of ref document: ES Kind code of ref document: B2 Effective date: 20200316 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1756896A|FR3069252A1|2017-07-20|2017-07-20|PERFUME MICROCAPSULES HAVING A BICOLET STRUCTURE|
    [返回顶部]