METHOD TO IMPROVE THE PERFORMANCE OF ENCAPSULATED FRAGRANCES

专利摘要:
method to improve the performance of encapsulated fragrances. The present invention relates to a perfume composition that includes a first perfume microcapsule that encapsulates a first perfume oil having a logt greater than -2.5 and a clogp greater than 2.5 and/or a volatility value. at least 30 µg/l of air; and a second perfume microcapsule that encapsulates a second perfume oil ingredient that has a logt less than -2.5 and a clogp greater than 2.5 and/or a volatility value of at least 30 µg/l of air. the invention also relates to the use of such microcapsule blends as a perfume ingredient or perfume composition for home or personal care products, as well as the resulting home and body care compositions. also, a method of increasing the shelf life of a home or personal care product containing a perfume composition comprising providing the perfume composition as one of the microcapsule blends described herein.
公开号:BR112015003180B1
申请号:R112015003180-3
申请日:2013-08-16
公开日:2021-09-08
发明作者:Stéphanie Budijono；Lahoussine Ouali；Valery Normand；Jean-Yves Billard De Saint Laumer；Suying Zhang
申请人:Firmenich Sa；
IPC主号:

专利说明:

FIELD OF TECHNIQUE
[001] The invention relates to perfume compositions comprising hybrid fragrance microcapsules and home and personal care product compositions containing such microcapsules together with surfactants and other conventional ingredients. BACKGROUND OF THE INVENTION
[002] Perfume additives make laundry compositions more aesthetically pleasing to the consumer, and in some cases, perfume imparts a pleasing fragrance to fabrics treated with it. The amount of perfume transfer from an aqueous wash bath onto fabrics, however, is generally irrelevant. By encapsulating the perfume additives in microcapsules, the delivery efficiency and active life of the perfume additives can be increased.
[003] Microcapsules provide several advantages, such as protecting perfumes against physical or chemical reactions with incompatible ingredients in the laundry composition, and against volatilization or evaporation. Microcapsules can be particularly effective in the delivery and preservation of perfumes in that the perfumes can be distributed and retained within the fabric by a microcapsule which breaks up, and therefore releases the perfume, when the fabric is dry. The disruption of microcapsules can be induced by various factors such as temperature such that the contents are distributed when the capsule degrades. Alternatively, the microcapsules can be compromised by physical forces such as crushing or other methods that compromise the integrity of the microcapsules. Additionally, the microcapsule contents can be distributed by means of diffusion through the capsule wall for a desired period of time.
[004] The aroma associated with washed laundry is important to many consumers. There are many so-called "touch points" that consumers associate with during the laundry experience. Non-limiting examples of these touch points include the experience of freshness associated with opening a laundry care container, opening a washing machine after washing clothes, opening a tumble dryer after drying clothes, and freshness associated with wearing clean clothes. It has been reported that there is a significant portion of consumers who will fold and store their laundry approximately one day after washing. Freshness while folding the laundry approximately one day after washing the laundry also indicates to the consumer that the laundry is clean.
[005] Several compositions have been proposed to provide fragrances at various "contact points" of the washing process. For example, WO 2011/094681 describes fabric softening compositions comprising two different encapsulated perfume compositions to provide an improved laundry experience for consumers. These two different encapsulated perfume compositions contain a specific blend of perfume ingredients that have a boiling point (at standard pressure) greater than 250°C and perfume ingredients that have a boiling point less than 250°C.
[006] Instead of using two different encapsulated perfume compositions, WO 2011/075353 describes a liquid detergent composition comprising a single type of perfume microcapsules containing two different perfume raw materials, with one having a lower boiling point than 250°C and the other having a boiling point greater than 250°C.
[007] It has been revealed that the boiling point of a perfume ingredient, which is often used as an indication of its rate of volatilization, is not correlated to its threshold odor concentration, that is, the lowest concentration of the perfume ingredient. perfume that is perceptible by the human sense of smell. Therefore, the selection of perfume ingredients is based only on physical properties as boiling points do not always provide the desired effect.
[008] Thus, there is a need in the industry for compositions comprising perfume ingredients that have different biological properties such as threshold odor concentrations, which release perfumes at the appropriate level during the desired period and time points during the washing process to provide consumers a pleasant experience. There is also a need to improve perfume release or diffusion in personal care applications. The present invention satisfies these and other industry needs. SUMMARY OF THE INVENTION
[009] An embodiment of the present invention relates to a perfume composition 30 comprising a mixture of microcapsules that include (a) a first perfume microcapsule that encapsulates a first perfume oil oil having a LogT greater than -2 .5 and a cLogP greater than 2.5 and/or a volatility value of at least 30 μg/1 air; and (b) a second perfume microcapsule that encapsulates a second perfume oil that has a LogT less than -2.5 and a cLogP greater than 2.5 and/or a volatility value of at least 30 µg/1 of air . Advantageously, the first or second perfume oil, or both, comprises a single perfume compound or a mixture of perfume compounds wherein preferably at least 80%, more preferably 100% of the perfume compounds individually contain the LogT, cLogP and/or volatility values listed. Also, the compound or compounds in the first or second perfume oil, or both, can have a boiling point of 250°C to 450°C or 100°C to 250°C, as desired depending on the application. Alternatively, the compound or compounds in the first or second perfume oil ingredients, or both, separately have a volatility value of 30 to 5 x 105 it' g/l of air.
[010] Preferably, the first or second or both perfume microcapsules have a shell/core structure in which the encapsulating material forms the shell while the perfume oil forms the core, in which one of the first or second microcapsules (a) has a wall made of a different resin than the other; (b) has a wall that includes a different amount of resin or monomer than another; or (c) contains a different amount of perfume oil ingredient than the other. Alternatively, one microcapsule may have a shell/core structure while the other has a matrix structure to provide different release rates of the perfume oil.
[011] In a more preferred embodiment, the first microcapsule contains 50% by weight or less of the first perfume oil with each compound of the first perfume oil separately having a boiling point of 250°C to 450°C, while the second The microcapsule contains 50% by weight or more of the second perfume oil with each compound of the second perfume oil separately having a boiling point of 100°C to 250°C.
[012] The invention also relates to the use of one of the microcapsule mixtures described herein as an ingredient or perfume composition, for home care or personal care products.
[013] Another embodiment of the invention is a consumer product in the form of a home or personal care product that includes a perfume composition as described herein. Such product may be in the form of a detergent composition, fabric softener, hard surface or general purpose cleaning composition. This can also be in the form of a shampoo, a hair conditioner, a bath mousse, oil or gel, a deodorant, or an antiperspirant.
[014] Yet another embodiment of the invention is a method for increasing the shelf life of a home or personal care product containing a perfume composition comprising providing the perfume composition as one of the microcapsule blends described herein. BRIEF DESCRIPTION OF THE DRAWINGS
[015] Figures 1A and B are graphs showing boiling points (A) and threshold odor concentrations (B) of prior art perfume ingredients.
[016] Figures 2A and B are graphs showing the threshold odor concentrations (A) and the 5 boiling points (B) of the perfume oil ingredients used in the compositions of the invention.
[017] Figures 3A and B are graphs showing that the threshold odor concentration is a crucial parameter for selecting perfume oil ingredients for encapsulation in different types of microcapsules (A) while the boiling point does not correlate with the appropriate options of encapsulation (B). DETAILED DESCRIPTION OF THE INVENTION
[018] The present invention has now determined an improved way to provide different release times and odors of fragrance materials in various products. If all perfume raw materials are encapsulated in the same microcapsules, some materials are released in a very high dosage and this makes the product have a very functional odor and more similar to a raw material. Also, dividing the perfume compounds of an oil into different capsules according to their boiling point was not considered ideal for providing the best distribution and hedonic effect one might expect from a perfume oil. It has now been discovered that it is not enough to simply mix several capsules to obtain satisfactory results. In fact, it is necessary to fulfill an adequate set of parameters that go far beyond the simple optimization of the known prior art. These parameters include the judicious grouping and selection of different oils of perfume and provide the same in different microcapsules. This opens up the perfumery palette of encapsulated fragrances, expanding the scope of encapsulated fragrance creation, allowing the encapsulated fragrance to have a less functional odor and providing the benefit of a more realistic or real fragrance bouquet. Also, the perception of the perfume bouquet is maintained for a longer period of time through the use of the different microcapsules of the present invention.
[019] The blended or hybrid microcapsules of the invention described herein can be used as perfume ingredients in consumer products of the home or personal care type. This result is highly surprising as consumer products contain high amounts (typically more than 10% of their own weight) of specific type of surfactant/solvents and are known to significantly reduce the stability and performance of such capsules. The use of the microcapsules described here provides for the deposition of perfume onto the treated surface along with enhanced stability in a chemically aggressive environment. In other words, the use of in various applications provides unpredictable advantages over the same use of other similar capsules of the prior art.
[020] The present invention also relates to the use of such microcapsules in a consumer product that is in the form of a personal care product. Such products can consist of a solid or liquid product. According to a particular embodiment, liquid products are preferred. The term "home care or personal care" here has the conventional meaning in the art, and in particular includes products such as body care, hair care or home care products. Examples of liquid products according to the invention can be selected from the group consisting of a shampoo or a hair conditioner, a liquid detergent, a fabric softener, a bath mousse, oil or gel, a deodorant or an antiperspirant. Preferably, the liquid perfume product is a shampoo, a liquid detergent, a deodorant or a fabric softener. Examples of solid products according to the invention can be selected from the group consisting of a soap bar, a powder detergent or an air freshener. Detergent products include applications such as detergent compositions or cleaning products for cleaning or washing various surfaces, for example intended for textiles, tableware or hard surfaces (floors, tiles, stone floors, etc.). Preferably, the surface is a textile or hard surface.
[021] Conveniently, the mixture of microcapsules can be used as to flavor consumer products. For example, the blend can be directly added to a consumer product in an amount of 0.1-30% by weight, for example, resulting in a total perfume content of about 0.0333-10% by weight. Preferably, a consumer product according to the invention comprises about 0.01 to 4% by weight, or even 4.5% of its own weight, in capsules as defined above and containing the perfume oil ingredients. Naturally, the above concentration can be adapted according to the olfactory effect desired in each product.
[022] In another embodiment, the mixture of microcapsules can be sprinkled on a dry, powdered product, such as a washing powder or powdered detergent, to give the desired fragrance. In the area of laundry products, for example, it has been recognized that it is desired to provide fragrances at different points of time during the washing process. Combinations of perfume ingredients that have different boiling points have been reported. WO 2011/094681 describes that perfume ingredients having a boiling point greater than 250°C are important for imparting signature characteristics as these are generally substantive in dry fabric while perfume ingredients having a boiling point less than 250°C they tend to separate from water to air and generally provide aroma in the air.
[023] In the present invention, it has surprisingly been revealed that a better perfume effect can be obtained by grouping perfume oil ingredients by considering their threshold odor concentrations, rather than by boiling points. The threshold odor concentration of a chemical compound is determined in part by its shape, polarity, partial charges, and molecular weight. For convenience, the threshold concentration is presented as the common logarithm of the threshold concentration, ie. Log [Threshold] ("LogT"). It has been revealed that perfume oil ingredients that have a LogT value greater than -2.5 need to be present in a greater amount that will be perceived than those that have a LogT value less than -2.5.
[024] As anticipated above, for purposes of clarity, by "perfume oil" is meant a single perfume compound or a mixture of several perfume compounds.
[025] Furthermore, the phrase "perfume oil having a LogT greater than/less than -2.5" means that preferably at least 80% of individual compounds, more preferably each separate perfume compound present in the perfume oil has a LogT greater/less than -2.5.
[026] It is also important to note that by "perfume compound" here is meant a compound, which is used in a perfume preparation or a composition to give a hedonic effect. In other words, such a compound, which will be considered as a perfumer, must be recognized by an expert in the art as capable of conferring or modifying in a positive or pleasant way the odor of a composition, and not just as having an odor.
[027] As shown in Figures 1A and B, in a sample of 200 previously reported perfume compounds that have a boiling point of 250°C or greater (such as about 450°C), and a LogP value greater than 2, 5 (like about 8 - data points marked by gray squares), greater than half of them with a LogT value below -2.5. Similarly, among 200 previously reported perfume compounds that have a boiling point of 250°C or less as 100°C and a LogP value greater than 2.5 (data points marked by black triangles), greater than half of them with a LogT value greater than -2.5. LogP is the common logarithm of the estimated octanol-water partition coefficient, which is known as a measure of lipophilicity. Perfume compounds that have a LogP greater than 2.5 are of particular interest as these can be easily encapsulated.
[028] In contrast, as shown in Figures 2A and B, the perfume compound that has a LogT value greater than -2.5 (data points marked by gray circles) have a similar boiling point distribution pattern as a perfume compound that has a LogT value less than -2.5 (data points marked by black circles). This result further confirms that there is no correlation between the boiling point and the threshold odor concentration of a perfume compound.
[029] In one embodiment, the invention provides a perfume composition comprising a first perfume microcapsule that encapsulates a first perfume oil, which has a LogT greater than -2.5 and a cLogP greater than 2.5 and/or a volatility value of at least 30 µg/l of air; and a second perfume microcapsule that encapsulates a second perfume oil, which has a LogT less than -2.5 and a cLogP greater than 2.5 and/or a volatility value of at least 30 µg/l of air.
[030] The threshold odor concentration of a perfume compound is determined using a gas chromatograph ("GC"). Specifically, the gas chromatograph is calibrated to determine the exact volume of perfume oil ingredient injected by the syringe, the precise separation ratio, and the hydrocarbon response using a hydrocarbon standard of known concentration and chain length distribution. The airflow rate is precisely measured and, assuming the duration of a human inhalation lasts 12 seconds, the sampled volume is calculated. Since the precise concentration in the detector at any point in time is known, the mass per inhaled volume is known and hence the concentration of the perfume compound. To determine the threshold concentration, solutions are delivered to the aspiration port at the back-calculated concentration. A panelist aspirates the GC effluent and identifies the retention time when odor is noticed. The average across all panelists determines the threshold odor concentration of the perfume compound. Odor threshold determination is described in more detail in C. Vuilleumier et al.. Multidimensional Visualization of Physical and Perceptual Data Leading to a Creative Approach in Fragrance Development, Perfume & Flavorist, Vol. -61. Several examples are provided in US Patent 6,458,754 B1. LogP values of many perfume compounds have been reported, for example, in the Pomona92 database, available from Daylight Chemical Information Systems, Inc. (Daylight CIS), Irvine, Calif., which also contains citations from the original literature. LogP values are most conveniently calculated by the "CLOGP" program, also available from Daylight CIS. This program also lists experimental logP values when these are available in the Pomona92 database. The "calculated logP" (cLogP) is determined by the Hansch and Leo fragment approach (cf., A. Leo, in Comprehensive Medicinal Chemistry, Vol. 4, C. Hansch, PG Sammens, JB Taylor and CA Ramsden, Eds. , p. 295, Pergamon Press, 1990). The fragment approach is based on the chemical structure of each perfume oil ingredient, and takes into account the numbers and types of atoms, atom connectivity, and chemical bonding. The cLogP values, which are more reliable and widely used in estimating this physicochemical property, are preferably used instead of the experimental LogP values in selecting perfume compounds that are useful in the present invention.
[031] Non-limiting examples of the perfume compounds comprised in the first perfume oil are as follows:
[032] 2,6,10-Trimethyl-9-undecenal
[033] 2-Propenyl Hexanoate
[034] cis-3-Hexenyl 2-methylbutanoate
[035] decan
[036] Cis-3-Hexenyl-methyl-carbonate
[037] nonal
[038] 9-decen-1-ol
[039] methyl-3-heptanone oxime
[040] (2S,5R)-2-isopropyl-5-methylcyclohexanone
[041] 1,7,7-Trimethylbicyclo[2.2.1]heptan-2-one
[042] for tert-butylcyclohexanone
[043] isobornyl acetate
[044] Cyclohexyl 2-hydroxybenzoate
[045] allyl cyclohexyl propionate
[046] dihydroterpenyl acetate
[047] 2,4,6-trimethyl-4-phenyl-meta-dioxation
[048] 2-heptyl-1-cyclopentanone
[049] (3,4-dihydroxyphenyl) acetate
[050] Trimethyl cyclodecatrin epoxide
[051] 6-ethyl-3,10,10-trimethy-4-oxaspiro[4.5]deca-1,6-diene
[052] 4-tert-butyl-cyclohexyl acetate.
[053] Non-limiting examples of the perfume compounds comprised in the second perfume oil are as follows:
[054] 1-(1-ethoxyethoxy)propane
[055] (2-Methylbutoxy) Allyl acetate
[056] Prop-2-enyl 2-(3-methylbutoxy) acetate
[057] 1-Octen-3-ol
[058] trans-Anethole
[059] 3-(4-tert-Butylphenyl)propanal
[060] 2,6-Nonadien-1-ol
[061] [(3,7-dimethyl-6-octenyl)oxy]“ acetaldehyde
[062] Lauronitrile
[063] 2,4-dimethyl-3-cyclohexene-1-carbaldehyde
[064] 1-(2,6,6-trimethyl-1,3-aclohexadien-1-yl)-2-buten-1-one
[065] 1{2,6,6-trimethi|-2-cidoexen-1-i|lk, (E)-2-buten-1-one
[066] Gamma-Decalactone
[067] trans-4-decenal
[068] 2-Pentyl cyclopentanone
[069] i-(2,6.6 Trimethyl-3-Cycloexen-1-yl)-2-8uten-1-one)
[070] 1'-oxybis-benzene
[071] 1-(5,5-dimethyl-1-cycloexen-1-yl-4-enten-1-one
[072] Ethyl-2-methylbutanoate
[073] 1,3,3-trimethyl-2-oxabicyclo[2.2.2]octane
[074] Eugenol
[075] 3-(3-isopropylphenyl)butanal
[076] methyl 2-octinoate
[077] 4-(2,6,6-trimethyl-1-cyclohexen-1-yl-3-buten-2-one
[078] 2-methoxy-3-(2-methylpropi]kpyrazine
[079] Isobutyl quinoline
[080] Isoeugenol
[081] tetrahydro-6-(3-penteny]-2H-Pyran-2-one.
[082] The determination of volatility values is further described in Vuilleumier et al., Multidimensional Visualization of Physical and Perceptual Data Leading to a Creative Approach in Fragrance Development, Perfume & Flavorist, Vol. 33, September, 2008, pages 54-61. As shown in Figure 3A, perfume oil ingredients that have a log T greater than -2.5 and a volatility value greater than 30 μg/l of air are the highest available (eg, 5x105 g/l of air ) are preferably encapsulated in mechanical release capsules or a more diffusive capsule (eg one with a smaller amount of monomer, or of a different monomer). In contrast, for a perfume oil ingredient that has a LogT less than -2.5 and lower volatilities (black circles), encapsulation is necessary to increase the stability of the raw materials in the base application, or to prevent degradation of raw materials in the base. It is noted that the boiling points of perfume oil ingredients, which are correlated with volatility values, do not provide any information regarding suitable encapsulation options (see Figure 3B).
[083] The perfume oil of the invention may comprise a single compound or a mixture of compounds. When a mixture of compounds is used, at least 80% of the compounds, preferably 90%, more preferably each compound in the mixture separately has a LogT and cLogP or volatility value in the ranges described herein. Preferably, at least 80% by weight of compounds that are encapsulated have the LogT and cLogPs or quoted volatility values described herein, i.e., the first perfume oil that has a LogT greater than -2.5 and a LogP greater than 2.5 and/or a volatility value of at least 30 μg/l of air, and the second perfume oil has a Log T less than -2.5 and a Log P greater than 2.5 and/or a volatility value of at least 30 μg/l of air.
[084] In a preferred embodiment of the invention, the first, second or both perfume microcapsules have a shell/core structure, wherein the encapsulating material forms the shell while the perfume oil ingredients form the core.
[085] For preferred uses of microcapsules in home care application in particular general purpose cleansers, fabric care application in particular fabric softener compositions, body care applications in particular deodorizing compositions, e.g. mixtures of microcapsules are desired. For these embodiments, first perfume microcapsules (that is, those with the most volatile perfume oil ingredient) generally contain a first perfume oil in which less than 50% by weight of its perfume oil compounds or constituents have a boiling point of 250°C or greater, and preferably 40% or less to as low as 1 to 5%. Also, second perfume microcapsules (i.e. those with the lower volatility perfume oil ingredient) generally contain a first perfume oil in which more than 50% by weight of its perfume oil compounds or constituents have a dot. boiling temperature of 250°C or less, and preferably 60% or more to as much as 95 to 100%.
[086] The previous combinations of microcapsules provide a highly desired diffusion of the perfume oil ingredients of the formulation, it is also possible that the first perfume microcapsules contain a smaller amount of compound(s) that have/have a boiling point of 250 °C or higher, such as 24 to 20% or less to as low as 1 to 5% by weight relative to the total oil, depending on the particular perfume oil ingredient that is encapsulated. Also, the second microcapsules of perfume may contain compound(s) which has/have a boiling point of 250°C or less in amounts of 65 to 80% by weight relative to the total oil, again depending on the particular oil that is encapsulated . The person skilled in the art performed this description before he could easily select the most desired compounds or combination of compounds for any particular application by conventional testing.
[087] The relative amounts of the two types of capsules in a particular formulation can range from 1 to 99% by weight of one type and 99 to 1% by weight of the other type. More specifically, the weight ratio of the two different microcapsules is between 5:1 and 1:5 and preferably it is between 3:1 and 1:3. The perfumer can determine the best combinations by conventional testing for any particular product that will be perfumed. For example, in some situations, it may be desired to have a greater aroma by opening the product, while for others, delayed release of the fragrance is desired as it can be transferred to the person's body, a surface that will be cleaned or a fabric that will be washed. And although the amounts of perfume oil by weight in the capsules can be varied as described above for fabric care applications in particular fabric softeners, home care applications in particular general purpose cleanser and body care applications in In particular deodorants, it is also possible to use capsules which contain only the perfume oil (i.e., which contain 100% by weight of the perfume oil ingredient). Furthermore, perfume oil may contain from 0% to 50% of other constituents that are not perfume compounds, such as solvents (eg, diisopropyl glycol or isopropyl myristate), stabilizers such as BHT, etc., or other constituents that are typically included with such oils or constituents. Again, a person skilled in the art can better determine what is needed for any particular application or formulation.
[088] Another way to obtain a desired release of different perfume oil could be to provide the first microcapsules with a thinner capsule wall than for the second microcapsules. When the resin type is the same, using less monomer to prepare the microcapsule resin generally provides thinner wall capsules. A larger amount of the monomer creates a less permeable barrier, while a smaller amount provides a barrier that is more easily penetrated. Yet another way could be to vary the monomer type of the two microcapsules. For example, TAKENATE® aromatic isocyanate monomers provide a less permeable barrier while DESMODUR® aliphatic isocyanate monomers provide a more permeable barrier. Furthermore, perfume oil can be encapsulated in different ways to achieve this difference, such as by solid wall encapsulation (for a greater barrier effect) compared to matrix encapsulation (for a lesser barrier effect). The person skilled in the art can select these different characteristics by conventional testing depending on the specific perfume oil ingredients that will be included in the blends.
[089] Thus, when a higher diffusion rate is provided by the microcapsules that contain the first perfume oil, fragrances are perceived when initially handling the product, that is, opening the bottle or packaging or when handling products that contain a mixture of the microcapsules. Therefore, the less permeable microcapsules prevent the release of the second perfume oil until a later time, such as when the product is used, for example, as a detergent or fabric softener in the washing machine to transfer the perfume oil onto clothes that will be washed, either in a cleaning product when the product is applied to clean a floor, or in a personal care product when it is used by the person.
[090] In an embodiment of the invention, the perfume microcapsules that encapsulate the first and second perfume oil have a shell/core structure, in which the encapsulating material forms the shell while the perfume oil forms the core.
[091] Encapsulation of perfume compositions can be accomplished in a variety of means that are known to those skilled in the art. Preferably, the perfume oil ingredients of the invention are encapsulated in a shell. The microcapsule shell for the respective first and second perfume microcapsules can be the same or different. Suitable perfume oil microcapsules may include those described in patent publication nos. US 2003/0215417; 2003/0216488:2003/0158344; 2003/0165692; 2004/0071742; 2004/0071746; 2004/0072719; 2004/0072720; 2003/0203829; 2003/0195133; 2014/0087477; 2004/00106536; 2008/00305982; and 2009/00247449; and in patent nos. US 7,119,057; 6,645,479; 6,200,949; 5,145,842; 4,917,920; 4,882,220; 4,514,461; 4,234,627; 4,081,384.
[092] In one embodiment, the shell comprises an aminoplast copolymer, such as melamine-formaldehyde or urea-formaldehyde or melamine formaldehyde or cross-linked glyoxal melamine, or polyurea made, for example, but not limited to, isocyanate-based monomers and amine-containing crosslinkers such as guanidine carbonate or guanazole, or polyurethane shells made, for example, but not limited to, polyisocyanate and polyols, polyamide, polyester, etc. Preferred polyurea microcapsules comprise a polyurea wall which is the reaction product of polymerization between at least one polyisocyanate comprising at least two isocyanate functional groups and at least one reagent selected from the group consisting of a soluble guanidine salt in water and guanidine; a colloidal stabilizer; and an encapsulated perfume. The colloidal stabilizer is an aqueous solution between 0.1% and 0.4% of polyvinyl alcohol, between 0.6% and 1% of a cationic vinylpyrrolidone copolymer and a quaternized vinylimidazole (all percentages are defined by weight in relation to to the total weight of the colloidal stabilizer). Methods for making such polyurea microcapsules are described in US patent application 12/993,190 filed June 8, 2009, the contents of which are expressly incorporated herein by reference.
[093] In another embodiment, the microcapsule comprises a wall material that surrounds the perfume oil. The element versed in the art is capable of modifying the release properties of microcapsules in a variety of ways. Wall permeability can be varied by using different types of resins or monomers, different amounts of such materials, or by different wall thicknesses of the same materials. The skilled person who carried out this description before could easily select most microcapsule structures and permeabilities for any particular application by conventional testing.
[094] In one aspect, at least 75%, 85% or even 90% of said microcapsules may have a particle size of about 1 micron to about 100 microns, about 5 microns to 80 microns, of about 5 microns to about 50 microns, or even from about 5 microns to about 40 microns. In another aspect, at least 75%, 85% or even 90% of the microcapsules may have a particle wall thickness of from about 10 nm to about 250 nm, from about 30 nm to about 180 nm, or even from about 40 nm to about 120 nm.
[095] In one aspect, said microcapsule wall material may comprise any suitable resin and especially including melamine, glyoxal, polyurea, polyurethane, polyamide, polyester, etc. Preferred resins include the reaction product of an aldehyde and an amine , suitable aldehydes include formaldehyde. Suitable amines include melamine, urea, benzoguanamine, glycoluril, and mixtures thereof. Suitable melamines include methylol melamine, methylated melamine methylol, imino melamine and mixtures thereof. Suitable ureas include, dimethylol urea, dimethylol methylated urea, urea-resorcinol, and mixtures thereof. Materials suitable for manufacturing can be obtained from one or more of the following companies Solutia Inc. (St. Louis, Missouri USA), Cytec Industries (West Paterson, New Jersey USA), Sigma-Aldrich (St. Louis, Missouri USA) It has been found that it is possible to prepare microcapsules comprising a melamine-formaldehyde aminoplast copolymer or terpolymer containing polyol moieties, and especially aromatic polyol moieties. Therefore, microcapsules are provided which comprise a perfume core, and an aminoplast polymer shell, the shell composition being 75-100% of a thermosetting resin comprising 50-90%, preferably 6085% , of a copolymer and 10-50%, preferably 10-25%, of a polymeric stabilizer; wherein the copolymer comprises: (a) from 20 to 60%, preferably 3050% of portions derived from at least one polyamine, (b) from 3-50%, preferably 5-25% of portions derived from at least one polyamine. minus one aromatic polyol; and (c) from 20-70%, preferably 40-60% moieties selected from the group consisting of alkylene and alkyleneoxy moieties having 1 to 6 methylene units, preferably 1 to 4 methylene units and most preferably, a methylene, dimethyl methylene and methylene dimethyl moiety.
[096] By "portion" is meant a chemical entity, which is part of the polymer and which is derived from a particular molecule. Examples of suitable polyamine moieties include, but are limited to, those derived from urea, melamine, 1 ,5-30 diamino-2,4,6-triazine and glycouryl Examples of suitable aromatic polyol moieties include, but are not limited to, those derived from phenol, 3,5-dihydroxy toluene, Bisphenol A, resorcinol, hydroquinone, xylenol, polyhydroxy naphthalene and polyphenols produced by the degradation of cellulose and humic acids.
[097] The use of the term "derived from" does not necessarily mean that the portion in the copolymer is directly derived from the substance itself, although this may be (and usually is) the case. In fact, one of the most convenient methods of preparing the copolymer involves using alkylated polyamines as starting materials; these combine in a single molecule both the (a) and (c) portions mentioned above. Suitable alkylated polyamines encompass mixtures of mono- or polyalkylated polyamines, which in turn can be partially alkylated with alcohols having from 1 to 6 methylene units. Alkylated polyamines especially suitable for the purposes of the present invention include mono- and polymethylol urea precondensates, such as those commercially available under the trademark URAC® (from Cytec Technology Corp.) and/or mono-precondensates and partially methylated polymethylol-1,3,5-triamino-2,4,6-triazine, such as those commercially available under the trademark CYMEL® (from Cytec Technology Corp.) or LURACOLL® (from BASF), and/or mono- and polyalkylol-benzoguanamine precondensates, and/or mono- and polyalkylol-glycouril precondensates. Such alkylated polyamines can be provided in partially alkylated forms, obtained by the addition of lower alcohols that typically have 1 to 6 methylene units. These partially alkylated forms are known to be less reactive and therefore more stable during storage. Preferred polyalkylol-polyamines are polymethylol-melamines and polymethylol-1-(3,5-dihydroxy-methylbenzyl)-3,5-triamino-2,4,6-triazine.
[098] A polymeric stabilizer can be used to prevent the microcapsules from agglomerating, thereby acting as a protective colloid. This is added to the monomeric mixture prior to polymerization, and this results in partial retention by the polymer. Particular examples of suitable polymeric stabilizers include acrylic copolymers having sulfonate groups, such as those commercially available under the trademark LUPASOL® (from BASF), such as LUPASOL® PA 140 or LUPASOL® VFR; copolymers of acrylamide and acrylic acid, copolymers of alkyl acrylates and N-vinylpyrrolidone, such as those available under the trademark LUVISKOL® (eg LUVISKOL® K 15, K 30 or K 90 from BASF); sodium polycarboxylates (from Polyscience Inc.) or sodium poly(styrene sulfonate) (from Polyscience Inc.); vinyl and methyl vinyl ether-maleic copolymers (eg, AGRIMER® #8482 or VEMA® #8482), and copolymers of ethylene, isobutylene or styrene-maleic anhydride. Thus, the preferred polymeric stabilizers are anionic polyelectrolytes.
[099] Microcapsules of the type described above are manufactured in the form of an aqueous slurry, which typically has 20 to 50% solids content, and more typically 30 to 45% solids content, where the term "content of solids" refers to the total weight of the microcapsules. The slurry may contain formulation aids such as stabilizing hydrocolloids and viscosity control, biocides, and additional formaldehyde scavengers.
[100] Typically, hydrocolloids or emulsifiers are used during the emulsification process of a perfume. Such colloids increase the stability of the slurry against coagulation, sedimentation and creaming. The term "hydrocolloid" refers to a broad class of water-soluble or water-dispersible polymers that are anionic, cationic, zwitterionic, or nonionic in character. Such hydrocolloids or emulsifiers may comprise a moiety selected from the group consisting of carboxy, hydroxyl, thiol, amine, amide and combinations thereof. Hydrocolloids useful for the purposes of the present invention include: polycarbohydrates such as starch, modified starch, dextrin, maltodextrin, and cellulose derivatives, and their quaternized forms; natural gums such as alginate esters, carrageenan, xanthans, agar-agar, pectins, pectic acid, and natural gums such as gum arabic, gum tragacanth and karaya gum, guar gums and quaternized guar gums; gelatin, protein hydrolysates and their quaternized forms; synthetic polymers and copolymers such as poly(vinyl pyrrolidone co-vinyl acetate), poly(vinyl alcohol-co-vinyl acetate), poly((meth)acrylic acid), poly(maleic acid), poly(alkyl(meth)acrylate- co-(meth)acrylic), poly(acrylic co-maleic acid) copolymer, poly(alkylene oxide), poly(vinylmethyl ether), poly(vinyl etherco-maleic anhydride), and the like, as well as poly(ethylene imine ), poly((meth)acrylamide), poly(alkylene-co-dimethylsiloxane), poly(amino dimethylsiloxane), and the like, and quaternized forms thereof. In one aspect, said emulsifier may have a pKa less than 5, preferably greater than 0, but less than 5. Emulsifiers include copolymers of acrylic acid alkyl acrylate, poly(acrylic acid), polyoxyalkylene sorbitan fatty esters, polyalkylene co-carboxy anhydrides, polyalkylene co-maleic anhydrides, poly(methyl vinyl ether-co-maleic anhydride), poly(butadiene co-maleic anhydride), and poly(vinyl acetate-co-maleic) anhydride, polyvinyl alcohols, polyalkylene glycols, polyoxyalkylene glycols and mixtures thereof. More preferably, the hydrocolloid is polyacrylic acid or modified polyacrylic acid. The pKa of colloids is preferably between 4 and 5, and so the capsule has a negative charge when the PMC slurry has a pH above 5.0.
[101] Microcapsules preferably comprise a nominal shell to core mass ratio of less than 15%, preferably less than 10% and more preferably less than 5%. Therefore, microcapsules can have extremely thin and frangible shells. The shell to core ratio is obtained by measuring the effective amount of encapsulated perfume microcapsules that have previously been washed with water and separated by filtration. This is achieved by extracting the wet microcapsule mass by microwave assisted solvent extraction and subsequent gas chromatographic analysis of the extract.
[102] Preferably, the perfume is encapsulated within a resin capsule of any of the types mentioned herein. For an aminoplast capsule, for example, the capsule shell comprises a polymer of urea-formaldehyde or melamine-formaldehyde. More preferably, the microcapsule is further coated or partially coated on a second polymer which comprises a polymer or copolymer of one or more anhydrides (such as maleic anhydride or ethylene/maleic anhydride copolymer).
[103] The microcapsules of the present invention can be positively or negatively charged. It is preferred that the microcapsules of the present invention are negatively charged, however, and have a zeta potential of -0.1 meV to -100 meV when dispersed in deionized water. By "zeta potential" (z) is meant the apparent electrostatic potential generated by any electrically charged objects in solution, as measured by specific measurement techniques. The zeta potential of an object is measured at some distance from the surface of the object and is generally not equal to and less than the electrostatic potential on the surface itself. However, its value provides an adequate measure of the object's ability to establish electrostatic interactions with other objects present in the solution, especially with molecules with multiple binding sites. The zeta potential is a relative measurement and its value depends on the way in which it is measured. In the present case, the zeta potential of the microcapsules is measured by the so-called phase analysis light scattering method, using a Malvern Zetasizer instrument (Malvern Zetasizer 3000; Malvern Instruments Ltd; Worcestershire UK, WR14 1XZ). The zeta potential of a given object can also depend on the amount of ions present in the solution. The zeta potential values specified in this application are measured in deionized water, where only the counterions of the charged microcapsules are present. Most preferably, the microcapsules of the present invention have zeta potential of -10 meV to -80 meV, and most preferably -20 meV to -75 meV.
[104] Processes for making microcapsules are described in the art, such as those described in Patent Nos. US 6,592,990 and 6,544,926. The resulting composition from this manufacturing process is a slurry. The slurry comprises microcapsules, water and precursor materials to produce the microcapsules. The slurry may comprise other minor ingredients such as an activator for the polymerization process and/or a pH buffer. To the slurry, a formaldehyde scavenger can be added.
[105] The perfume composition of the present invention may comprise other ingredients selected from the list of optional ingredients presented below. Except where otherwise specified below, an "effective amount" of a particular wash adjunct is preferably from 0.01%, more preferably from 0.1%, even more preferably from 1% to 20%, most preferably from 1% to 20%. preferably 15%, most preferably 10%, even more preferably 7%, most preferably 5% by weight of the detergent compositions. IONIC SPECIES
[106] The compositions of the present invention preferably comprise an ionic species that has at least 2 anionic sites. It is further believed that the ionic species in some cases is aided by an interaction with cations and ions in the composition.
[107] In one aspect of the invention, the ionic species is selected from the group consisting of carboxylic acids, polycarboxyylate, phosphate, phosphonate, polyphosphate, polyphosphonate, borate and mixtures thereof, which have 2 or more anionic sites.
[108] In one aspect, the ionic species is selected from the group consisting of oxydisuccinic acid, aconitic acid, citric acid, tartaric acid, malic acid, maleic acid, fumaric acid, succinic acid, sepacic acid, citaconic acid, acid adipic, itaconic acid, dodecanoic acid and mixtures thereof.
[109] In a further aspect of the present invention, the composition comprises an ionic species selected from the group consisting of homopolymers of acrylic acid and copolymers of acrylic acid and maleic acid and mixtures thereof.
[110] In a preferred aspect of the present invention, the composition comprises positively charged ions that comprise at least 2 cationic sites. In one aspect of the invention, the positively charged ion is selected from ions of calcium, magnesium, iron, manganese, cobalt, copper, zinc and mixtures thereof.
[111] Ionic species that have at least 2 anionic sites are present in the composition such that they provide an ionic strength greater than 0.045 mol/kg. More preferably, the ionic strength distributed by ionic species having at least 2 anionic sites is from 0.05 to 2 mol/kg, more preferably from 0.07 to 0.5 mol/kg. Ionic resistance is calculated by the equation: Ionic Resistance = vW(CiZi2)
[112] where Ci = concentration of ionic species in finished product (mol/kg), z is the charge of ionic species. FORMALDEHYDE SEQUENTANT
[113] The compositions of the present invention preferably comprise a formaldehyde scavenger. Formaldehyde scavengers are preferably selected from the group consisting of acetoacetamide, ammonium hydroxide, alkali or alkaline earth metal sulfite, bisulfite and mixtures. More preferably, the formaldehyde scavenger is a combination of potassium sulfite and acetoacetamide. The formaldehyde scavenger according to the present invention is present at a total level of from 0.001% to about 3.0%, more preferably from about 0.01% to about 1%. PEARLIZING AGENT
[114] In one embodiment of the present invention, the composition may comprise a pearlizing agent. Preferred inorganic pearling agents include those selected from the group consisting of mica, metal oxide coated mica, silica coated mica, bismuth oxychloride coated mica, bismuth oxychloride, myristyl myristate, glass, oxide coated glass of metal, guanine, gloss (polyester or metallic) and mixtures thereof, BENEFIT AGENTS
[115] The compositions of the present invention may comprise a beneficial agent. As used herein, "benefit agent" refers to any material that can provide benefits to the surface or fabric to which it is applied. As an example, fabric care benefits include fabric softener, color protection, mottle/lint reduction. , anti-abrasion, anti-crease, and the like for garments and fabrics, particularly in cotton and cotton-rich garments and fabrics, when an adequate amount of the material is present in the garment/fabric. Non-limiting examples of such beneficial agents include cationic surfactants, silicones, polyolefin waxes, latex, oily sugar derivatives, cationic polysaccharides, polyurethanes, fatty acids and mixtures thereof. DETERSIVE ENZYMES
[116] Detersive enzymes suitable for optional use herein include protease, amylase, lipase, cellulase, carbohydrase including mannanase and endoglucanase, and mixtures thereof. Enzymes can be used at their art-taught levels, for example, at levels recommended by vendors such as Novo and Genencor. Typical levels in the compositions are from about 0.0001% to about 5%. When enzymes are present, they can be used at very low levels, for example, of about 0.001% or less, in certain embodiments of the invention; or these can be used in heavier wash detergent formulations in accordance with the invention at higher levels, for example about 0.1% and greater. In accordance with a preference of some consumers of "non-biological" detergents, the present invention includes both enzyme-containing and enzyme-free embodiments. DEPOSITION ASSISTANT
[117] As used herein, "deposition aid" refers to any cationic or amphoteric polymer or combination of cationic and amphoteric polymers that significantly increase the deposition of the fabric care benefit agent onto the fabric during laundering or other applications where the perfume oil ingredient will be transferred to a surface or fabric. Preferably, the deposition aid, when present, is a cationic or amphoteric polymer. RHEOLOGY MODIFIER
[118] In a preferred embodiment of the present invention, the composition comprises a rheology modifier. Generally, the rheology modifier will comprise from 0.01% to 1% by weight, preferably from 0.05% to 0.75% by weight, more preferably from 0.1% to 0.5% by weight. weight, of the compositions here. Preferred rheology modifiers include crystalline modifiers, hydroxyl containing rheology modifiers include castor oil and its derivatives, polyacrylate, pectin, alginate, arabinogalactan (gum arabic), carrageenan, gellan gum, xanthan gum, guar gum and mixtures thereof. CONSTRUCTOR
[119] Compositions of the present invention may optionally comprise a builder. Suitable builders include polycarboxylate builders, citrate builders, nitrogen-containing, phosphorus-free aminocarboxylates include ethylene diamine disuccinic acid and salts thereof (ethylene diamine disuccinates, EDDS), ethylene diamine tetraacetic acid and salts thereof (tetraacetates of ethylene diamine, EDTA), and diethylene triamine pentaacetic acid and salts thereof (diethylene triamine penta acetates, DTPA) and water-soluble salts of homo and copolymers of aliphatic carboxylic acids such as maleic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, citraconic acid and methylenemalonic acid.
[120] The perfume composition of the invention is useful in consumer products where releases of perfume at different time points are desired. In a preferred embodiment, the invention provides a laundry and cleaning composition comprising the perfume composition of the invention and a detersive ingredient. Preferably, the laundry and cleaning composition is selected from the group consisting of a detergent composition, a hard surface cleaning composition, and a dishwashing composition. laundry and cleaning, which comprises the step of combining the perfume composition of the invention, by means selected from spraying, dry mixing, and mixtures thereof, with the detersive ingredient.
[121] Most preferably, the laundry and cleaning composition is a laundry detergent or fabric softener composition. Typical examples of detergent or fabric softener composition into which the perfume composition of the invention can be incorporated are described in WO 97/34986 or in Patent Nos. U.S. 4,137,180 and 5,236,615 or EP 799,885. Other typical detergent and softener compositions that can be used are described in works such as Ullman's Encyclopedia of Industrial Chemistry, vol. A8, pages 315-448 (1987) and vol. A25, pages 747-817 (1994); Flick, Advanced Cleaning Product Formulations, Noye Publication, Park Ridge, N.J. (1989); Showell, in Surfactant Science Series, vol. 71: Powdered Detergents, Marcel Dekker, New York (1988); Proceedings of the World Conference on Detergents (4th, 1998, Montreux, Switzerland), AOCS print.
[122] Another advantage of the invention is that microcapsule preparation mixtures as described herein result in beneficial effects on the retention of perfume oil ingredients in the microcapsules over time. Thus, the aging process of microcapsules is reduced such that microcapsules or products containing them can be stored over time for longer periods compared to other microcapsule formulations which are not prepared as noted herein. Thus, the present invention extends the shelf life of home or personal care products that contain such microcapsule mixtures. CAPSULE PERFORMANCE
[123] The performance of the present microcapsules can be determined by olfactory evaluations and measurements (see Example 1), as well as by analytical methods (headspace) (see Examples 2-4),
[124] In the case of olfactory assessments, the measurement process begins with determining the intensity of a perfume oil smelled by the panellists (this is called perceived intensity). This is done in a session where panelists assess the strength of the study ingredient at four different concentrations selected between its volatility value and 10'6 μg/l of air, which corresponds to a low threshold value. The ratings for these four initial concentration steps serve as the basis for selecting the next four concentration levels used in a second experiment, and thus span the supra-threshold concentration domain where intensity visibly changes with concentration. The experimental points are fitted here to a sigmoidal curve using a non-linear regression as follows:

[125] A sigmoidal curve is defined by 3 parameters. These are Imax (the asymptotic value for the perceived intensity), Tetal (the logarithmic gas concentration value corresponding to the inflection point of the curve) and the Curve Parameter. The latter is related to the value of the tangent, Slopel, in the concentration of Tetal by the following equation:

[126] A steep slope may suggest that the fragrance ingredient is more sensitive to the dosage applied to a fragrance, this results in a rapid reduction in intensity if the concentration decreases. washing, rinsing and drying operations for laundry or body care products. Dose-Response curves are useful for predicting a perceived intensity based on a gas phase concentration. EXAMPLES
[127] The following non-limiting examples are illustrative of the present invention. EXAMPLE 1 REFERENCE MICROCAPSULES
[128] Oil composition:
1) 1-(5,5-dimethyl-1-cyclohexen-1-yl)-4-penten-1-one: origin; Firmenich SA 2) dodecahydro-3a,6,6.9a-tetramethyl-naphtho[2,1-b[furan; origin: Firmenich SA 3) 1-(octahydro-2,3,8,8-tetramethyl-1-2-naphthalenyl)-1-ethanone; origin: International Flavors & Fragrances. USA 4) 3-(4-tert-butylphenyl)-2-methylpropanal; origin: Givaudan SA, Vernier, Switzerland 5) Methyl dihydrojasmonate, origin: Firmenich SA 6) pentadecenolide; origin: Firmenich SA 7) 1,2.3.5,6,7-hexacidrθ'1,1,2.3,3-pentamethyl-4-indenone; origin: International Flavors & Fragrances, USA MANUFACTURING OF REFERENCE MICRO CAPSULES
[129] All oil ingredients were encapsulated in the same capsule, regardless of ODT values.
[130] 4.38 g of TAKENATE® D 110N (from Mitsui Chemicals) was dissolved in 40 g of the perfume oil described above. This oil phase was introduced into a 150 ml beaker equipped with an extractor stirrer and an Ika-rotor/stator system (6500-24000 rpm). The oil phase was stirred at 50 rpm with the extractor stirrer for 5 minutes.
[131] An aqueous stabilizer solution at 1% by weight, based on the total weight of the stabilizer solution, was prepared by dissolving polyvinyl alcohol (MOWIOL® 18-88) in 50.8 g of deionized water.
[132] An emulsion was then prepared by homogenizing the perfume phase in the aqueous phase with the Ika-digitaf Ultra-Turax system for 3 minutes at 24000 rpm. The resulting emulsion solution was introduced into a 100 ml reactor at room temperature and agitation was set at 500 rpm.
[133] Then, a solution of 0.90 g of the guanidine carbonate in 2.7 g of deionized water was added to the reactor for one hour at room temperature. The reaction temperature was raised to 50°C over 30 minutes, to 70°C over the next 30 minutes and was maintained at 70°C for the next 2 hours. The reaction was cooled to room temperature for 30 minutes.
[134] In this batch, 12 mmol of isocyanate and 20 mmol of amine were used as the resin to encapsulate 40 g of oil. With this composition, compounds with a high ODT are present in the headspace in a very high amount that it produces a dominant note, and compounds with a low ODT are not present in the headspace in a sufficient amount and thus are not noticeable. CAPSULES ACCORDING TO THE INVENTION FIRST MICRO CAPSULES:
[135] Composition of the first perfume oil (log T > -2.5):
MANUFACTURING OF THE FIRST MICROCAPSULAS
[136] 1.15 g of DESMODUR® N 100 was dissolved in 40 g of the first perfume oil. This oil phase was introduced into a 150 ml beaker equipped with an extractor stirrer and an Ika-rotor/stator system (6500-24000 rpm). The oil phase was stirred at 50 rpm with the extractor stirrer for 5 minutes.
[137] An aqueous stabilizer solution at 1% by weight, based on the total weight of the stabilizer solution, was prepared by dissolving polyvinyl alcohol (MOWIOL® 18-88) in 50.8 g of deionized water.
[138] An emulsion was then prepared by homogenizing the perfume phase in the aqueous phase with the Ika-digital Ultra-Turax system for 3 minutes at 24000 rpm. The resulting emulsion solution was introduced into a 100 ml reactor at room temperature and agitation was set at 500 rpm.
[139] Then, a solution of 0.45 g of the guanidine carbonate in 2.7 g of deionized water was added to the reactor for one hour at room temperature. The reaction temperature was raised to 50°C over 30 minutes, to 70°C over the next 30 minutes and was maintained at 70°C for the next 2 hours. The reaction was cooled to room temperature for 30 minutes. The capsule was made with 6 mmol (1.15 g) of isocyanate and 10 mmol (0.45 g) of amine to encapsulate 40 g of oil. Therefore, the resin to oil weight ratio is 1:25.Second Microcapsules: Composition of the second perfume oil (log T < -2.5)
MANUFACTURING OF SECOND MICROCAPSULAS
[140] 2.29 g of DESMODUR® N 100 were dissolved in 40 g of the second perfume oil. This oil phase was introduced into a 150 ml beaker equipped with an extractor stirrer and an Ika-rotor/stator system (6500-24000 rpm). The oil phase was stirred at 50 rpm with the extractor stirrer for 5 minutes.
[141] An aqueous stabilizer solution at 1% by weight, based on the total weight of the stabilizer solution, was prepared by dissolving polyvinyl alcohol in 50.8 g of deionized water.
[142] An emulsion was then prepared by homogenizing the perfume phase into the aqueous phase with the Ika-digital Ultra-Turax system for 3 minutes at 24000 rpm. The resulting emulsion solution was introduced into a 100 ml reactor at room temperature and agitation was set at 500 rpm.
[143] Then, 0.9 g of the guanidine carbonate in 5.4 g of deionized water was added to the reactor over one hour at room temperature. The reaction temperature was raised to δC’C over 30 minutes, to 70°C over the next 30 minutes and was maintained at 70°C for the next 2 hours. The reaction was cooled to room temperature for 30 minutes.
[144] The perfume content in the capsule suspension is about 40%, relative to the total weight of the suspension. The capsule was made with 12 mmol (2.29 g) of isocyanate and 20 mmol (0.90 g) of amine to encapsulate 40 g of oil. Therefore, the resin to oil ratio is 1:12.5. FREE PERFUME OIL:
[145] Composition of the third perfume oil

[146] An emulsion of the third perfume oil was prepared by homogenizing the oil in a polyvinyl alcohol solution with the Ika-digital Ultra-Turax system for 3 minutes at 24000 rpm. MIXING OF CAPSULES ACCORDING TO THE INVENTION AND FREE PERFUME OIL
[147] Batches containing the first and second capsules and the third perfume oil were mixed in a ratio of 3.5:2.2:4.3, which in the end gives in total the same perfume composition as the perfume capsule. reference. RESULTS
[148] Headspace samples from deposited capsules were collected at the 24-hour time point and concentrations were analyzed using GC-MS. GC column temperature setting is: 2 min isothermal period at 80°C, then temperature program 3°C/min at 180°C, followed by a 10°C/min rise to 250°C. The perceived intensity values were computed/correlated from the measured headspace concentrations using the equation described above.
[149] Table 1 shows an increase in all perceived intensity values of Perfumery Raw Materials (PRMs) before and after the perfumery raw materials are pooled.
[150] The Perceived Intensity (PI) is on a scale of 0 to 6. The invention accommodates a new parameter to modulate the amounts of PRMs that will be sniffed in the headspace. TABLE 1: PERCEIVED INTENSITY VALUES

[151] A panel of people (trained and untrained) describes the total olfactory effect provided by the composition of the invention as being more balanced, natural and a rounder signature while the reference capsules provided a very unbalanced or unstructured effect where it was possible to detect specific raw materials instead of a harmonious fragrance. This is because some raw materials, which do not penetrate sufficiently if these are encapsulated in a traditional method, are now present in the headspace in an amount that makes them noticeable.
[152] As shown in the examples, the perfume oil of the microcapsules of the present invention can be designed with any number of different perfume compounds with one to about 50 different compounds being typical. Of course, larger amounts, even 100 different compounds, can be used based on the perfumer's preference and the total olfactory character that will be achieved. Generally, some (ie, 2 to 10) to an upper limit of about 25 different compounds are present in the microcapsules. EXAMPLE 2 REFERENCE MICROCAPSULES MANUFACTURING OF REFERENCE MICRO CAPSULES:
[153] A perfume oil (40 g) (see composition below) was mixed well with polyisocyanate monomers (Takenate' D 110N (2.19 g, 6 mmol NCO) and Desmodur® N100 (1.15 g, mmol of NCO)). Polyvinyl alcohol (PVOH Mowiol 18-88) (0.5445 g) was dissolved in deionized water (50.86 g) at 70°C and once dissolved, the PVOH solution was cooled to room temperature. The oil blend was then slowly added to the PVOH solution as the oil-in-water (0/W) emulsion was formed at room temperature using the homogenizer (Ultra Turrax, IKA T25 digital) set at 24000 rpm for 3 minutes. The 0/W emulsion was then transferred to a 100 ml jacketed reactor and the stirrer (Eurostar power control-vise, IKA-WERKE) was set at 500 rpm. Guanazol (1.0 g, 10 mmol) was dissolved in deionized water (5.38 g). The guanidine carbonate solution was added to the reactor distributed using a pump (Pump 11 Elite, Harvard Apparatus) set at a flow rate of 0.100 ml/min. at room temperature, and this process should take about 60 minutes. Once the addition was complete, the reaction temperature was increased from room temperature to 50°C for the first 30 minutes, and then to 70°C for the next 30 minutes. The reaction temperature was then maintained at 70°C for a further 2 hours. A Julabo heating immersion circulator (MA model, by Julabo Labortechnik GmbH, Seelbach, Germany) was used to maintain the reaction temperature. Then, the reaction was cooled to room temperature. PERFUME OIL:
MICROCAPSULES ACCORDING TO THE INVENTION FIRST MICRO CAPSULES: MANUFACTURING OF THE FIRST MICROCAPSULAS;
[154] Same as the reference preparation described above, except that only the polyisocyanate monomer used was Desmodur® N100 (2.30 g, 12 mmol NCO) and Takenate® D 110N was not used.PERFUME OIL IN FIRST MICROCAPSLES
SECOND MICRO CAPSULES MANUFACTURING OF SECOND MICROCAPSULAS:
[155] Same as the reference preparation described above, except that only the polyisocyanate monomer used was Desmodur® N100 (1.15 g, 6 mmol NCO) and Takenate® D 110N was not used.PERFUME OIL IN THE SECOND MICROCAPSLES

[156] The first and second microcapsules were added in a 3:2 weight ratio respectively, and this was used as the stock microcapsule slurry according to the invention.2.1 RESULTS IN GENERAL PURPOSE CLEANER APPLICATION (APC) BASE OF APC:
1) C9-11 Pareth-8 2) Sodium dodecylbenzenesulfonate
[157] An amount of 10% diluted APC was prepared as follows: 0.1 g of reference or mixed capsules was mixed well with 9.9 g of APC base (unthickened, CEN 07002, lot 1, LABO , APC standard neutral base) in a 200 ml glass bottle and this was charged to 100 ml with cold tap water. A 1 g aliquot of the above diluted 10% APC was applied to a ceramic tile of size 10.8 cm x 10.8 cm. The tile was allowed to dry at room temperature for a few minutes in the hood and was subjected to analysis. This corresponds to fresh samples. In another case, capsules in the undiluted APC base were allowed to age for one month and applied to the tile using the above method. This corresponds to aged samples. HEADSPACE AFTER 16 HOURS OF BALANCE
[158] Headspace collection of tiles with APC was performed as follows: A dry tile with capsules was placed in a 3 I reactor and all outlets were closed for overnight equilibration at room temperature. After the headspace reached equilibrium, a Tenax tube was connected to a pump (speed calibrated at 130 mLmin ± 5%) to absorb the headspace. A coal tube was placed over the other opening for filtered air to enter it when the HS is pumped out of the reactor. Each reactor was pumped for 30 min. (total volume 130 mL/min x 30 min = 3900 mL) for each sample.TABLE 2: ANALYTICAL RESULTS OF HEADSPACE IN GENERAL PURPOSE CLEANER APPLICATION

[159] The headspace intensity of all perfumery raw materials in the capsules according to the invention has increased significantly. This shows that grouping the raw materials allows you to adapt the intensity of the perfume compound and increase the intensity of perfume ingredients especially those with high volatility and high odor threshold.2.2 RESULTS IN A DEODORANT APPLICATION DEODORANT BASE:

[160] An amount of 1% deodorant with capsules was prepared as follows: 0.1 g of reference or mixed capsules was mixed well with 9.9 g of deodorant base (see example 2) in a bottle of 20 ml glass. An amount of 0.5 g of deodorant with 1% capsules was applied to a piece of blotting paper measuring 5cm x 5cm in area. The blotter was rolled into the sample cell and its headspace was collected for 30 min. at t = 0 and t = 6 hours.
[161] The blotter was rolled up and placed in the GC cell tube. The tube was 1 cm above the bottom of the cell. A 39 wt% sodium bromide solution was used to control the N2 flow moisture, resulting in a water activity of 0.738 at 22.4°C. The N2 flow rate was 40 mL/min and the water bath temperature was adjusted to 32°C. After 0 and 6 hours, a preconditioned Tenax cartridge was inserted into the tube, where the cartridge was 4 cm above the tube. cell. HS was captured for 30 min. Then the HS samples were thermally desorbed (Perkin Elmer Turbo Matrix 650) and analyzed by GC-MS (Agilent Z5975C).
[162] GC-MS method: scan at 80 °C for 2 min, 3 °C/min at 180 °C, then 10 °C/min at 250 °C, MSD (El, 70 eV) was operated in monitoring mode selected for quantitative measurements. The GC was equipped with an Agilent DB-Ims capillary column (30 µm film, 0.25 mm i d 0.25 µm). The desorption parameters were: valve temperature 240°C, desorption temperature 240°C, transfer line 250°C, trap (-30°C to 250°C at 40°C/sec), purge time 1.0 min , desorption time 5 min, trap retention time 5 min., trap desorption flow time 0 min, cycle time 13 min, output split (5.2% injected), column flow 1.1 mL /min, desorption flow 50 ml/min
[163] For aged samples, deodorant-based capsules were allowed to age for one month, applied to blotter, and analyzed in the same manner as described above.TABLE 3: ANALYTICAL RESULTS OF HEADSPACE IN DEODORANT APPLICATION

[164] The headspace intensity of all perfumery raw materials in the capsules according to the invention has significantly increased compared to the reference. This shows that grouping raw materials allows you to adapt the intensity of the perfume compound and increase the intensity of perfume ingredients especially those with high volatility and high odor threshold. Furthermore, the results also show increased intensity in the sixth hour, which signifies the long-lasting property of the invention. This result shows that the invention is applicable to body and home care applications, EXAMPLE 3 REFERENCE MICROCAPSULES MANUFACTURING OF REFERENCE MICRO CAPSULES
[165] A perfume oil (40 g) (see composition below) was mixed well with polyisocyanate monomers (Takenate0 D 110N (2.19 g, 6 mmol NCO) and Desmoduπ® N100 (1.15 g, mmol) of NCO)). Polyvinyl alcohol (PVOH Mowiol 1888) (0.5445 g) was dissolved in deionized water (50.86 g) at 70°C and once dissolved, the PVOH solution was cooled to room temperature. The oil mixture was slowly added to the PVOH solution as the oil-in-water (0/W) emulsion was formed at room temperature using the homogenizer (Ultra Turrax, IKA T25 digital) set at 24000 rpm for 3 minutes. The 0/W emulsion was then transferred to a 100 ml jacketed reactor and the stirrer (Eurostar power controlvise, IKA-WERKE) was set at 500 rpm. Guanazol (1.0 g, 10 mmol) was dissolved in deionized water (5.38 g). The guanidine carbonate solution was added to the reactor distributed using a pump (Pump 11 Elite, Harvard Apparatus) set at a flow rate of 0.100 ml/min. at room temperature, and this process should take about 60 minutes. Once the addition was complete, the reaction temperature was increased from room temperature to 50°C for the first 30 minutes, and then to 70°C for the next 30 minutes. The reaction temperature was then maintained at 70°C for a further 2 hours. A Julabo heating immersion circulator (model MA, by Julabo Labortechnik GmbH, Seelbach, Germany) was used to maintain the reaction temperature. Then, the reaction was cooled to room temperature.PERFUME OIL:
MICROCAPSULES ACCORDING TO THE INVENTION FIRST MICRO CAPSULES PRODUCTION OF FIRST MICROCAPSULAS:
[166] Same as the reference preparation described above, except that only the polyisocyanate monomer used was Desmodur® N100 (2.30 g, 12 mmol NCO) and Takenate® D 110N was not used. PERFUME OIL IN FIRST MICROCAPSLES
SECOND MICRO CAPSULES MANUFACTURING OF SECOND MICROCAPSULAS:
[167] Same as the reference preparation described above, except that only the polyisocyanate monomer used was Desmodur® N100 (2.30 g, 12 mmol NCO) and Takenate® D 110N was not used.PERFUME OIL IN THE SECOND MICROCAPSLES

[168] The first and second microcapsules were added in a 3:2 weight ratio respectively, and this is used as the stock microcapsule slurry according to the invention. RESULTS IN DEODORANT APPLICATION
[169] An amount of 1% deodorant with capsules was prepared as follows: 0.1 g of reference or mixed capsules was mixed well with 9.9 g of deodorant base (see example 2) in a bottle of 20 ml glass. An amount of 0.5 g of deodorant with 1% capsules was applied to a piece of blotting paper measuring 5cm x 5cm in area. The blotter was rolled into the sample cell and its headspace was collected for 30 min. at t = 0 and t = 6 hours.
[170] The blotter was rolled up and placed in the GC cell tube. The tube was 1 cm above the bottom of the cell. A 39 wt% sodium bromide solution was used to control the N2 flow moisture, resulting in a water activity of 0.738 at 22.4°C. The N2 flow rate was 40 mL/min and the water bath temperature was adjusted to 32°C. After 0 and 6 hours, a preconditioned Tenax cartridge was inserted into the tube, where the cartridge was 4 cm above the tube. cell. HS was captured for 30 min. Then the HS samples were thermally desorbed (Perkin Elmer Turbo Matrix 650) and analyzed by GC-MS (Agilent /5975C).
[171] GC-MS method: scan at 80 °C for 2 min, 3 °C/min at 180 °C, then 10 °C/min at 250 °C. The MSD (El, 70 eV) was operated in the ion monitoring mode selected for quantitative measurements. The GC was equipped with an Agilent DB-Ims capillary column (30 µm film, 0.25 mm id 0.25 µm). The desorption parameters were: valve temperature 240°C, desorption temperature 240°C, transfer line 250°C, trap (-30°C to 250°C at 40°C/sec), purge time 1, 0 min, desorption time 5 min, trap retention time 5 min., trap desorption flow time 0 min, cycle time 13 min, output split (5.2% injected), column flow 1, 1 mL/min, 50 ml/min desorption flow TABLE 4: ANALYTICAL RESULTS OF HEADSPACE IN DEODORANT APPLICATION

[172] The headspace intensity of all perfumery raw materials in the capsules according to the invention has significantly increased compared to the reference. This shows that grouping raw materials allows you to adapt the intensity of the perfume compound and increase the intensity of perfume ingredients especially those with high volatility and high odor threshold. Furthermore, the results also show increased intensity in the sixth hour, which signifies the long-lasting property of the invention. This example also shows that the invention is applicable to different perfume oils. EXAMPLE 4 REFERENCE MICROCAPSULES MANUFACTURING OF REFERENCE MICRO CAPSULES:
[173] In a round-bottomed flask, oxalaldehyde (4.22 g, 40% by weight in water), 2.2 dimethoxyacetaldehyde (3.36 g, 60% by weight in water), 2-oxoacetic acid (1 .44 g, 50% by weight in water), and 1,3,5-triazine-2,4,6-triamine (2.22 g) were dispersed in water (3.80 g). The pH was adjusted to 9.30 with sodium hydroxide (2.23 g, 30% by weight in water) and the reaction mixture was heated at 45°C for 25 minutes to obtain a solution (pH - 8.75) . Finally, water (16.40 g) was added to the solution which was stirred for 5 minutes.
[174] The oligomer solution was introduced into a 200 ml reactor in the presence of 2,4-diamino-1,3,5-triazole (1.96 g) and an Ambergum 1221 solution (66.38 g, 2 % by weight in water, origin: Ashland). A solution of perfume oil (42.00 g) and Takenate® D-110N (5.28 g) was added and emulsified with Ultra-turrax at 21500 rpm for 2 min. (pH = 7.90). The pH was adjusted to 5.30 with formic acid (0.42 g, 30% by weight in water). The reaction mixture was heated at 45°C for 1 h, at 60°C for 1 h, at 80°C for 3 h and finally cooled to room temperature (pH = 5.70). PERFUME OIL
MICROCAPSULES ACCORDING TO THE INVENTION FIRST MICRO CAPSULES PRODUCTION OF FIRST MICROCAPSULAS:
[175] Same as the reference preparation described above, except that 2.64 g of Takenate® D-110N was used.PERFUME OIL IN FIRST MICROCAPSLES
SECOND MICRO CAPSULES MANUFACTURING OF SECOND MICROCAPSULAS:
[176] Same as the reference preparation described above, except that 1.32 g of Takenate® D-110N was used.PERFUME OIL IN THE SECOND MICROCAPSLES

[177] The first and second microcapsules were added in a 3:2 weight ratio respectively, and this is used as the stock microcapsule slurry according to the invention. RESULTS IN DEODORANT APPLICATION:
[178] An amount of 1% deodorant with capsules was prepared as follows: 0.1 g of reference or mixed capsules was mixed well with 9.9 g of deodorant base (see example 2) in a bottle of 20 ml glass. An amount of 0.5 g of deodorant with 1% capsules was applied to a piece of blotting paper measuring 5cm x 5cm in area. The blotter was rolled into the sample cell and its headspace was collected for 30 min. at t = 0 and t = 6 hours.
[179] The blotter was rolled up and placed in the GC cell tube. The tube was 1 cm above the bottom of the cell. A 39 wt% sodium bromide solution was used to control the N2 flow moisture, resulting in a water activity of 0.738 at 22.4°C. The N2 flow rate was 40 mL/min and the water bath temperature was adjusted to 32°C. After 0 and 6 hours, a preconditioned Tenax cartridge was inserted into the tube, where the cartridge was 4 cm above the tube. cell. HS was captured for 30 min. Then the HS samples were thermally desorbed (Perkin Elmer Turbo Matrix 650) and analyzed by GC-MS (Agilent /5975C).
[180] GC-MS method: scan at 80 °C for 2 min, 3 °C/min at 180 °C, then 10"C/min at 250 °C. The MSD (El, 70 eV) was operated in mode ion monitoring device selected for quantitative measurements. The GC was equipped with an Agilent DB-Ims capillary column (30 m film, 0.25 mm id 0.25 μm). The desorption parameters were: valve temperature 240°C, desorption temperature 240°C, transfer line 250°C, trap (-30°C to 250°C at 40°C/sec), purge time 1.0 min, desorption time 5 min, retention time of trap 5 min., trap desorption flow time 0 min, cycle time 13 min, output split (5.2% injected), column flow 1.1 mL/min, desorption flow 50 ml/minTABLE 5 : HEADSPACE ANALYTICAL RESULTS

[181] The headspace intensity of all perfumery raw materials in the capsules according to the invention significantly increases compared to the reference. This shows that grouping raw materials allows you to adapt the intensity of the perfume compound and increase the intensity of perfume ingredients especially those with high volatility and high odor threshold. Furthermore, the results also show increased intensity in the sixth hour, which signifies the long-lasting property of the invention. This example also shows that the invention is applicable to different types of capsules.

权利要求:
Claims (15)
[0001]
1. Perfume composition comprising a mixture of microcapsules characterized in that it includes: (a) a first perfume microcapsule which encapsulates a first perfume oil having a LogT greater than -2.5 and a cLogP greater than 2, 5 and a volatility value of at least 30 µg/l of air; and (b) a second perfume microcapsule that encapsulates a second perfume oil that has a LogT less than -2.5 and a cLogP greater than 2.5 and a volatility value of at least 30 µg/l of air.
[0002]
2. Perfume composition according to claim 1, characterized in that each of the first or second perfume oils, or both, comprises a mixture of perfume compounds in which at least 80% of the perfume compounds contain the quoted logT and cLogP and volatility values.
[0003]
3. Perfume composition according to claim 1, characterized in that each of the first or second perfume oils, or both, comprises a single perfume compound or a mixture of perfume compounds in which each compound has o LogT and cLogP or quoted volatility values.
[0004]
4. Perfume composition according to claim 3, characterized in that the perfume compound or perfume compounds in the first or second perfume oils, or both, each separately have a boiling point of 250°C to 450°C.
[0005]
5. Perfume composition according to claim 3, characterized in that the perfume compound or perfume compounds in the first or second perfume oils, or both, separately have a boiling point of 100°C to 250° Ç.
[0006]
6. Perfume composition according to claim 3, characterized in that the perfume compound or perfume compounds in the first or second perfume oils, or both, separately have a volatility value of 30 to 5x 105 it' g/l of air.
[0007]
7. Perfume composition according to claim 1, characterized in that the first or second perfume microcapsule(s) or both have a shell/core structure in which the encapsulating material forms the shell while the oil of perfume forms the core, one of the first or second microcapsules (a) having a wall made of a different resin than the other; (b) has a wall that includes a different amount of resin or monomer than the other; or (c) contains a different amount of perfume oil than another; or wherein one of the first and second perfume microcapsules has a core/shell structure and the other has a matrix structure.
[0008]
8. A perfume composition according to claim 1, characterized in that the first microcapsule contains 50% by weight or less of the first perfume oil with each perfume compound of the first perfume oil separately having a boiling point of 250°C to 450°C, while the second microcapsule contains 50% by weight or more of the second perfume oil with each perfume compound of the second perfume oil separately having a boiling point of 100°C to 250°C.
[0009]
9. Use of a mixture of microcapsules as a perfume ingredient or composition defined in claim 1, for home and personal care products, characterized in that the mixture includes: (a) a first perfume microcapsule that encapsulates a first perfume oil that has a LogT greater than -2.5 and a cLogP greater than 2.5 and a volatility value of at least 30 μg/l of air; and (b) a second perfume microcapsule that encapsulates a second perfume oil that has a LogT less than -2.5 and a cLogP greater than 2.5 and a volatility value of at least 30 µg/l of air.
[0010]
10. Consumer product in the form of a home or personal care product, characterized in that it includes the perfume composition of one of claims 1 to 8.
[0011]
A consumer product according to claim 10, characterized in that it is in the form of a detergent composition, a fabric softener, a hard surface cleaning composition, or a dishwashing composition.
[0012]
12. Consumer product according to claim 10, characterized in that it is in the form of a shampoo, a hair conditioner, a bath mousse, oil or gel, a deodorant, or an antiperspirant.
[0013]
13. A method of increasing the shelf life of a home or personal care product containing a perfume composition, characterized in that it comprises providing the perfume composition as a mixture of microcapsules including: (a) a first microcapsule of perfume that encapsulates a first perfume oil ingredient that has a LogT greater than -2.5 and a cLogP greater than 2.5 and a volatility value of at least 30 μg/l of air; and (b) a second perfume microcapsule that encapsulates a second perfume oil ingredient that has a LogT less than -2.5 and a cLogP greater than 2.5 and a volatility value of at least 30 μg/l of air .
[0014]
14. The method of claim 13, wherein the consumer product is in the form of a detergent composition, a fabric softener, a hard surface cleaning composition, or a dishwashing composition.
[0015]
15. Method according to claim 13, characterized in that the consumer product is in the form of a shampoo, a hair conditioner, a bath mousse, oil or gel, a deodorant, or an antiperspirant.

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法律状态:
2018-03-06| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2018-03-13| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2018-03-20| B06I| Publication of requirement cancelled [chapter 6.9 patent gazette]|Free format text: ANULADA A PUBLICACAO CODIGO 6.6.1 NA RPI NO 2462 DE 13/03/2018 POR TER SIDO INDEVIDA. |

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2019-09-17| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2021-04-06| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|

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2021-06-08| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-08-03| B09X| Republication of the decision to grant [chapter 9.1.3 patent gazette]|

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2021-09-08| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 16/08/2013, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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US2012051725|2012-08-21|

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USPCT/US2012/051725|2012-08-21|

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PCT/EP2013/067121|WO2014029695A1|2012-08-21|2013-08-16|Method to improve the performance of encapsulated fragrances|

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