polyurea capsule composition, method for preparing a polyurea capsule composition and, consumer prod

专利摘要:
POLYURETH OR POLYURETHANE CAPSULE COMPOSITION, METHOD FOR PREPARING A POLYURETH OR POLYURETHANE CAPSULE COMPOSITION, AND, CONSUMER PRODUCT Polyurea or polyurethane capsule compositions. A subset of these compositions contains a plurality of capsules and a capsule formulation aid, wherein each capsule contains a polyurea or polyurethane wall and an oil core; the polyurea or polyurethane wall is formed from a reaction product of a polyisocyanate and a crosslinking agent in the presence of the capsule-forming aid; and the oil core contains an active material. Polyisocyanate, crosslinking agent and capsule forming aids are described here. Also described are methods for preparing polyurea and polyurethane capsule compositions, as well as consumer products containing one of these compositions.
公开号:BR112016003137B1
申请号:R112016003137-7
申请日:2014-08-15
公开日:2020-10-27
发明作者:Yabin Lei；Li Xu；Lewis Michael Popplewell
申请人:International Flavors & Fragrances Inc；
IPC主号:

专利说明:

CROSS REFERENCE WITH RELATED REQUESTS
[001] This application claims the priority of the three US patent applications, Series N ° 13 / 967,800, 13 / 968,862 and 13 / 969,038, all filed on August 13, 2013. Each of these applications is partly a continuation of the Application US Series Patent No. 13 / 163,320, filed on June 17, 2011, which is a continuation in part of US Series Patent Application No. 12 / 883,337, filed on September 16, 2010, now abandoned, which is a part of continuation of US Patent Application No. 12 / 562,578, filed September 18, 2009, now US Patent No. 8,299,011. The contents of the orders mentioned are hereby incorporated by reference in their entirety. FUNDAMENTALS
[002] Nano or microencapsulation are used in a variety of different applications where there is a need to deliver, apply or release an active material including a fragrance, flavor or odor-preventing agent, flavor and agent to a target area in a delayed or time-controlled manner. Various techniques for preparing capsules are known in the art and are used, depending on the contents to be encapsulated, the environment in which the capsules must maintain their integrity and the desired release mechanisms.
[003] Interfacial polycondensation is a known technique for the preparation of capsules and versatile capsule wall materials are used, including polyureas and polyurethanes (WO 2011/154893, WO 2012/107323, US 2011/0077188, US 5,635,211, US 6,586,107 and US 6,797,670). Such wall materials are produced by means of the first phase which is immiscible in water and includes a polyfunctional isocyanate having two or more isocyanate groups and a second aqueous phase which includes (a) polyfunctional alcohol (i.e., a polyol) having two or more -OH groups to obtain a polyurethane capsule wall or (ii) a polyfunctional amine (i.e., a polyamine) having two or more -NH2 and / or -NH groups to obtain a polyurea capsule wall.
[004] If the active material to be encapsulated is hydrophobic, it will be included in the water immiscible phase, then the two phases are mixed by high-cut mixture to form an oil-in-water emulsion. In this emulsion, the polycondensation reaction will take place. In this way, the small droplets of the water immiscible phase will be surrounded by the capsule wall formed by the polycondensation of the isocyanate and the poly-alcohol or polyamine as the starting materials. Conversely, if the material to be encapsulated is hydrophilic, it will be included in the aqueous phase and in the mixture of two phases converted into a water-in-oil emulsion. The polycondensation reaction will then form the capsule walls that surround the water-miscible phase droplets. Suitable emulsifiers are often used to assist in the preparation and stabilization of the emulsion.
[005] Suitable raw materials and processes for preparing capsules by polycondensation are described in US 4,640,709 and the literature described therein. As exemplified in this, and also in US 6,133,197, polyurea and polyurethane capsules are often used for uneven applications, such as for the encapsulation of agrochemicals, for example, herbicides and pesticides, where release by time is desired to fix free agents. For such applications, the capsules also require relatively high mechanical strength. For the polycondensation reaction, suitable symmetric diisocyanate and triisocyanate starting materials are described in the art.
[006] WO 2011/154893 describes a process for the preparation of capsules, which include mixing with at least one aliphatic polyisocyanate and at least one aromatic polyisocyanate, in which the molar ratio between the two polyisocyanates is between 75 : 25 and 20:80.
[007] WO 2013/000587 describes a process for the preparation of polyurea capsules, which includes dissolving at least one polyisocyanate having at least two functional isocyanate groups, in a perfume to form a solution; add an aqueous solution of an emulsifier or colloidal stabilizer to the solution and add the mixture 3,5-diamino-1,2,4-triazole to form a polyurea wall.
[008] US 5,304,448 describes an encapsulated toning composition using the reaction of amino acids and polyisocyanates.
[009] The known polyurea or polyurethane capsules face several issues, for example, low olfactory intensity, low stability and high toxicity. Its deposition on target surfaces is also problematic.
[0010] There is a need to develop a safe, stable and highly efficient capsule for use in laundry, washing, cleaning, surface care and personal or skin care. For such applications, faster and easier to release and / or less mechanical force are often less desirable. Also, it should be desirable to more precisely influence the capsule wall permeability and other capsule wall properties to achieve the desired release profile and consumer benefits. SUMMARY OF THE INVENTION
[0011] This invention is based on the discovery that certain capsule compositions have unexpected desired properties including perceived olfactory intensity, prolonged stability, low toxicity and improved deposition.
[0012] Accordingly, one aspect of this invention concerns a method for preparing a polyurea or polyurethane capsule composition. The method includes the steps of: (a) preparing an oil phase having an active material and a polyisocyanate; (b) preparing an aqueous phase having a cross-linking agent which is a multifunctional amine or multifunctional alcohol; (c) emulsifying the oil phase in the aqueous phase to form an active emulsion; (d) causing polyurea or polyurethane capsules to form in the active emulsion to obtain a capsule slurry; (e) curing the capsule slurry and (f) purifying the capsule slurry by washing with water, diafiltration or centrifugation. Purification is usually performed after the curing stage.
[0013] Another aspect of this invention relates to a method for preparing a polyurea or polyurethane capsule composition. This method includes the steps of: (a) providing a capsule slurry containing polyurea or polyurethane capsules and water and (b) purifying the capsule slurry by washing with water, diafiltration or centrifugation.
[0014] In the above two methods, preferably, the capsule slurry is purified by washing with water until a neutral pH in a capsule slurry is reached. A salt can be added to the capsule slurry before washing it.
[0015] Yet another aspect of this invention relates to polyurea or polyurethane capsule compositions prepared by any method described above. These capsule compositions can still contain a surfactant, polymer, deposition aid, alcohol (for example, ethanol) or any combination thereof. The polymer is an anionic, cationic, non-ionic or amphoteric polymer.
[0016] In any of the above capsule compositions, an active material is encapsulated in a polyurea or polyurethane capsule wall. The active material can be a fragrance, flavor, neutralizing agent of bad smell or combination thereof.
[0017] Also within the scope of this invention are polyurea and polyurethane capsule compositions having a plurality of polyurea or polyurethane capsules and a capsule formulation aid. Each of the capsules contains a polyurea or polyurethane wall and an oil core, where the polyurea or polyurethane wall is formed from a polyisocyanate reaction product and a crosslinking agent in the presence of the formation aid. capsule and oil core contains an active material (for example, a fragrance, flavor, neutralizing agent for smelling and combining them). The crosslinking agent includes, but is not limited to, multifunctional alcohol (for example, polyols), multi-functional amines (for example, polyamines) and any combinations thereof. Exemplary multi-functional alcohols are pentaerythritol and dipentaerythritol; glycerol and polyglycerol; trimethylolpropane, neopentyl glycol and sorbitol. Exemplary multi-functional amines are ethylenediamine, 1,3-diaminopropane, 1,4-diamino-butane, diethylene-triamine, pentaethylene-hexamine, hexamethylene diamine, bis (3-aminopropyl) amine, bis (hexanylene) triamine, tris ( 2-aminoethylene) amine, triethylene-tetramine, N, N-bis (3-aminopropyl) -1, 3-propanediamine, tetraethylenepentamine, pentaethylene-hexamine, branched polyethyleneimine, chitosan, nisin, gelatin, 1,3-diamino-guanidine, 1,1-di-methylbiguanide, guanidine, arginine, lysine, ornithine or a combination thereof. In some embodiments, compounds having one or more -OH groups and one or more -NH- or NH2 groups are used as the crosslinking agent.
[0018] Branched polyethyleneimine useful as crosslinking agents typically has a molecular weight of 200 to 2,000,000 Da (eg 800 to 2,000,000 Da, 2,000 to 1,000,000, 10,000 to 2,000,000 Da and 20,000 to 100,000 Da).
Suitable capsule-forming aids include polyvinyl alcohols, polystyrene sulfonates, carboxymethyl celluloses, naphthalene sulfonate, polyvinylpyrrolidones, vinyl pyrrolidone copolymers and quaternized dimethylaminoethyl methacrylate or any mixture thereof. Typical examples of the mixture are mixtures of carboxymethyl celluloses and polystyrene sulfonates, mixtures of carboxymethyl cellulose and polyvinylpyrrolidones and mixtures of polyvinylpyrrolidones and vinyl pyrrolidones copolymers of quaternized dimethylaminoethyl methacrylates.
[0020] The polyisocyanates useful in this invention can be aromatic polyisocyanates, aliphatic polyisocyanates or any combination thereof. Aromatic polyisocyanates include those containing a phenyl, tolyl, xylyl, naphthyl or diphenyl moiety or a combination thereof, such as a toluene diisocyanate polyisocyanurate, a toluene diisocyanate adduct trimethylol and a trimethylol-propane adduct xylylene diisocyanate adduct. Suitable aliphatic polyisocyanates include a hexanetylene diisocyanate trimer, an isophorone diisocyanate trimer, a hexanetylene biuret diisocyanate or a combination thereof. In certain embodiments, aliphatic polyisocyanates are used. In other embodiments, some capsule compositions are prepared without using any aromatic polyisocyanate.
[0021] In addition to the fragrances, flavors and neutralizing agents of bad smell contained in the oil cores, the core modifiers are usually included.
[0022] Deposition aids, typically an anionic, cationic, non-ionic or zwitterionic polymer, can also be included in any capsule composition described above.
[0023] A method of preparing polyurea or polyurethane capsule compositions is still within the scope of this invention. The method includes the steps of: (a) preparing an oil phase comprising an active material and a polyisocyanate; (b) preparing a dispersing solution containing a capsule-forming aid (c) emulsifying the oil phase in the dispersing solution to form an active emulsion; (d) adding a crosslinking agent to the active emulsion to form a capsule slurry and (e) curing the capsule slurry, thereby obtaining a polyurea or polyurethane capsule composition of this invention. Polyisocyanates, active materials and crosslinking agents are described above. These will be further elaborated below, as well as capsule training aids.
[0024] The crosslinking agent can be added at 0 to 45 ° C (for example, from 20 to 40 ° C and from 25 to 35 ° C). The capsule slurry can be cured from 55 to 135 ° C (for example, from 65 to 135 ° C, from 75 to 135 ° C, from 85 to 135 ° C and from 95 to 35 ° C).
[0025] The base is optionally added to the active emulsion, especially when a salt (eg, guanidine carbonate, 1,3-diaminoguanidine monohydrochloride, 1,1-dimethylbiguanide hydrochloride and arginine monohydride) is used as an agent of crosslinking. Typical bases include metal carbonate (for example, sodium carbonate, cesium carbonate, potassium carbonate, and lithium carbonate), a metal bicarbonate (for example, sodium bicarbonate and potassium bicarbonate) and metal hydroxide (for example, sodium hydroxide, potassium hydroxide, lithium hydroxide and magnesium hydroxide). These bases can neutralize the salt-containing crosslinking agents and also catalyze the reaction between a polyisocyanate and a crosslinking agent. Sometimes, one or more additional catalysts can be added, for example, 1,4'diazabicyclo [2.2.2] octane (“DABCO”).
[0026] In some embodiments, a core modifier is added to the oil phase before emulsification. In other embodiments, a deposition aid is added before or after curing the capsule slurry. Both the core modifier and the deposition aid are described above.
[0027] The above method can still include the purification of the cured capsules by diafiltration, centrifugation or washing with water until the neutral pH is reached. Before washing with water, a salt is optionally added to the cured capsule slurry to improve washing efficiency.
[0028] Polyurea or polyurethane capsule compositions prepared by any of the methods described above are also provided in this description.
[0029] A consumer product containing any of the above capsule composition is also provided. Exemplary consumer products include a shampoo, hair conditioner, soap, body wash, cosmetic preparation, body liquid detergent, all-purpose cleaner, fabric softener or soda, ironing water , a fabric detergent, a fabric softener, a drying blade, a fine fragrance, a cologne product, a deodorant, a roll-on product and an aerosol product.
[0030] Details of one or more embodiments of the invention are presented in the description below. Other characteristics, objectives and advantages of the invention will be evident from the description and claims. BRIEF DESCRIPTION OF THE DRAWINGS
[0031] Figure 1A shows a scanning electron microscopy (SEMI) image of capsules prepared in accordance with the present invention.
[0032] Figure 1B shows an optical image of capsules prepared in accordance with the present invention.
[0033] Figure 2 shows the sensory performance of polyurea capsules of the invention in a capillary conditioner formulation.
[0034] Figure 3 shows the sensory performance of the polyurea capsule composition prepared in Example 20 in a capillary conditioner formulation.
[0035] Figure 4 shows a scanning electron microscopy image of capsules prepared in Example 20.
[0036] Figure 5 shows the sensory performance of polyurea (PU) capsules compared to a pure fragrance in a hydroalcoholic aerosol formulation. The perceived intensity is shown using the labeled magnitude scale (LMS). N = 14.
[0037] Figure 6 shows a sensory performance of hydro-alcoholic capsules (80:20 EtOfEFEO) compared to the pure fragrance. The capsules were composed of 9.6 g (IX M), 19.2 g (2X M) or 28.8 g (3 X M) LUPRANATE M20 or 10.8 g (IX H), 21.6 g (2 X H) ) or 32.4 g (3X H), with (+) or without (-) CMC or FLEXAN / CMC (F / C). All samples were purified and had a pH of 7.
[0038] Figure 7 shows the sensory performance of Figure 6 polyurea capsules in hydroalcoholic medium after being aged at 25 ° C for 4 weeks.
[0039] Figures 8A to 8D show the thermogravimetric analyzes of samples prepared with polyvinyl alcohol (PVA) and carboxymethyl cellulose (CMC) (Figures 8A and 8); PVA and Polyquaternium-44 (Figure 8B); or PVA only (Figure 8C). These results demonstrate the thermal stability of the samples prepared with a capsule forming aid of Figures 8A to 8C that were prepared with the DESMODUR N100 aliphatic polyisocyanate and guanidine carbonate, since the polyurea capsules of Figure 8D were prepared with the DESMODUR 3600 aliphatic polyisocyanate and guanidine carbonate.
[0040] Figures 9A and 9B show a scanning electron microscopy (SEM) image and optical image of the capsules of sample 2-C in Example 44 respectively. DETAILED DESCRIPTION OF THE INVENTION
[0041] It has been observed that polyurethane polyurethane capsule compositions prepared with a polyisocyanate and a crosslinking agent are very suitable for making various types of hydrophobic or hydrophilic active materials for use in products intended for application to animated or inanimate surfaces .
[0042] The polyurea / polyurethane capsule compositions of this invention are useful in a wide range of consumer applications, for example, personal care products including shampoo, hair conditioners, personal washes such as soaps, body wash, cleansers personal and sanitizing, care with fabric, such as fabric restorers, fabric softeners and drying surfaces, ironing water, industrial cleaners, liquid and powder detergents, rinse conditioners, fine fragrances, a cologne product, a deodorant , a roll-on product or an aerosol product.
[0043] Specifically, the capsule compositions of this invention are well adapted for use in hydroalcoholic medium, such as fine fragrance and for use in leave-on personal care applications. In addition, the inclusion of a capsule forming aid in the capsule wall forming reaction provides capsules with excellent storage stability and retention of an encapsulated fragrance.
[0044] Certain capsules prepared from anionic capsule formation help to have a positive zeta-potential of 5 mV to 200 mV (for example, 20 to 80 mV), which provides strong affinity to specific animated or inanimate surfaces.
[0045] The capsule compositions of this invention can be prepared by reacting a polyisocyanate with a crosslinking agent in the presence of a capsule forming aid (for example, a dispersant) and / or a catalyst (for example, a base) so that an active material is encapsulated in an oil core by a capsule wall. The oil core optionally contains a core modifier.
[0046] These capsule forming materials are described in detail below.
[0047] Polyisocyanate. The polyurea or polyurethane capsules of this invention are prepared using one or more polyisocyanates. Each of these has two or more isocyanate groups, that is, O-C = N-, wherein said polyisocyanate can be aromatic, aliphatic, linear or cyclic. In certain embodiments, the polyisocyanate contains, on average, 2 to 4 groups -N = C = O. In particular embodiments, the polyisocyanate contains at least three functional isocyanate groups. In certain embodiments, the polyisocyanate is insoluble in water.
[0048] In particular embodiments, the polyisocyanate used in this invention is an aromatic polyisocyanate. Desirably, the aromatic polyisocyanate includes a phenyl, tolyl, xylyl, naphthyl or diphenyl moiety as the aromatic component. In certain embodiments, the aromatic polyisocyanate is a toluene diisocyanate polyisocyanurate, a toluene diisocyanate trimethylol propane adduct or a xylylene diisocyanate trimethylol propane adduct.
[0049] In other embodiments, the polyisocyanate is an aliphatic polyisocyanate. In certain embodiments, the aliphatic polyisocyanate is a hexamethylene diisocyanate trimer, an isophorone diisocyanate trimer or a hexamethylene diisocyanate biuret. Exemplary aliphatic polyisocyanates include those commercially available, for example, BAYHYDUR N304 and BAYFIYDUR N305, which are aliphatic water-dispersible polyisocyanates based on hexamethylene diisocyanate DESMODUR N3600, DESMODUR N3700 and DESMODUR N3900, which are polymers low viscosity polyfunctional aliphatic isocyanates based on hexamethylene diisocyanate and DESMODUR 3600 and DESMODUR NIOO which are aliphatic polyisocyanates based on hexamethylene diisocyanate, each of which is available from Bayer Corporation, Pittsburgh, PA).
[0050] A class of suitable polyisocyanates are aromatic polyisocyanates having generic structure below and structural isomers thereof
wherein it cannot vary from zero to a desired number depending on the type of polyamine or polyol used. For the purpose of this invention, the number of n is limited to less than 6. The starting polyisocyanate can also be a mixture of polyisocyanates where the values of n can vary from 0 to 6. In the case where the poly - starting isocyanate is a mixture of several polyisocyanates, the average value of n is preferably between 0.5 and 1.5.
[0051] Specific examples of wall monomer isocyanates include, for example, 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate (MOI), hydrogenated MDI (H12MDI), diisocyanate of xylene (XDI), tetramethylxylol diisocyanate (TMXDI), 4,4'-diphenyldimethylmethane diisocyanate, di- and tetraalkyl diphenylmethane diisocyanate, 4,4'-dibenzil diisocyanate, diisocyanate 1,3-phenylene, 1,4-phenylene diisocyanate, tolylene diisocyanate (TDI) isomers, optionally in a mixture, 1-methyl-2,4-diisocyanatocyclohexane, 1,6 -di-isocyanato- 2,2,4-trimethylhexane, 1,6-diisocyanate-2,4,4-trimethylhexane, 1 - isocyanatomethyl-3-isocyanate, 1,5,5-trimethylcyclohexane , chlorinated and brominated diisocyanates, phosphorus-containing diisocyanates, 4,4'-diisocyanatophenylperfluoroethane, tetramethoxybutane 1,4-diisocyanate, butane 1,4-diisocyanate, 1,6-diisocyanate hexane (HDI), dicyclohexylmethane diisocyanate, 1,4-diisocyanate cycle -hexane, ethylene diisocyanate, phthalic acid bisisocyanatoethyl ester, also polyisocyanates with reactive halogen atoms, such as 1-chloromethylphenyl 2,4-diisocyanate, 1-bromomethylphenyl 2,6-diisocyanate, 3,3-bischloromethyl ether 4,4'-diphenyldiisocyanate. Sulfur-containing polyisociants are obtained, for example, by reacting 2 mol of hexamethylene diisocyanate with 1 mol of thiodiglycol or dihydroxydihexyl sulfide. Additional suitable diisocyanates are trimethylhexamethylene diisocyanate, 1,4-diisocyanatobutane, 1,2-diisocyanatododecane and dimeric fatty acid diisocyanate.
[0052] Other commercially suitable polyisocyanates include LUPRANATE M20 (BASF), where the mean n is 0.7; PAPI 27 (Dow Chemical) where the mean n is 0.7; MONDUR MR (Bayer) where the mean n is 0.8; MONDUR MR Light (Bayer) where the mean n is 0.8; MONDUR 489 (Bayer) where the mean n is 1.0; poly [(phenylisocyanate) -coformaldehyde] (Aldrich Chemical, Milwaukee, WI), other isocyanate monomers, such as DESMODUR N3200 (Bayer) and TAKEN ATE D110-N (Mitsui Chemicals Corporation, Rye Brook, NY).
[0053] In the particular modalities, the invention's polyisocyanate has the structure:
or structural isomer thereof. Representative polyisocyanates having the structure are TAKEN ATE Dl ION (Mitsui), DESMODUR L75 (Bayer) and DESMODUR IL (Bayer).

[0054] In some embodiments, the polyisocyanate used in the preparation of the polyurea or polyurethane capsules of this invention is a simple polyisocyanate. In other embodiments, the polyisocyanate is a mixture of polyisocyanates. In some embodiments, the mixture of polyisocyanates includes an aliphatic polyisocyanate and an aromatic polyisocyanate. In particular embodiments, the polyisocyanate blend is a hexamethylene diisocyanate biuret and a trimethylol propane adduct from xylylene diisocyanate. In certain embodiments, the polyisocyanate is an aromatic isocyanate or a mixture of aliphatic isocyanate, free of any aromatic isocyanate. In other words, in these embodiments, no aromatic isocyanate is used for the preparation of the polyurea compositions of this invention.
[0055] The average molecular weight of certain polyisocyanates useful in this invention range from 250 to 1000 Da and preferably from 275 to 500 Da. In general, the range of polyisocyanate concentration in the composition of this invention varies from 0.1% to 10%, preferably from 0.1% to 8%, more preferably from 0.2 to 5% and even more preferably from 1.5% to 3.5%, all based on the total capsule composition.
[0056] More examples of isocyanates can be found in PCT 2004/054362; EP 0 148 149; EP 0 017 409 BI; Pat. No. 4,417,916, Pat. No. 4,124,526, Pat. No. 5,583,090, Pat. No. 6,566,306, Pat. No. 6,730,635, PCT 90/08468, PCT WO 92/13450, Pat. No. 4,681,806, Pat. No. 4,285,720 and U.S. Pat. No. 6,340,653.
[0057] Crosslinking Agent. Cross-linking agents are used to form the capsule walls. These agents, in general, contain multiple functional groups (i.e., two or more) (for example, -NH-, -NH2 and -OH) that can react with polyisocyanates to form polyureas or polyurethanes. Examples include multi-functional amines (for example, polyamines) and multi-functional alcohols (for example, polyols).
[0058] Suitable polyamines contain two or more amine groups including -NH2 and -R * NH, R * being C1-C20 alkyl, C1-C20 heteroalkyl, C1-C20 cycloalkyl, 3-8 membered heterocycloalkyl, aryl, and heteroaryl replaced or not replaced.
[0059] Two classes of such polyamines include polyalkylene polyamines having the following structures:

[0060] Where R is hydrogen or -CH3 and m, n, x, y and z are each integers from 0 to 2000 (for example, 1, 2, 3, 4 and 5). Examples include ethylene diamine, 1,3-diaminopropane, diethylene triamine, triethylene tetramine, 1,4-diaminobutane, hexanetylene diamine, hexamethylene diamine, pentaethylene hexamine and others.
[0061] Another class of polyamines are polyalkylene polyamines of the type:
where R equals hydrogen on -CH3, medium 5 to 5, for example, diethylene triamine, triethylene tetraamine and others. Exemplary amines of this type also include diethylenetriamine, bis (3-aminopropyl) amine, bis (hexanylene) triamine.
[0062] Another class of amine that can be used in the invention is that of polyetheramines. These primary amino groups are attached to the end of a polyether backbone. The main polyether chain is normally based on propylene oxide (PO), ethylene oxide (EO) or mixed PO / EO. The amine ether can be monoamine, diamine or triamine, based on its core structure. An example is:

Exemplary polyetheramines include 2,2'-ethylenedioxy) bis (ethylamine) and 4,7,10-trioxa-1,13-tridecanediamine.
[0064] Other suitable amines include, but are not limited to, tris (2-aminoethyl) amine, triethylenetetramine, N, N'-bis (3-aminopropyl) -1,3-propanediamine, tetraethylene pentamine, 1,2- diaminopropane, N, N, N ', N'-tetrakis (2-hydroxyethyl) ethylene diamine, N, N, N', N'-tetrakis (2-hydroxypropyl) ethylene diamine, branched polyethyleneimine, 2,4-diamino-6 - hydroxypyrimidine and 2,4,6-triaminopyrimidine.
[0065] Amphoteric amines, that is, amines that can react with an acid as well as a base, are another class of amines used in this invention. Examples of amphoteric amines include proteins and amino acids, such as gelatin, 1-lysine, D-lysine, 1-arginine, D-arginine, 1-lysine monochloride, D-lysine monochloride, 1-arginine monochloride, D-arginine, L-ornithine monochloride, D-ornithine monochloride or a mixture of these.
[0066] Guanidine amines and guanidine salts are yet another class of multi-functional amines in use in this invention. Exemplary guanidine amines and guanidine salts include, but are not limited to, 1,3-diaminoguanidine monohydrochloride, 1,1-dimethylbiguanide hydrochloride, guanidine carbonate and guanidine hydrochloride.
[0067] Commercially available examples of amines include JEFFAMINE FOR-148 (where x = 2), JEFFAMINE EDR176 (where x = 3) (from Huntsman). Other polyether amines include the JEFFAMINE ED series, JEFFAMINE TRIAMINES, BASF polyethylonimines (Ludwigshafen, Germany) under LUPASOL grades (eg Lupasol FG, Lupasol G20 water-free, Lupasol PR 8515, Lupasol WF, Lupasol FC, Lupasol FC, Lupasol FC, Lupasol FC, Lupasol FC, G35, Lupasol G100, Lupasol G500, Lupasol HF, Lupasol PS, Lupasol HEO 1, Lupasol PN50, Lupasol PN60, Lupasol POIOO and Lupasol SK). Other commercially available polyethyleneimines include EPOMIN P-1000, EPOMIN P-1050, EPOMIN RP18W AND EPOMIN PP-061 FROM NIPPON SHOKUBAI (New York, NY). Polyvinylamines, such as those sold by BASF under LUPAMINE grades, can also be used. A wide range of polyetheramines can be selected by those skilled in the art. In certain embodiments, the crosslinking agent is hexamethylene diamine, polyetheramine or a mixture thereof.
[0068] The structures of specific cross-linking agents are shown in the table below: (copy the table on pages 13 to 16) - diethylenetriamine - Bis (3-aminopropyl) amine - Tris (2-aminoethyl) amine - bis (hexanoethylene) triamine - pentaethylene-hexamine - triethylene tetramine - 1,3-diaminoguanidine monochloride - N, N'-Bis (3-aminopropyl) -1, 3-propanediamine monochloride - 1,1-dimethylbiguanide hydrochloride - tetraethylenepentamine - guanidine carbonate - polyethylene branched - chitosan - nisin - gelatin.



[0069] The polyols used in this invention, in general, have at least two nucleophilic centers, for example, ethylene glycol, hexylene glycol, pentaerythritol, glucose, sorbitol and 2-aminoethanol.
[0070] The concentration range of polyamine or polyol can vary from 0.1% to 5% for example, from 0.2% to 3%, from 0.2% to 2%, from 0.5% to 2% , and 0.5% to 1%) by weight of the polyurea and polyurethane capsule composition.
[0071] By adding the excess amount of a crosslinking agent, it was observed that the formation of polyurea / polyurethane is conducted at completion, thereby reducing the amount of residual polyisocyanate. Reaction stoichiometry requires an amine / hydroxyl group for an isocyanate group. By way of illustration, when LUPRANATE M20 (having a molecular weight of 360 and isocyanate functionality of 2.7) and hexamethylenediamine (HMDA; having a molecular weight of 116.21 and amine functionality of 2) are combined, the stoichiometry of system indicates that for each gram of HMDA, 2.23 grams of LUPRANATE is added. The amount of amine will be in excess if more than one gram of HMDA is used per 2.23 grams of LUPRANATE M20. Using a crosslinker according to this invention, the residual amounts of isocyanate are reduced by at least 30%.
[0072] In one embodiment of the invention, the crosslinking agent is added to the capsule reaction at a temperature of 0 to 55 ° C (for example, 10 to 50 ° C, 15 to 45 ° C, 20 to 40 ° C and 22 to 35 ° C.
[0073] Capsule Training Aid. Some capsules useful in the composition of this invention also contain a capsule-forming aid, which can be a surfactant or dispersant. Not being bound by any theory, capsule forming aids improve the performance of the capsule system. Performance is measured by the intensity of the fragrance release during the pre-rub and post-rub phase. The pre-scrubbing stage is the stage when the capsules have been deposited on clothing, for example, after a fabric softener containing capsules containing capsules is used during the wash cycle. The post-rub phase occurs after the capsules have been deposited and the capsules are broken by friction or other similar mechanisms.
[0074] In some embodiments, the capsule-forming aid is a protective colloid or emulsifier including, for example, maleicovinyl copolymers, such as vinyl ethers copolymers with maleic anhydride or acid, sodium lignosulfates, maleic anhydride / styrene copolymers , ethylene / maleic anhydride copolymers and propylene oxide and ethylene oxide copolymers, polyvinylpyrrolidone (PVP), polyvinyl alcohols (PVA), naphthalene sulfonate condensate, carboxymethyl cellulose (CMC) sodium salt, fatty acid esters polyoxyethylene, sodium dodecyl sulfate and any combinations thereof. In general, the surfactant concentration range in the capsule composition ranges from 0.1 to 5% (for example, from 0.5% to 4%, from 0.2% to 2% and from 1% to 2%) .
[0075] Commercially available surfactants include, but are not limited to, sulfonated naphthalene-formaldehyde condensates, such as MORWET D425 (naphthalene sulfonate, Akzo Nobel, Fort Worth, TX); partially hydrolyzed polyvinyl alcohols, such as MOWIOLs, for example, MOWIOL 3-83 (Air Products); block copolymers of ethylene oxide-propylene oxide or poloxamers, such as PLURONIC, SYNPERONIC or PLURACARE (BASF) materials; sulfonated polystyrenes, such as FLEXAN II (Akzo Nobel); ethylenemalleic anhydride polymers, such as ZEMAC (Vertellus Specialties Inc.) and Polyquaternium series, such as Polyquaternium 11 ("PQII;" a vinyl pyrrolidone copolymer and quaternized dimethylaminomethyl methacrylate; sold by BASF as LUVIQUAT PQ11 ATI).
[0076] Processing aids can include hydrocolloid, which improves all colloidal stability of the slurry against coagulation, sedimentation and skimming. The term "hydrocolloid" refers to a broad class of water-soluble or water-dispersible polymers having an anionic, cationic, zwitterionic or non-ionic character. Hydrocolloids useful in the present invention include, but are not limited to, polycarbohydrates, such as starch, modified starch, dextrin, maltodextrin and cellulose derivatives and their quaternized forms; natural gums, such as esters of alginate, carrageenan, xanthans, agar-agar, pectins, pectic acids and natural gums, such as gum arabic, tragacanth and karaya gum, guar gums and quaternized guar gums; gelatins, protein hydrolysates and their quaternized forms; synthetic polymers and copolymers, such as polyvinyl pyrrolidone-covinyl acetate), polyvinyl alcohol (covinyl acetate), poly ((meth) acrylic), poly (maleic acid), poly (alkyl (meth) acrylate-co (meth) acrylic acid ), copolymer of poly (acrylic acid comaleic acid), poly (alkyleneoxide), poly (vinylmethyl ether), poly (vinyl-anhydride ether) and others, as well as poly (ethyleneimine), poly ((meth) acrylamide), poly (alkyleneoxide-codimethylsiloxane), poly (amino dimethylsiloxane) and others and their quaternized forms.
[0077] The capsule forming aid can also be used in combination with CMC and / or a surfactant during processing to facilitate capsule formulation. Examples of surfactants that can be used in combination with the capsule forming aid include, but are limited to, cetyl trimethyl ammonium chloride (CTAC), poloxamers, such as PLURONICS (eg, PLURONIC F127), PLURAFAC (eg , PLURAFAC F127) or MIRANET-N, saponins, such as QNATURALE (National Starch Food Innovation) or an arabic gum, such as Seyal or Senegal. The amount of surfactant present in the capsule slurry may vary depending on the surfactant used. In some embodiments, the amount of surfactant is in the range of 0.05% to 0.2% by weight of the capsule composition, in particular when CTAC is used. In another modality, the amount of surfactant is in the range of 1% to 3%.
[0078] When combined with CMC, a lighter colored PVA is preferred. According to the invention, the CMC polymer can be represented by the following structure: (copy the formula on page 17)

[0079] In certain embodiments, the CMC polymer has a molecular weight range between about 90,000 Daltons to 1,500,000 Daltons, preferably between about 250,000 Daltons to 750,000 Daltons and more preferably between 400,000 Daltons to 750,000 Daltons. The CMC polymer has a degree of substitution between about 0.1 to about 3, preferably between about 0.65 to about 1.4 and more preferably between about 0.8 to about 1.0.
[0080] The polymer of carboxymethyl cellulose is present in a capsule slurry at a level of about 0.1% to about 2% and preferably from about 0.3% to about 0.7%.
[0081] In some embodiments, capsules formed in the presence of a capsule aid may unexpectedly provide an increase in perceived fragrance intensity greater than about 15% and preferably a greater than about 25% increase compared to formed capsules without a capsule-forming aid.
[0082] Additional Polymers. In addition to the polyisocyanate, crosslinking agent, the encapsulating polymer can also include one or more additional polymers. Additional polymers that can be added to the wall in capsule formation include, for example, polyamines (polyethylimine, poly vinyl amines, etc.), polyacrylates and polyquaterniums. In certain embodiments, additional polymers can be selected from, but are not limited to, amphoteric and cationic polymers having a molecular weight in the range of 1,000 to 1,000,000, preferably 10,000 to 500,000 and most preferred between 100,000 to 200,000.
[0083] Examples of amphoteric and cationic polymers include, but are not limited to, polyquaternium (eg, polyquaternium-6 commercially available as MERQUAT 100, polyquaternium-47 commercially available as MERQUAT 2001) and polyvinylamine and copolymers thereof with vinylformamide and mixtures thereof of these. Polyamines are polymers that are prepared by acidic or alkaline hydrolysis of poly (N-vinylformamides), as described, for example, by Gu, et al. ((2002) J. Appl. Pol. Sdi. 86: 3412-3419). The corresponding products are produced in various molecular weights by BASF AG under the brand "LUPAMIN". These products are used on a scale, for example, as paper chemicals, in the personal care sector, as superabsorbents or dispersants. Commercial LUPAMIN products will still contain the hydrolysis salts. For the sector of application described, the modification of waveguide surfaces, both the salt-containing and the desalted form can be used. Desalination can be carried out, for example, by ultrafiltration. In a preferred embodiment, polyvinylamine is LUPAMIN 9095 (polyvinylamine PVAm 340,000 g / mol) commercially available from BASF.
[0084] In some embodiments, the encapsulating polymer contains from 0.01 to 20 weight percent of the additional polymer, on a solid basis. In other embodiments, the encapsulating polymer contains from 0.1 to 10 weight percent of the additional polymer, on a solid basis. In particular embodiments, the additional polymer is polyquaternium-6 and is present, on a solid basis, in the range of 0.25 to about 10 weight percent. In an additional embodiment, the polymer is a mixture of polyquaternium-6 and a polyvinyl amine, specifically LUPAMIN 9095, in which polyquaternium-6 may be present, on a solid basis, in the range of preferably 0.5 to 5 percent in weight and the polyvinylamine present, on a solid basis, from about 0.25 to 10 weight percent. In yet another embodiment, the additional polymer is a mixture of polyquaternium-6 and polyvinylamine in which polyquaternium-6 is present, on a solid base, in the range of preferably 0.5 to 5 weight percent and polyvinylamine is present. present, on a solid basis, in the range of preferably 0.5 to 8 weight percent. In yet another embodiment, the additional polymer is a mixture of polyquaternium-6 and polyvinylamine in which polyquaternium-6 is present, on a solid base, at a level of about 1.5 weight percent and polyvinylamine is present. present, on a solid basis, 1 percent by weight.
[0085] According to certain other embodiments of the invention, the additional polymer is added between 35 ° C and 55 ° C.
[0086] Catalysts. Catalysts suitable for use in the invention are metal carbonates, metal hydroxide, amino or organometallic compounds and include, for example, sodium carbonate, cesium carbonate, potassium carbonate, lithium hydroxide, 1,4-diazabicyclo [2.2.2 ] octane (i.e., DABCO), N, N-dimethylaminoethanol, N, N-dimethylcyclohexylamine, bis- (2-dimethylaminoethyl) ether, N, N-dimethylacetylamine, stannous octanoate and dibutyltin dilaurate.
[0087] Core / Active materials. The core of the capsules of the invention can include one or more active materials including, but not limited to, flavor and / or fragrance ingredients, such as fragrance oils. The individual perfume ingredients that can be included in the capsules of this invention include fragrances containing: i) hydrocarbons, such as, for example, 3-carene, a-pinene, β-pinene, a-terpinene, y-terpinene, p-cymene , bisabolene, camphene, karyophylene, cedrene, farnesene, limonene, longifolene, mircene, ocimene, valencene, (E, Z) -1, 3,5-undecatriene, styrene and diphenylmethane; ii) aliphatic alcohols, such as, for example, hexanol, octanol, 3-octanol, 2,6-dimethyl-heptanol, 2-methyl-2-heptanol, 2-methyl-2-octanol, (E) -2-hexenol , (E) - and (Z) -3-hexenol, l-octen-3-ol, a mixture of 3,4,5,6,6-pentamethyl-3/4-hepten-2-ol and 3,5 , 6,6-tetramethyl-4-methylene-heptan-2-ol, (E, Z) - 2,6-nonadienol, 3,7-dimethyl-7-methoxyoctan-2-ol, 9-decenol, 10-tridecenol , 4-methyl-3-decen-5-ol, aliphatic and acetal aldehydes thereof, such as, for example, hexanal, heptanal, octanal, nonanal, decanal, undecanal, dodecanal, tridecanal, 2-methyloctanal, 2-methylnonanal, (E) -2-hexenal, (Z) -4-heptenal, 2,6-dimethyl-5-heptenal, O-undecenal, (E) -4-decennial, 2-dodecenal, 2,6,10-trimethyl- 5,9-undecadienal, heptanal-diethylacetal, 1,1-dimethoxy-2,2,5-trimethyl-4-hexene and citronellyl oxyacetaldehyde; iii) aliphatic ketones and oximes thereof, such as, for example, 2-heptanone, 2-octanone, 3-octanone, 2-nonanone, 5-methyl-3-heptanone, 5-methyl-3-heptanone oxime, 2, 4,4,7-tetramethyl-6-octen-3-one, aliphatic sulfur-containing compounds, such as, for example 3-methylthiohexanol, 3-methylthiohexyl acetate, 3-mercaptohexanol, 3-mercaptohexyl acetate, 3-mercaptohexyl butyrate, 3-acetylthiohexyl acetate, l-mentene-8-thiol, and aliphatic nitriles (eg, 2-nonenonitrile, 2-tridecenonitrile, 2,12-tridecenonitrile, 3,7-dimethyl -2,6-octadienonitrile and 3,7-dimethyl-6-octenonitrile); iv) aliphatic carboxylic acids and esters thereof, such as, for example, (E) - and (Z) -3-hexenylformate, ethyl acetoacetate, isoamyl acetate, hexyl acetate, 3,5,5-trimethyl acetate hexyl, 3-methyl-2-butenyl acetate, (E) -2-hexenyl acetate, (E) - and (Z) -3-hexenyl acetate, octyl acetate, 3-octyl acetate, l -octen-3-yl, ethyl butyrate, butyl butyrate, isoamyl butyrate, hexylbutyrate, (E) - and (Z) - 3-hexenyl, hexyl crotonate, ethylisovalerate, ethyl-2-methyl pentanoate, ethyl hexanoate, allyl hexanoate, ethyl heptanoate, alyl heptanoate, ethyl octanoate, ethyl- (E, Z) -2,4-decadienoate, methyl-2-octinate, methyl-2-noninate, allyl oxyacetate 2-isoamyl and methyl-3,7-dimethyl-2,6-octadienoate; v) Terpene acyclic alcohols, such as, for example, citronellol; geraniol; nerol; linalool; lavandulol; nerolidol; farnesol; tetrahydrolinalool; tetrahydrogeraniol; 2,6-dimethyl-7-octen-2-ol; 2,6-dimethyloctan-2-ol; 2-methyl-6-methylene-7-octan-2-ol; 2,6-dimethyl-5,7-octadien-2-ol; 2,6-dimethyl-3,5-octadien-2-ol; 3,7-dimethyl-4,6-octadien-3-ol; 3,7-dimethyl-1,5,7-octatrien-3-ol 2,6-dimethyl-2,5,7-octatrien-1-ol; as well as formats, acetates, propionates, isobutyrates, butyrates, isovalerates, pentanoates, hexanoates, crotonates, tiglinates and 3-methyl-2-butenoates thereof; vi) terpene aldehydes and cyclic ketones, such as, for example, geranial, neral, citronellal, 7-hydroxy-3,7-dimethylethanal, 7-methoxy-3,7-dimethyloctanal, 2,6,10-trimethyl-9- undecenal, α-sinensal, β-sinensal, geranylacetone, as well as dimethyl and diethylacetals of geranial, neral and 7-hydroxy-3,7-dimethyloctanal; vii) terpene cyclic alcohols, such as, for example, menthol, isopulegol, alfaterpineol, terpinen-4-ol, mentan-8-ol, mentan-l-ol, mentan-7-ol, borneol, isoborneol, linalool oxide, nopol, cedrol, ambrinol, vetiverol, guaiol and the formates, acetates, propionates, isobutyrates, butyrates, isovalerates, pentanoates, hexanoates, crotonates, tiglinates and alpha-terpineol 3-methyl-2-butenoates, terpinen-4-ol, rnetan -8-ol, uretan-l-ol, uretan-7-ol, borneol, isoborneol, linalool oxide, nopol, cedrol, ambrinol, vetiverol and guaiol; viii) terpene aldehydes and cyclic ketones, such as, for example, menthol, isomentone, 8-mercaptomentan-3-one, carvone, camphor, fenchone, α-ionone, β-ionone, α-n-methionone, β-n- methionone, α-isomethionone, β-isomethionone, alpha-irona, α-damask, β-damask, β-damask, δ-damask, y-damask, l- (2,4,4-trimethyl-2-cyclohexen -l- yl) -2-buten-1-one, 1,3,4,6,7,8a-hexahydro-1,1,5,5-tetramethyl-2H-2,4a- methanonaphthalen-8 ( 5H -) - one, nootkatona, dihydronootkatona; acetylated cedar oil (cedril methyl ketone); ix) Cyclic alcohols, such as, for example, 4-tert-butylcyclohexanol, 3,3,5-trimethylcyclohexanol, 3-isocamfilcyclohexanol, 2,6,9-trimethyl-Z2, Z5, E9-cyclododecatrien -1-ol, 2-isobutyl-4-methyltetrahydro-2H-pyran-4-ol; x) cycloaliphatic alcohols, such as, for example, alpha, 3,3-trimethylcyclohexylmethanol, 2-methyl-4- (2,2,3-trimethyl-3-cyclopent-1-yl) butanol, 2-methyl- 4- (2,2,3-trimethyl-3-cyclopentyl) -2-buten-1-ol, 2-ethyl-4- (2,2,3-trimethyl-3-cyclopent-l-yl) -2- buten-l-ol, 3-methyl-5- (2,2,3-trimethyl-3-cyclopent-l-yl) - pentan-2-ol, 3-methyl-5- (2,2,3-trimethyl -3-cyclopent-1-yl) -4-penten-2-ol, 3,3-dimethyl-5- (2, 2, 3-trimethyl-3-cyclopent-1-yl) -4-penten-2- ol, 1- (2,2,6-trimethylcyclohexyl) pentan-3-ol, trimethylcyclohexyl) hexan-3-ol; xi) cyclic and cycloaliphatic ethers, such as, for example, cineole, cedryl methyl ether, cyclododecyl methyl ether; xii) (ethoxymethoxy) cyclododecane; alpha-cedrene epoxide, 3a, 6,6,9a-tetramethyldodecahydrone [2, lb] furan, 3a-ethyl- 6,6,9a-trimethyldodecahydrone [2,1-b] furan, 1,5, 9-trimethyl-13-oxabicyclo [10.1.0] -trideca-4,8-diene, rose oxide, 2- (2,4-dimethyl-3-cyclohexen-1-yl) -5-methyl-5 - (1-methylpropyl) -1,3 -dioxan-; xiii) Cyclic ketones, such as, for example, 4-tert-butylcyclohexanone, 2,2,5-trimethyl-5-pentylcyclopentanone, 2-heptylcyclopentanone, 2-pentylcyclopentanone, 2-hydroxy-3-methyl-2-cyclopenten -l-one, 3-methyl-cis-2-penten-l-yl-2-cyclopenten-l-one, 3-methyl-2-pentyl-2-cyclopenten-l -one, 3-methyl-4-cyclopentadecenone , 3-methyl-5-cyclopentadecenone, 3-methylcyclopentadecanone, 4- (1-ethoxyvinyl) - 3,3,5,5-tetramethylcyclohexanone, 4-tert-pentylcyclohexanone, 5-cyclohexadecen-l-one , 6,7-dihydro-1,2,3,3-pentamethyl-4 (5 H) -indanone, 5-cyclo-hexadecen-l-one, 8-cyclohexadecen-l-one , 9-cycloheptadecen-1-one, cyclopentadecanone, cycloaliphatic aldehydes, such as, for example, 2,4-dimethyl-3-cyclohexene carbaldehyde, 2-methyl-4- (2,2,6-trimethyl- cyclohexen-1-yl) -2-butenal, 4- (4-hydroxy-4-methylpentyl) -3-cyclohexene carbaldehyde, 4- (4-methyl-3-penten-yl) -3-cyclo- hexene carbaldehyde; xiv) cycloaliphatic ketones, such as, for example, 1- (3,3-dimethylcyclohexyl) -4-penten-1-one, 1 45,5-dimethyl-1-cyclohexen-1-yl) -4 - penten-l-one, 2,3,8,8-tetramethyl-1,2,3,4,5,6,7,8-octahydro-2-naphthalenyl methyl ketone, methyl-2,6, 10-trimethyl-2,5,9-cyclododecatrienyl ketone, tert-butyl- (2,4-dimethyl-3-cyclohexen-1-yl) ketone; xv) cyclic alcohol esters, such as, for example, 2-tert-butylcyclohexyl acetate, 4-tert-butylcyclohexyl acetate, 2-tert-pentylcyclohexyl acetate, 4-tert-pentylcyclo acetate -hexyl, decahydro-2-naphthyl acetate, 3-pentiltetrahydro-2H-pyran-4-yl acetate, decahydro-2,5,5,8a-tetramethyl-2-naphthyl acetate of 4,7-methane-3a, 4,5,6,7,7a-hexahydro-5 or 6-indenyl, 4,7-methane-3a, 4,5,6,7,7a-hexa propionate -hydro-5 or 6-indenyl, 4,7-methane-3a, 4,5,6,7,7a-hexahydro-5 or 6-indenyl-isobutyrate, 4,7-methanooctahydro-5 acetate or 6-indenyl; xvi) aliphatic cyclocarboxylic acid esters, such as, for example, allyl 3-cyclohexyl-propionate, allyl cyclohexyl oxyacetate, methyl dihydrojasmonate, methyl jasmonate, methyl 2-hexyl-3-oxocyclopentanecarboxylate Ethyl 2-ethyl-6,6-dimethyl-2-cyclohexenecarboxylate, ethyl 2,3,6,6-tetramethyl-2-cyclohexenecarboxylate, 2-methyl-1,3-dioxolane-2-acetate ethyl; xvii) aromatic and aliphatic alcohols, such as, for example, benzyl alcohol, 1-phenylethyl alcohol, 2-phenylethyl alcohol, 3-phenylpropanol, 2-phenylpropanol, 2-phenoxyethanol, 2,2-dimethyl-3-phenylpropanol, 2, 2-dimethyl-3- (3-methylphenyl) propanol, 1,1-dimethyl-2-phenylethyl alcohol, 1,1-dimethyl-3-phenylpropanol, 1-ethyl-1-methyl-3-phenylpmpanol, 2-methyl- 5-phenyl pentanol, 3-methyl-5-phenylpentanol, 3-phenyl-2-propen-1-ol, 4-methoxybenzyl alcohol, 1- (4-isopropylphenyl) ethanol; xviii) esters of aliphatic alcohols and aliphatic carboxylic acids, such as, for example, benzyl acetate, benzyl propionate, benzyl isobutyrate, benzyl isovalerate, 2-phenylethyl acetate, 2-phenylethyl propionate, 2-phenylethyl isobutyrate , 2-phenylethyl isovalerate, 1-phenylethyl acetate, α-trichloromethylbenzyl acetate, α, α-dimethylphenylethyl acetate, alpha butyrate, alpha-dimethylphenylethyl butyrate, cinnamyl acetate, 2-phenoxyethyl isobutyrate, 4 acetate -methoxybenzyl, araliphatic esters, such as, for example, 2-phenylethyl methyl ether, 2-phenylethyl isoamyl ether, 2-phenylethyl-1-ethoxyethyl ether, phenylacetaldehyde dimethyl acetal, phenylacetaldehyde diethyl acetal, glycetyl acetaldehyde, acetyl acetal, phenylacetaldehyde, glycolic acid, phenyl acetal, 2-phenylacetal. 4,6-trimethyl-4-phenyl-1,3-dioxane, 4,4a, 5,9b-tetrahydroindene [1,2-d] -m-dioxin, 4,4a, 5,9-tetrahydro -2,4-dimethylindene [1,2-d] -m-dioxin; xix) aromatic and aliphatic aldehydes, such as, for example, benzaldehyde; phenylacetaldehyde, 3-phenylpropanal, hydratropaldehyde, 4-methylbenzaldehyde, 4-methylphenylacetaldehyde, 3- (4-ethylphenyl) -2,2-dimethylpropanal, 2-methyl-3- (4-isopropylphenyl) propanal, 2-methyl-3- ( 4-tert-butylphenyl) propanal, 3- (4-tert-butylphenyl) propanal, cinnamaldehyde, alpha-butylcinnamaldehyde, alpha-amylcinnamaldehyde, alpha-hexylcinnamaldehyde, 3-methyl-5-phenylpentanal, 4-methoxybenzaldehyde, 4-methoxybenzaldehyde, 4-hydroxy-3-hydroxy -methoxybenzaldehyde, 4-hydroxy-3-ethoxybenzaldehyde, 3,4-methylene-dioxibenzaldehyde, 3,4-dimethoxybenzaldehyde, 2-methyl-3- (4-methoxyphenyl) propanal, 2-methyl-3- (4-methylendioxyphenyl) propanal ; xx) aromatic and aliphatic ketones, such as, for example, acetophenone, 4-methylacetophenone, 4-methoxyacetophenone, 4-tert-butyl-2,6-dimethylacetophenone, 4-phenyl-2-butanone, 4- (4-hydroxyphenyl) -2-butanone, 1- (2-naphthalenyl) ethanone, benzophenone, 1,1,3,3,6,6-hexamethyl-5-indanyl methyl ketone, 6-tert-butyl-1,1-dimethyl-4- indanyl methyl ketone, 1- [2,3-dihydro-1,2,6-tetramethyl-3- (I-methylethyl) -IH-5-indenyl] ethanone, 5 ', 6', 7 ', 8'-tetrahydro-3 ', 5', 5 ', 6', 8 'S-hexaxnetyl-2-acetonephton; xxi) aromatic and araliphatic carboxylic acids and esters thereof, such as, for example, benzoic acid, phenylacetic acid, methyl benzoate, ethyl benzoate, hexyl benzoate, benzyl benzoate, methyl phenylacetate, ethyl phenylacetate, geranyl phenylacetate , phenylethyl phenylacetate, methyl cinnamate, ethyl cinnamate, benzyl cinnamate, phenylethyl cinnamate, cinnamyl cinnamate, allyl enoxyacetate, methyl salicylate, isoamyl salicylate, hexyl salicylate, cyclohexyl salicylate, salicylate 3-hexenyl, benzyl salicylate, phenylethyl salicylate, methyl 2,4-dihydroxy-3,6-dimethylbenzoate, ethyl 3-phenylglycidate, ethyl 3-methyl-3-phenylglycidate; xxii) nitrogen-containing aromatics, such as, for example, 2,4,6-trinitro-1,3-dimethyl-5-tert-butylbenzene, 3,5-dinitro-2,6-dimethyl-4-tert-butylacetophenone , cinnamonitrile, 5-phenyl-3-methyl-2-pentenonitrile, 5-phenyl-3-methylpentanonitrile, methyl anthranylate, methyl-N-methylanthranilate, methyl anthranylate Schiffs' bases with 7-hydroxy-3,7-dimethylethannel , 2-methyl-3- (4-tert-butylphenyl) propanal or 2,4-dimethyl-3-cyclohexene carbaldehyde, 6-isopropylquinoline, 6-isobutylquinoline, 6-sec-butylquinoline, indole, eschatol, 2-methoxy -3-isopropylpyrazine, 2-isobutyl-3-methoxypyrazine; xxiii) phenols, phenyl ethers and phenyl esters, such as, for example, estragol, anethole, eugenol, eugenyl methyl ether, isoeugenol, isoeugenol methyl ether, thymol, carvacrol, diphenyl ether, beta-naphthyl methyl ether, beta-naphthyl ethyl ether , betanafty isobutyl ether, 1,4-dimethoxybenzene, eugenyl acetate, 2-methoxy-4-methylphenol, 2-ethoxy-5- (l-propenyl) phenol, p-cresyl phenylacetate; xxiv) heterocyclic compounds, such as, for example, 2,5-dimethyl-4-hydroxy-2H-furan-3-one, 2-ethyl-4-hydroxy-5-methyl-2H-furan-3-one, 3 - hydroxy-2-methyl-4H-pyran-4-one, 2-ethyl-3-hydroxy-4H-pyran-4-one; xxv) lactones, such as, for example, 1,4-octanolide, 3-methyl-1,4-octanolide, 1,4-nonanolide, 1,4-decanolide, 8-decan-1,4,4-olide, 1, 4-undecanolide, 1,4-dodecanolide, 1,5-decanolide, 1,5-dodecanolide, 1,15-pentadecanolide, cis- and trans-11-pentadecen-1,15-olide, cis- and trans-12- pentadecen-l, 15-olide, 1,16-hexadecanolide, 9-hexadecen-l, 16-olide, 10-oxa-1,16-hexadecanolide, 11-oxa-1,16-hexadecanolide, 12-oxa-1, 16-hexadecanolide, ethylene-1,12-dodecanedioate, ethylene-1,13-tridecanedioate, coumarin, 2,3-dihydrocoumarine and octahydrocoumarine; and xxvi) essential oils, concretes, absolutes, resins, resinoids, balms, tinctures, such as, for example, gray amber tincture, amyris oil, angelica seed oil, angelica root oil, anise seed oil , valerian oil, basil oil, tree moss absolute, bay oil, mugweed oil, benzoe resin, bergamot oil, beeswax absolute, lardo oil, bitter almond oil, savory oil, buchu leaf oil, cabbage oil, Cade oil, calamus oil, camphor oil, canang oil, cardamom oil, cascarilla oil, cassia oil, absolute cassia absolute, castor oil absolute, leaf oil cedarwood, cedarwood oil, cyst oil, citronella oil, lemon oil, copaiba balm, copaiba balm oil, coriander oil, costus root oil, cumina oil, cypress oil, oil davana, dill herb oil, dill seed oil, eau de brouts absolute, moss of oak, elemi oil, tarragon oil, eucalyptus citriodora oil, eucalyptus oil (cineole type), fennel oil, pine needle oil, galbanum oil, galbanum resin, geranium oil, grapefruit oil, from guava pods, gurjun balm, gurjun balm oil, helichrysum absolute, helichrysum oil, ginger oil, iris root absolute, iris root oil, jamim absolute, calamus oil, chamomile oil blue, roman chamomile oil, carrot seed oil, cascarilla oil, pine needle oil, mint oil, caraway oil, lafano absolute, lafano resin, lavender absolute, lavender oil, lavender absolute , lavender oil, lemongrass oil, ligament oil, distilled moss oil, expressed moss oil, linalool oil, Litsea cubeba oil, bay leaf oil, apple oil, marjoram oil, tangerine oil , massoi oil (peel), absolute mimosa oil, abelmosque seed, oil musk tincture oil, sage, nutmeg oil, myrrh absolute, myrrh oil, myrtle oil, clove leaf oil, clove oil, neroli oil, absolute oliban absolute, oliban oil, opopanace oil, orange flower absolute, orange oil, origanum oil, palmarosa oil, patchouli oil, perilla oil, Peru balm oil, parsley leaf oil parsley seed oil, petitgrain oil, peppermint oil, pepper oil, pepper oil, pine oil, pennyroyal oil, rose absolute, rose wood wood oil, rose oil, rosemary oil, Dalmatian sage oil, Spanish sage oil, sandalwood oil, celery seed oil, prickly lavender oil, star anise oil, storax oil, tagetes oil, fir needle oil, tree oil tea, turpentine oil, thymus oil, tolu balm oil, tonka bean absolute, tuberose absolute, balnilha extract, ab violet leaf solute, verbena oil, vetiver oil, juniper berry oil, wine sediment oil, absinthe oil, gualteria oil, ylang-ylang oil, hyssop oil, civet absolute, oil mug leaf, cinnamon bark oil, and fractions thereof or isolated ingredients thereof.
[0088] In some embodiments, the amount of encapsulated active material is from about 0.5% to 80% by weight of the capsule composition, preferably from about 10% to about 60% and more preferably from about 20% about 50%.
[0089] In addition to fragrance materials, the present invention also considers the incorporation of other core additives including solvent, emollients and core modifying materials by the encapsulating polymer.
[0090] The present invention also considers the incorporation of solvent materials, particles or polymeric core modifiers in the core. Solvent materials are hydrophobic materials that are miscible in active materials. Solvent materials serve to increase compatibility and various active materials, increase the total hydrophobicity of the mixture containing the active materials, influence the vapor pressure or serve to structure the mixture. Suitable solvents are those having reasonable affinity for the active materials and a ClogP greater than 2.5, preferably greater than 3.5 and more preferably greater than 5.5. In some embodiments, the solvent is combined with the active materials that have the ClogP values as shown above. It should be noted that selecting a solvent and active material with high affinity for each other will result in improved stability. Suitable solvents include triglyceride oil, mono- and diglycerides, mineral oil, silicone oil, diethyl phthalate, polyalpha olefins, castor oil, isopropyl myristate, mono-, di- and tri-esters and mixtures of these fatty acids and glycerin . The fatty acid chain can vary from C4-C26 and can have any level of unsaturation. For example, one of the following solvents can be used: capric / caprylic triglyceride known as NEOBEE MS (Stepan Corporation); the CAPMUL series by Abitec Corporation (for example, CAPMUL MCM); isopropyl myristate; fatty acid esters of polyglycerol oligomers, for example, R2CO [OCH2-CH (OCOR1) -CH2O-] n, where RI and R2 can be H or C4-C26 aliphatic chains, or mixtures thereof vary between 2 and 50, preferably 2 and 30; non-ionic fatty alcohol alkoxylates similar to NEODOL surfactants by BASF; dobanol surfactants by Shell Corporation or BIO-SOFT surfactants by Stepan, in which the alkoxy group is ethoxy, propoxy, butoxy, or mixtures thereof and said surfactants can be covered at the end with methyl groups in order to increase their hydrophobicity; chain of di- and tri-fatty acid containing nonionic, anionic and cationic surfactants, and mixtures thereof; fatty acid esters of polyethylene glycol, polypropylene glycol and polybutylene glycol, or mixtures thereof; polyalphaolefins such as the EXXONMOBIL PURESYM PAO line; esters such as EXXONMOBIL PURESYN esters; mineral oil; silicone oils such as polydimethyl siloxane and polydimethylcyclosyloxane; diethyl phthalate; di-octyl adipate and di-isodecyl adipate. In certain embodiments, ester oils have at least one ester group in the molecule. One type of common ester oil useful in the present invention are fatty acid mono and polyesters such as cetyl octanoate, octyl isonanoate, myristyl lactate, cetyl lactate, isopropyl myristate, myristyl myristate, isopropyl palmitate, adipate isopropyl, butyl stearate, decyl oleate, cholesterol isostearate, glycerol monostearate, glycerol distearate, glycerol tristearate, alkyl lactate, alkyl citrate and alkyl tartrate; ester of sucrose and polyesters, sorbitol ester and others. A second type of ester oil is predominantly composed of modified triglycerides and triglycerides. These include vegetable oils such as jojoba, soy, canola, sunflower, safflower, rice bran, avocado, almond, olive, sesame, peach, castoro, coconut and mars oils. Synthetic triglycerides can also be used as long as they are liquid at room temperature.
[0091] The modified triglycerides include materials such as derivatives of ethoxylated and maligned triglycerides as long as they are liquid. Patented ester combinations such as those sold under FINETEX as FINSOLV are also suitable, as is ethylhexanoic acid glyceride. A third type of ester oil is liquid polyester formed from the reaction of a dicarboxylic acid and a diol. Examples of suitable polyesters for the present suitable invention are those polyesters marketed by EXXONMOBIL under the trade name PURESYN ESTER.
[0092] While no solvent is required in the core, it is preferable that the level of the solvent in the core of the capsule product is about 80% by weight or less, preferably about 50% by weight or less (e.g. 0-20 % by weight),
[0093] When the active material is a fragrance, it is preferred that fragrance ingredients within a fragrance having a high ClogP are used. For example, ingredients having a ClogP value between 2 and 7 (for example, between 2 and 6 and between 2 and 5) are about 25% or more (for example, 50% or more or 90% or more) by weight of the fragrance. That person skilled in the art will appreciate that many fragrances can be created using various solvents and fragrance ingredients. The use of intermediate to relatively low ClogP fragrance ingredients will result in fragrances that are suitable for encapsulation. These fragrances are generally insoluble in water, to be released through the capsule systems of this invention in consumer products at different stages such as wet and dry tissue. Without encapsulation, free fragrances should normally be evaporated or dissolved in water during use, for example, washing. While logP materials have excellent encapsulation properties they are generally well released from a regular (unencapsulated) fragrance in a consumer product. Such fragrance chemicals, in general, only need encapsulation for the purposes of total fragrance character, fragrance release of very long duration or overcoming incompatibility with the consumer product, for example, fragrance materials that must be from another unstable ways, which cause the product to thicken or discolor or otherwise negatively affect the desired product properties for the consumer.
[0094] Nanoscale solid particulate materials such as those described in US 7,833,960 can also be incorporated into the core and can be selected from, but not limited to, metal or metal particles, metal alloys, polymer particles, particles wax, inorganic particles, mineral particles and clays.
[0095] Metal particles can be selected from a non-limiting list of elements in the main group, transition and post-transition metal elements including aluminum (Al), silica (Si), titanium (Ti), chromium (CO, manganese (Mn), iron (Fe), nickel (Ni), cobalt (Co), copper (Cu), gold (Au), silver (Ag), platinum (Pt) and palladium (Pd),
[0096] Polymer particles of any chemical composition and nature are suitable for the present invention as long as their physical dimension differs in the prescribed region and a liquid core is generated. The polymer particles can be selected from a non-limiting and cocopolymer list based on polystyrene, polyvinyl acetate, polylactides, polyglycolides, ethylene maleic anhydride copolymer, polyethylene, polypropylene, polyamide, polyimide, polycarbonate, polyester, polyurethane, polyurea, cellulose and cellulose and combinations and blends of such polymers.
[0097] The inorganic particulate can be selected from a non-limiting list including silica, titanium dioxide (THO2), zinc oxide (ZnO), FeoCh and other metal oxides such as but not limited to NiO, AI2O3, SnO, SnÜ2, CeCh, ZnO, CdO, R11O2, FeO, CuO, AgO, MnÜ2, as well as other transition metal oxides.
[0098] Examples of the nanoscale material include AEROSIL 8812, which has a particle size less than 25 nm according to the manufacturer's specification, Degussa Corp. Other suitable Degussa materials include, but are not limited to, AEROSIL 8972, AEROSIL 8974, AEROSIL 8104, AEROSIL 8106, AEROSIL 8202, AEROSIL 8805, AEROSIL R812, AEROSIL R812S, AEROSIL R8I6, AEROSIL RX200, AEROSIL RX200, AEROSER RX200, T805, AEROXIDE LAW, AEROXIDE LE2, AEROXIDE TiO2 NKT 90, AEROXIDE Alu 0805, titanium dioxide PF2, SIPERNAT Dl 10, SIPERNAT D-380. Hydrophobic materials from Deguassa Corp, such as including AEROSILE 8812 and 8972 are especially preferred.
[0099] Nano-scale materials such as UVINUL TIO2 and Z-COTE HP1 manufactured by BASF can also be used as well as and titanium dioxide TI-PURE, TI-PURE R-700 and TI-SELECT. Additional suitable materials include TS-6200 from Dupont and ZEROFREE 516, HUBERDERM 2000 and HUBERDERM 1000 from J.M. Huber Corporation, Havre De Grace, MD. Silica products such as SYLOID 63, 244, 72, 63FP 244FP, 72FP, SYLOX 15, 2 and zeolites such as Grace Davison's SYLOSIV A3, SYLOSIV A4 and SYLOSIV K300 can also be used.
[00100] Polymeric core modifiers are also considered. It has been observed that the addition of hydrophobic polymers to the core can also improve stability by reducing the diffusion of the fragrance from the core. The level of the polymer is usually less than 80% of the core by weight, preferably less than 50% and more preferably less than 20%. The basic requirement for the polymer is that it be miscible or compatible with the other components of the core, ie the fragrance and another solvent. Preferably, the polymer also thickens or turns the gel core, thereby still reducing diffusion. Polymeric core modifiers include ethylene copolymers; copolymers of ethylene and vinyl acetate (ELVAX polymers by DOW Corporation); copolymers of ethylene and vinyl alcohol (EVAL polymers by Kuraray); acrylic / ethylene elastomers such as VAINAC polymers by Dupont; polyvinyl polymers, such as vinyl polyacetate; substituted alkyl cellulose, such as ethyl cellulose (ETOCEL made by DOW Corporation) and hydroxypropyl celluloses (KLUCEL polymers by Hercules); cellulose acetate butyrate available from Eastman Chemical; polyacrylates (for example, AMPHOMER, DEMACRIL LT and DERMACRIL 79, made by National Amide and Chemical Company, AMERHOLD polymers by Amerchol Corporation and ACUDYNE 258 by ISP Corporation); copolymers of acrylic or methacrylic acid and fatty esters of acrylic or methacrylic acid such as INTELIMER POLYMERS made by Landes Corporation (see also US Patent No. 4,830,855, 5,665,822, 5,783,302, 6,255,367 and 6,492,462) ; propylene polyoxide; poly (tetrahydrofuran) polybutylene oxide; polyethylene terephthalate; polyurethanes (DYNAM X by National Starch); alkyl esters of poly (methyl vinyl ether); maleic anhydride copolymers, such as the GANTREZ and OMNIREZ 2000 copolymers by ISP Corporation; carboxylic acid esters of polyamines, for example, ester-terminated polyamides (ETPA) made by Arizona Chemical Company; polyvinyl pyrrolidone (LUVISKOL series from BASF); block copolymers of ethylene oxide, propylene oxide and / or butylene oxide including, for example, PLURONIC and SYNPERONIC polymers / dispersants by BASF. Another class of polymers includes polymers of polyethylene oxide-copropylene oxide-cobuthene oxide of any ratio of ethylene oxide / propylene oxide / butylene oxide with cationic groups resulting in a theoretical positive charge or equal to zero (amphoteric). The general structure is: R3- (BuO) z "(PO) y" (EO) x " / (EO) x (PO) y (BuO) z-R1 HN- (CH2) y-NH R4- (BuO ) z ”'(PO) y”' (EO) x ”'/ (EO) x' (PO) y '(BuO) z'-R2 where R1, R2, R3 and R4 are independently H or any alkyl or alkyl grease chain group Examples of such polymers are commercially known as TETRONICS by BASF Corporation.
[00101] The sacrificial core ingredients can also be included. These ingredients are designed to be lost during or after manufacture and include, but are not limited to, volatile or highly water-soluble materials.
[00102] One or more adjunct materials can be added to the capsule compositions in the amount of about 0.01% to about 25% (for example, from about 0.5% to about 10%).
[00103] The adjunct material can be a solubility modifier, an antibacterial, an active sunscreen, an antioxidant, an odor-neutralizing ingredient, a density modifier, a stabilizer, a viscosity modifier, a pH modifier or any combination thereof. These modifiers can be present on the wall or core of the capsules, or outside the capsules in the compositions of this invention. Preferably, these are in the core as a core modifier.
[00104] Non-limiting examples of a solubility modifier include surfactants (for example, SLS and Tween 80), acidic compounds (for example, mineral acids, such as sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid and carboxylic acids such with acetic acid, citric acid, gluconic acid, glucoheptonic acid and lactic acid), basic compounds (eg, ammonia, alkaline earth metal hydroxides and alkali metal, primary, secondary, tertiary amines and primary, secondary or tertiary alkanolamines), ethyl alcohol , glycerol, glucose, galactose, inositol, mannitol, glactitol, adonitol, arabitol and amino acids.
Exemplary antibacterials include bisguanidines (e.g., chlorhexidine digluconate), diphenyl compounds, benzyl alcohols, trihalocarbanilides, quaternary ammonium compounds, ethoxylated phenols and phenolic compounds, such as halogen-substituted phenolic compounds, similar to PCMX (ie, p-chloro-m-xylenol), triclosan (ie 2,4,4-trichloro-2 hydroxy-diphenyl ether), thymol and triclocarbon,
[00106] Suitable active sunscreens include oxybenzone, octylmethoxy cinnamate, butylmethoxy dibenzoyl ethane, p-aminobenzoic acid and octyl dimethyl-p-aminobenzoic acid.
[00107] Examples of antioxidants include beta-carotene, vitamin C (ascorbic acid) or an ester thereof, vitamin A or an ester thereof, vitamin E or an ester thereof, lutein or an ester thereof, lignan, lycopene, selenium, flavonoids , vitamin-like antioxities such as coenzyme Q 10 (CoQ10) and glutathione and antioxidant enzymes such as superoxide dismutase (SOD), catalase and glutathione peroxidase.
[00108] Smelly neutralizing ingredients include, but are not limited to, an unsaturated carbonyl compound including but not limited to those described in US 6,610,648 and EP 2,524,704, amyl cinnamaldehyde, benzophenone, benzyl benzoate, benzyl isoeugenol, acetate benzyl phenyl, benzyl salicylate, butyl cinnamate, cinamyl butyrate, cinamyl isovalerate, cinamyl propionate, decyl acetate, ethyl myristate, isobutyl cinnamate, isoamyl salicylate, phenethyl benzoate, phenethyl acetate phenylate, citrate triethyl, tripropylene glycol n-butyl ether, bicyclo [2.2,1 l] hept-5-ene-2-carboxylic acid isomers, ethyl ester, nano silver and zinc undecenylate. More suitable smelly neutralizing ingredients are those described in U.S. 2013/0101544 and 2013/0101545.
[00109] The density of the capsule slurry and / or the oil core can be adjusted so that the capsule composition has a substantially uniform distribution of the capsules using known density modifiers or technologies such as those described in the Ordering Publications WO 2000/059616, EP 1 502 646 and EP 2 204 155. Suitable density modifiers include hydrophobic materials and materials having a desired molecular weight (for example, greater than about 12,000), such as silicone oils, petrolatums , vegetable oils, especially sunflower oil and rapeseed oil and hydrophobic solvents having a desired density (for example, less than about 1,000 Kg / m3 at 25 ° C, such as limonene and octane). In some embodiments, a stabilizer (e.g., a colloidal stabilizer) is added to a capsule composition to stabilize the capsule emulsion and / or slurry. Examples of colloidal stabilizers are polyvinyl alcohol, cellulose derivatives such hydroxyethyl cellulose, polyethylene oxide, polyethylene and polyethylene oxide copolymers or propylene polyoxide, or acrylamide and acrylic acid copolymers.
[00110] Viscosity control agents (for example, suspending agents), which can be polymeric or colloidal (for example, cellulose polymers modified such as methylcellulose, hydroxyethylcellulose, hydrophobically modified hydroxyethylcellulose and crosslinked acrylate polymers such as Carbomer, hydrophobically modified polyethers) can be included in the capsule composition, in the capsule core or wall, or in the capsule slurry outside the capsules. Optionally, silicas, hydrophobic or hydrophilic, can be included in a concentration of about 0.01% to about 20%, more preferably from 0.5% to about 5%, by weight of the capsule composition. Examples of hydrophobic silicas include silanols, surfaces of which are treated with halogen silanes, alkoxysilanes, silazanes and siloxanes, such as SIPERNAT D17, AEROSIL 8972 and 8974 available from Degussa. Exemplary hydrophilic silicas are AEROSIL 200, SIPERNAT 22S, SIPERNAT 50S (available from Degussa) and SYLOID 244 (available from Grace Davison).
[00111] One or more humectants are optionally included with hot water in the capsule composition for a long period of time. Examples include glycerin, propylene glycol, phosphate alkyl esters, quaternary amines, inorganic salts (e.g., potassium polymetaphosphate, sodium chloride, etc.), polyethylene glycol and others.
[00112] Still suitable humectants, as well as viscosity control / suspending agents, are described in U.S. 4,428,869, 4,464,271, 4,446,032 and 6,930,078. The details of hydrophobic silicas as a functional release vehicle for active materials other than a free-flowing / anti-pie forming agent are described in U.S. 5,500,223 and 6,608,017.
[00113] In some embodiments, one or more pH modifiers are included in the capsule composition to adjust the pH value of a capsule slurry and / or the capsule cores. PH modifiers also aid in the formation of capsule walls by changing the reaction rate of the crosslinking reactions that form the capsule walls. Exemplary pH modifiers include metal hydroxides (for example, LiOH, NaOH, KOH and Mg (OH) 2), metal carbonates and bicarbonates (CsCOs L2CO3, K2CO3, NaHCOs and CaCOs), metal phosphates / hydrogen phosphates / di phosphates -hydrogen, metal sulfates, ammonia, mineral acids (HCl, H2SO4, H3PO4 and HNO3), carboxylic acids (eg, acetic acid, citric acid, lactic acid, benzoic acid and sulfonic acids) and amino acids.
[00114] The capsule compositions of this invention can also include one or more unconfined, non-encapsulated active materials from about 0.01% to about 50%, more preferably from about 5% to about 40%.
[00115] The level of the solvent materials, particles, adjuncts, or core modifiers can be greater than about 10% (for example, greater than about 30% and greater than about 70%). In addition to the solvent, it is preferred that the larger Clog P fragrance materials are used. It is preferred that more than about 60 weight percent, preferably more than 80 and more preferably more than about 90 weight percent fragrance chemicals have Clog P values greater than about 3.3, preferably more than about 4 and more preferably more than about 4.5. That person skilled in the art will appreciate that many formulations can be created using various solvents and fragrance chemicals. The use of a high level of high Clog P fragrance chemicals will also require a lower level of hydrophobic solvent than lower Clog P fragrance chemicals to achieve similar performance stability. As one skilled in the art will appreciate, in a highly preferred embodiment, high Clog P fragrance chemicals and hydrophobic solvents that comprise more than about 80, preferably more than about 90 and more preferably more than 95 percent in weight of the fragrance composition. As discussed above, specific Clog P values can be measured between candidate solvents and water for the fragrance materials to be included in the core. In this way, an ideal solvent choice can be made. In fact, since more fragrances will have many ingredients, it may be preferable to measure the division of a specific fragrance combination in the solvent and water in order to determine the effect of any material interactions.
[00116] In addition to the capsules and adjunct materials described above, the capsule composition of this invention may contain one or more other release compositions such as polymer-assisted release compositions (see US 8,187,580), fiber-assisted release compositions (US 2010/0305021), cyclodextrin host complexes (US 6,287,603 and US 2002/0019369), fragrances (WO 2000/072816 and EP 0 922 084) and any combinations thereof.
[00117] Deposition aids. Deposition aids can also be used to assist in depositing capsules on surfaces such as tissue, hair or skin. These include, but are not limited to, water-soluble polymers loaded anionically, cationically, non-ionically, or zwitterionically that can be applied to the polyurea or polyurethane capsule. This water-soluble polymer can also be an amphoteric polymer with a ratio of cationic and anionic functionalities resulting in a total net load of zero and positive, that is, cationic. That person skilled in the art will appreciate that the charge of these polymers can be adjusted by changing the pH, depending on the product in which this technology is used. Any method suitable for deposition aid coatings on encapsulated fragrance materials can be used. The nature of polymers suitable for assisted capsule release from interfaces depending on compatibility with the capsule wall chemistry since there was some association with the capsule wall. This association can be through physical interactions, such as hydrogen bonding, ionic interactions, hydrophobic interactions, electron transfer interactions or, alternatively, the polymer coating must be chemically grafted (covalently) to the capsule or particle surface. Chemical modification of the capsule or particle surface is another way to optimize the attachment of the polymer coating to the surface of the capsule or particle. In addition, the capsule and the polymer need to go to the desired interface and, therefore, necessary to be compatible with the chemistry (polarity, for example) of that interface. Therefore, depending on which capsule and interface chemistry (for example, cotton, polyester, hair, skin, wool), the polymer can be selected from one or more polymers with a total zero (amphoteric: mixture of cationic and anionic functional groups) or positive network charge, based on the following polymer structures: polysaccharides, polypeptides, polycarbonates, polyesters, polyolefin (vinyl, acrylic, acrylamide, polydiene), polyester, polyether, polyurethane, polyoxazoline, polyamine, silicone, polyphosphate, oligoaromatic, poly - heterocyclic, or polyionene, with molecular weight (MW) ranging from about 1,000 to about 1,000,000,000, preferably from about 5,000 to about 10,000,000. As used herein, the molecular weight is given as the weighted average molecular weight.
[00118] Particular examples of cationic polymers that can be used to coat the polyurea or polyurethane capsule include, for example, polysaccharides such as guar, alginates, starch, xanthan, chitosan, cellulose, dextrans, arabic, carrageenan and hyaluronates. These polysaccharides can be used with cationic modification and cationic modifications of alkoxy such as cationic hydroxyethyl or cationic hydroxypropyl. For example, cationic reagents of choice are 3-chloro-2-hydroxypropyl trimethylammonium chloride or its epoxy version. Another example is polyDADMAC graft copolymers on cellulose, for example, CELQUAT 1-200 (POLYQUATERNIO 4), POLYQUATERNIO-IO and POLIQUATERNIO-24, commercially available from National Starch, Bridgewater, NJ. Alternatively, polysaccharides can be used with aldehyde, carboxyl, succinate, acetate, alkyl, amide, sulfonate, ethoxy, propoxy, butoxy and combinations of these features; or any hydrophobic modification (compared to the polarity of the polysaccharide structure). The above modifications can be for any reason and the degree of functionalization can even be to complete the replacement of all functionalizable groups, as long as the theoretical net load of the polymer is zero (mixture of cationic and anionic functional groups) or preferably positive. In addition, up to 5 different types of functional groups can be linked to polysaccharides. Also, the polymer graft chains can be modified differently to the structure. Counterions can be any halide ion or counter organic ion. See U.S. Patent No. 6,297,203 and 6,200,554.
[00119] Another source of the cationic polymers contains protonable amine groups so that the total net charge is zero (amphoteric: mixture of cationic and anionic functional groups) or positive. The pH during use will determine the total polymer net load. Examples include silk protein, zein, gelatin, keratin, collagen and any polypeptide, such a polylysine.
[00120] Still the cationic polymers include polyvinyl polymers with up to 5 different types of monomers can be used. The monomers of such a polymer have the generic formula: -C (R2) (RI) -CR2R3- where, Ri is any C1-C25 alkane or where the number of double bond bands 0-5, Ri is a alkoxylated fatty alcohol of any length of C1-C25 alkoxy carbon, or Ri is a liquid crystalline portion that can provide the polymer with the thermotropic liquid crystalline properties R2 is H or CH3; and R3 is -Cl, -NH2 (i.e., polyvinyl amine or copolymers thereof with N-vinyl formamide.
[00121] Such polyvinyl polymers are sold under the name LUPAMIN 9095 by BASF Corporation. Also suitable cationic polymers containing hydroxylalkylvinylamine units, as discussed in U.S. Patent No. 6,057,404.
[00122] Another class of materials are polyacrylates with up to 5 different types of monomers. The polyacrylate monomers have the generic formula: -CH (RI) -C (R2) (COR3-R4) - where, Ri is any C1-C25 or H alkane with double bonds number from 0-5, Ri is an alkoxylated fatty alcohol with a C1-C25 alkyl chain length, or R1 is a liquid crystalline moiety which provides the polymer with thermotropic liquid crystalline properties; R2 is H or CH3; R3 is a Cl-25 alkyl alcohol or an alkylene oxide with any number of double bonds, or R3 may be absent such that the bond C = O is (via atom C) directly connected to R4; and R4 can be -NH2, -NHRb-NRIR2, -NRIR2R6 (where R6 = Ri, R2, OU -CH2-COOH OR salt thereof), -NH-C (O) -, sulfobetaine, betaine, polyethylene oxide, poly grafts (ethylene oxide / propylene oxide / butylene oxide) with any final group, H, OH, styrene sulfonate, pyridine, quaternized pyridine, pyrrolidone or alkyl substituted pyridine-N-oxide, imidazoline halide , imidazolium halide, imidazole, piperidine, -ORi, -OH, alkaline salt -COON, sulfonate, ethoxy sulfate, pyrrolidone, caprolactam, phenyl-R4 or naphthalene-Rs, where R4 and Rs are Ri, R2, R3, acid sulfonic or alkaline salt or against organic ion. Also, glyoxylated cationic polyacrylamides can be used. Typical polymers of choice are those containing cationic monomer dimethylaminoethyl methacrylate (DMAEMA) or trimethyl ammonium methacrylamidopropyl chloride (MAPTAC). DMAEMA can be observed in GAFQUAT and GAFFIX VC-713 polymers from ISP. MAPTAC can be seen in BASF’s LUVIQUAT PQ11 PN and ISP’s GAFQUAT HS 100.
[00123] Another group of polymers that can be used are those that contain the cationic groups in the main chain or structure. Included in this group are: polyalkylene imines such as polyethylene imine, commercially available as LUPASOL from BASF. Any molecular weight and any degree of crosslinking of this polymer can be used in the present invention; ionenes as described in U.S. Patent No. 4,395,541 and U.S. Patent No. 4,597,962; adipic acid / dimethyl amino hydroxypropyl diethylene triamine copolymers, such as CARTARETIN F-4 and F-23, commercially available from Sandoz; polymers of the general formula: - [N (CH3) 2- (CH2) X-NH- (CO) -NH- (CH2) yN (CH3) 2) - (CH2), - O - (- CH2) p] n -, with x, y, z, p = 1-12 en according to the molecular weight requirements. Examples are Polyquaternium-2 (MIRAPOL A-15). Polyquaternium-17 (MIRAPOL AD-1) and Polyquaternium-18 (NIIRAPOL AZ-1). Other polymers include cationic polysiloxanes and cationic polysiloxanes with carbon-based grafts with a theoretical net positive charge or equal to zero (mixture of cationic and anionic functional groups). This includes the functionalized silicones of the final cationic group (ie, Polyquaternium-80). Silicones with general structure: - Si (Ri) (R2) -O-] x- [Si (R3) (R2) -O-] y- where Ri is any C1-C25 or H alkane with number of double bonds 0-5, aromatic portions, polysiloxane grafts, or mixtures of these Ri can also be a liquid crystalline portion that can provide the polymer with thermotropic liquid crystalline properties. R2 can be H or CH3; and R3 can be -R1-R4, where R4 can be - NH2, -NHRI, -NR1R2, -NR1R2R6 (where R6 = Ri, R2, or -CH2-COOH or salt thereof), -NHC (O) -, -COON, -COO- alkaline salt, any Cl-25 alcohol, - C (O) -NH2 (amide), -C (O) -N (R2) (R2 ') (R2 "), sulfobetaine, betaine, oxide polyethylene, poH grafts (ethylene oxide / propylene oxide / butylene) with any final group, H, -OH, styrene sulfonate, pyridine, quaternized pyridine, pyrrolidone or alkyl substituted pyridine-N-oxide, halide imidazoline, imidazolium halide, imidazole, piperidine, pyrrolidone, caprolactam, sulfonate, phenyl ethoxysulfate -R5 or naphthalene-Ró where R5 and RÔ are Ri, R2, R3, sulfonic acid or salt of the same alkali or against organic ion. it can also be - (CH2) XO-CH2-CH (OH) -CH2-N (CH3) 2-CH2- COOH and salts thereof. Any mixture of these R3 groups can be selected. X and y can be varied as long as the charge theoretical polymer network is zero (amphoteric) or positive. In addition, polysiloxanes containing up to 5 different types of monomer units can be used. Examples of suitable polysiloxanes are seen in U.S. Patent No. 4,395,541 4,597,962 and 6,200,554. Other groups of polymers that can be used to improve capsule / particle deposition are phospholipids that are modified with cationic polysiloxanes. Examples of these polymers are seen in U.S. Patent No. 5,049,313, Patent Application WO 95 / 18096A1 and European Patent EP0797183B1.
[00124] In addition, copolymers of silicones and polysaccharides and proteins can be used (for example, the one commercially available as CRODASONE brand products).
[00125] Another class of polymers includes polymers of polyethylene oxide-copropylene oxide-cobuthene oxide of any ratio of ethylene oxide / propylene oxide / butylene oxide with cationic groups resulting in a theoretical positive net charge or equal to zero (amphoteric). Examples of such polymers are the commercially available TETRONIC brand polymers.
[00126] Suitable polyheterocyclic polymers (the different molecules that appear in the structure) include the piperazine alkylene main chain copolymers described by Kashiki and Suzuki (1986) Ind Eng. Chem. Found. 25: 120-125.
[00127] As indicated, the addition of hydrophobic polymers to the core can also improve stability by decreasing the diffusion of the fragrance from the core. The polymer level is normally less than 80% of the core by weight, preferably less than 50% and more preferably less than 20Y6. The basic requirement for the polymer is that it be miscible or compatible with the other components of the core, that is, the fragrance and another solvent. Preferably, the polymer also thickens or turns the core into gel, thereby still reducing diffusion.
[00128] Any compound, polymer, agent discussed above can be the compound, polymer, or agent itself as shown above, or salt thereof, precursor, hydrate, or solvate. A salt can be formed between an anion and a positively charged group in the compound, polymer, or agent. Suitable anions include chloride, bromide, iodide, sulfate, nitrate, phosphate, citrate, methanesulfonate, trifluoroacetate, acetate, malate, tosylate, tartrate, fumarate, glutamate, glucuronate, lactate, glutarate and maleate. Likewise, a salt can also be formed between a cation and a negatively charged group in the compound, polymer or agent. Suitable cations include sodium ion, potassium ion, magnesium ion, calcium ion and an ammonium cation (for example, tetramethylammonium ion). A precursor can be an ester and another suitable derivative, which, during the process of preparing a polyurea or polyurethane capsule composition of this invention, is capable of converting to the compound, polymer or agent and being used in the preparation of the polyurea capsule composition. or polyurethane. A hydrate refers to the compound, polymer or agent that contains water. A solvate refers to a complex formed between the compound, polymer, or agent and a suitable solvent. A suitable solvent can be water, ethanol, isopropanol, ethyl acetate, acetic acid and ethanolamine. Certain compounds, polymers and agents have one or more stereocenters, each of which may be in the R configuration, the S configuration, or a mixture. In addition, some compounds, polymers and agents have one or more double bonds in which each double bond in the E (trans) or Z (cis) configuration, or combinations thereof. The compounds, polymers and agents include all possible configurational stereoisomeric, regioisomeric, diastereomeric, enantiomeric and epimeric forms as well as any mixtures thereof. As such, lysine used in this includes 1-lysine, D-lysine, 1-lysine monohydrochloride, D-lysine monohydrochloride, lysine carbonate and so on. Similarly, arginine includes 1-arginine monochloride, D-arginine, 1-arginine, D-arginine monochloride, arginine carbonate, arginine monohydrate and etc. Guanidine includes guanidine chloride, guanidine carbonate, guanidine thiocyanate and other guanidine salts including hydrates thereof. Ornithine includes 1-ornithine and salts / hydrates thereof (for example, monochloride) and D-ornithine and salts / hydrates thereof (for example, monochloride).
[00129] According to the compositions and methods discussed herein, the level of wall polymer in the polyurea / polyurethane capsules can be from about 0.1% to about 15% of the total capsule suspension, preferably from about 1 % to about 10% of the total capsule suspension, or more preferably from about 2% to about 5% of the total capsule suspension.
[00130] In a further embodiment of the invention, the amount of the encapsulated active material is from about 5% to about 80% of the total capsule suspension, preferably from about 10% to about 60% of the total capsule suspension, or more preferably from about 20% to about 50% of the total capsule suspension.
[00131] In certain embodiments of the invention, the capsule slurry is cured at a temperature greater than about 55 ° C; greater than about 65 ° C; greater than about 75 ° C; greater than about 85 ° C; greater than about 95 ° C; greater than about 105 ° C or greater than 120 ° C.
[00132] Capsules prepared according to this invention preferably have a size in the range of 0.01 to 1000 microns (for example, 0.5 to 150 microns and 2 to 15 microns). The capsule distribution can be narrow, wide or multi-modal.
[00133] In some embodiments, capsule compositions prepared in accordance with the present invention are subsequently purified. Purification can be achieved by washing with water, diafiltration and centrifugation. Suitable diafiltration processes are those described in U.S. Patent Application Publication 2014/0134242 and Shet et al., J. of Membr. Know. 2003, 211.2, 251-61. The capsule slurry can also be washed with water until a neutral pH in a capsule slurry is reached. For the purposes of the present invention, the capsule compositions can be washed using any conventional method including the use of a separating funnel, filter paper, centrifugation and the like. The capsule suspension can be washed once, twice, three, four, five, six, seven, eight, nine, ten or more times until a neutral pH, i.e., pH 7 ± 0.5, is reached. The pH of the purified capsules can be determined using any conventional method including, but not limited to, a pH role, pH indicators, or a pH meter.
[00134] A capsule suspension of this invention is "purified" in which it is 80%, 90%, 95%, 97%, 98% or 99% homogeneous to the capsules. According to the present invention, purity is achieved by washing the capsules until a neutral pH is reached, which is indicative of the removal of unwanted impurities and / or starting materials, for example, polyisocyanate, crosslinking agent and others.
[00135] In certain embodiments of this invention, the purification of the capsules includes the additional step of adding a salt to a capsule suspension before the step of washing the capsule suspension with water. Exemplary salts in use at this stage of the invention include, but are not limited to, sodium chloride, potassium chloride or disulfide salts.
[00136] Applications. The capsule compositions of the present invention are well suited for use in personal care products including, without limitation, deodorants and antiperspirants, shampoos, hair conditioners, hair rinses, hair restorers, body washes such as shower gels, body lotions, sprayers body products, antiperspirants, deodorants, soap products and others. In particular embodiments, the compositions are for use in an aerosol antiperspirant, stick antiperspirant, roll-on antiperspirant, antiperspirant emulsion spray, clear emulsion stick antiperspirant, soft antiperspirant solid, roll-on antiperspirant emulsion, emulsion stick antiperspirant clear, opaque emulsion stick antiperspirant, clear gel antiperspirant, clear stick deodorant or deodorant spray. Personal care product formulations are provided in the examples below.
[00137] Capsule compositions are also well suited for use in fabric care products such as rinse conditioners and liquid and powder detergents; household care products such as all-purpose cleaners including bathroom cleaners; bath fabrics; carpet deodorizers; candles; room deodorants; floor cleaners; disinfectants; window cleaners; and fabric renovators; personal hygiene products, such as hand sanitizers; toiletries and oral care products, such as dental powders.
[00138] Also, capsule compositions are useful in the following products: (a) household devices including paper towels, disposable towels, room deodorants and fabric softening drying blades, (b) baby care products, such as cream / balm against diaper rash and baby powder, (c) baby care devices, eg diapers, bibs and wipes, (d) health care products including toothpaste, oral rinse, tooth whiteners, adhesives for dentures, hand sanitizers and balms, anti-inflammatory ointments or sprayers, (e) health care devices, for example, dental floss, toothbrushes, feminine hygiene products such as tampons, napkins and feminine and absorbent tissues; (f) personal care products including personal cleaners (soap bar, body wash), sunscreen (spray or lotion), wax-based deodorant, glycol / soap deodorants, lotion, body powder, shaving cream, bath immersion, exfoliating, (g) personal care devices such as facial tissues and cleaning towels, (h) hair care products including shampoo (liquid and dry powder), hair conditioners (rinse and leave-in), fixative and hair aids hair styling, hair bleaches, pigments and dyes, (i) beauty care with fine fragrances (see, for example, US 4,428,869), solid perfume, liquid foundation, powder foundation, eye shadow, lipstick / lip balm , (j) confectionery, such as chewing gums, breath fresheners, orally dissolvable strips, chewable sweets, hard candies, (k) snacks / breakfast foods, potatoes, tortilla, vegetable or multigrain snacks, popcorn, pretzel, bars cereal, extruded snacks ready-to-heat cereal, cooked cereal, (1) drinks including ready-to-drink liquid drinks, liquid drink concentrates, powdered soft drinks, coffee, tea, alcoholic drinks, (m) combinations of spices and prepared consumer foods, for example example, powdered sauces, sauce mixes, condiments and fermented products, (n) ready-to-heat foods including soups, sauces, stewed meats and frozen dishes and (o) dairy products, soybeans, milk-grain products such as dairy drinks flavored, yogurt, ice cream, tofu, cheese and prepared egg products.
[00139] The applications listed above are all well known in the art. For example, fabric softening systems are described in U.S. Patent No. 6,335,315, 5,674,832, 5,759,990, 5,877,145, 5,574,179; 5,562,849, 5,545,350, 5,545,340, 5,411,671, 5,403,499, 5,288,417 and 4,767,547, 4,424,134. Liquid laundry detergents include those systems described in U.S. Patent No. 5,929,022, 5,916,862, 5,731,278, 5,565,145, 5,470,507, 5,466,802, 5,460,752, 5,458,810, 5,458,809, 5,288,431, 5,194,639, 4,968,451, 4,597,898, 4,561,998, 4,550,862, 4,537,707, 4,537,706, 4,515,705, 4,446,042 and 4,318,818. Liquid dishwashing detergents are described in U.S. Patent No. 6,069,122 and 5,990,065. The shampoo and conditioners that can use the present invention include those described in U.S. Patent No. 6,162,423, 5,968,286, 5,935,561, 5,932,203, 5,837,661, 5,776,443, 5,756,436, 5,661,118, 5,618,523, 5,275,755, 5,085,857, 4,673,568, 4,387. 090 and 4,705,681. Automatic dishwashers are described in U.S. Patent No. 6,020,294, 6,017,871, 5,968,881, 5,962,386, 5,939,373, 5,914,307, 5,902,781, 5,705,464, 5,703,034, 5,703,030, 5,679,630, 5,597,936, 5,581,005, 5,559,261, 4,515,705, 5,169,552 and 4,714,562.
[00140] The invention is described in more detail by the following non-limiting examples. EXAMPLE 1: Preparation of Polyurea Capsules with TAKENATE D- 110N
[00141] Preparation of a fragrance emulsion. Ninety-six grams of a fragrance, Greenfields (International Flavors and Fragrance, Union Beach, NJ) were weighed and combined with 24 g of NEOBEE oil (Stepan, Chicago, IL) and 9.6 g of isocyanate monomer, TAKENATE Dl ION (Mitsui Chemicals Corporation, Rye Brook, NY), to form the oil phase. In a separate beaker, a 1.0% surfactant solution (160 g) was prepared by dissolving sufficient FLEXAN II (Akzo Nobel, Bridgewater, NJ) in deionized water (DI). The oil phase was then emulsified in the aqueous phase to form a fragrance emulsion under cut (ULTRA TURRAX, T25 Basic and IKA WERKE) at 6500 rpm for two minutes.
[00142] Formation of fragrance capsules. The fragrance emulsion was heated to 35 ° C in a round bottom vessel and 10.4 g of 56% tris (2-aminoethyl) amine (Sigma-Aldrich, St. Louis, MO) were added under constant mixing with a suspended mixer. The capsule formation was immediately visible by light microscopy. The speed of the mixer was reduced after the addition of tris (2-aminoethyl) amine was complete. The capsule slurry was cured in four hours. EXAMPLE 2: Polyurea capsules cured at elevated temperature
[00143] Preparation of a fragrance emulsion. Ninety-six grams of a fragrance, Greenfields (International Flavors and Fragrance, Union Beach, NJ) were weighed and combined with 24 g of NEOBEE oil (Stepan, Chicago, IL) and 9.6 g of isocyanate monomer, TAKENATE Dl ION (Mitsui Chemicals Corporation, Rye Brook, NY), to form the oil phase. In a separate beaker, a 1.0% surfactant solution (160 g) was prepared by dissolving sufficient FLEXAN II (Akzo Nobel, Bridgewater, NJ) in water. The oil phase was then emulsified in the aqueous phase to form a fragrance emulsion under cut (ULTRA TURRAX, T25 Basic and IKA WERKE) at 6500 rpm for two minutes.
[00144] Formation of fragrance capsules. The fragrance emulsion was heated to 35 ° C in a round bottom vessel and 10.4 g of 56% tris (2-aminoethyl) amine (Sigma-Aldrich, St. Louis, MO) were added under constant mixing with a suspended mixer. The formation of capsules was immediately visible by light microscopy. The speed of the mixer was reduced after the addition of tris (2-aminoethyl) amine was complete. The temperature was raised and maintained for 2 hours and raised to 75 ° C for 2 hours. EXAMPLE 3: Polyurea capsules prepared with a combination of dispersants
[00145] Preparation of a fragrance emulsion. Ninety-six grams of a fragrance, Greenfields (International Sabors and Fragrance, Union Beach, NJ) were weighed and combined with 24 g of NEOBEE oil (Stepan, Chicago, IL) and 9.6 g of isocyanate monomer, TAKENATE D- 11 ON (Mitsui Chemicals Corporation, Rye Brook, NY), to form the oil phase. In a separate beaker, a solution (130 g) containing 1.0% FLEXAN II (Akzo Nobel, Bridgewater, NJ) was mixed with a solution (30 g) of 1% CMC in water to form an aqueous phase. The oil phase was then emulsified in the aqueous phase to form a fragrance emulsion under cut (ULTRA TURRAX, T25 Basic, IKA WERKE) at 6500 rpm for two minutes.
[00146] Formation of fragrance capsules. The fragrance emulsion was heated to 35 ° C in a round bottom vessel and 10.4 g of 56% tris (2-aminoethyl) amine (Sigma-Aldrich, St. Louis, MO) were added under constant mixing with a suspended mixer. The formation of capsules was immediately visible by light microscopy. The speed of the mixer was reduced after the addition of tris (2-aminoethyl) amine was complete. The capsule slurry was cured at 55 ° C for two hours. EXAMPLE 4: Preparation of Polyurea Capsules with DESMODUR L75
[00147] Polyurea capsules were prepared with DESMODUR L75 by carrying out the process described in Example 1 and replacing TAKENATE D-1 ION with DESMODUR L75. EXAMPLE 5: Polyurea capsule with high amounts of isocyanate precursors and amine crosslinkers
[00148] Preparation of a fragrance emulsion. Ninety-six grams of a fragrance, Greenfields (International Sabors and Fragrance, Union Beach, NJ) were weighed and combined with 24 g of NEOBEE oil (Stepan, Chicago, IL) and 14.4 g of isocyanate monomer, TAKENATE DI ION (Mitsui Chemicals Corporation, Rye Brook, NY), to form the oil phase. In a separate beaker, a 1.0% surfactant solution (150 g) was prepared by dissolving sufficient FLEXAN II (Akzo Nobel, Bridgewater, NJ) in water. The oil phase was then emulsified in the aqueous phase to form a fragrance emulsion under cut (ULTRA TURRAX, T25 Basic and IKA WERKE) at 6500 rpm for two minutes.
[00149] Formation of fragrance capsules. The fragrance emulsion was placed in a round bottom vessel and 15.6 g of 56% tris (2-aminoethyl) amine (Sigma-Aldrich, St. Louis, MO) were added under constant mixing with a suspended mixer. The formation of capsules was immediately visible by light microscopy. The speed of the mixer was reduced after the addition of tris (2-aminoethyl) amine was complete. The capsule slurry was cured at 55 ° C for two hours. EXAMPLE 6: Polyurea capsules prepared with Diethylenetriamine
[00150] Preparation of a fragrance emulsion. Ninety-six grams of a fragrance, Greenfields (International Sabors and Fragrance, Union Beach, NJ) were weighed and combined with 24 g of NEOBEE oil (Stepan, Chicago, IL) and 9.6 g of isocyanate monomer, TAKENATE Dl ION (Mitsui Chemicals Corporation, Rye Brook, NY, USA), to form the oil phase. In a separate beaker, a solution (130 g) containing 1.0% FLEXAN II (Akzo Nobel, Bridgewater, NJ) was mixed with a solution (30 g) of 1% CMC in water to form the aqueous phase. The oil phase was then emulsified in the aqueous phase to form a fragrance emulsion under cut (ULTRA TURRAX, T25 Basic, IKA WERKE) at 6500 rpm for two minutes.
[00151] Formation of fragrance capsules. The fragrance emulsion was heated to 35 ° C in a round bottom vessel and 10.4 g of 40% diethylene triamine (Sigma-Aldrich, St. Louis, MO) was added under constant mixing with a suspended mixer. The formation of capsules was immediately visible by light microscopy. The mixer speed was reduced after the addition of diethylenetriamine was complete. The capsule slurry was cured at 55 ° C for two hours. EXAMPLE 7: Polyurea capsules prepared with T riethylenetetramina
[00152] Preparation of a fragrance emulsion. Ninety-six grams of a fragrance, Greenfields (International Sabors and Fragrance, Union Beach, NJ) were weighed and combined with 24 g of NEOBEE oil (Stepan, Chicago, IL) and 9.6 g of isocyanate monomer, TAKENATE Dl ION (Mitsui Chemicals Corporation, Rye Brook, NY), to form the oil phase. In a separate beaker, a solution (130 g) containing 1.0% FLEXAN II (Akzo Nobel, Bridgewater, NJ) was mixed with a solution (30 g) of 1% CMC in water to form an aqueous phase. The oil phase was then emulsified in the aqueous phase to form a fragrance emulsion under cut (ULTRA TURRAX, T25 Basic, IKA WERKE) at 6500 rpm for two minutes.
[00153] Formation of fragrance capsules. The fragrance emulsion was heated to 35 ° C in a round bottom vessel and 10.4 g of 70% triethylene tetramine (Sigma-Aldrich, St. Louis, MO) was added under constant mixing with a suspended mixer. The formation of capsules was immediately visible by light microscopy. The mixer speed was reduced after the addition of triethylene tetramine was complete. The capsule slurry was cured at 55 ° C for two hours. EXAMPLE 8: Polyurea capsules prepared with Tetraethylenepentamine
[00154] Preparation of a fragrance emulsion. Ninety-six grams of fragrance, Greenfields (International Sabors and Fragrance, Union Beach, NJ) were weighed and combined with 24 g of NEOBEE oil (Stepan, Chicago, IL) and 9.6 g of isocyanate monomer, TAKENATE D-110N (Mitsui Chemicals Corporation, Rye Brook, NY), to form the oil phase. In a separate beaker, a solution (130 g) containing 1.0% FLEXAN II (Akzo Nobel, Bridgewater, NJ) was mixed with a solution (30 g) of 1% CMC in water to form an aqueous phase. The oily phase was then emulsified in the aqueous phase to form the fragrance emulsion under cut (ULTRA TURRAX, T25 Basic, IKA WERKE) at 6500 rpm for two minutes.
[00155] Formation of fragrance capsules. The fragrance emulsion was heated to 35 ° C in a round bottom vessel and 10.4 g of 70% tetraethylenepentamine (Sigma-Aldrich, St. Louis, MO) was added under constant mixing with a suspended mixer. The formation of capsules was immediately visible by light microscopy. The mixer speed was reduced after the addition of tetraethylenepetamine was complete. The capsule slurry was cured at 55 ° C for two hours. EXAMPLE 9: Polyurea capsules prepared with Pentaethylene-hexamine
[00156] Preparation of a fragrance emulsion. Ninety-six grams of a fragrance, Greenfields (International Sabors and Fragrance, Union Beach, NJ) were weighed and combined with 24 g of NEOBEE oil (Stepan, Chicago, IL) and 9.6 g of isocyanate monomer, TAKENATE D- 110N (Mitsui Chemicals Corporation, Rye Brook, NY), to form the oil phase. In a separate beaker, a solution (130 g) containing 1.0% FLEXAN II (Akzo Nobel, Bridgewater, NJ) was mixed with a solution (30 g) of 1% CMC in water to form an aqueous phase. The oil phase was then emulsified in the aqueous phase to form a fragrance emulsion under cut (ULTRA TURRAX, T25 Basic, IKA WERKE) at 6500 rpm for two minutes.
[00157] Formation of fragrance capsules. The fragrance emulsion was heated to 35 ° C in a round bottom vessel and 10.4 g of 70% pentaethylene-hexamine (Sigma-Aldrich, St. Louis, MO) was added under constant mixing with a suspended mixer. The formation of capsules was immediately visible by light microscopy. The mixer speed was reduced after the addition of pentaethylene-hexamine was complete. The capsule slurry was cured at 55 ° C for two hours. EXAMPLE 10: Polyurea capsules prepared with branched Polyethyleneimide
[00158] Preparation of a fragrance emulsion. Ninety-six grams of a fragrance, Greenfields (International Sabors and Fragrance, Union Beach, NJ) were weighed and combined with 24 g of NEOBEE oil (Stepan, Chicago, IL) and 9.6 g of isocyanate monomer, TAKENATE D- 110N (Mitsui Chemicals Corporation, Rye Brook, NY), to form the oil phase. In a separate beaker, a solution (130 g) containing 1.0% FLEXAN II (Akzo Nobel, Bridgewater, NJ) was mixed with a solution (30 g) of 1% CMC in water to form an aqueous phase. The oil phase was then emulsified in the aqueous phase to form a fragrance emulsion under cut (ULTRA TURRAX, T25 Basic, IKA WERKE) at 6500 rpm for two minutes.
[00159] Formation of fragrance capsules. The fragrance emulsion was heated to 35 ° C in a round bottom vessel and 10.4 g of 49% branched polyethyleneimide (Sigma-Aldrich, St. Louis, MO) was added under constant mixing with a suspended mixer. The formation of capsules was immediately visible by light microscopy. The mixer speed was reduced after the addition of branched polyethyleneimide was complete. The capsule slurry was cured at 55 ° C for two hours. EXAMPLE 11: Polyurea capsules prepared with Nisin
[00160] Preparation of a fragrance emulsion. Ninety-six grams of a fragrance, Greenfields (International Sabors and Fragrance, Union Beach, NJ) were weighed and combined with 24 g of NEOBEE oil (Stepan, Chicago, IL) and 9.6 g of isocyanate monomer, TAKENATE D- 110N (Mitsui Chemicals Corporation, Rye Brook, NY), to form the oil phase. In a separate beaker, a solution (120 g) containing 1.0% MOWIOL 3-83 (Kuraray America Inc., Houston, TX) was mixed with a solution (30 g) of 1% CMC in water to form a aqueous phase. The oil phase was then emulsified in the aqueous phase to form a fragrance emulsion under cut (ULTRA TURRAX, T25 Basic, IKA WERKE) at 6500 rpm for two minutes.
[00161] Formation of fragrance capsules. The fragrance emulsion was heated to 35 ° C in a round bottom vessel and a mixture containing 20.1 g of 60% Nisin (Sigma-Aldrich, St. Louis, MO) and 0.3 g of catalyst, crystalline DABCO (1,4-diazabicyclo [2.2.2] octane) (Dow Chemical, Midland, MI), was added under constant mixing with a suspended mixer. The formation of capsules was immediately visible by light microscopy. The mixer speed was reduced after the addition of Nisin was complete. The capsule slurry was cured at 75 ° C for two hours. EXAMPLE 12: Polyurea capsules prepared with 1,3-Diaminoguanidine monochloride
[00162] Preparation of a fragrance emulsion. Ninety-six grams of a fragrance, Greenfields (International Sabors and Fragrance, Union Beach, NJ) were weighed and combined with 24 g of NEOBEE oil (Stepan, Chicago, IL) and 9.6 g of isocyanate monomer, TAKENATE Dl ION (Mitsui Chemicals Corporation, Rye Brook, NY), to form the oil phase. In a separate beaker, a solution (120 g) containing 1.0% MOWIOL 3-83 (Kuraray America Inc., Houston, TX) was mixed with a solution (30 g) of 1% CMC in water to form a aqueous phase. The oil phase was then emulsified in the aqueous phase to form a fragrance emulsion under cut (ULTRA TURRAX, T25 Basic, IKA WERKE) at 6500 rpm for two minutes.
[00163] Formation of fragrance capsules. The fragrance emulsion was heated to 35 ° C in a round bottom vessel and a mixture containing 10.1 g of 48% 1,3-Diaminoguanidine monochloride (Sigma-Aldrich, St, Louis, MO), 10 g of 50 % sodium carbonate (Sigma-Aldrich, St. Louis, MO) and 0.3 g of catalyst, crystalline DABCO (1,4-diazabicyclo [2.2.2] octane) (Dow Chemical, Midland, MI), was added under constant mixing with a suspended mixer. The formation of capsules was immediately visible by light microscopy. The mixer speed was reduced after the addition of 1,3-Diaminoguanidine monochloride. The capsule slurry was cured at 75 ° C for two hours. EXAMPLE 13: Polyurea capsules prepared with 1,1-Dimethylbiguanide hydrochloride
[00164] Preparation of a fragrance emulsion. Ninety-six grams of a fragrance, Greenfields (International Sabors and Fragrance, Union Beach, NJ) were weighed and combined with 24 g of NEOBEE oil (Stepan, Chicago, IL) and 9.6 g of isocyanate monomer, TAKENATE Dl ION (Mitsui Chemicals Corporation, Rye Brook, NY), to form the oil phase. In a separate beaker, a solution (120 g) containing 1.0% MOWIOL 3-83 (Kuraray America Inc., Houston, TX) was mixed with a solution (30 g) of 1% CMC in water to form a aqueous phase. The oil phase was then emulsified in the aqueous phase to form a fragrance emulsion under cut (ULTRA TURRAX, T25 Basic, IKA WERKE) at 6500 rpm for two minutes.
[00165] Formation of fragrance capsules. The fragrance emulsion was heated to 35 ° C in a round bottom vessel and a mixture containing 10.1 g of 46% 1,1-Dimethylbiguanide hydrochloride (Santa Cruz Biotechnoloy, Dallas, TX), 10 g of 50% sodium carbonate (Sigma-Aldrich, St. Louis, MO) and 0.3 g of catalyst, crystalline DABCO (1,4-diazabicyclo [2.2.2] octane) (Dow Chemical, Midland, MI), was added under a constant mixing with a suspended mixer. The formation of capsules was immediately visible by light microscopy. The mixer speed was reduced after the addition of 1,1-Dimethylbiguanide hydrochloride was complete. The capsule slurry was cured in four hours, EXAMPLE 14 Polyurea capsules prepared with Guanidine Carbonate
[00166] Preparation of a fragrance emulsion. Ninety-six grams of a fragrance, Greenfields (International Sabors and Fragrance, Union Beach, NJ) were weighed and combined with 24 g of NEOBEE oil (Stepan, Chicago, IL) and 9.6 g of isocyanate monomer, TAKENATE Dsl ION (Mitsui Chemicals corporation, Rye Brook, NY), to form the oil phase. In a separate beaker, a solution (130 g) containing 1.0% MOWIOL 3-83 (Kuraray America Inc., Houston, TX) was mixed with a solution (30 g) of 1% CMC in water to form a aqueous phase. The oil phase was then emulsified in the aqueous phase to form a fragrance emulsion under cut (ULTRA TURRAX, T25 Basic, IKA WERKE) at 6500 rpm for two minutes.
[00167] Formation of fragrance capsules. The fragrance emulsion was heated to 35 ° C in a round bottom vessel and a mixture containing 10.1 g of 36% Guanidine carbonate (Sigma-Aldrich, St. Louis, MO) and 0.3 g of catalyst, DABCO crystalline (1,4-diazabicyclo [2.2.2] octane) (Dow Chemical, Midland, MI), was added under constant mixing with a suspended mixer. The formation of capsules was immediately visible by light microscopy. The mixer speed was reduced after the addition of Guanidine carbonate was complete. The capsule slurry was cured for two hours. EXAMPLE 15: Physical Characterization of Polyurea Capsules
[00168] The capsules prepared in Example 5 were analyzed with scanning electron microscopy (Figure IA) and optical microscopy (Figure 1B). Capsules prepared in accordance with the present invention have been found to have robust mechanical stability. EXAMPLE 16: Fragrance leakage from polyurea capsules
[00169] Capsule slurries prepared in Examples 3-15 were analyzed for fragrance leakage. The fragrance capsule slurries were diluted with DOWNY fabric softener (Procter & Gamble, Cincinnati, OH) to produce mixtures containing 0.5% of the capsule slurry. The mixtures were aged in an oven for 0, 3 and 6 days at 50 ° C. Three samples were prepared by filtration as mixtures through 1 pm of filters (Fisher Scientific, Pittsburgh, PA). The free fragrance content in the mixtures was analyzed. The results are shown in table 1.

[00170] The results showed that the capsules prepared according to the present method have excellent stability. EXAMPLE 17: Perfumery performance of polyurea capsules in a capillary restorative application
[00171] To establish the consumer benefits of the capsules of this invention, the capsule slurry prepared in Example 3 was combined into a capillary restorative base and evaluated for its consumer benefits. The fragrance charge was 0.25% pure equivalent. For comparison, a similar solution was prepared using 0.5% pure fragrance. The hair samples were sprayed with the dispersion and dried in air overnight before being evaluated by a panel of 12 judges. The fragrance intensity was calculated from a scale ranging from 0 to 10. A numerical value of 5 indicates hair samples that produce a strong intensity, while a value of 10 indicates hair samples that generate a very strong smell. . The results of this analysis are shown in table 2. TABLE 2

[00172] The data demonstrated that the samples containing capsules prepared in accordance with this invention gave much stronger perfumery intensity both in the pre-rubbing and post-rubbing stages. The fragrance intensity of the samples containing capsules was 2.5 times that of the pure samples in the pre-rubbing stage and 5.25 that of the pure sample in the post-rubbing stage. This analysis indicated that the post-urea capsule provided significant and long-lasting perfumery benefits and suitable for a personal care application. EXAMPLE 18: Perfumery performance of polyurea capsules in a tissue restorative application
[00173] To establish the consumer benefits of the capsules of this invention, the capsule slurry prepared in Example 3 was combined into a tissue restorative base and evaluated for its consumer benefits. The fragrance charge was 0.2% pure equivalent. For comparison, a similar solution was prepared using 0.2% pure fragrance. The hair samples were sprayed with the dispersion and dried in air for 72 hours before being evaluated by a panel of 6 judges. The fragrance intensity was calculated on a scale ranging from 0 to 10. A numerical value of 5 indicates hair samples that produce a strong intensity, while a value of 10 indicates hair samples that generate a very strong smell. The results of the analysis are shown in table 3. TABLE 3

[00174] The results showed that the samples containing capsules prepared according to this invention gave a much stronger perfumery intensity both in the pre-rubbing and post-rubbing stages. The fragrance intensity of the samples containing capsules was unexpectedly 2 times that of the pure samples in the pre-rubbing stage and 5.5 times that of the pure sample in the post-rubbing stage. This analysis indicated that a polyurea capsule provided significant and long-lasting perfumery benefits and suitable for tissue care application. EXAMPLE 19: Benefit of applying the polyurea capsule when applying hair conditioner
[00175] The benefit of applying the capsules present in a personal care product was evaluated using a hair conditioner formulation. To conduct the experiment, the capsule slurry was dispersed in a capillary conditioner base at 0.5% equivalent pure fragrance. The hair conditioner base was an oil-free conditioner base Magick Botanicals. The base was added 1.0 g of polyurea capsules. The formulation was applied to bundles of hair (40 g each), which contains four strands of hair. The bundles were subsequently washed by moistening the two bundles under water (8 threads) (water temperature: 100 ° F / 38 ° C; flow rate: 1 gallon / minute 3.79 liters / minutes) and slightly removing excess water. The hair was placed on a scale and 2 g of fragrance-free shampoo was applied directly to damp hair. The hair was lathered between the palms of the hands, 10x clockwise and 10x counterclockwise, keeping part of the sample wax between two fingers (does not spread the wax on the surface of the hair). The hair samples were left to stand for 15 seconds and subsequently rinsed under a stream of water for 45 seconds. The process was repeated with the hair conditioner. The excess water was gently removed by compression and the hair was left to dry overnight.
[00176] The dry samples were then evaluated by 16 trained participants and the results are shown in Figure 2. The results clearly demonstrate that the product containing polyurea capsules has a much stronger perfumery intensity than the pure fragrance. In this way, the polyurea capsules of this invention can deliver excellent benefits to the consumer both in the pre-rub and post-rub stage. EXAMPLE 20. Preparation of polyurea capsule using branched polyethyleneimine
[00177] Preparation of a fragrance emulsion. Ninety-six grams of a fragrance, Greenfields (International Sabors and Fragrance, Union Beach, NJ) were weighed and combined with 24 g of NEOBEE M-5 oil (caprylic / capric triglyceride, Stepan, Chicago, IL) and 9.6 g of isocyanate monomer, TAKENATE D110-N (trimethylol propane diisocyanate xylylene adduct, Mitsui Chemicals Corporation, Rye Brook, NY), to form the oil phase. In a separate beaker, a solution (130 g) containing 1% FLEXAN II (polystyrene sulfonate, Akzo Nobel, Bridgewater, NJ) was mixed with a solution (30 g) of 1% CMC (WALOCEL CRT 50000 PA 07, Dow , Midland, MI) in water to form an aqueous phase. The oil phase was then emulsified in the aqueous phase to form a fragrance emulsion under cut (ULTRA TURRAX, T25 Basic, IKA WERKE) at 6500 rpm for two minutes.
[00178] Formation of fragrance capsules. The fragrance emulsion was heated to 35 ° C in a round bottom vessel and 10.4 g of 49% branched polyethyleneimine (Sigma-Aldrich, St. Louis, MO) was added under constant mixing with a suspended mixer. The formation of capsules was immediately visible by light microscopy. The mixer speed was reduced after the addition of branched polyethyleneimine was complete. The capsule slurry was cured at 55 ° C for two hours. EXAMPLE 21. Preparation of polyurea capsule with PVP and PQ11 as dispersants
[00179] Preparation of a fragrance emulsion. Ninety-six grams of a fragrance, Greenfields (International Sabors and Fragrance, Union Beach, NJ) were weighed and combined with 24 g of NEOBEE M-5 oil (caprylic / capric triglyceride, Stepan, Chicago, IL) and 9.6 g of isocyanate monomer, TAKENATE D110-N (trimethylol propane diisocyanate xylylene adduct, Mitsui Chemicals Corporation, Rye Brook, NY), to form the oil phase. In a separate beaker, a solution (122.5 g) containing 0.6% PVP (pohvinylpyrrolidone, Luviskol C) K 90 Pulver, BASF, Ludwigshafen, Germany) was mixed with a 20% solution (37.5 g) of POLYQUATÉRNIO-1 1 (PQ11, Vinyl Copolymer pyrrolidone / dimethylaminoethyl methacrylate, cationic polymer, LUVIQUAT POI 1 AT 1, Ludwigshafen, Germany) in water to form an aqueous phase. The oil phase was then emulsified in the aqueous phase to form a fragrance emulsion under cut (ULTRA TURRAX, T25 Basic, IKA WERKE) at 6500 rpm for two minutes.
[00180] Formation of fragrance capsules. The fragrance emulsion was heated to 35 ° C in a round bottom vessel and 10.4 g of 49% branched polyethyleneimine (Sigma-Aldrich, St. Louis, MO) was added under constant mixing with a suspended mixer. The mixer speed was reduced after the addition of the crosslinker was complete. The capsule slurry was cured for two hours. EXAMPLE 22. Preparation of polyurea capsule with crosslinking agent of a different molecular weight
[00181] Preparation of a fragrance emulsion, Ninety-six grams of a fragrance, Greenfields (International Sabors and Fragrance, Union Beach, NJ) were weighed and combined with 24 g of NEOBEE M-5 oil (caprylic / capric triglyceride, Stepan , Chicago, IL) and 9.6 g of isocyanate monomer, TAKENATE DI10-N (trimethylol propane-xylylene adduct diisocyanate, Mitsui Chemicals Corporation, Rye Brook, NY), to form the oil phase. In a separate beaker, a solution (130 g) containing 1% FLEXAN II (polystyrene sulfonate, Akzo Nobel, Bridgewater, NJ) was mixed with a solution (30 g) of 1% CMC (WALOCEL CRT 50000 PA 07, Dow , Midland, MI) in water to form an aqueous phase. The oil phase was then emulsified in the aqueous phase to form a fragrance emulsion under cut (ULTRA TURRAX, T25 Basic, IKA WERKE) at 6500 rpm for two minutes.
[00182] Formation of fragrance capsules. The fragrance emulsion was heated in a round bottom vessel and 10.4 g of 49% Lupasol P (multifunctional cationic polyethyleneimine; MW 750,000 Da; BASF, Tarrytown, NY, USA) were added under constant mixing with a suspended mixer . The formation of capsules was immediately visible by light microscopy. The mixer speed was reduced after the addition of the crosslinker was complete. The capsule slurry was cured for two hours. EXAMPLE 23 Preparation of polyurea capsule cured at elevated temperature
[00183] Preparation of a fragrance emulsion. Ninety-six grams of a fragrance, Greenfields (International Sabors and Fragrance, Union Beach, NJ) were weighed and combined with 24 g of Neobee Oil M-5 (caprylic / capric triglyceride, Stepan, Chicago, IL, USA) and 9 , 6 g of isocyanate monomer and Takenate DI 10-N (trimethylol propane-xylylene adduct diisocyanate, Mitsui Chemicals corporation, Rye Brook, NY, USA) to form the oil phase. In a separate beaker, 1% of a surfactant solution (160 g) was prepared by dissolving enough Flexan II (polystyrene sulfonate, Akzo Nobel, Bridgewater, NJ, USA) and CMC (carboxymethyl cellulose, WALOCEL CRT 50000 PA 07 , Dow, Midland, MI) in water. The oil phase was then emulsified in the aqueous phase to form a fragrance emulsion under cut (Ultra Tufrax®, T25 Basic and IKA® WERKE) at 6500 rpm for two minutes.
[00184] Formation of fragrance capsules. The fragrance emulsions prepared in step I were heated to 35 ° C in a round bottom vessel and in which 10.4 g of 49% branched polyethyleneimine (Sigma-Aldrich, St. Louis, MO) were added under constant mixing with a suspended mixer. The capsule formation was immediately visible by light microscopy. The mixer speed was reduced after the addition of the grating was complete. The temperature was raised to 75 ° C and maintained at 75 ° C for 2 hours. EXAMPLE 24. Preparation of polyurea capsule with ample amount of isocyanate and amine crosslinking agent
[00185] Preparation of a fragrance emulsion. Ninety-six grams of a fragrance, Greenfields (International Sabors and Fragrance, Union Beach, NJ) were weighed and combined with 24 g of Neobee Oil (Stepan, Chicago, IL, USA) and 14.4 g of isocyanate monomer, Takenate Dl 10-N (Mitsui Chemicals corporation, Rye Brook, NY, USA) to form the oil phase. In a separate beaker, a 1.0% surfactant solution (145 g) was prepared by dissolving sufficient Flexan II (Akzo Nobel, Bridgewater, NJ, USA) in water. The oil phase was then emulsified in the aqueous phase to form a fragrance emulsion under cut (Ultra Turrax®, T25 Basic and IKA® WERKE) at 6500 rpm for two minutes.
[00186] Formation of fragrance capsules. The fragrance emulsions prepared in step 1 were placed in a round bottom vessel and into which 15.4 g of 50% branched polyethyleneimine (Sigma-Aldrich, St. Louis, MO) was added under constant mixing with a suspended mixer . The capsule formation was immediately visible by light microscopy. The mixer speed was reduced after the addition of the crosslinker was complete. The capsule slurry was cured at 55 ° C for two hours.
[00187] The amounts of the isocyanate and cross-linking agent are about three times those used in example 20. EXAMPLE 25: Encapsulation performance of polyurea capsules
[00188] The composition of the capsule prepared in Example 20 was combined in a model hair conditioner solution. The fragrance charge was 0.5% pure equivalent. A comparative solution was prepared with 0.5% pure fragrance. The perfumery benefit of the capsules was assessed by conducting a hair washing experiment using standard protocols. More specifically, the hair was used for washing experiments and was dried in air overnight before being evaluated by a panel of 12 judges. The fragrance intensity was calculated from a scale ranging from 0 to 10. A numerical value of 2 suggests that the hair only produces weak intensity while a value of 10 indicates that the individual generated a very strong smell. The results are shown in figure 3.
[00189] Unexpectedly, this polyurea capsule composition provides much greater fragrance intensity than pure fragrance on the basis of hair conditioner both in the pre-brushing and post-brushing stages. EXAMPLE 26. Physical characterization of polyurea capsules
[00190] Scanning electron microscopy. A scanning electron microscopic photo was taken for the capsules prepared in Example 20. See figure 4. Unexpectedly, the capsules showed robust mechanical stability.
[00191] Zeta potential. The zeta potential of the capsules prepared in the examples above was measured. More specifically, it was evaluated in a 0.14 wt.% Capsule solution in water following an experimental protocol provided by Zetasizer Nano-ZS (Malvern, Inc.). The results are shown in table 4 below. Unexpectedly, the capsules prepared in Example 20 have a positive zeta Potential as high as 51 mV.
EXAMPLE 27: Preparation of a polyurea capsule slurry with improved stability
[00192] To improve stability, twenty-six grams of a capsule slurry as prepared in Example 20 were weighed and 4 g of POLYQUATHERIN-1 (PQ11, vinyl pyrrolidone copolymer / dimethylaminoethyl methacrylate, cationic polymer, LUVIQUAT PQ11 AT 1, BASF, Ludwigshafen, Germany) was added. The mixture was stirred for approximately 30 minutes by means of a suspended 1KA lab mixer until the surfactant was completely dissolved and homogeneous.
[00193] Alternatively, a solution of 10% POLYQUATÉRNIO-1 I was prepared by dissolving 20 grams of LUVIQUAT PQ11 AT 1 in 20 grams of water. The stabilized capsule slurry was prepared by mixing 7.5 grams of fragrance capsule slurry prepared as in Example 20 with 22.5 grams of 5% POLYQUATHERIN-11 solution under consistent mixing for 30 minutes.
[00194] Unexpectedly, the stability of capsule mixtures has been improved. EXAMPLE 28-33: Polyurea Capsule Formulations containing surfactants and polymers as Adjuvants
[00195] Evaluating other adjuvants, polyurea capsule slurries prepared in Example 20 were combined with one or more adjuvants as listed in table 5 to obtain six capsule formulations. More specifically, a 10% polyquaternium-6 solution was prepared by adding water to a 40% polyquaternium-6 solution, commercially available from Nalco Inc. The 10% polyquaternium-6 solution was then mixed with a paste fluid from polyurea capsule.
[00196] The resulting mixture was homogenized using an atomized upper part at 500 rpm for 30 minutes before being placed in the oven for storage tests. TABLE 5
EXAMPLE 34. Performance investigation of polyurea capsule slurries with and without polymer adjuvants based on EU liquid detergent
[00197] To evaluate the performance of the polyurea capsules, the capsule slurries prepared in Example 20-27 were combined in a European model liquid detergent solution that was provided by Unilever Company. The fragrance charge was 0.5% pure equivalent. A comparative formulation was prepared using melamine-formaldehyde (MF) capsules described in US2007 / 0138671 at 0.5%. Another comparative capsule formulation was prepared using polyurea capsules without adding a dispersant. Each formulation was aged for 4 weeks at 37 ° C. The perfumery benefit of the capsules was assessed by conducting a laundry experiment using standard experimental protocols with a European washing machine. Terry towels were used for the washing experiments and were air dried overnight before being evaluated by a panel of 12 judges. The fragrance intensity is calculated from a scale ranging from 0 to 10. A numerical value of 2 suggests that only the fabric produces a weak intensity while a value of 10 indicates that the individual generated a very strong smell.
[00198] Unexpectedly, polyurea formulations using the compositions prepared in Examples 20-27 have a much higher fragrance intensity than the polyurea formulation without a dispersant, in both pre-rub and post-rub tests; and two polyurea formulations, that is, one containing PVP / CMC and the other PVP / CA111, has a much higher fragrance intensity than the MF formulation, also in both pre-rub and post-rub tests. EXAMPLE 35: Performance of polyurea capsule slurries with polymer adjuvants on the base of the tissue conditioner
[00199] To evaluate the performance of the polyurea capsules, the capsule slurries prepared in Example 20-27 were combined in a European model tissue conditioner solution that was provided by Unilever Company. The fragrance charge was 0.5% pure equivalent. A comparative formulation was prepared using melamine-formaldehyde (MF) capsules described in US2007 / 0138671 at 0.5%. Another comparative capsule formulation was prepared using polyurea capsules without adding a dispersant. Each formulation was aged for 4 weeks at 37 ° C. The perfumery benefit of the capsules was assessed by conducting a laundry experiment using a standard experimental protocol with a European washing machine. Terry towels were washed with one of the formulations and then air dried overnight before being evaluated by the panel of 12 judges. The fragrance intensity is calculated from a scale ranging from 0 to 10. A numerical value of 2 should suggest that the fabric only produces a weak intensity while a value of 10 indicates that the individual generated a very strong smell.
[00200] Unexpectedly, polyurea formulations using the compositions prepared in Examples 20-27 have a much higher fragrance intensity than the polyurea formulation without a dispersant, in both pre-rub and post-rub tests; and two polyurea formulations, that is, one containing CAI 06 and the other CA301, has a much higher fragrance intensity than the MF formulation, also in both pre-rub and post-rub tests. EXAMPLE 36: Performance of polyurea capsule slurries with polymer adjuvants on the basis of hair conditioner
[00201] To evaluate its performance, the capsule slurries prepared in Example 20-27 were combined in a model capillary conditioner base. The fragrance charge was 0.5% pure equivalent. A comparative formulation was prepared using melamine-formaldehyde (MF) capsules described in US2007 / 0138671 at 0.5%. Another comparative capsule formulation was prepared using polyurea capsules without adding a dispersant. The perfumery benefit of the capsules was assessed by conducting a personal washing experiment using a standard experimental protocol. The hair samples were washed with one of the formulations and then dried in air overnight before being evaluated by a panel of 12 judges. The fragrance intensity is calculated from a scale ranging from 0 to 10. A numerical value of 2 should suggest that the hair only produces a weak intensity while a value of 10 indicates that the individual generated a very strong smell,
[00202] Unexpectedly, polyurea formulations using the compositions prepared in Examples 20-27 have a much higher fragrance intensity than the polyurea formulation without a dispersant, in both rubbed and non-rubbed tests and three polyurea formulations, i.e. , one containing CA202, one CA111 / CA202 and the last CA301, has a much higher fragrance intensity than the MF formulation, also in both rubbed and non-rubbed tests. EXAMPLE 37: Performance of polyurea capsule slurries with polymer adjuvants at the base of the shampoo
[00203] To evaluate its performance, the capsule slurries prepared in Example 20-27 were combined in a model shampoo base. The fragrance charge was 0.5% pure equivalent. A comparative formulation was prepared using melamine-formaldehyde (MF) capsules described in US2007 / 0138671 at 0.5%. Another comparative capsule formulation was prepared using polyurea capsules without adding a dispersant. The perfumery benefit of the capsules was assessed by conducting a personal washing experiment using a standard experimental protocol. The hair samples were washed with one of the formulations and then dried in air overnight before being evaluated by a panel of 12 judges. The fragrance intensity is calculated from a scale ranging from 0 to 10, a numerical value of 2 should suggest that the hair only produces weak intensity while a value of 10 indicates that the individual has generated a very strong smell.
[00204] Unexpectedly, polyurea formulations using the compositions prepared in Examples 20-27 have a much higher fragrance intensity than the polyurea formulation without a dispersant, in both rubbed and non-rubbed tests; and three polyurea formulations, that is, one containing CA106, one CA106 / CA202 and the last CA201, has a much higher fragrance intensity than the MF formulation, also in both rubbed and non-rubbed tests. EXAMPLE 38: Composition of polyurea capsule
[00205] Preparation of sample I-A. Ninety-six grams of a fragrance, Apple (International Sabors and Fragrance, Union Beach, NJ) were weighed and combined with 24 g of NEOBEE oil (Stepan, Chicago, IL) and 9.6 g of isocyanate monomer, LUPRANATE M20 ( BASF Corporation, Wyandotte, MI) to form the oil phase. In a separate beaker, a 1% surfactant solution (160 g) was prepared by dissolving sufficient amount of MORWET D-425 (Akzo Nobel, Fort Worth, TX) in water. The oil phase was then emulsified in the aqueous phase to form a fragrance emulsion under cut (ULTRA TURRAX, T25 Basic, IKA WERKE) at 6500 rpm for two minutes.
[00206] The fragrance emulsion was placed in a round bottom container and 10.8 g of 40% hexamethylene diamine (HMDA) (INVISTA, Wichita, KS) were added under constant mixing with a suspended mixer. The capsule formation was immediately visible by light microscopy. The mixer speed was reduced after the addition of HMDA was complete. The capsule slurry was cured at 55 ° C for three hours.
[00207] Sample preparation 2-A, ninety-six grams of a fragrance, Greenfields (International Sabors and Fragrance, Union Beach, NJ) were weighed and combined with 24 g of NEOBEE oil (Stepan, Chicago, IL) and 9, 6 g of isocyanate monomer, LUPRANATE M20 (BASF Corporation, Wyandotte, MI) to form the oil phase. In a separate beaker, a solution (160 g) containing 1% MORWET D-425 (Akzo Nobel, Fort Worth, TX) was used as the aqueous phase. The oil phase was then emulsified in the aqueous phase to form a fragrance emulsion under cut (ULTRA TURRAX, T25 Basic and IKA WERKE) at 6500 rpm for two minutes.
[00208] The fragrance emulsion was placed in a round bottom container and 10.8 g of 40% HMDA (INVISTA, Wichita, KS) were added under constant mixing with a suspended mixer. The capsule formation was immediately visible by light microscopy. The mixer speed was reduced after the addition of HMDA was complete. The capsule slurry was cured for three hours.
[00209] After preparing the capsule, the capsule slurry was washed with water using a separating funnel. Specifically, 300 ml of water was mixed with 300 g of capsule slurry in a 1000 ml separating funnel. The funnel was then sealed and gently separated and allowed to stand overnight so that the capsule slurry separates from the water. The aqueous layer was then renewed. This process was repeated several times until the slurry pH was 7.0. The analytical measurement indicates how the HMDA concentration is less than 0.05%.
[00210] While 9.6 g of LUPRANATE M20 was used in this example, the amount of LUPRANATE M20 can be varied from 9.6 g to 28.8 g, with the addition of the corresponding 40% amount of the HMDA solution (10.8 ga 32.4g). Likewise, the amount of MORWET D-425 can be varied from 0.5 to 4% depending on the formulation required. In addition, other dispersants include PVA (polyvinyl alcohol), CMC (carboxymethyl cellulose), PSSS (polystyrene sulfonic acid, sodium salt) can be used.
[00211] Preparation of sample 3-A. Ninety-six grams of a fragrance, Greenfields (International Sabors and Fragrance, Union Beach, NJ) were weighed and combined with 24 g of NEOBEE oil (Stepan, Chicago, IL) and 9.6 g of isocyanate monomer, LUPRANATE M20 ( BASF Corporation, Wyandotte, MI) to form the oil phase. In a separate beaker, a solution (160 g) containing 1% MORWET D-425 (Akzo Nobel, Fort Worth, TX) was used as the aqueous phase. The oil phase was then emulsified in the aqueous phase to form a fragrance emulsion under cut (ULTRA TURK AX, T25 Basic and IK-A. WERKE) at 6500 rpm for two minutes,
[00212] The fragrance emulsion was placed in a round bottom container and 10.8 g of 40% HMDA (INVISTA, Wichita, KS) were added under constant mixing with a suspended mixer. The capsule formation was immediately visible by light microscopy. The mixer speed was reduced after the addition of HMDA was complete. The capsule slurry was cured at 55 ° C for three hours.
[00213] After preparation, the capsule slurry was washed with 1M aqueous NaCl solution using a separating funnel. Specifically, 300 ml of 1M aqueous NaCl solution was mixed with 300 g of the capsule slurry in a separate 1000 ml funnel. The funnel was then sealed and gently separated and allowed to stand overnight so that the capsule slurry could separate from the aqueous solution. The aqueous layer was then renewed. This process was repeated several times until the slurry pH was 7.0. The capsule slurry was further washed with water several times using a separating funnel. Example 39: Sensory performance of polyurea capsules
[00214] To establish the consumer benefit of polyurea capsules, sample IA as prepared in Example 38 was incorporated into an aerosol formulation. The composition of the aerosol is given in table 6. TABLE 6

[00215] A technique applied (sprayed) 1 g of each aerosol formulation on an upper forearm using the fragrance. Eight arms were tested per sample using 15 trained judges. The judges rated the intensity of the product on the skin 5 hours after application under two conditions, before activation (pre-rub) and again in the post-rub condition. For post-rub evaluation, each user gently rubbed the upper forearm up and down in a count of six with two fingers. The judges smell the upper part of the forearm when evaluating the sample. The analysis of two pathways of variation was conducted with sample and participants as independent variables and intensity as dependent variable and again with condition (pre and post) and participants as independent variables and intensity as dependent variable. The post hoc analysis was performed using Duncan's Multiple Comparison with significance adjustment at 95% of Cl.
[00216] The sensory results are given in Figure 5. This analysis indicated that the polyurea capsules significantly provide the much higher fragrance intensity at all time points compared to the pure fragrance. In addition, polyurea capsules have a significant increase in fragrance intensity from pre to post evaluation. Example 40: Sensory performance of purified polyurea capsules
[00217] To establish the consumer benefit of the purified polyurea capsules prepared according to Sample 2-A in Example 38 it was mixed in a hydroalcoholic solution containing 80% ethanol and 20% water. The concentration of the capsules was 4.5%. The polyurea capsule solution (0.3 g) was then sprayed on a blotter (4x6) and allowed to dry overnight before being evaluated by a panel of 12 judges. The fragrance intensity was calculated on a scale ranging from 0 to 10. A numerical value of 10 should suggest that the individual generated a strong smell. The results are shown in Figure 6.
[00218] The results of this analysis indicated that the capsules prepared according to the present invention have a much higher fragrance intensity compared to the pure fragrance in the post-rub stage and were able to release the full benefit of the fragrance formulation. In addition, the sensory performance of the polyurea capsules was retained after the samples were aged at 25 ° C for 4 weeks (Figure 7), demonstrating the unexpected robust storage stability and performance of the capsules. Examples 41 and 42. Washed capsule compositions
[00219] Two capsule compositions, i.e., Samples 12-A and 1-6A, were prepared following a similar procedure as Sample 3-A in Example 38.
[00220] More specifically, Sample 12-A was prepared following a procedure like Sample 3-A except that the following different variables were applied: (i) violet fragrance (International Sabors and Fragrance, Union Beach, NJ), instead Greenfields, (ii) cut at 6000 rpm, instead of cut at 6500 rpm and (iii) that the amount of the fragrance being 0.3 times that of Sample 3-A, Sample 16-A was prepared following a similar procedure as Sample 3-A except the following different variables were applied: (i) the amount of a wall of polyurea or polyurethane material being 0.2 times that of Sample 3-A and (ii) the amount of Morwet D-425 0.5 times that of Sample 3-A.
[00221] Two comparative samples, 12-A 'and 16-A', were also prepared following the same procedures as 12-A and 16-A, respectively, except that the comparative samples were not washed with water, that is, not purified.
[00222] The contents of the crosslinking agent HMDA were analyzed. Each of 12-A and 16-A showed an HMDA level of less than 0.06%.
[00223] Still, 12-A and 16-A showed a much higher fragrance intensity than unpurified air counterparts, that is, 12-A 'and 16-A'. Example 43: Polyurea capsules prepared with Aliphatic / Aromatic Polyisocyanate and Guanidine Amines / Salts
[00224] Sample 1-B: Polyurea capsule. Ninety-six grams of a fragrance, Greenfields (IFF, Union Beach, NJ) were weighed and combined with 24 g of NEOBEE oil (Stepan, Chicago, IL) and 9.6 g of isocyanate monomer, DESMODUR N100 (Bayer Corp. , Pittsburgh, PA) to form the oil phase. In a separate beaker, a solution (130 g) containing 1.0% MOWIOL 3-83 (Kuraray America Inc., Houston, TX) was mixed with deionized water (DI) (30 g) to form an aqueous phase. The oil phase was then emulsified in the aqueous phase under cut (ULTRA TURRAX, T25 Basic and IKA WERKE) at 6500 rpm for two minutes to form a fragrance emulsion.
[00225] The fragrance emulsion was placed in a round bottom container and 10.4 g of 36% Guanidine carbonate (Sigma-Aldrich, St. Louis, MO) was slowly added under constant mixing with a suspended mixer. The capsule formation was immediately visible by light microscopy. The mixer speed was reduced after the addition of Guanidine carbonate was complete. The capsule slurry was cured at 75 ° C for three hours.
[00226] Sample 2-B: Polyurea capsules with a mixture of nonionic and anionic dispersants. Ninety-six grams of a fragrance, Greenfields (IFF, Union Beach, NJ) were weighed and combined with 24 g of NEOBEE oil (Stepan, Chicago, IL) and 9.6 g of isocyanate monomer, DESMODUR N100 (Bayer Corp. , Pittsburgh, PA) to form the oil phase. In a separate beaker, a solution (130 g) containing 1.0% MOWIOL 3-83 (Kuraray America Inc., Houston, TX) was mixed with a solution (30 g) of 1% CMC in water to form a aqueous phase. The oil phase was then emulsified in the aqueous phase under cut (ULTRA TURRAX, T25 Basic, IKA WERKE) at 6500 rpm for two minutes to form a fragrance emulsion.
[00227] The fragrance emulsion was placed in a round bottom container and 10.4 g of 36% Guanidine carbonate (Sigma-Aldrich, St. Louis, MO) was slowly added under constant mixing with a suspended mixer. The capsule formation was immediately visible by light microscopy. The mixer speed was reduced after the addition of Guanidine carbonate was complete. The capsule slurry was cured for three hours.
[00228] Sample 3-B: Polyurea capsules with a mixture of nonionic and anionic dispersants and a catalyst. Ninety-six grams of a fragrance, Greenfields (IFF, Union Beach, NJ) were weighed and combined with 24 g of NEOBEE oil (Stepan, Chicago, IL) and 9.6 g of isocyanate monomer, DESMODUR NI00 (Bayer Corp. , Pittsburgh, PA) to form the oil phase. In a separate beaker, a solution (130 g) containing 1.0% MOWIOL 3-83 (Kuraray America Inc., Houston, TX) was mixed with a solution (30 g) of 1% CMC in water to form a aqueous phase. The oil phase was then emulsified in the aqueous phase under cut (ULTRA TURRAX, T25 Basic and IKA WERKE) at 6500 rpm for two minutes to form a fragrance emulsion.
[00229] The fragrance emulsion was heated to 35 ° C before adding drops of Guanidine carbonate (10.1 g, 36%) and 0.30 g of DABCO (1,4-diazabicyclo [2.2.2] octane ). The capsules were formed immediately after the addition of guanidine carbonate. The capsule slurry was transferred to a round bottom vessel and cured at 75 ° C for three hours.
[00230] Sample 4-B: Polyurea capsules prepared with DESMODUR 3600, a mixture of nonionic and anionic dispersants and a catalyst. Ninety-six grams of a fragrance, Greenfields (IFF, Union Beach, NJ) were weighed and combined with 24 g of NEOBEE oil (Stepan, Chicago, IL) and 9.6 g of isocyanate monomer, DESMODUR 3600 (Bayer Corp. , Pittsburgh, PA) to form the oil phase. In a separate beaker, a solution (130 g) containing 1.0% MOWIOL 3-83 (Kuraray America Inc., Houston, TX) was mixed with a solution (30 g) of 1% CMC in water to form a aqueous phase. The oil phase was then emulsified in the aqueous phase under cut (ULTRA TURRAX, T25 Basic and IKA WERKE) at 6500 rpm for two minutes to form a fragrance emulsion.
[00231] The fragrance emulsion was heated to 35 ° C before addition to the drops of Guanidine carbonate (10.1 g, 36%) and 0.30 g of DABCO. The capsules were formed immediately after the addition of Guanidine carbonate. The capsule slurry was transferred to a round bottom vessel and cured at 75 ° C for three hours.
[00232] Sample 5-B: Polyurea capsules prepared with LUPRANATE M20, a mixture of nonionic and anionic dispersants and a catalyst. Ninety-six grams of a fragrance, Greenfields (IFF, Union Beach, NJ) were weighed and combined with 24 g of NEOBEE oil (Stepan, Chicago, IL, USA) and 9.6 g of isocyanate monomer, LUPRANATE M20 (BASF Corp., Wyandotte, MI) to form the oil phase. In a separate beaker, a solution (130 g) containing 1.0% MOWIOL 3- 83 (Kuraray America Inc., Houston, TX) was mixed with a solution (30 g) of 1% CMC in water to form a aqueous phase. The oil phase was then emulsified in the aqueous phase under cut (ULTRA TURRAX, T25 Basic and IKA WERKE) at 6500 rpm for two minutes to form a fragrance emulsion.
[00233] The fragrance emulsion was heated to 35 ° C before addition to the drops of Guanidine carbonate (10.1 g, 36%) and 0.30 g of DABCO. The capsules were formed immediately after the addition of Guanidine carbonate. The capsule slurry was transferred to a round bottom vessel and cured at 75 ° C for three hours.
[00234] Sample 6-B: Polyurea capsules containing a combination of nonionic and cationic dispersants. Ninety-six grams of a fragrance, Greenfields (IFF, Union Beach, NJ) were weighed and combined 24 g of NEOBEE oil (Stepan, Chicago, IL) and 9.6 g of isocyanate monomer, DESMODUR N100 (Bayer Corp., Pittsburgh, PA) to form the oil phase. In a separate beaker, a solution (130 g) containing 0.6% MOWIOL 18-88 (Kuraray America Inc., Houston, TX) was mixed with a solution (7.5 g) of 1% LUVIQUAT Ultra Care (polyquaternium -44, BASF, Tarrytown, NY) in water to form an aqueous phase. The oil phase was then emulsified in the aqueous phase under cut (ULTRA TURRAX, T25 Basic, IKA WERKE) at 6500 rpm for two minutes to form a fragrance emulsion.
[00235] The fragrance emulsion was heated to 35 ° C before addition to the drops of Guanidine carbonate (10.1 g, 36%) and 0.30 g of DABCO. The capsules were formed immediately after the addition of Guanidine carbonate. The capsule slurry was transferred to a round bottom vessel and cured at 75 ° C for three hours.
[00236] Sample 7-B Polyurea capsules containing guanidine hydrochloride. Ninety-six grams of a fragrance, Greenfields (IFF, Union Beach, NJ) were weighed and combined 24 g of NEOBEE oil (Stepan, Chicago, IL) and 9.6 g of isocyanate monomer, DESMODUR N100 (Bayer Corp., Pittsburgh, PA) to form the oil phase. In a separate beaker, a solution (130 g) containing 1.0% PVA (polyvinyl alcohol, MOWIOL 3-83, (Kurray, Houston, TX) was mixed with a solution (30 g) of 1% CMC in water to form an aqueous phase. The oil phase was then emulsified into the aqueous phase under cut (ULTRA TURRAX, T25 Basic, IKA WERKE) at 6500 rpm for two minutes to form a fragrance emulsion.
[00237] The fragrance emulsion was heated to 35 ° C before adding the drops of guanidine hydrochloride (10.1 g, 36%) and 0.30 g of DABCO. The capsules were formed immediately after the addition of guanidine hydrochloride. The capsule slurry was transferred to a round bottom vessel and cured at 75 ° C for three hours.
[00238] Sample 8-B: Polyurea capsules containing guanidine hydrochloride prepared under basic conditions. Ninety-six grams of a fragrance, Greenfields (International IFF, Union Beach, NJ) were weighed and combined with 24 g of NEOBEE oil (Stepan, Chicago, IL) and 9.6 g of isocyanate monomer, DESMODUR NI00 (Bayer Corp ., Pittsburgh, PA) to form the oil phase. In a separate beaker, a solution (130 g) containing 1.0% PVA (polyvinyl alcohol, MOWIOL 3-83, (Kurray, Houston, TX) was mixed with a solution (30 g) of 1% CMC in water to form an aqueous phase. The oil phase was then emulsified into the aqueous phase under cut (ULTRA TURRAX, T25 Basic, IKA WERKE) at 6500 rpm for two minutes to form a fragrance emulsion.
[00239] A mixture of guanidine hydrochloride (10.1 g, 36%) and catalyst (0.30 g), DABCO (Dow Chemical, Midland, MI) were adjusted to pH 12 using 12 mol / L sodium hydroxide . The fragrance emulsion was heated prior to adding the drops of the aqueous mixture. The capsules were formed immediately after the addition of guanidine hydrochloride. The capsule slurry was transferred to a round bottom vessel and cured at 75 ° C for three hours.
[00240] Sample 9-B: Polyurea capsules containing guanidine hydrochloride and sodium carbonate prepared under basic conditions. Ninety-six grams of a fragrance, Greenfields (IFF, Union Beach, NJ) were weighed and combined with 24 g of NEOBEE oil (Stepan, Chicago, IL) and 9.6 g of isocyanate monomer, DESMODUR NI 00 (Bayer Corp ., Pittsburgh, PA) to form the oil phase. In a separate beaker, a solution (130 g) containing 1.0% PVA (polyvinyl alcohol, MOWIOL 3-83, (Kurray, Houston, TX) was mixed with a solution (30 g) of 1% CMC in water to form an aqueous phase. The oil phase was then emulsified into the aqueous phase under cut (ULTRA TURRAX, T25 Basic, IKA WERKE) at 6500 rpm for two minutes to form a fragrance emulsion.
[00241] A mixture containing guanidine hydrochloride (10.1 g, 36%), sodium carbonate (3 g) and catalyst (0.30 g), DABCO (Dow Chemical, Midland, MI) were adjusted to pH 12 by 12 mol / L sodium hydroxide. The fragrance emulsion was heated to 35 ° C before adding the drops of the aqueous mixture. The capsules were formed immediately after the addition of guanidine hydrochloride. The capsule slurry was transferred in a round bottom vessel and cured at 75 ° C for two hours.
[00242] Physical characterization of the polyurea capsule. Microscopic analysis indicated that the capsules prepared according to this invention had robust mechanical stability. In addition, thermogravimetric analyzes (Figures 8A-8D) indicated that samples prepared with a mixture of PVA and CMC as capsule formation aids (Figures 8A and 8D) released their contents at a higher temperature than the capsules made from a mixture of PVA and POLYQUATÉRNIO-44 (Figure 1B) or PVA alone (Figure 8C). These results demonstrated the thermal stability of the samples prepared with a capsule-forming aid.
[00243] Performance of encapsulation of polyurea capsules. Sample 2-B was diluted with distilled water to produce a mixture containing 0.2% of the capsule slurry. One gram of each of the diluted capsule slurries was applied directly to each side of a 4x6 tissue sample. Two samples were prepared. The samples were air dried overnight and the upper tissue space was analyzed before and after shaking with stainless steel ball bearings to break the capsules intact. The results of this analysis are shown in table 7. TABLE 7

[00244] This analysis indicated that there is a dramatic increase in the upper space after the capsules are broken by crushing. This demonstrated that the perception of increased perfumery can be achieved once the capsules are deposited in the tissue and broken by physical forces.
[00245] Sensory performance of polyurea capsules. To establish the consumer benefits of polyurea capsules, a capsule slurry was combined on a roll-on basis and evaluated for its consumer benefits. The fragrance charge was 0.50% pure equivalent. For comparison, a similar solution was prepared using 0.5% pure fragrance. The sample (0.3 g) was then applied to a blotting pad (4x6) and was allowed to dry overnight before being evaluated by a panel of 12 judges. The fragrance intensity was calculated on a scale ranging from 0 to 10. A numerical value of 10 should suggest that the individual generated a very strong smell. The results of this analysis are shown in table 8. TABLE 8

[00246] This analysis indicated that the capsules prepared according to the present invention had a much stronger fragrance intensity compared to pure fragrance in the post-rub stage and was able to release the full benefit of the fragrance formulation.
[00247] Perfumery performance of polyurea capsules. To establish the performance of the polyurea capsules, samples 3-B and 4-B were combined in a model rinse conditioner solution containing 24% cationic surfactant. The fragrance charge was 0.5% pure equivalent. For comparison, a similar solution was prepared using 1% pure fragrance. The perfumery benefit of the capsules was assessed by conducting a laundry experiment using conventional experimental protocols. Terry towels were used for the washing experiments and were air dried overnight before being evaluated by a panel of 12 judges. The fragrance intensity was calculated on a scale ranging from 0 to 10. A numerical value of 2 should suggest that the fabric only produces very low intensity while a value of 10 indicates how the individual generated a strong smell. The results of this analysis are shown in table 9. TABLE 9

[00248] This analysis indicated that fragrance polyurea capsules produce much greater fragrance intensity in the pre-rub and post-rub stages. The increase in fragrance intensity was much more striking in the post-scrubbing stage. This demonstrated that fragrance polyurea capsules prepared according to a current invention are capable of effectively retaining fragrance and are able to release the full consumer benefits of fragrance products.
[00249] Benefit of applying polyurea capsules. The benefit of applying to a personal care product was further assessed using a hair conditioner formulation. To conduct the experiment, the capsule slurry was dispersed in a capillary conditioner base at 0.5% equivalent pure fragrance. The hair conditioner base was an oil-free conditioner base Magick Botanicals. The base was added to Sample 3-B. The formulation was applied to bundles of hair (40 g each), which contains four strands of hair. The bundles were subsequently washed by moistening two bundles (8 threads) under water (water temperature: 100F / 38C; flow rate: 1 gallon / minute) and squeezing lightly by squeezing the excess water slightly. The hair was placed on a scale and 2 g of fragrance-free shampoo was applied directly to damp hair. The hair was lathered between the palms of the hands, 10x clockwise and 10x counterclockwise, keeping part of the sample wax between two fingers (does not spread the wax on the surface of the hair). The hair samples were left to stand for 15 seconds and subsequently rinsed under a stream of water for 45 seconds. The process was repeated with hair conditioner. The excess water was gently removed and the hair was left to dry overnight. The dry samples were then evaluated by 16 trained participants and the results are shown in table 10. TABLE 10

[00250] This analysis will demonstrate that the product containing polyurea capsules has a much stronger perfumery intensity than the pure fragrance. In this way, the polyurea capsule delivered excellent benefits to the consumer both in the pre-scrubbing and post-scrubbing stages. Example 44: Polyurea capsules prepared with polyaliphatic isocyanate and amphoteric amines
[00251] Sample 1-C. Preparation of polyurea capsule. Ninety-six grams of a fragrance, Greenfields (IFF, Union Beach, NJ) were weighed and combined with 24 g of NEOBEE oil (Stepan, Chicago, IL) and 9.6 g of isocyanate monomer, DESMODUR NI00 (Bayer Corp. , Pittsburgh, PA) to form the oil phase. In a separate beaker, a 1.0% surfactant solution (160 g) was prepared by dissolving a sufficient amount of MORWET D-425 (Akzo Nobel, Fort Worth, TX) in water. The oil phase was then emulsified in the aqueous phase under cut (ULTRA TURRAX, T25 Basic and IKA WERKE) at 6500 rpm for two minutes to form a fragrance emulsion.
[00252] The fragrance emulsion was placed in a round bottom vessel and 10.4 g of 56% lysine (Sigma-Aldrich, St. Louis, MO) was added under constant mixing with a suspended mixture. The capsule formation was immediately visible by light microscopy. The mixer speed was reduced after the addition of lysine was complete. The capsule slurry was cured at 55 ° C for three hours.
[00253] Sample 2-C. Polyurea capsules prepared with a catalyst. Ninety-six grams of a fragrance, Greenfields (IFF, Union Beach, NJ) were weighed and combined with 24 g of NEOBEE oil (Stepan, Chicago, IL) and 9.6 g of isocyanate monomer, DESMODUR N100 (Bayer Corp. , Pittsburgh, PA) to form the oil phase. In a separate beaker, a solution (130 g) containing 1.0% FLEXAN II (Akzo Nobel, Bridgewater, NJ) was mixed with a solution (30 g) of 1% CMC in water to form an aqueous phase. The oil phase was then emulsified in the aqueous phase under cut (ULTRA TURRAX, T25Basic, IKA WERKE) at 6500 rpm for two minutes to form a fragrance emulsion.
[00254] The fragrance emulsion was heated to 35 ° C before adding a mixture containing lysine (10.1 g, 58%) and DABCO (0.30 g, Dow Chemical, Midland, MI) to the drops. The capsules were formed immediately after adding lysine and catalyst. The capsule slurry was transferred into a round bottom container and the capsules were cured for 2 hours.
[00255] Sample 3-C: Polyurea capsule prepared with more amino acid. Ninety-six grams of fragrance, Greenfields (IFF, Union Beach, NJ) were weighed and combined with 24 g of NEOBEE oil (Stepan, Chicago, IL) and 9.6 g of isocyanate monomer, DESMODUR NI00 (Bayer Corp., Pittsburgh, PA) to form the oil phase. In a separate beaker, a 1.0% surfactant solution (160 g) was prepared by dissolving sufficient amount of MORWET D-425 (Akzo Nobel, Fort Worth, TX) in water. The oil phase was then emulsified in the aqueous phase under cut (ULTRA TURRAX, T25 Basic, IKA WERKE) at 6500 rpm for two minutes to form a fragrance emulsion.
[00256] The fragrance emulsion was placed in a round bottom container and 19.8 g of 57% DE lysine (Sigma-Aldrich, St. Louis, MO) and 0.60 g of DABCO were added under constant mixing with a suspended mixer. The capsule formation was immediately visible by light microscopy. The mixer speed was reduced after the addition of lysine was complete. The capsule slurry was cured at 55 ° C for three hours.
[00257] Sample 4-C: Polyurea capsules prepared with the addition of amino acid at elevated temperature. Ninety-six grams of a fragrance, Greenfieds (IFF, Union Beach, NJ) were weighed and combined with 24 g of NEOBEE oil (Stepan, Chicago, IL) and 9.6 g of isocyanate monomer, DESMODUR NI00 (Bayer Corp. , Pittsburgh, PA) to form the oil phase. In a separate beaker, a 1.0% surfactant solution (160 g) was prepared by dissolving sufficient amount of MORWET D-425 (Akzo Nobel, Fort Worth, TX, USA) in water. The oil phase was then emulsified in the aqueous phase under cut (ULTRA TURRAX, T25 Basic, IKA WERKE) at 6500 rpm for two minutes to form a fragrance emulsion.
[00258] The fragrance emulsion was heated to 35 ° C before adding the drops of lysine (10.1 g, 58%) and 0.30 g of DABCO. The capsule formation was immediately visible by light microscopy. The capsule slurry was transferred in a round bottom vessel and cured at 55 ° C for two hours.
[00259] Sample 5-C: Polyurea capsule prepared with the addition of amino acid at high temperature and cure at high temperature. Ninety-six grams of a fragrance, Greenfields (IFF, Union Beach, NJ) were weighed and combined with 24 g of NEOBEE oil (Stepan, Chicago, IL) and 9.6 g of isocyanate monomer, DESMODUR NI00 (Bayer Corp. , Pittsburgh, PA) to form the oil phase. In a separate beaker, a 1.0% surfactant solution (160 g) was prepared by dissolving a sufficient amount of MORWET D-425 (Akzo Nobel, Fort Worth, TX) in water. The oil phase was then emulsified in the aqueous phase under cut (ULTRA TURRAX, T25 Basic, IKA WERKE) at 6500 rpm for two minutes to form a fragrance emulsion.
[00260] The fragrance emulsion was heated before adding the drops of lysine (10.1 g, 58%) and 0.30 g of DABCO. The capsule formation was immediately visible by light microscopy. The capsule slurry was transferred in a round bottom container and the capsule slurry was cured at 55 ° C for 2 hours and then for 2 hours.
[00261] Sample 6-C: Polyurea capsules prepared with a combination of dispersants. Ninety-six grams of a fragrance, Greenfields (IFF, Union Beach, NJ) were weighed and combined with 24 g of NEOBEE oil (Stepan, Chicago, IL) and 9.6 g of isocyanate monomer, DESMODUR N100 (Bayer Corp. , Pittsburgh, PA) to form the oil phase. In a separate beaker, a solution (130 g) containing 1.0% FLEXAN II (Akzo Nobel, Bridgewater, NJ) was mixed with a solution (30 g) of 1% CMC in water to form an aqueous phase. The oil phase was then emulsified in the aqueous phase under cut (ULTRA TURRAX, T25 Basic, IKA WERKE) at 6500 rpm for two minutes to form a fragrance emulsion.
[00262] The fragrance emulsion was heated to 35 ° C before adding the drops of lysine (10.1 g, 58%) and 0.30 g of DABCO. The capsule formation was immediately visible by light microscopy. The capsule slurry was transferred to a round bottom vessel and cured at 55 ° C for 2 hours.
[00263] Sample 7-C: Polyurea capsules prepared with arginine. Ninety-six grams of a fragrance, Greenfields (IFF, Union Beach, NJ) were weighed and combined with 24 g of NEOBEE oil (Stepan, Chicago, IL) and 9.6 g of isocyanate monomer, DESMODUR N100 (Bayer Corp. , Pittsburgh, PA) to form the oil phase. In a separate beaker, a solution (120 g) containing 1.0% FLEXAN II (Akzo Nobel, Bridgewater, NJ) was mixed with a solution (30 g) of 1% CMC in water to form an aqueous phase. The oil phase was then emulsified in the aqueous phase under cut (ULTRA TURRAX, T25 Basic, IKA WERKE) at 6500 rpm for two minutes to form a fragrance emulsion.
[00264] The fragrance emulsion was heated to 35 ° C before adding the drops of arginine (20.1 g, 25%) and 0.30 g of DABCO. The fragrance capsule was immediately after adding lysine and catalyst. The capsule formation was immediately visible by light microscopy. The capsule slurry was transferred to a round bottom vessel and cured at 55 ° C for 2 hours.
[00265] Sample 8-C: Polyurea capsules prepared with arginine monochloride. Ninety-six grams of a fragrance (IFF, Union Beach, NJ) were weighed and combined with 24 g of NEOBEE oil (Stepan, Chicago, IL) and 9.0 g of isocyanate monomer, DESMODUR N100 (Bayer Corp., Pittsburgh, PA) to form the oil phase. In a separate beaker, a solution (120 g) containing 1.1% PVA (polyvinyl alcohol, MOWIOL 3-83; Kunay, Houston, TX) was combined with 30 g of water to form an aqueous phase. The oil phase was then emulsified in the aqueous phase under cut (ULTRA TURRAX, T25 Basic, IKA WERKE) at 6500 rpm for two minutes to form a fragrance emulsion.
[00266] The fragrance emulsion was heated to 35 ° C before adding the drops of arginine monochloride (20.1 g, 32%) and 0.30 g of DABCO. The capsule formation was immediately visible by light microscopy. The capsule slurry was transferred to a round bottom vessel and cured at 55 ° C for 2 hours.
[00267] Sample 9-C: Polyurea capsules prepared with lysine under basic conditions. Ninety-six grams of a fragrance, Greenfield (IFF, Union Beach, NJ) were weighed and combined with 24 g of NEOBEE oil (Stepan, Chicago, IL) and 9.6 g of isocyanate monomer, DESMODUR NI00 (Bayer Corp ., Pittsburgh, PA) to form the oil phase. In a separate beaker, a solution (130 g) containing 1.0% PVA (polyvinyl alcohol, MOWIOL 3-83; Murray, Houston, TX) was mixed with a solution (30 g) of 1% CMC in water to form an aqueous phase. The oil phase was then emulsified in the aqueous phase under cut (ULTRA TURRAX, T25 Basic, IKA WERKE) at 6500 rpm for two minutes to form a fragrance emulsion,
[00268] A mixture containing lysine (10.1 g, 58%) and DABCO (0.30 g) were adjusted to pH 12 by 12 mol / L sodium hydroxide. The fragrance emulsion was heated to 35 ° C before the aqueous mixture was added to the drops. The capsule formation was immediately visible by light microscopy. The capsule slurry was transferred to a round bottom vessel and cured at 55 ° C for 2 hours.
[00269] Sample 10-C. Polyurea capsules prepared with lysine and sodium carbonate under basic conditions. Ninety-six grams of a fragrance, Greenfields (IFF, Union Beach, NJ) were weighed and combined with 24 g of NEOBEE oil (Stepan, Chicago, IL) and 9.6 g of isocyanate monomer, DESMODUR NI00 (Bayer Corp. , Pittsburgh, PA) to form the oil phase. In a separate beaker, a solution (130 g) containing 1.0% PVA (polyvinyl alcohol, MOWIOL 3-83; Murray, Houston, TX) was mixed with a solution (30 g) of 1% CMC in water to form an aqueous phase. The oil phase was then emulsified in the aqueous phase under cut (ULTRA TURRAX, T25 Basic, IKA WERKE) at 6500 rpm for two minutes to form a fragrance emulsion.
[00270] A mixture containing lysine (10.1 g, 56%), sodium carbonate (4 g) and DABCO (0.30 g) were adjusted to pH 12 by 12 mol / L sodium hydroxide. The fragrance emulsion was heated to 35 ° C before adding the drops of the aqueous mixture. The capsule formation was immediately visible by light microscopy. The capsule slurry was transferred to a round bottom vessel and cured at 55 ° C for 2 hours.
[00271] Sample 11-C: Polyurea capsules prepared with arginine monochloride under basic condition. Ninety-six grams of a fragrance, Greenfields (IFF, Union Beach, NJ) were weighed and combined with 24 g of NEOBEE oil (Stepan, Chicago, IL) and 9.6 g of isocyanate monomer, DESMODUR NI00 (Bayer Corp. , Pittsburgh, PA) to form the oil phase. In a separate beaker, a solution (120 g) containing 1.1% PVA (polyvinyl alcohol, MOWIOL 3-83; Murray, Houston, TX) was mixed with a solution (30 g) of 1% CMC in water to form an aqueous phase. The oil phase was then emulsified in the aqueous phase under cut (ULTRA TURRAX, T25 Basic, IKA WERKE) at 6500 rpm for two minutes to form a fragrance emulsion.
[00272] The fragrance emulsion was heated to 35 ° C before adding to the drops a mixture containing arginine monochloride (18.9 g, 35%), sodium hydroxide (1.2 g) and DABCO (0.30 g). The capsule formation was immediately visible by light microscopy. The capsule slurry was transferred to a round bottom vessel and cured at 55 ° C for 2 hours.
[00273] Sample 12-C: Polyurea capsules prepared with arginine monochloride and sodium carbonate. Ninety-six grams of a fragrance, Greenfields (IFF, Union Beach, NJ) were weighed and combined with 24 g of NEOBEE oil (Stepan, Chicago, IL) and 9.6 g of isocyanate monomer, DESMODUR NI00 (Bayer Corp. , Pittsburgh, PA) to form the oil phase. In a separate beaker, a solution (120 g) containing 1.0% PVA (polyvinyl alcohol, MOWIOL 3-83; Kurray, Houston, TX) was mixed with a solution (30 g) of 1% CMC in water to form an aqueous phase. The oil phase was then emulsified in the aqueous phase under cut (ULTRA TURRAX, T25 Basic, IKA WERKE) at 6500 rpm for two minutes to form a fragrance emulsion.
[00274] The fragrance emulsion was heated to 35 ° C before adding to the drops a mixture containing arginine monochloride (16.1 g, 41%), sodium carbonate (4 g) and DABCO (0.30 g) . The capsule formation was immediately visible by light microscopy. The capsule slurry was transferred to a round bottom vessel and cured at 55 ° C for 2 hours.
[00275] Physical characterization of polyurea capsules. The capsules from Sample 2-C were analyzed with scanning electron microscopy (Figure 9A) and optical microscopy (Figure 9B). Capsules prepared in accordance with the present invention have been found to have robust mechanical stability.
[00276] Performance of encapsulation of polyurea capsules. The fragrance capsule slurry (Sample 2-C) was diluted with distilled water to produce a mixture containing 0.2% of the capsule slurry. One gram of the diluted capsule slurry was applied directly to each side of a 4x6 tissue sample. Two experiments were prepared. The samples were air dried overnight and the upper tissue space was analyzed before and after shaking with stainless steel ball bearings to break the capsules intact. The results of this analysis are shown in table 11. TABLE 11

[00277] This analysis indicated that there is a dramatic increase in the upper space after the capsules are broken by crushing. This demonstrated that the perception of increased perfumery can be achieved once the capsules are deposited in the tissue and broken by physical forces.
[00278] Sensory performance of polyurea capsules. To establish the consumer benefits of polyurea capsules, a capsule slurry prepared with an aliphatic isocyanate and amphoteric amine was combined on a roll-on basis and evaluated for its consumer benefits. The fragrance charge was 0.5% pure equivalent. For comparison, a similar solution was prepared using 0.5% pure fragrance. The sample (0.3 g) was then applied to a blotting pad (4x6) and was allowed to dry overnight before being evaluated by a panel of 12 judges. The fragrance intensity was calculated on a scale ranging from 0 to 10. A numerical value of 10 should suggest that the individual generated a very strong smell. The results of this analysis are shown in table 12. TABLE 12

[00279] The capsules prepared with current invention had a much stronger fragrance intensity compared to pure fragrance in the post-rub stage and were able to release the full benefit of the fragrance formulation. Example 45: Polyurea capsules prepared with polyaliphatic isocyanate and Diamine
[00280] Sample I-D: Preparation of polyurea capsule. Ninety-six grams of a fragrance, Greenfields (IFF, Union Beach, NJ) were weighed and combined with 24 g of NEOBEE oil (Stepan, Chicago, IL) and 9.6 g of isocyanate monomer, DESMODUR N3600 (Bayer corporation, Pittsburgh, PA) to form the oil phase. In a separate beaker, a 1.5% surfactant solution (160 g) was prepared by dissolving a sufficient amount of MORWET D-425 (Akzo Nobel, Fort Worth, TX) in water. The oil phase was emulsified in the aqueous phase under cut (ULTRA TURRAX, T25 Basic, IKA WERKE) at 6500 rpm for two minutes to form a fragrance emulsion.
[00281] The fragrance emulsion was placed in a round bottom container and 10.8 g of 70% hexamethylene diamine (HMDA) (INVISTA, Wichita, KS) were added under constant mixing with a suspended mixer. The capsule formation was immediately visible by light microscopy. The mixer speed was reduced after the addition of HMDA was complete. The capsule slurry was cured at 55 ° C for three hours.
[00282] Sample 2-D: Preparation of polyurea capsule with more amine. Ninety-six grams of a fragrance, Greenfields (IFF, Union Beach, NJ) were weighed and combined with 24 g of NEOBEE oil (Stepan, Chicago, IL) and 9.6 g of isocyanate monomer, DESMODUR N3600 (Bayer Corporation, Pittsburgh, PA) to form the oil phase. In a separate beaker, a 1.5% surfactant solution (160 g) was prepared by dissolving a sufficient amount of MORWET D-425 (Akzo Nobel, Fort Worth, TX) in water. The oil phase was emulsified in the aqueous phase under cut (ULTRA TURRAX, T25 Basic, IKA WERKE) at 6500 rpm for two minutes to form a fragrance emulsion.
[00283] The fragrance emulsion was placed in a round bottom container and 21.6 g of 70% HMDA (INVISTA, Wichita, KS) were added under constant mixing with a suspended mixer. The capsule formation was immediately visible by light microscopy. The mixer speed was reduced after the addition of 14MDA was complete. The capsule slurry was cured for three hours.
[00284] Sample 3-D: Polyurea capsule with the addition of HMDA at elevated temperature. Ninety-six grams of a fragrance, Greenfields (IFF, Union Beach, NJ) were weighed and combined with 24 g of NEOBEE oil (Stepan, Chicago, IL) and 9.6 g of isocyanate monomer, DESMODUR N3600 (Bayer corporation, Pittsburgh, PA) to form an oily phase. In a separate beaker, a 1.5% surfactant solution (160 g) was prepared by dissolving a sufficient amount of MORWET D-425 (Akzo Nobel, Fort Worth, TX) in water. The oil phase was emulsified in the aqueous phase under cut (ULTRA TURRAX, T25 Basic, IKA WERKE) at 6500 rpm for two minutes to form a fragrance emulsion.
[00285] The fragrance emulsion was heated to 35 ° C before adding the drops of HMDA (10.8 g, 70%). The capsule formation was immediately visible by light microscopy. The capsule slurry was cured at 55 ° C for two hours.
[00286] Sample 4-D: Polyurea capsule with addition of HMDA at high temperature and cure at high temperature. Ninety-six grams of a fragrance, Greenfields (IFF, Union Beach, NJ) were weighed and combined with 24 g of NEOBEE oil (Stepan, Chicago, IL) and 9.6 g of isocyanate monomer, DESMODUR N3600 (Bayer corporation, Pittsburgh, PA) to form the oil phase. In a separate beaker, a 1.5% surfactant solution (160 g) was prepared by dissolving a sufficient amount of MORWET D-425 (Akzo Nobel, Fort Worth, TX) in water. The oil phase was emulsified in the aqueous phase under cut (ULTRA TURRAX, T25 Basic, IKA WERKE) at 6500 rpm for two minutes to form a fragrance emulsion.
[00287] The fragrance emulsion was heated to 35 ° C before adding the drops of HMDA (10.8 g, 70%). The capsule formation was immediately visible by light microscopy. The capsule slurry was transferred in a round bottom vessel and the capsule slurry was cured at 55 ° C for 2 hours and then at 80 ° C for 2 hours.
[00288] Sample 5-D: Polyurea capsules prepared with a combination of dispersants. Ninety-six grams of a fragrance, Greenfields (IFF, Union Beach, NJ) were weighed and combined 24 g of NEOBEE oil (Stepan, Chicago, IL) and 9.6 g of isocyanate monomer, DESMODUR N3600 (Bayer corporation, Pittsburgh , PA) to form the oil phase. In a separate beaker, a solution (130 g) containing 1.85% FLEXAN II (Akzo Nobel, Bridgewater, NJ) was mixed with a solution (30 g) of 1% CMC in water to form an aqueous phase. The oil phase was emulsified in the aqueous phase under cut (ULTRA TURRAX, T25 Basic, IKA WERKE) at 6500 rpm for two minutes to form a fragrance emulsion.
[00289] The fragrance emulsion was heated to 35 ° C before adding the drops of HMDA (10.8 g, 70%). The capsule formation was immediately visible by light microscopy. The capsule slurry was transferred in a round bottom container and the capsule slurry was cured at 55 ° C for 2 hours.
[00290] Sample 6-D: Polyurea capsules prepared with a catalyst. Ninety-six grams of a fragrance, Greenfields (IFF, Union Beach, NJ) were weighed and combined 24 g of NEOBEE oil (Stepan, Chicago, IL) and 9.6 g of isocyanate monomer, DESMODUR N3600 (Bayer corporation, Pittsburgh , PA) to form the oil phase. In a separate beaker, a solution (130 g) containing 1.85% FLEXAN II (Akzo Nobel, Bridgewater, NJ) was mixed with a solution (30 g) of 1% CMC in water to form an aqueous phase, A oily phase was emulsified in the aqueous phase under cut (ULTRA TURRAX, T25 Basic, IKA WERKE) at 6500 rpm for two minutes to form a fragrance emulsion.
[00291] The fragrance emulsion was heated to 35 ° C before adding 1-IMDA drops (10.8 g, 70%) and 0.30 g DABCO catalyst. The capsule formation was immediately visible by light microscopy. The capsule slurry was transferred in a round bottom container and the capsule slurry was cured at 55 ° C for 2 hours.
[00292] Physical characterization of polyurea capsules. SEM analysis of the capsules indicated that the capsules prepared with current invention had robust mechanical stability.
[00293] Performance of encapsulation of polyurea capsules. The fragrance capsule slurry (Sample 5-D) was diluted with distilled water to produce a mixture containing 0.2% of the capsule slurry. One gram of the diluted capsule slurry was applied directly to each side of a 4x6 tissue sample. Two experiments were prepared. The samples were air dried overnight and the upper tissue space was analyzed before and after shaking with stainless steel ball bearings to break the capsules intact. The results are shown in table 13. TABLE 13

[00294] This analysis indicated that there is a dramatic increase in the upper space after the capsules are broken by crushing. This demonstrated that the perception of increased perfumery can be achieved once the capsules are deposited on the tissue and broken by physical forces.
[00295] Sensory performance of polyurea capsules. To establish the consumer benefits of polyurea capsules, the capsule slurry was combined on a roll-on basis and evaluated for its consumer benefits. The fragrance charge was 0.5% pure equivalent. For comparison, a similar solution was prepared using 0.5% pure fragrance. The sample (0.3 g) was then applied to a blotting pad (4x6) and was allowed to dry overnight before being evaluated by a panel of 12 judges. The fragrance intensity was calculated on a scale ranging from 0 to 10. A numerical value of 10 should suggest that the individual generated a very strong smell. The results are shown in table 14. TABLE 14

[00296] This analysis indicated that the capsules had a much stronger fragrance intensity compared to pure fragrance in the post-rub stage and were able to release the full benefit of the fragrance formulation. Example 46. Preparation of polyurea capsule composition
[00297] Preparation of a fragrance emulsion. Ninety-six grams of a fragrance, Greenfields (International Sabors and Fragrance, Union Beach, NJ) were weighed and combined with 24 g of NEOBEF, oil (Stepan, Chicago, IL) and 9.6 g of isocyanate monomer, Desmodure NI00 (Bayer corporation, Pittsburgh, PA, USA), to form the oil phase. In a separate beaker, an aqueous solution (120 g) containing 1.25% FLEXAN II (Akio Nobel, Bridgewater, NJ) was mixed with a solution (30 g) of 1% CMC in water to form an aqueous phase. The oil phase was then emulsified in the aqueous phase to form a fragrance emulsion under cut (ULTRA TURRAX, T25 Basic, IKA WERKE) at 12500 rpm for two minutes.
[00298] Formation of fragrance capsules. The fragrance emulsion was heated to 35 ° C in a round bottom vessel before adding the drops of arginine monochloride (20.1 g, 32%) and DABCO (0.3 g) under constant mixing with a suspended mixer . The formation of capsules was immediately visible by light microscopy. The mixer speed was reduced after the addition of arginine monochloride was complete. The capsule slurry was cured at 55 ° C for two hours. Example 47. Preparation of polyurea capsule with high cutting speed
[00299] Preparation of a fragrance emulsion. Ninety-six grams of a fragrance, Greenfields (International Sabors and Fragrance, Union Beach, NJ) were weighed and combined with 24 g of NEOBEE oil (Stepan, Chicago, IL) and 9.6 g of isocyanate monomer, Desmodur NI00 ( Bayer corporation, Pittsburgh, PA, USA), to form the oil phase. In a separate beaker, an aqueous solution (120 g) containing 1.25% FLEXAN II (Akzo Nobel, Bridgewater, NJ) was mixed with a solution (30 g) of 1% CMC in water to form an aqueous phase. The oil phase was then emulsified in the aqueous phase to form the fragrance emulsion under cut (ULTRA TURRAX, 725 Basic, IKA WERKE) at 9500 rpm for two minutes.
[00300] Formation of fragrance capsules. The fragrance emulsion was heated to 35 ° C in a round bottom vessel before adding the drops of arginine monochloride (20.1 g, 32%) and DABCO (0.3 g) under constant mixing with a suspended mixer . The formation of capsules was immediately visible by light microscopy. The mixer speed was reduced after the addition of arginine monochloride was complete. The capsule slurry was cured at 55 ° C for two hours. Example 48. Preparation of polyurea capsule cured at elevated temperature
[00301] Preparation of a fragrance emulsion. Ninety-six grams of a fragrance, Greenfields (International Sabors and Fragrance, Union Beach, NJ) were weighed and combined with 24 g of NEOBEE oil (Stepan, Chicago, IL) and 9.6 g of isocyanate monomer, Desmodur NI00 ( Bayer corporation, Pittsburgh, PA, USA), to form the oil phase. In a separate beaker, an aqueous solution (120 g) containing 1.25% FLEXAN II (Akzo Nobel, Bridgewater, NJ) was mixed with a solution (30 g) of 1% CMC in water to form an aqueous phase. The oil phase was then emulsified in the aqueous phase to form a fragrance emulsion under cut (ULTRA TURRAX, T25 Basic, IKA WERKE) at 12500 rpm for two minutes.
[00302] Formation of fragrance capsules. The fragrance emulsion was heated to 35 ° C in a round bottom vessel before adding the drops of arginine monochloride (20.1 g, 32%) and DABCO (0.3 g) under constant mixing with a suspended mixer .
[00303] Capsule formation was immediately visible by optical microscopy. The mixer speed was reduced after the addition of arginine monochloride was complete. The temperature was raised to 75 ° C and then maintained at 75 ° C for 2 hours. Example 49. Preparation of polyurea capsule with more isocyanate precursors and amine crosslinkers
[00304] Preparation of a fragrance emulsion. Ninety-six grams of a fragrance, Greenfields (International Sabors and Fragrance. Union Beach, NJ) were weighed and combined with 24 g of NEOBEE oil (Stepan, Chicago, IL) and 14.4 g of isocyanate monomer, Desmodur NI00 ( Bayer corporation, Pittsburgh, PA, USA), to form the oil phase. In a separate beaker, an aqueous solution (115.2 g) containing 1.3% FLEXAN II (AkzoNobel, Bridgewater, NJ) was mixed with a solution (30 g) of 1% CMC in water to form an aqueous phase . The oil phase was then emulsified in the aqueous phase to form a fragrance emulsion under cut (ULTRA TURRAX, T25 Basic, IKA WERKE) at 12500 rpm for two minutes.
[00305] Formation of fragrance capsules. The fragrance emulsion was heated to 35 ° C in a round bottom vessel before adding the drops of arginine monochloride (20 g, 48%) and DABCO (0.4 g) under constant mixing with a suspended mixer. The formation of capsules was immediately visible by light microscopy. The mixer speed was reduced after the addition of arginine monochloride was complete. The temperature was raised to 55 ° C and then maintained at 55 ° C for 2 hours. Example 50. Preparation of a polyurea capsule with more isocyanate precursors and amine crosslinkers
[00306] Preparation of a fragrance emulsion. Ninety-six grams of a fragrance, Greenfields (International Sabors and Fragrance, Union Beach, NJ) were weighed and combined with 24 g of NEOBEE oil (Stepan, Chicago, IL) and 19.2 g of isocyanate monomer, Desmodur NI00 ( Bayer corporation, Pittsburgh, PA, USA), to form the oil phase. In a separate beaker, an aqueous solution (115.2 g) containing 1.36% FLEXAN II (AkzoNohel, Bridgewater, NJ) was mixed with a solution (30 g) of 1% CMC in water to form an aqueous phase . The oil phase was then emulsified in the aqueous phase to form a fragrance emulsion under cut (ULTRA TURRAX, T25 Basic, IKA WERKE) at 12500 rpm for two minutes.
[00307] Formation of fragrance capsules. The fragrance emulsion was heated in a round bottom vessel before adding the drops of arginine monochloride (19.8 g, 64%) and DABCO (0.6 g) under constant mixing with a suspended mixer. The formation of capsules was immediately visible by light microscopy. The mixer speed was reduced after the addition of arginine monochloride was complete. The temperature was raised to 55 ° C and then maintained at 55 ° C for 2 hours. Example 51: Preparation of a polyurea capsule slurry with improved stability
[00308] To improve stability, twenty-six grams of a capsule slurry as prepared in Example 46 were weighed and 4 g of POLYQUATHERIN-11 (PQ11, Vinyl Pyrrolidone Copolymer / Dimethylaminoethyl Methacrylate, Cationic Polymer, LUVIQUAT PQ11 AT 1, BASF, Ludwigshafen, Germany) was added. The mixture was stirred for approximately 30 minutes by means of a suspended IKA lab mixer until the surfactant was completely dissolved and homogeneous.
[00309] Alternatively, a 10% POLYQUATHERIN-1 solution was prepared by dissolving 20 grams of LUVIQUAT PQ11 AT 1 in 20 grams of water. The stabilized capsule slurry was prepared by mixing 7.5 grams of fragrance capsule slurry prepared as in Example 46 with 22.5 grams of 5% POLYQUATHERIN-11 solution under consistent mixing for 30 minutes. Example 52: Preparation of polyurea capsules incorporating surfactants and polymers as adjuvants
[00310] To evaluate other adjuvants, polyurea capsule slurries were prepared as described in Example 46 and combined with one or more adjuvants as listed in table 15. A general procedure for preparing the formulations is provided using Polyquaternium-6 as a example. A 10% Polyquaternium-6 solution was prepared by adding water in a commercially available 40% Polyquaternium-6 solution from Nalco. The diluted polymer solution was then mixed with the polyurea capsule slurry to give the polyurea capsules with the appropriate level of the adjuvant. The mixture was homogenized using an atomized upper part at 500 rpm for 30 minutes before being placed in the oven for storage tests. TABLE 15
Example 53. Physical characterization of polyurea capsules
[00311] A scanning electron microscopic photo was taken for the capsules prepared in Example 46. The photo showed that the capsules prepared with the current invention have robust mechanical stability. Example 54. Fragrance loading capacity from polyurea capsules
[00312] The composition of the capsules prepared in Examples 46 and 47 was used to evaluate their fragrance loading capabilities. The free fragrance content in the slurries and the average particle size of the capsules were analyzed following known procedures. The results are shown in table 16. TABLE 16
Example 55: Encapsulation performance of polyurea capsules
[00313] The composition of the capsule prepared in Example 46 was combined in a model hair conditioner solution. The fragrance charge was 0.5% pure equivalent. For comparison, similar solutions were prepared with 0.5% pure fragrance. The perfumery benefit of the capsules was assessed by conducting a hair washing experiment using an accepted experimental protocol. The hair was washed and then air-dried overnight before being evaluated by a panel of 12 judges. The fragrance intensity is calculated from a scale ranging from 0 to 10. A numerical value of 2 should suggest that the hair only produces a weak intensity while a value of 10 indicating a very strong smell.
[00314] Hair treated with the capsule composition prepared in Example 46 showed a fragrance intensity of 4.5 post-brushing and an intensity of 2 pre-brushing. In contrast, the hair treated with the pure fragrance showed an intensity of only 3 post-brushing and an intensity of only 1 pre-brushing. Example 56: Investigation of the performance of polyurea capsule slurries with liquid detergent-based polymer adjuvants
[00315] To evaluate the performance of the polyurea capsule compositions, the capsule slurries prepared in Examples 51 and 52 were combined in a European model liquid detergent solution to prepare five capsule formulations, that is, (i) capsules and 2.5% CAI 11, (ii) capsules and 2.5% CA202, (iii) capsules, 1% CAI 11 and 1.5% CA202, (iv) capsules, 1.5% CA301 and 1% CA202 and (v) capsules and 2.5% CA201. The fragrance charge was 0.5% pure equivalent. The comparative capsule formulation was prepared using capsules without any adjuvant to 0.5% pure fragrance equivalent. The perfumery benefit of the capsules was assessed by conducting a laundry experiment using an experimental protocol accepted with a European washing machine. Terry towels were washed and then air dried overnight before being evaluated by a panel of 12 judges. The fragrance intensity is calculated from an LMS scale ranging from 0 to 10. A numerical value of 2 should suggest that the fabric only produces weak intensity while a value of 10 indicating a very strong smell. The five capsule formulations with adjuvants each showed a greater fragrance intensity than that of the comparative capsule formulation. More specifically, the fragrance intensity of the formulation (i) was 4 and that of the comparative was only 2.2, both measured in the post-scrubbing stage. Example 57. Performance of polyurea capsule slurries with polymer adjuvants on the basis of the tissue conditioner
[00316] To evaluate its performance, the composition of the capsules prepared in Example 51 and 52 was combined in a European model tissue conditioner solution to obtain two formulations: one with 2.5% CAI 11 and the other with 2.5 % of CA202. A comparative formulation was prepared using capsules without any adjuvants. The perfumery benefit of the capsules was assessed by conducting a laundry experiment using an accepted experimental protocol with a European washing machine. Terry towels were washed and then air dried overnight before being evaluated by a panel of 12 judges. The results showed that the two capsule formulations showed a fragrance intensity of 3.7 and 3.4 and the comparative formulation had a fragrance intensity of 3.1. Example 58: Investigation of the performance of polyurea capsule slurries with polymer adjuvants on the basis of hair conditioner
[00317] To evaluate its performance, the composition of the capsules prepared in Examples 51 and 52 was combined in a model hair conditioner solution. The fragrance charge was 0.5% pure equivalent. Two capsule formulations were prepared: one with 2.5% CA202 and the other with 1% CA 111 and 1.5% CA202. Two comparative formulations were prepared, one using hydrogel capsules described in Patent W02014011860A2 and the other using polyurea capsules without any adjuvant. In both comparative formulations, the fragrance charge was 0.5% pure equivalent. Each formulation was aged 4 weeks at 37 ° C. The perfumery benefit of the capsules was assessed by conducting a hair washing experiment using an accepted experimental protocol. The hair was washed and then air-dried overnight before being evaluated by a panel of 12 judges. The fragrance intensity is calculated from a scale ranging from 0 to 10. Unexpectedly, the two capsule formulations had a fragrance intensity of 6.8 and 6.3, after brushing. In contrast, the comparative formulations had a fragrance intensity of 3.1. Other modalities
[00318] All features described in this specification can be combined in any combination. Each feature described in this specification can be replaced by an alternative feature that serves the same or similar purpose. Thus, unless otherwise expressly stated, each characteristic described is only an example of the generic series of equivalent or similar characteristics.
[00319] Instead of achieving the purpose of encapsulating an active material, a person skilled in the art can design and prepare a capsule composition by using different polyisocyanates, crosslinking agents and / or capsule forming aids, that vary a concentration of these wall-forming materials and / or catalysts to achieve or release desired organoleptic profiles in a consumable product. In addition, the ratios between polyisocyanates, crosslinking agents, capsule forming auxiliaries, adjuvants, core modifiers, active materials and catalysts can also be determined by a skilled technician through tests known in the art to prepare capsule compositions with desirable properties.
[00320] From the description above, a skilled technician can easily determine the essential characteristics of the present invention and without diverging from the spirit and scope of these, can carry out various changes and modifications of the invention to adapt to various uses and conditions. In this way, other modalities are also within the claims.

权利要求:
Claims (19)
[0001]
1. Polyurea capsule composition, characterized by the fact that it comprises a plurality of capsules and a capsule formulation aid, in which each capsule contains a polyurea wall and an oil core; the polyurea wall is formed from a polyisocyanate reaction product and a crosslinking agent in the presence of the capsule forming aid; polyisocyanate is present at a level of 0.1 to 10%; the oil core contains an active material at a level of 0.5 to 80%; the cross-linking agent contains a branched polyethyleneimine at a level of 0.1 to 5%; the capsule-forming aid is a mixture of polyvinylpyrrolidone and a copolymer of vinyl pyrrolidone and quaternized dimethylaminoethyl methacrylate; polyvinylpyrrolidone is present at a level of 0.1 to 5%; the copolymer of vinyl pyrrolidone and quaternized dimethylaminoethyl methacrylate is present at a level of 0.1 to 5%; the active material contains a fragrance; and all percentages are based on the weight of the polyurea capsule composition.
[0002]
2. Polyurea capsule composition according to claim 1, characterized by the fact that the branched polyethyleneimine has a molecular weight of 10,000 to 2,000,000 Da.
[0003]
3. Polyurea capsule composition according to claim 1, characterized by the fact that the polyisocyanate is an aromatic polyisocyanate, aliphatic polyisocyanate or combination thereof, the aromatic polyisocyanate containing a phenyl, tolyl, xylyl, naphthyl or diphenyl or a combination thereof and the aliphatic polyisocyanate being a hexamethylene diisocyanate trimer, an isophorone diisocyanate trimer, a hexamethylene diisocyanate biuret or a combination thereof.
[0004]
4. Polyurea capsule composition according to claim 3, characterized by the fact that the polyisocyanate is an aromatic polyisocyanate selected from the group consisting of a toluene diisocyanate polyisocyanurate, a propane-adduct trimethylol of toluene diisocyanate and a trimethylol propane-xylylene diisocyanate adduct.
[0005]
5. Polyurea capsule composition according to claim 3, characterized by the fact that the polyisocyanate is an aliphatic polyisocyanate.
[0006]
6. Polyurea capsule composition according to claim 1, characterized by the fact that the active material additionally contains a flavor or a neutralizing odor agent.
[0007]
7. Polyurea capsule composition according to claim 1, characterized by the fact that the oil core still contains a core modifier.
[0008]
8. Polyurea capsule composition according to claim 1, characterized by the fact that it additionally comprises a deposition aid which is an anionic, cationic, non-ionic or zwitterionic polymer.
[0009]
9. Method for preparing a polyurea capsule composition as defined in claim 1, characterized by the fact that it comprises: (a) preparing an oil phase comprising an active material and a polyisocyanate; (b) preparing a dispersing solution containing a capsule-forming aid; (c) emulsifying the oil phase in the dispersing solution to form an active emulsion; (d) adding a cross-linking agent to the active emulsion to form a capsule slurry; (e) curing the capsule slurry, thereby obtaining a polyurea capsule composition, wherein the capsule composition has a plurality of capsules and the capsule forming aid; each of the capsules contains a polyurea wall and an oil core; the polyurea wall is formed from a polyisocyanate reaction product and the crosslinking agent in the presence of the capsule forming aid; polyisocyanate is present at a level of 0.1 to 10%; the oil core contains the active material at a level of 0.5 to 80%; the cross-linking agent contains a branched polyethyleneimine at a level of 0.1 to 5%; the capsule-forming aid is a mixture of polyvinylpyrrolidone and a copolymer of vinyl pyrrolidone and quaternized dimethylaminoethyl methacrylate; polyvinylpyrrolidone is present at a level of 0.1 to 5%; the copolymer of vinyl pyrrolidone and quaternized dimethylaminoethyl methacrylate is present at a level of 0.1 to 5%; the active material contains a fragrance; and all percentages are based on the weight of the polyurea capsule composition.
[0010]
Method according to claim 9, characterized in that it additionally comprises adding the base to the active emulsion.
[0011]
11. Method according to claim 10, characterized by the fact that the base is a metallic carbonate, metallic bicarbonate, metallic hydroxide or combination thereof.
[0012]
Method according to claim 9, characterized in that it further comprises adding a catalyst to the active emulsion, wherein the catalyst is able to increase the rate of reaction between the polyisocyanate and the crosslinking agent.
[0013]
13. Method according to claim 9, characterized in that the crosslinking agent is added to the active emulsion at 20-45 ° C.
[0014]
Method according to claim 9, characterized in that the capsule slurry is cured at 55-135 ° C.
[0015]
Method according to claim 9, characterized in that it further comprises purifying the capsule slurry by diafiltration, centrifugation, or washing with water until a neutral pH is reached.
[0016]
Method according to claim 15, characterized in that it further comprises adding a salt to the cured capsule slurry before washing the capsule slurry with water.
[0017]
17. Polyurea capsule composition, characterized by the fact that it is prepared by a method as defined in claim 9.
[0018]
18. Consumer product, characterized by the fact that it comprises a capsule composition as defined in claim 1.
[0019]
19. Consumer product according to claim 18, characterized by the fact that the consumer product is a shampoo, a hair conditioner, a soap, a body wash, a cosmetic preparation, a body liquid detergent, a cleanser for all purposes, a fabric softener or soft drink, an ironing water, a fabric detergent, a fabric softener, a dryer blade, a fine fragrance, a cologne product, a deodorant, a roll-on product or a product aerosol.

类似技术:

---

公开号 | 公开日 | 专利标题

---

US10434045B2|2019-10-08|Polyurea or polyurethane capsules

---

BR112016003137B1|2020-10-27|polyurea capsule composition, method for preparing a polyurea capsule composition and, consumer product

---

US10842721B2|2020-11-24|Purified polyurea capsules, methods of preparation, and products containing the same

---

US10537503B2|2020-01-21|Microcapsule compositions with high performance

---

US9816059B2|2017-11-14|Stabilized capsule compositions

---

US9687424B2|2017-06-27|Polyurea capsules prepared with aliphatic isocyanates and amines

---

US10555879B2|2020-02-11|Polyurea capsule compositions

---

ES2790417T3|2020-10-27|Hybrid fragrance encapsulation formulation and method of using it

---

US11129778B2|2021-09-28|Compositions containing microcapsules coated with deposition proteins

---

US20160166480A1|2016-06-16|Microcapsule compositions

---

US20200360244A1|2020-11-19|Polyurea capsules prepared with aliphaticisocyanates and amines

---

WO2016028875A1|2016-02-25|Processes for preparing multiple capsules

---

BR102014025407A2|2016-06-21|terpolymer-coated polymer encapsulated active material

---

US20140287008A1|2014-09-25|Hybrid polyurea fragrance encapsulate formulation and method for using the same

---

BR102015000412A2|2016-07-12|hybrid encapsulated fragrance formulation and method of use

同族专利:

---

公开号 | 公开日

---

BR112016003137A2|2017-09-12|

---

CN105722495B|2020-02-28|

---

MX361658B|2018-12-13|

---

EP3033066A4|2017-05-03|

---

WO2015023961A1|2015-02-19|

---

MX2016002041A|2016-09-13|

---

EP3033066A1|2016-06-22|

---

MX2019014263A|2020-01-23|

---

BR122019023314B1|2020-10-06|

---

CN105722495A|2016-06-29|

引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

---

US3886085A|1971-08-31|1975-05-27|Fuji Photo Film Co Ltd|Process for producing fine oil-containing microcapsules having strong protective shells and microcapsules produced thereby|

---

BE795421A|1972-02-14|1973-05-29|Fuji Photo Film Co Ltd|PROCESS FOR THE PRODUCTION OF MICROCAPSULES HAVING STRONG CELLULAR WALLS|

---

US4285720A|1972-03-15|1981-08-25|Stauffer Chemical Company|Encapsulation process and capsules produced thereby|

---

GB1524307A|1976-06-16|1978-09-13|Monsanto Europe Sa|Encapsulation process|

---

FR2413123B1|1977-12-30|1981-10-23|Rhone Poulenc Agrochimie|

---

US4280833A|1979-03-26|1981-07-28|Monsanto Company|Encapsulation by interfacial polycondensation, and aqueous herbicidal composition containing microcapsules produced thereby|

---

DE2930409A1|1979-07-26|1981-02-12|Bayer Ag|SPRAY DRYING OF MICROCAPSEL DISPERSIONS|

---

US4318818A|1979-11-09|1982-03-09|The Procter & Gamble Company|Stabilized aqueous enzyme composition|

---

FR2471996B1|1979-12-21|1985-05-24|Oreal|

---

US4387090A|1980-12-22|1983-06-07|The Procter & Gamble Company|Hair conditioning compositions|

---

US4446032A|1981-08-20|1984-05-01|International Flavors & Fragrances Inc.|Liquid or solid fabric softener composition comprising microencapsulated fragrance suspension and process for preparing same|

---

US4464271A|1981-08-20|1984-08-07|International Flavors & Fragrances Inc.|Liquid or solid fabric softener composition comprising microencapsulated fragrance suspension and process for preparing same|

---

US4428869A|1981-08-20|1984-01-31|International Flavors & Fragrances Inc.|Cologne consisting of microcapsule suspension|

---

US4561998A|1982-05-24|1985-12-31|The Procter & Gamble Company|Near-neutral pH detergents containing anionic surfactant, cosurfactant and fatty acid|

---

US4446042A|1982-10-18|1984-05-01|The Procter & Gamble Company|Brightener for detergents containing nonionic and cationic surfactants|

---

US4550862A|1982-11-17|1985-11-05|The Procter & Gamble Company|Liquid product pouring and measuring package with self draining feature|

---

US4597898A|1982-12-23|1986-07-01|The Proctor & Gamble Company|Detergent compositions containing ethoxylated amines having clay soil removal/anti-redeposition properties|

---

US4424134A|1983-06-15|1984-01-03|The Procter & Gamble Company|Aqueous fabric softening compositions|

---

LU84894A1|1983-07-01|1985-04-17|Oreal|HAIR COMPOSITION AND METHOD FOR TREATING HAIR|

---

DE3333654A1|1983-09-17|1985-03-28|Cassella Ag, 6000 Frankfurt|ENCLOSED, SLOWLY SOLUBLE IN WATER, THEIR PRODUCTION AND THEIR USE|

---

US4515705A|1983-11-14|1985-05-07|The Procter & Gamble Company|Compositions containing odor purified proteolytic enzymes and perfumes|

---

US4563212A|1983-12-27|1986-01-07|Monsanto Company|High concentration encapsulation by interfacial polycondensation|

---

AT45085T|1984-03-21|1989-08-15|Richardson Vicks Ltd|HAIR TREATMENT.|

---

US4537707A|1984-05-14|1985-08-27|The Procter & Gamble Company|Liquid detergents containing boric acid and formate to stabilize enzymes|

---

US4537706A|1984-05-14|1985-08-27|The Procter & Gamble Company|Liquid detergents containing boric acid to stabilize enzymes|

---

US4640709A|1984-06-12|1987-02-03|Monsanto Company|High concentration encapsulation by interfacial polycondensation|

---

US4681806A|1986-02-13|1987-07-21|Minnesota Mining And Manufacturing Company|Particles containing releasable fill material and method of making same|

---

GB2188653A|1986-04-02|1987-10-07|Procter & Gamble|Biodegradable fabric softeners|

---

US4714562A|1987-03-06|1987-12-22|The Procter & Gamble Company|Automatic dishwasher detergent composition|

---

US4830855A|1987-11-13|1989-05-16|Landec Labs, Inc.|Temperature-controlled active agent dispenser|

---

US4785048A|1988-02-08|1988-11-15|Moore Business Forms, Inc.|Polyurea and polyurea-epoxy microcapsules|

---

US4968451A|1988-08-26|1990-11-06|The Procter & Gamble Company|Soil release agents having allyl-derived sulfonated end caps|

---

US5169552A|1989-10-04|1992-12-08|The Procter & Gamble Company|Stable thickened liquid cleaning composition containing bleach|

---

GB9021061D0|1990-09-27|1990-11-07|Unilever Plc|Encapsulating method and products containing encapsulated material|

---

US5194639A|1990-09-28|1993-03-16|The Procter & Gamble Company|Preparation of polyhydroxy fatty acid amides in the presence of solvents|

---

EP0570382B1|1991-02-06|1999-03-10|Zeneca Inc.|Microencapsulated herbicidal composition|

---

FR2673179B1|1991-02-21|1993-06-11|Oreal|CERAMIDES, THEIR PREPARATION PROCESS AND THEIR APPLICATIONS IN COSMETICS AND DERMOPHARMACY.|

---

US5665822A|1991-10-07|1997-09-09|Landec Corporation|Thermoplastic Elastomers|

---

DE69333120T2|1992-05-12|2004-07-01|The Procter & Gamble Company, Cincinnati|Concentrated fabric softener compositions with biodegradable fabric softeners|

---

US5304448A|1992-06-15|1994-04-19|Xerox Corporation|Encapsulated toner compositions|

---

AU4398793A|1992-06-15|1994-01-04|Procter & Gamble Company, The|Liquid laundry detergent compositions with silicone antifoam agent|

---

US5288417A|1992-07-06|1994-02-22|Lever Brothers Company, Division Of Conopco, Inc.|Fabric conditioning compositions and process for making them|

---

EP0581752B1|1992-07-15|1998-12-09|The Procter & Gamble Company|Built dye transfer inhibiting compositions|

---

US5458810A|1992-07-15|1995-10-17|The Procter & Gamble Co.|Enzymatic detergent compositions inhibiting dye transfer|

---

US5458809A|1992-07-15|1995-10-17|The Procter & Gamble Co.|Surfactant-containing dye transfer inhibiting compositions|

---

DK0687291T4|1993-03-01|2005-12-05|Procter & Gamble|Concentrated, biodegradable, quaternary ammonium softener compositions and compounds containing unsaturated fatty acid chains with high iodine levels|

---

US5403499A|1993-04-19|1995-04-04|Lever Brothers Company, Division Of Conopco, Inc.|Concentrated fabric conditioning compositions|

---

WO1995010591A1|1993-10-14|1995-04-20|The Procter & Gamble Company|Protease-containing cleaning compositions|

---

US5466802A|1993-11-10|1995-11-14|The Procter & Gamble Company|Detergent compositions which provide dye transfer inhibition benefits|

---

US6225489B1|1993-12-28|2001-05-01|Mona Industries, Inc.|Silicone modified phospholipid compositions|

---

US5849313A|1995-04-12|1998-12-15|Mona Industries, Inc.|Silicone modified phospholipid compositions|

---

FR2718961B1|1994-04-22|1996-06-21|Oreal|Compositions for washing and treating hair and skin based on ceramide and polymers with cationic groups.|

---

US5916862A|1995-06-20|1999-06-29|The Procter & Gamble Company|Detergent compositions containing amines and anionic surfactants|

---

DE19501479A1|1995-01-19|1996-07-25|Bayer Ag|Microcapsules with walls made from reaction products of polyisocyanates and guanidines|

---

DE69608541T2|1995-02-02|2001-01-18|Procter & Gamble|MACHINE DISHWASHER COMPOSITIONS WITH COBALT CHELATE CATALYSTS|

---

US5968881A|1995-02-02|1999-10-19|The Procter & Gamble Company|Phosphate built automatic dishwashing compositions comprising catalysts|

---

US6255367B1|1995-03-07|2001-07-03|Landec Corporation|Polymeric modifying agents|

---

WO1997000311A1|1995-06-16|1997-01-03|The Procter & Gamble Company|Bleach compositions comprising cobalt catalysts|

---

US5581005A|1995-06-16|1996-12-03|The Procter & Gamble Company|Method for manufacturing cobalt catalysts|

---

US5597936A|1995-06-16|1997-01-28|The Procter & Gamble Company|Method for manufacturing cobalt catalysts|

---

ES2158320T3|1995-06-16|2001-09-01|Procter & Gamble|COMPOSITIONS FOR AUTOMATIC DISHWASHERS THAT INCLUDE COBALT CATALYSTS.|

---

US5583090A|1995-06-26|1996-12-10|Monsanto Company|Herbicidal microencapsulated clomazone compositions with reduced vapor transfer|

---

US5559261A|1995-07-27|1996-09-24|The Procter & Gamble Company|Method for manufacturing cobalt catalysts|

---

US5929022A|1996-08-01|1999-07-27|The Procter & Gamble Company|Detergent compositions containing amine and specially selected perfumes|

---

EP0859594B1|1995-10-16|2001-08-22|The Procter & Gamble Company|Conditioning shampoos containing polyalkylene glycol|

---

US5703034A|1995-10-30|1997-12-30|The Procter & Gamble Company|Bleach catalyst particles|

---

CZ191598A3|1995-12-20|1998-11-11|The Procter & Gamble Company|Combined particles containing bleaching catalyst and enzyme, their composition and preparation as well as their incorporation into cleansing agent|

---

US5776443A|1996-03-18|1998-07-07|Chesebrough-Pond's Usa Co., Division Of Conopco, Inc.|Hair care compositions|

---

AR006355A1|1996-03-22|1999-08-25|Procter & Gamble|BIODEGRADABLE SOFTENING ASSET AND CONTAINING COMPOSITION|

---

US5935561A|1996-03-27|1999-08-10|Procter & Gamble Company|Conditioning shampoo compositions containing select hair conditioning agents|

---

US5932203A|1996-03-27|1999-08-03|Proctor & Gamble Company|Conditioning shampoo compositions containing select hair conditioning esters|

---

US5756436A|1996-03-27|1998-05-26|The Procter & Gamble Company|Conditioning shampoo compositions containing select cationic conditioning polymers|

---

DE19617983A1|1996-05-06|1997-11-13|Basf Ag|Polymers containing β-hydroxyalkylvinylamine units, process for their preparation and their use|

---

ZA974359B|1996-05-23|1998-05-12|Zeneca Ltd|Microencapsulated compositions.|

---

FR2751532B1|1996-07-23|1998-08-28|Oreal|WASHING AND CONDITIONING COMPOSITIONS BASED ON SILICONE AND DIALKYLETHER|

---

WO1998007813A2|1996-08-19|1998-02-26|The Procter & Gamble Company|LAUNDRY DETERGENT COMPOSITIONS COMPRISING β-KETOESTER PRO-FRAGRANCES|

---

US5914307A|1996-10-15|1999-06-22|The Procter & Gamble Company|Process for making a high density detergent composition via post drying mixing/densification|

---

US6200554B1|1996-10-16|2001-03-13|The Procter & Gamble Company|Conditioning shampoo compositions having improved silicone deposition|

---

BR9713263A|1996-10-21|2000-10-24|Procter & Gamble|Concentrated fabric softener composition|

---

US5990065A|1996-12-20|1999-11-23|The Procter & Gamble Company|Dishwashing detergent compositions containing organic diamines for improved grease cleaning, sudsing, low temperature stability and dissolution|

---

US6297203B1|1997-05-05|2001-10-02|The Procter & Gamble|Styling shampoo compositions containing cationic styling polymers and cationic deposition polymers|

---

US6069122A|1997-06-16|2000-05-30|The Procter & Gamble Company|Dishwashing detergent compositions containing organic diamines for improved grease cleaning, sudsing, low temperature stability and dissolution|

---

US5968286A|1997-10-03|1999-10-19|Helene Curtis, Inc.|Heat-mediated conditioning from shampoo and conditioner hair care compositions containing silicone|

---

US6492462B2|1998-01-16|2002-12-10|Landec Corporation|Side chain crystalline polymer as rheology modifier for crosslinked polymer|

---

DE19840583A1|1998-09-05|2000-03-09|Bayer Ag|Microcapsule formulations|

---

WO2000059616A1|1999-04-07|2000-10-12|Petramec, Inc.|Methods of making and using microcapsules with controlled density|

---

WO2000072816A1|1999-06-01|2000-12-07|The Procter & Gamble Company|Pro-fragrances|

---

BR0012673B1|1999-07-20|2011-01-25|encapsulated oil particle, process for its preparation, and granular cleaning composition or its component containing an encapsulated oil particle.|

---

US6287603B1|1999-09-16|2001-09-11|Nestec S.A.|Cyclodextrin flavor delivery systems|

---

DK1272267T3|2000-03-17|2004-06-07|Bayer Cropscience Ag|microcapsule|

---

SG98393A1|2000-05-19|2003-09-19|Inst Materials Research & Eng|Injectable drug delivery systems with cyclodextrin-polymer based hydrogels|

---

DE10051194A1|2000-10-16|2002-04-25|Bayer Ag|Microcapsules with walls made of polyurea|

---

DE10051190A1|2000-10-16|2002-04-25|Bayer Ag|Micro-capsules for production of carbon-less copying paper, comprise micro-capsules with walls consisting of reaction products of polyisocyanate with guanidine compounds and amine compounds|

---

US6610648B2|2000-12-22|2003-08-26|Givaudan Sa|Malodor counteractant compositions|

---

US8828902B2|2001-07-12|2014-09-09|Reaxa Limited|Microencapsulated catalyst methods of preparation and method of use thereof|

---

CA2482038A1|2002-04-22|2003-10-30|The Procter & Gamble Company|Shampoo containing a cationic guar derivative|

---

US20050271735A1|2002-05-31|2005-12-08|Stover Harald D H|Method of encapsulating hydrophobic organic molecules in polyurea capsules|

---

US8187580B2|2002-11-01|2012-05-29|The Procter & Gamble Company|Polymeric assisted delivery using separate addition|

---

EP1502646B1|2003-08-01|2016-07-13|The Procter & Gamble Company|Microcapsules|

---

US20070078071A1|2005-09-30|2007-04-05|Kaiping Lee|Spray dry capsule products and methods for preparing and using same|

---

US20070138671A1|2005-12-15|2007-06-21|Anastasiou Theodore J|Encapsulated active material with reduced formaldehyde potential|

---

US7786027B2|2006-05-05|2010-08-31|The Procter & Gamble Company|Functionalized substrates comprising perfume microcapsules|

---

US20070275866A1|2006-05-23|2007-11-29|Robert Richard Dykstra|Perfume delivery systems for consumer goods|

---

US7833960B2|2006-12-15|2010-11-16|International Flavors & Fragrances Inc.|Encapsulated active material containing nanoscaled material|

---

WO2009126766A2|2008-04-10|2009-10-15|Boston Scientific Scimed, Inc.|Medical devices with an interlocking coating and methods of making the same|

---

CN102056656B|2008-06-16|2014-01-29|弗门尼舍有限公司|Process for preparing polyurea microcapsules|

---

WO2010014172A2|2008-07-30|2010-02-04|Appleton Papers Inc.|Delivery particle|

---

EP2204155A1|2008-12-30|2010-07-07|Takasago International Corporation|Fragrance composition for core shell microcapsules|

---

US8299011B2|2009-09-18|2012-10-30|International Flavors & Fragrances Inc.|Encapsulated active materials|

---

MX339276B|2010-06-11|2016-05-19|Firmenich & Cie|Process for preparing polyurea microcapsules.|

---

ES2539491T3|2011-02-07|2015-07-01|Firmenich Sa|Polyurea microcapsules|

---

US20120294821A1|2011-05-20|2012-11-22|International Flavors & Fragrances Inc.|Low Volatile Reactive Malodor Counteractives and Methods of Use Thereof|

---

US9499769B2|2011-06-28|2016-11-22|Firmenich Sa|Process for preparing polyurea microcapsules|

---

US9126890B2|2011-10-20|2015-09-08|International Flavors & Fragrances Inc.|Low volatile reactive malodor counteractives and methods of use thereof|

---

US9061965B2|2011-10-20|2015-06-23|International Flavors & Fragrances Inc.|Low volatile reactive malodor counteractives and methods of use thereof|

---

EP2872118B1|2012-07-13|2018-12-26|International Flavors & Fragrances Inc.|Hydrogel fragrance capsule, formulations and process for preparing the same|

---

TW201441721A|2013-04-25|2014-11-01|Hon Hai Prec Ind Co Ltd|Optic-electro modulator|US20180015009A1|2015-12-30|2018-01-18|International Flavors & Fragrances Inc.|Microcapsule compositions with improved deposition|

---

MX2018009997A|2016-02-18|2019-02-07|Int Flavors & Fragrances Inc|Polyurea capsule compositions.|

---

EP3265065A4|2015-03-06|2018-08-01|International Flavors & Fragrances Inc.|Microcapsule compositions with high performance|

---

CN107427807B|2015-04-07|2021-06-18|弗门尼舍有限公司|Process for preparing polyurea microcapsules|

---

US10993466B2|2015-04-24|2021-05-04|International Flavors & Fragrances Inc.|Delivery systems and methods of preparing the same|

---

CN107666897B|2015-06-05|2021-12-28|弗门尼舍有限公司|Microcapsules with high surface deposition|

---

WO2017074995A1|2015-10-27|2017-05-04|Encapsys, Llc|Encapsulation|

---

JP6890592B2|2015-12-15|2021-06-18|フイルメニツヒ ソシエテ アノニムＦｉｒｍｅｎｉｃｈ Ｓａ|How to make polyurea microcapsules with improved adhesion|

---

US9974720B2|2015-12-30|2018-05-22|International Flavors & Fragrances Inc.|Compositions containing microcapsules coated with deposition proteins|

---

ES2876160T3|2016-03-18|2021-11-12|Int Flavors & Fragrances Inc|Silica microcapsules and methods to prepare them|

---

US20190184364A1|2016-05-03|2019-06-20|International Flavors & Fragrances Inc.|Fragrance compositions containing microcapsules|

---

BR112018072391A2|2016-05-03|2019-02-19|International Flavors & Fragrances Inc.|microcapsule, microcapsule composition, method for preparing a microcapsule composition, and consumer product.|

---

WO2018006089A1|2016-07-01|2018-01-04|International Flavors & Fragrances Inc.|Stable microcapsule compositions|

---

EP3295929A1|2016-09-19|2018-03-21|S.P.C.M. Sa|Use of an ampholyte copolymer as colloidal stabilizer in a process of encapsulating fragrance|

---

US20180085291A1|2016-09-28|2018-03-29|International Flavors & Fragrances Inc.|Microcapsule compositions containing amino silicone|

---

WO2018077570A1|2016-10-28|2018-05-03|Unilever N.V.|A personal care composition comprising particles|

---

CN108299438A|2017-01-13|2018-07-20|国家纳米科学中心|PH response near infrared fluorescent probe compounds and its preparation method and application|

---

US20180346648A1|2017-05-30|2018-12-06|International Flavors & Fragrances Inc.|Branched polyethyleneimine microcapsules|

---

JP2020529306A|2017-07-31|2020-10-08|ダウ グローバル テクノロジーズ エルエルシー|Encapsulation method|

---

US10233278B1|2017-09-14|2019-03-19|Fxi, Inc.|Cesium and rubidium derivatives as catalysts for polyurethane foams|

---

EP3470134B1|2017-10-13|2020-06-03|Agfa Nv|A composition comprising solvent and heat resistant capsules|

---

CN108066165A|2017-12-22|2018-05-25|江山|A kind of toothpaste particle and preparation method thereof and the application in toothpaste|

---

CN109679055B|2018-12-12|2020-12-08|中国农业科学院农业质量标准与检测技术研究所|Anti-ultraviolet modified degradable microcapsule material and preparation method and application thereof|

---

WO2020202187A1|2019-04-05|2020-10-08|Council Of Scientific & Industrial Research|Bio-compatible polyurethane microcapsules and process for the preparation thereof|

---

US20210047586A1|2019-08-15|2021-02-18|International Flavors & Fragrances Inc.|Catalytic wicks and candles containing the same|

---

WO2021073774A1|2019-10-16|2021-04-22|Symrise Ag|Polyurea microcapsules and liquid surfactant systems containing them|

法律状态:
2019-08-06| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|

---

2020-06-02| B09A| Decision: intention to grant|

---

2020-10-27| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 15/08/2014, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

---

申请号 | 申请日 | 专利标题

---

US13/967,800|US20130330292A1|2009-09-18|2013-08-15|Polyurea capsules prepared with a polyisocyanate and cross-linking agent|

---

US13/967,800|2013-08-16|

---

US13/969,038|2013-08-16|

---

US13/968,962|2013-08-16|

---

US13/968,862|US10226405B2|2009-09-18|2013-08-16|Purified polyurea capsules, methods of preparation, and products containing the same|

---

US13/969,038|US9687424B2|2009-09-18|2013-08-16|Polyurea capsules prepared with aliphatic isocyanates and amines|

---

PCT/US2014/051309|WO2015023961A1|2013-08-15|2014-08-15|Polyurea or polyurethane capsules|BR122019023314-4A| BR122019023314B1|2013-08-15|2014-08-15|POLYUREA CAPSULE COMPOSITION, METHOD FOR PREPARING A POLYUREA CAPSULE COMPOSITION, AND CONSUMER PRODUCT|