US 2016O158121A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2016/0158121 A1 LEI et al. (43) Pub. Date: Jun. 9, 2016

(54) POLYUREA CAPSULE COMPOSITIONS Publication Classification (71) Applicant: INTERNATIONAL FLAVORS & (51) Int. Cl. FRAGRANCES INC., NEW YORK, A618/II (2006.01) NY (US) A68/73 (2006.01) A61O 13/00 (2006.01) (72) Inventors: Yabin LEI, Holmdel, NJ (US); Lewis A68/92 (2006.01) Michael POPPLEWELL, Morganville, A61O5/12 (2006.01) NJ (US); Li XU, Edison, NJ (US); John A618/8 (2006.01) BRAHMS, Morris Plains, NJ (US); A618/87 (2006.01) Xiang FENG, Edison, NJ (US) (52) U.S. Cl. CPC ...... A61K 8/11 (2013.01); A61 K8/81 17 (21) Appl. No.: 15/047,364 (2013.01); A61K 8/731 (2013.01); A61 K 8/8III (2013.01); A61K 8/87 (2013.01); A61 K (22) Filed: Feb. 18, 2016 8/922 (2013.01); A61O5/12 (2013.01); A61O Related U.S. Application Data 13/00 (2013.01) (63) Continuation-in-part of application No. 14/911,433, (57) ABSTRACT filed on Feb. 10, 2016, filed as application No. PCT/ US2014/051309 on Aug. 15, 2014, Continuation-in- A microcapsule composition useful in delivering an active part of application No. 13/968,862, filed on Aug. 16 material contains a first microcapsule and a second m1crocap 2013. Continuation-in-part O fapplication No. 13jo 69. Sule. The first microcapsule has a Zeta potential of 10 mV or O38 filed on Aug. 16, 2013, Continuation-in-part of greater, the second microcapsule has a Zeta potential of 5 mV l tion N i/967 8OO fil d on Aug. 15, 2013 or less, and the weight ratio of the first microcapsule and the applicauon No. SUU, Illed on Aug. 1), second microcapsule is between 1:10 and 10:1. Also dis (60) Provisional application No. 62/272,740, filed on Dec. closed are consumer products containing such a microcapsule 30, 2015. composition. US 2016/0158121 A1 Jun. 9, 2016

POLYUREA CAPSULE COMPOSITIONS 4,640,709 and the literature described therein. As is exempli fied therein, and also in U.S. Pat. No. 6,133,197, polyurea and CROSS-REFERENCE TO RELATED polyurethane capsules are often used for rugged applications, APPLICATIONS Such as for encapsulation of agrochemicals, e.g., herbicides and pesticides, where slow time-release is desired to set the 0001. This application claims priority to U.S. application agents free. For Such applications, the capsules also require a Ser. No. 14/911,433, filed on Feb. 10, 2016, and 62/272,740, relatively high mechanical strength. For the polycondensa filed on Dec. 30, 2015. U.S. Ser. No. 14/911,433 is a national tion reaction, Suitable diisocyanate and symmetrical triisocy phase entry under 35 USC 371 for International Application anate starting materials are disclosed in the prior art. No. PCT/US14/051309 filed on Aug. 15, 2014. The interna 0006 WO 2011/154893 discloses a process for the prepa tional application claims priority to three US patent applica ration of capsules, which includes mixing at least one ali tions, Ser. No. 13/967,800 (filed on Aug. 15, 2013), Ser. No. phatic polyisocyanate and of at least one aromatic polyisocy 13/968,862 (filed on Aug. 16, 2013), and Ser. No. 13/969,038 anate, wherein the molar ratio between the two (filed on Aug. 16, 2013). Each of these three applications is a polyisocyanates is between 75:25 and 20:80. continuation-in-part of U.S. patent application Ser. No. 0007 WO 2013/000587 discloses a process for the prepa 13/163,320, filed on Jun. 17, 2011, which is a continuation ration of polyurea capsules, which includes dissolving at least in-part of U.S. patent application Ser. No. 12/883,337, filed one polyisocyanate having at least two isocyanate functional on Sep. 16, 2010, now abandoned, which is a continuation groups, in a perfume to form a solution; adding to the Solution in-part of U.S. patent application Ser. No. 12/562,578, filed an aqueous solution of an emulsifier or of a colloidal stabi on Sep. 18, 2009, now U.S. Pat. No. 8,299,011. The contents lizer, and adding to the mixture to 3.5-diamino-1,2,4-triazole of the above-mentioned applications are incorporated herein to form a polyurea wall. by reference in their entirety. 0008 U.S. Pat. No. 5,304,448 describes an encapsulated toner composition using reaction of amino acids and polyiso BACKGROUND cyanates. 0002 Nano- or micro-encapsulation is used in a variety of 0009 Known polyurea or polyurethane capsules face vari different applications where there is a need to deliver, apply, ous issues, e.g., low olfactory intensity, low stability, and high or release an active material including a fragrance, flavor, and toxicity. Their deposition to target Surfaces is also problem malodor counteraction agent to a target area in a time-delayed atic. or controlled manner. Various techniques for preparing cap 0010. There is a need to develop a safe, stable, and high Sules are known in the art and are used, depending on the efficient capsules for use in laundry, washing, cleaning, Sur contents to be encapsulated, the environment in which the face care and personal and skin care. For Such applications capsules should retain their integrity and the desired release quicker and easier release and/or less mechanical strength are mechanism. often desirable. Also, it would be desirable to more precisely 0003 Interfacial polycondensation is a known technique influence the capsule wall permeability and other capsule for preparing capsules and versatile capsule wall materials are wall properties to achieve the desired release profile and used including polyureas and polyurethanes (WO 2011/ consumer benefits. 154893, WO 2012/107323, US 2011/0077188, U.S. Pat. No. 5,635,211, U.S. Pat. No. 6,586,107, and U.S. Pat. No. 6,797, SUMMARY OF THE INVENTION 670). Such wall materials are produced by having a first phase 0011. This invention is based on the discovery that certain which is water-immiscible and includes a polyfunctional iso capsule compositions possess unexpected desirable proper cyanate, i.e., a polyisocyanate having two or more isocyanate ties including high perceived olfactory intensity, prolonged groups, and a second aqueous phase which includes (i) a stability, low toxicity, and improved deposition. polyfunctional alcohol (i.e., a polyol) having two or more 0012. Accordingly, one aspect of this invention relates to a —OH groups for obtaining a polyurethane capsule wall, or microcapsule compositions comprising a first microcapsule (ii) a polyfunctional amine (i.e., a polyamine) having two or and a second microcapsule, in which the first microcapsule more —NH and/or —NH groups for obtaining a polyurea has a Zeta potential of 10 mV or greater (e.g., 25 mV or capsule wall. greater, 40 mV or greater, 40 to 200 mV, and 40 to 100 mV), 0004 If the active material to be encapsulated is hydro the second microcapsule has a Zeta potential of 5 mV or less phobic, it will be included in the water-immiscible phase, (e.g., -5 to 5 mV, -10 mV or less, -20 mV or less, -40 mV or thereafter the two phases are mixed by high shear mixing to less, -20 to -200 mV, and -20 to -100 mV), and the weight forman oil-in-water emulsion. In this emulsion, the polycon ratio of the first microcapsule and the second microcapsule is densation reaction will take place. Thus, the small droplets of between 1:10 and 10:1 (e.g., 20:80 to 80:20, 30:70 to 70:30, the water-immiscible phase will be surrounded by the capsule and 40:60 to 60:40). wall formed by polycondensation of the isocyanate and the 0013 The first microcapsule contains a first oil core and a polyalcohol or polyamine as starting materials. Conversely, if first microcapsule wall encapsulating the first oil core. the material to be encapsulated is hydrophilic, it will be 0014. The first microcapsule wall is typically formed of a included in the aqueous phase and the mixture of the two first encapsulating polymer that is the reaction product of a phases converted into a water-in-oil emulsion. The polycon multi-functional nucleophile and a multi-functional electro densation reaction will then form capsule walls Surrounding phile. Suitable multi-functional nucleophiles include a the droplets of water-miscible phase. Suitable emulsifiers are branched polyethyleneimine, a mixture of the branched poly often utilized to aid in the preparation and stabilization of the ethyleneimine and a polyfunctional amine, and a mixture of emulsion. the branched polyethyleneimine and a polyfunctional alco 0005 Suitable raw materials and processes for preparing hol. Exemplary polyfunctional amines include, but are not capsules by polycondensation are described in U.S. Pat. No. limited to hexamethylenediamine, ethylenediamine, 1,3-di US 2016/0158121 A1 Jun. 9, 2016 aminopropane, 1,4-diamino-butane, diethylenetriamine, polyduaternium-101, polyvinylamine, polyethyleneimine, pentaethylenehexamine, bis(3-aminopropyl)amine, bis(hex polyvinylamine and vinylformamide copolymer, and combi anethylene)triamine, tris(2-aminoethyl)amine, triethylene nations thereof. tetramine, N,N'-bis(3-aminopropyl)-1,3-propanediamine, 0019. In other embodiments, the microcapsule composi tetraethylenepentamine, penta-ethylenehexamine, chitosan, tions of this invention further comprise a capsule formation nisin, gelatin, 1.3-diamino-guanidine, 1,1-dimethylbigu aid selected from the group consisting of a polyvinyl alcohol, anide, guanidine, arginine, lysine, ornithine, and combina polystyrene Sulfonate, carboxymethyl cellulose, naphthalene tions thereof. The multi-functional electrophile has a first Sulfonate, polyvinylpyrrolidone, copolymer of vinyl pyrroli functional group and a second functional group, each of done and quaternized dimethylaminoethyl methacrylate, and which, independently, is an electrophilic group reactive combination thereof. 0020. The microcapsule compositions of this invention towards the multi-functional nucleophile. can further comprise a third, fourth, fifth, or sixth delivery 00.15 Preferably, the first encapsulating polymer is the system. reaction product of a branched polyethyleneimine and a poly 0021 Any of the microcapsule compositions described isocyanate. The branched polyethyleneimine can have a above can be in the form of a solid or liquid (e.g., a slurry). molecular weight of 750 to 50000 Dalton (“Da”). Exemplary 0022. Another aspect of this invention relates to a con polyisocyanates are polymeric methylene diphenyl diisocy Sumer product containing an above-described microcapsule anates, hydrogenated polymeric methylene diphenyl diisocy composition. Examples of the consumer product include a anates, methylene diphenyl diisocyanates, hydrogenated hair care product such as shampoos and hair conditioners, a methylene diphenyl diisocyanates, trimers of hexamethylene personal care product such as bar Soaps and body washes, a diisocyanate, trimers of isophorone diisocyanate, biurets of fabric care product (e.g., powder or liquid fabric detergents, hexamethylene diisocyanate, polyisocyanurates of toluene fabric conditioners, and fabric refreshers), and a home care diisocyanate, trimethylol propane-adducts of toluene diiso product. cyanate, trimethylol propane-adducts of xylylene diisocyan 0023 The details of one or more embodiments of the ate, and combinations thereof. invention are set forth in the description below. Other fea 0016. The second microcapsule contains a second oil core tures, objects, and advantages of the invention will be appar and a second microcapsule wall encapsulating the second oil ent from the description and the claims. core. The second microcapsule wall is formed of a second encapsulating polymer, which can be selected from the group DETAILED DESCRIPTION OF THE INVENTION consisting of melamine-formaldehyde polymers, polyureas, 0024. It has been found that the capsule performance (e.g., polyurethanes, gelatins, urea formaldehyde polymers, Solgel fragrance intensity) is unexpectedly improved when combin polymers, starch polymers, carbohydrates, polyureas (pre ing in a microcapsule composition a cationic microcapsule pared from polyvinyl alcohol as a dispersant) and combina (having a Zeta potential of 10 mV or greater) with an anionic tions thereof. In some preferred embodiments, the second microcapsule (having a Zeta potential of -10 mV or less) or encapsulating polymer is the reaction product of a polyiso with a neutral microcapsule (having a Zeta potential of -5 to cyanate and hexamethylenediamine. The polyisocyanate is 5 mV). defined above. 0025. The microcapsule compositions of this invention 0017. The first and second oil cores, respectively, contain are useful in a wide range of consumer applications, e.g., a first and second active materials, which are, independently, personal hair care products including shampoos and hair con selected from the group consisting of a fragrance, pro-fra ditioners; personal washes such as Soaps, body wash, per grance, flavor, vitamin or derivative thereof, malodor coun Sonal cleaners, and sanitizers; fabric care such as fabric teractive agent, anti-inflammatory agent, fungicide, anes refreshers, softeners, and dryer sheets; ironing water; indus thetic, analgesic, antimicrobial active, anti-viral agent, anti trial cleaners; liquid and powder detergent; rinse condition infectious agent, anti-acne agent, skin lightening agent, insect ers; fine fragrances; an Eau De Toilette product; a deodorant; repellant, emollient, skin moisturizing agent, wrinkle control an roll-on product; and an aerosol product. The capsule com agent, UV protection agent, fabric Softener active, hard Sur positions of this invention are also well-suited for use in face cleaning active, skin or hair conditioning agent, insect hydroalcoholic medium such as fine fragrance and for use in repellant, animal repellent, Vermin repellent, flame retardant, leave-on personal care applications. Moreover, the inclusion antistatic agent, nanometer to micron size inorganic solid, of a capsule formation aid in the capsule wall-forming reac polymeric or elastomeric particle, and combination thereof. tion provides capsules with excellent storage stability and retention of an encapsulated fragrance. 0018. In some embodiments, the microcapsule composi 0026. The microcapsule compositions of this invention tions described above further comprise a deposition aid selected from the group consisting of polyduaternium-4. contain at least two microcapsules, e.g., a first microcapsule polyduaternium-5, polyduaternium-6, polyduaternium-7. and a second microcapsule. polyduaternium-10, polyduaternium-16, polyduaternium 22, polyduaternium-24, polyduaternium-28, polyduater The First Microcapsule nium-39, polyduaternium-44. polyduaternium-46, 0027. The first microcapsule is a positively charged micro polyduaternium-47, polyduaternium-53, polyduaternium capsule having a Zeta potential of 10 mV or greater, prefer 55, polyguaternium-67, polyduaternium-68, polyduater ably 25 mV or greater (e.g., 25 mV to 200 mV), and more nium-69, polyduaternium-73, polyduaternium-74, preferably 40 mV or greater (e.g., 40 mV to 100 mV.). Not to polyduaternium-77, polyduaternium-78, polyduaternium be bound by any theory, these positively charged microcap 79, polyduaternium-80, polyduaternium-81, polyduater Sules not only have a strong affinity to specific animate and nium-82, polyduaternium-86, polyduaternium-88, inanimate Surfaces, but also immobilize other neutral or nega US 2016/0158121 A1 Jun. 9, 2016 tively charged microcapsules and thus also bind them to the 0035. Preferred polyfunctional amines are polyamines animate and inanimate surfaces. containing two or more amine groups such as —NH and 0028. The first microcapsule can be prepared by reacting —R*NH. R* being substituted and unsubstituted C-Co (e.g., via an interfacial polymerization) a polyfunctional alkyl, C-C heteroalkyl, C-C cycloalkyl, 3- to 8-mem nucleophile and a polyfunctional electrophile in the presence bered heterocycloalkyl, aryl, and heteroaryl. of a capsule formation aid (e.g., a dispersant) and/or a catalyst 0036 Two classes of such polyamines include polyalky (e.g., a base) so that an active material is encapsulated in a first lene polyamines having the following structures: oil core by a first microcapsule wall. The first oil core option ally contains a core modifier. The first microcapsule wall is formed of a first encapsulating polymer that is the reaction product of a polyfunctional nucleophile and a polyfunctional electrophile. 0029. A preferred first microcapsule has a microcapsule H.NCH, x-g-NCHy- g-NH. wall formed of a first encapsulating polymer that is a reaction product of a branched polyethyleneimine (a polyfunctional (CH2)2 nucleophile) and an aromatic/aliphatic polyisocyanate (a HC-R polyfunctional electrophile). 0030 Polyfunctional Nucleophiles. 0031. The polyfunctional nucleophiles each are a branched polyethyleneimine or a mixture containing a In which R is hydrogen or—CH; and each of m, n, X, y, and branched polyethyleneimine and a polyfunctional amine/al Z, independently, is an integer from 0-2000 (e.g., 1-1000, cohol. In a preferred embodiment, the polyfunctional nucleo 1-100, 1-10, and 1-5). Examples include ethylene diamine, phile is a branched polyethyleneimine. 1,3-diaminepropane, diethylene triamine, triethylene tetra 0032 Suitable branched polyethyleneimines each have a mine, 1,4-diaminobutane, hexanethylene diamine, hexam molecular weight of 200 to 1,000,000 Da (e.g., 300 to 500, ethylene diamine, pentaethylenehexamine, and the like. 000 Da, 500 to 200,000 Da, 750 to 100,000 Da, and 750 to 0037 Another class of polyamines are polyalykylene 50,000 Da). They each have a main chainandone or more side polyamines of the type: chains attached to the main chain. The main chain has 2 to 25,000 (e.g., 3 to 10,000, 5 to 5000, and 5 to 500) repeat ethylene amine ( CHCH-NH ) units. The side chains R R each have one or more ethylene amine terminals ( CHCH-NH). The representative structure of the branched polyethyleneimine is shown below: where R equals hydrogen or—CH m is 1-5 and n is 1-5, e.g., diethylene triamine, triethylene tetraamine and the like. 1n-NH2 Exemplary amines of this type also include diethylenetri rN, 1N H amine, bis(3-aminopropyl)amine, bis(hexanethylene)tri amine. 0038 Another class of amine that can be used in the inven HN --- NH2, tion is polyetheramines. They contain primary amino groups N attached to the end of a polyether backbone. The polyether HN 1n 1 Na1n NH2 backbone is normally based on either propylene oxide (PO). ethylene oxide (EO), or mixed PO/EO. The ether amine can be monoamine, diamine, or triamine, based on this core struc in which n is 1 to 5000 (e.g., 1 to 2000, 1 to 1000, and 1 to ture. An example is: 100). 0033. Other suitable polyfunctional nucleophiles include polyfunctional amines (e.g., polyamines) and polyfunctional H alcohols (e.g., polyols). HN O l 0034 Polyfunctional amines are those having at least a isH N-1No NH2. primary/secondary amine group (-NH and —NH-) and one or more additional functional groups such as a primary/ secondary amine and hydroxyl group (-OH). Exemplary Additional examples include 2,2'-ethylenedioxy)bis(ethy polyfunctional amines include hexamethylenediamine, hexa lamine) and 4,7,10-trioxa-1, 13-tridecanediamine. ethylenediamine, ethylenediamine, 1,3-diamino-propane, 0039. Other suitable amines include, but are not limited to, 1,4-diamino-butane, diethylenetriamine, pentaethylenehex tris(2-aminoethyl)amine, triethylenetetramine, N,N'-bis(3- amine, bis(3-amino-propyl)amine, bis(hexanethyl-ene)tri aminopropyl)-1,3-propanediamine, tetraethylene pentamine, amine, tris(2-aminoethyl)amine, triethylene-tetramine, N,N'- 1,2-diaminopropane, N.N.N',N'-tetrakis(2-hydroxyethyl) bis(3-aminopropyl)-1,3-propanediamine, ethylene diamine, N.N.N',N'-tetrakis(2-hydroxypropyl)eth tetraethylenepentamine, amino-2-methyl-1-propanol, a sec ylene diamine, branched polyethylenimine, 2,4-diamino-6- ond branched polyethylenimine, chitosan, 1.3-diamino hydroxypyrimidine and 2,4,6-triaminopyrimidine. guanidine, 1,1-dimethylbiguanide, and guanidine. Suitable 0040 Amphoteric amines, i.e., amines that can react as an amino acids/peptides include arginine, lysine, histidine, orni acid as well as a base, are another class of amines of use in this thine, nisin, and gelatin. invention. Examples of amphoteric amines include proteins US 2016/0158121 A1 Jun. 9, 2016 and amino acids Such as gelatin, L-lysine, D-lysine, L-argin shafen, Germany) under LUPASOL grades (e.g., Lupasol ine, D-arginine, L-lysine monohydrochloride, D-lysine FG, Lupasol G20 waterfree, Lupasol PR 8515, Lupasol WF, monohydrochloride, L-arginine monohydrochloride, D-argi Lupasol FC, Lupasol G20, Lupasol G35, Lupasol G 100, nine monohydrochloride, L-ornithine monohydrochloride, Lupasol G500, Lupasol HF, Lupasol PS, Lupasol HEO 1, D-ornithine monohydrochloride or a mixture thereof. Lupasol PN50, Lupasol PN60, Lupasol P0100 and Lupasol 0041 Guanidine amines and guanidine salts are yet SK). Other commercially available polyethylenimines another class of multi-functional amines of use in this inven include EPOMIN P-1000, EPOMIN P-1050, EPOMIN tion. Exemplary guanidine amines and guanidine salts RP18W and EPOMINPP-061 from NIPPON SHOKUBAI include, but are not limited to, 1,3-diaminoguanidine mono (New York, N.Y.). Polyvinylamines such as those sold by hydrochloride, 1,1-dimethylbiguanide hydrochloride, guani BASF under LUPAMINE grades can also be used. A wide dine carbonate and guanidine hydrochloride. range of polyetheramines may be selected by those skilled in 0042 Commercially available examples of amines the art. In certain embodiments, the polyfunctional nucleo include JEFFAMINE EDR-148 (where x=2), JEFFAMINE phile is hexamethylene diamine, polyetheramine or a mixture EDR-176 (where x=3) (from Huntsman). Other polyether thereof. amines include the JEFFAMINE ED Series, JEFFAMINE 0043. The structures of specific polyfunctional nucleo TRIAMINES, polyethylenimines from BASF (Ludwig philes are shown in Table 1 below. TABLE 1 Exemplary Polyfunctional Nucleophiles

HN NH 2 N-11N-1 2 H 1S-1N1\-1N H 2 H 2 Diethylenetriamine Bis(3-aminopropyl)amine

H r NH2 HN 1N1 N1-1 N-1N1-1N NH2 N HN 1N1 n1n NH2 Bis(hexanethylene)triamine Tris(2-aminoethyl)amine

H HN2 N-1 n1n-1 N N1). NH, Pentaethylenehexamine H Triethylenetetramine

NH N1-1-1)n-1\1\-1N,H H HN n N ls N Y NH, HCI H H N,N'-Bis(3-aminopropyl)-1,3-propanediamine 1,3-Diaminoguanidine monohydrochloride

NH NH oHCI H H HN1)-1 N n-n-n- NN1\N, HN ull-chN N1 H Tetraethylenepentamine CH3 1,1-Dimethylbiguanide hydrochloride

NH O NH H ls o1.2 ls r NH2 r^- 2 H HN NH2 HO OH HN Guanidine carbonate N-N-N-N-N-N- NH2

HN1\1 N n1n NH2 Branched Polyethylenimine US 2016/0158121 A1 Jun. 9, 2016

TABLE 1-continued Exemplary Polyfunctional Nucleophiles

OH OH OH

HO O O R Lo & OH HO HO HO NH2 NH2 NH2 pi Chitosan

O H

S O HNNN

Nisin O O O O CH | H | H | H.

O O ------|--CH N CH H wn----|-- CH2 CH2 -s-ch-- CH H l, =o O O Crviv, NH O O O=NH | * NH2

Gelatin

0044 Polyfunctional alcohols are those having two or 0045 The polyfunctional nucleophile as used in this more hydroxyl groups. Non-limiting examples are pen invention can be a single compound (e.g., a branched poly taerythritol, glucose, 2-aminoethanol, dipentaerythritol, glycerol, polyglycerol, ethylene glycol, hexylene glycol, ethyleneimine) or a mixture of a branched polyethyleneimine polyethylene glycol, trimethylolpropane, neopentyl glycol, with one or more polyfunctional amines/alcohols. sorbitol, erythritol, threitol, arabitol, xylitol, ribitol, mannitol, The range of polyfunctional nucleophile content can galactitol, fucitol, iditol, inositol, Volemitol, isomalt, maltitol, 0046) lactitol, maltotriitol, maltotetraitol, polyglycitol, and combi vary from 0.05 to 5% (e.g., 0.1 to 3%, 0.1 to 2%, 0.25 to 2%, nations thereof. More suitable polyfunctional alcohols are and 0.25 to 1%) by weight of the microcapsule composition described in WO 2015/023961. of this invention. US 2016/0158121 A1 Jun. 9, 2016

0047. In one embodiment, the polyfunctional nucleophile able from BASF containing isocyanate group “NCO' 31.5 wt is added to the polymerization reaction at a temperature of %), where the averagen is 0.7: PAPI 27 (PMDI commercially 0-55° C. (e.g., 10-50° C., 15-45° C., 20-40° C., and 22-35° available from Dow Chemical having an average molecular C.). weight of 340 and containing NCO 31.4 wt %) where the 0048 Polyfunctional Electrophiles. average n is 0.7: MONDURMR (PMDI containing NCO at 0049. The polyfunctional electrophiles each have at least 31 wt % or greater, commercially available from Bayer) two electrophilic functional groups reactive towards the where the average n is 0.8; MONDUR MR Light (PMDI branched polyethyleneimine, the polyfunctional amine, or containing NCO 31.8 wt %, commercially available from the polyfunctional alcohol to form a network of the first Bayer) where the average n is 0.8; MONDUR 489 (PMDI encapsulating polymer. Examples of the electrophilic group commercially available from Bayer containing NCO30–31.4 include formyl, keto, carboxyl, an isocyanate group, a car boxylate ester group, an acyl halide group, an amide group, a wt %) where the average n is 1; poly(phenylisocyanate)-co carboxylic anhydride group, an alkyl halide group, an formaldehyde (Aldrich Chemical, Milwaukee, Wis.), other epoxide group, an aziridine group, an oxetane group, an aZe isocyanate monomers such as DESMODURN3200 (poly tidine group, a Sulfonyl halide group, a chlorophosphate (hexamethylene diisocyanate) commercially available from group, an O.f3-unsaturated carbonyl group, an O.f3-unsatur Bayer), and TAKENATE D110-N(xylene diisocyanate ated nitrile group, a trifluoromethanesulfonate group, a adduct polymer commercially available from Mitsui Chemi p-toluenesulfonate group, and an O.B-unsaturated methane cals corporation, Rye Brook, N.Y., containing NCO 11.5 wt Sulfonyl group. %), DESMODUR L75 (a polyisocyanate base on toluene 0050 Suitable polyfunctional electrophiles include glu diisocyanate commercially available from Bayer), and DES taric dialdehyde, Succinic dialdehyde, and glyoxal; as well as MODURIL (another polyisocyanate based on toluene diiso compounds such as glyoxyl trimer and paraformaldehyde, cyanate commercially available from Bayer). bis(dimethyl) acetal, bis(diethyl) acetal, polymeric dialde hydes, such as oxidized starch. Preferably the cross-linking 0054 The structures of certain commercially available agent is a low molecular weight, difunctional aldehyde, Such polyisocyanates of the invention are shown below: as glyoxal, 1,3-propane dialdehyde, 1,4-butane dialdehyde, 1.5-pentane dialdehyde, or 1.6-hexane. 0051. Other non-limiting polyfunctional electrophiles are polyfunctional isocyanates (i.e., polyisocyanate), each of OCN which contains two or more isocyanate (—NCO) groups. -O- These polyisocyanate can be aromatic, aliphatic, linear, branched, or cyclic. In certain embodiments, the polyisocy anate contains, on average, 2 to 4 isocyanate groups. In par ticular embodiments, the polyisocyanate contains at least three isocyanate functional groups. In certain embodiments, O the polyisocyanate is water insoluble. 0052. In particular embodiments, the polyisocyanate used or its structural isomer. R can be a C-C alkyl, C-C ester, in this invention is an aromatic polyisocyanate. Desirably, the or an isocyanurate. Representative polyisocyanates having aromatic polyisocyanate includes a phenyl, tolyl. Xylyl, naph this structure are TAKENATE D-110N (Mitsui), DESMO thyl or diphenyl moiety as the aromatic component. In certain DURL75 (Bayer), and DESMODURIL (Bayer). embodiments, the aromatic polyisocyanate is a polyisocya nurate of toluene diisocyanate, a trimethylol propane-adduct of toluene diisocyanate or a trimethylol propane-adduct of Xylylene diisocyanate. H H 0053) One class of suitable aromatic polyisocyanates are those having the generic structure shown below, and its struc os-Cu-C-O-O O O tural isomers O

NCO NCO

TAKENATE D-11 ON

H H wherein in can vary from Zero to a desired number (e.g., 0-50, 0-20, 0-10, and 0-6) depending on the type of polyamine or DO O O O scr" polyol used. Preferably, the number of n is limited to less than O 6. The starting polyisocyanate may also be a mixture of poly isocyanates where the value of n can vary from 0 to 6. In the NCO case where the starting polyisocyanate is a mixture of various polyisocyanates, the average value of n preferably falls in between 0.5 and 1.5. Commercially-available polyisocyan DESMODURL75 ates include LUPRANATEM20 (PMDI, commercially avail US 2016/0158121 A1 Jun. 9, 2016

-continued more preferably from 0.2 to 5%, and even more preferably from 1.5 to 3.5%, all based on the total capsule composition. 0058. In some embodiments, the polyfunctional isocyan ate used in the preparation of the capsules of this invention is OCN N N NCO a single polyisocyanate. In other embodiments the polyiso cyanate is a mixture of polyisocyanates. In some embodi ments, the mixture of polyisocyanates includes an aliphatic polyisocyanate and an aromatic polyisocyanate. In particular embodiments, the mixture of polyisocyanates is a biuret of hexamethylene diisocyanate and a trimethylol propane-ad duct of xylylene diisocyanate. In certain embodiments, the NCO polyisocyanate is an aliphatic isocyanate or a mixture of aliphatic isocyanate, free of any aromatic isocyanate. In other words, in these embodiments, no aromatic isocyanate is used DESMODURIL to prepare the polyurea/polyurethane polymers as capsule wall materials. 0055. Other specific examples of wall monomer isocyan 0059 More examples of suitable isocyanates can be found ates include 1.5-naphthylene diisocyanate, 4,4'-diphenyl in PCT 2004/054362; EP 0 148149; EP 0017 409 B1; U.S. methane diisocyanate (MDI), hydrogenated MDI (H12MDI), Pat. No. 4,417,916, U.S. Pat. No. 4,124,526, U.S. Pat. No. xylylene diisocyanate (XDI), tetramethylxylol diisocyanate 5,583,090, U.S. Pat. No. 6,566,306, U.S. Pat. No. 6,730,635, (TMXDI), 4,4'-diphenyldimethylmethane diisocyanate, di PCT 90/08468, PCTWO 92/13450, U.S. Pat. No. 4,681,806, and tetraalkyldiphenylmethane diisocyanate, 4,4'-dibenzyl U.S. Pat. No. 4,285,720 and U.S. Pat. No. 6,340,653. diisocyanate, 1.3-phenylene diisocyanate, 1,4-phenylene 0060 Capsule Formation Aids. diisocyanate, the isomers oftolylene diisocyanate (TDI), 4,4'- 0061 The first microcapsule is typically prepared in the diisocyanatophenylperfluoroethane, phthalic acid bisisocy presence of a capsule formation aid, which can be a surfactant anatoethyl ester, also polyisocyanates with reactive halogen or dispersant. Not to be bound by any theory, capsule forma atoms, such as 1-chloromethylphenyl 2,4-diisocyanate, tion aids improve the performance of the microcapsule com 1-bromomethylphenyl 2,6-diisocyanate, and 3.3-bischlo position. Performance is measured by the intensity of the romethyl ether 4,4'-diphenyldiisocyanate, and combinations fragrance release during the pre-rub and post-rub phases. The thereof. pre-rub phase is the phase when the capsules have been 0056. In other embodiments, the polyisocyanate is an ali deposited on the cloth, e.g., after a fabric Softener containing phatic polyisocyanate. In certain embodiments, the aliphatic capsules has been used during the wash cycle. The post-rub polyisocyanate is a trimer of hexamethylene diisocyanate, a phase is after the capsules have been deposited and the cap trimer of isophorone diisocyanate or abiuret of hexamethyl Sules are broken by friction or other similar mechanisms. ene diisocyanate. Exemplary aliphatic polyisocyanates 0062. In some embodiments, the capsule formation aid is include those commercially available, e.g., BAYHYDUR a protective colloid or emulsifier including, e.g., maleic-vinyl N304 and BAYHYDUR N305, which are aliphatic water copolymers such as the copolymers of vinyl ethers with dispersible polyisocyanates based on hexamethylene diiso maleic anhydride or acid, sodium lignoSulfonates, maleic cyanate; DESMODUR N3600, DESMODUR N3700, and anhydride? styrene copolymers, ethylene/maleic anhydride DESMODUR N3900, which are low viscosity, polyfunc copolymers, and copolymers of propylene oxide and ethylene tional aliphatic polyisocyanates based on hexamethylene oxide, polyvinylpyrrolidone (PVP), polyvinyl alcohols diisocyanate; and DESMODUR 3600 and DESMODUR (PVA), sodium salt of naphthalene Sulfonate condensate, car N100 which are aliphatic polyisocyanates based on hexam boxymethyl cellulose (CMC), fatty acid esters of polyoxy ethylene diisocyanate, each of which is available from Bayer ethylenated Sorbitol, Sodium dodecylsulfate, and any combi Corporation, Pittsburgh, Pa.). More examples include 1-me nation thereof. In general, the range of Surfactant thyl-2,4-diisocyanatocyclohexane, 1,6-diisocyanato-2,2,4- concentration in the capsule composition varies from 0.1 to trimethylhexane, 1,6-diisocyanato-2,4,4-trimethylhexane, 5% (e.g., 0.5 to 4%, 0.2 to 2%, and 1 to 2%). 1-isocyanatomethyl-3-isocyanato-1.5.5-trimethylcyclohex 0063 Commercially available surfactants include, but are ane, chlorinated and brominated diisocyanates, phosphorus not limited to, sulfonated naphthalene-formaldehyde conden containing diisocyanates, tetramethoxybutane 1,4-diisocyan sates such as MORWET D425 (naphthalene sulfonate, Akzo ate, butane 1,4-diisocyanate, hexane 1,6-diisocyanate (HDI), Nobel, Fort Worth, Tex.); partially hydrolyzed polyvinyl dicyclohexylmethane diisocyanate, cyclohexane 1,4-diisocy alcohols such as MOWIOLs, e.g., MOWIOL3-83 (Air Prod anate, ethylene diisocyanate, and combinations thereof. Sul ucts); ethylene oxide-propylene oxide block copolymers or fur-containing polyisocyanates are obtained, for example, by poloxamers such as PLURONIC, SYNPERONIC or PLU reacting hexamethylene diisocyanate with thiodiglycol or RACARE materials (BASF); sulfonated polystyrenes such as dihydroxydihexyl sulfide. Further suitable diisocyanates are FLEXAN II (Akzo Nobel); ethylene-maleic anhydride poly trimethylhexamethylene diisocyanate, 1,4-diisocyanatobu mers such as ZEMAC (Vertellus Specialties Inc.); and tane, 1,2-diisocyanatododecane, dimer fatty acid diisocyan Polyduaternium series such as Polyduaternium 11 (“PQ11:” a ate, and combinations thereof. copolymer of vinyl pyrrolidone and quaternized dimethy 0057 The average molecular weight of certain polyisocy laminoethyl methacrylate; sold by BASF as LUVIQUAT anates useful in this invention varies from 250 to 1000 Da and PQ11 AT 1). preferable from 275 to 500 Da. In general, the range of the 0064 Processing aids can also be used as capsule forma polyisocyanate concentration in the composition of this tion aids. They include hydrocolloids, which improve the invention varies from 0.1 to 10%, preferably from 0.1 to 8%, colloidal stability of the slurry against coagulation, sedimen US 2016/0158121 A1 Jun. 9, 2016 tation and creaming. The term “hydrocolloid” refers to a Catalysts. broad class of water-soluble or water-dispersible polymers having anionic, cationic, Zwitterionic or non-ionic character. 0070 Catalysts suitable for use in the invention are metal Hydrocolloids useful in the present invention include, but are carbonates, metal hydroxide, amino or organometallic com not limited to, polycarbohydrates, such as starch, modified pounds and include, for example, sodium carbonate, cesium starch, dextrin, maltodextrin, and cellulose derivatives, and carbonate, potassium carbonate, lithium hydroxide, 1,4-diaz their quaternized forms; natural gums such as alginate esters, abicyclo[2.2.2]octane (i.e., DABCO), N,N-dimethyl amino carrageenan, Xanthanes, agar-agar, pectines, pectic acid, and ethanol, N,N-dimethylcyclohexylamine, bis-(2-dimethy natural gums such as gum arabic, gum tragacanth and gum laminoethyl) ether, N.N dimethylacetylamine, stannous karaya, guar gums and quaternized guar gums, gelatine, pro octoate and dibutyltin dilaurate. tein hydrolysates and their quaternized forms; synthetic poly mers and copolymers, such as poly(vinyl pyrrolidone-co The Second Microcapsule vinyl acetate), poly(vinyl alcohol-co-vinyl acetate), poly 0071. The second microcapsule can be any of the micro ((met)acrylic acid), poly(maleic acid), poly(alkyl(meth) capsules described above but different to the first microcap acrylate-co-(meth)acrylic acid), poly(acrylic acid-co-maleic Sule in term of the microcapsule size, the degree of polymer acid)copolymer, poly(alkyleneoxide), poly(Vinyl-methyl ization, the degree of crosslinking, the encapsulating ether), poly(vinylether-co-maleic anhydride), and the like, as polymer, the thickness of the wall, the active material, the well as poly-(ethyleneimine), poly(meth)acrylamide), poly ratio between the wall material and the active material, the (alkyleneoxide-co-dimethylsiloxane), poly(amino dimethyl Zeta potential, the rupture force or fracture strength, and the siloxane), and the like, and their quaternized forms. like. 0065. The capsule formation aid may also be used in com 0072. In some other embodiments, the second microcap bination with CMC and/or a surfactant during processing to sule has a second microcapsule wall different from that of the facilitate capsule formation. Examples of surfactants that can first microcapsule. The second microcapsule wall can be be used in combination with the capsule formation aid formed of a second encapsulating polymer selected from the include, but are not limited to, cetyl trimethyl ammonium group consisting of Sol-gel polymer (e.g., silica), polyacry chloride (CTAC), poloxamers such as PLURONICS (e.g., late, polyacrylamide, poly(acrylate-co-acrylamide), poly PLURONIC F127), PLURAFAC (e.g., PLURAFAC F127), urea, polyurethane, starch, gelatin and gum Arabic, poly or MIRANET-N, saponins such as QNATURALE (National (melamine-formaldehyde), poly(urea-formaldehyde), and Starch Food Innovation); or a gum Arabic such as Seyal or combinations thereof. Senegal. The amount of Surfactant present in the capsule 0073. These encapsulating polymers are described in slurry can vary depending on the Surfactant used. In some detail below. embodiments the amount of surfactant is in the range of 0.05 (0074 Sol-Gel Microcapsules. to 0.2% by weight of the capsule compositions, in particular 0075. These microcapsules have a microcapsule wall when CTAC is employed. In another embodiment, the formed of a sol-gel polymer, which is a reaction product of a amount of surfactant is in the range of 1 to 3%. sol-gel precursor via a polymerization reaction (e.g., hydro 0066. When combined with CMC, a lighter color PVA is lyZation). Suitable sol-gel precursors are compounds capable preferred. According to the invention, the CMC polymer may of forming gels such as compounds containing silicon, boron, aluminum, titanium, zinc, Zirconium, and Vanadium. Pre be represented by the following structure: ferred precursors are organosilicon, organoboron, and orga noaluminum including metal alkoxides and b-diketonates. 0076 Sol-gel precursors suitable for the purposes of the invention are selected in particular from the group of di-, tri and/or tetrafunctional silicic acid, boric acid and alumoesters, more particularly alkoxysilanes (alkyl orthosilicates), and precursors thereof. OR 0077 One example of sol-gel precursors suitable for the purposes of the invention are alkoxysilanes corresponding to R = H or CHCO2H the following general formula: 0067. In certain embodiments, the CMC polymer has a molecular weight range between 90,000 to 1,500,000 Da. wherein X can be hydrogen or —OR: X can be hydrogen or preferably between 250,000 to 750,000 Da, and more prefer —OR; and R. R. R. and R independently represent an ably between 400,000 to 750,000 Da. The CMC polymer has organic group, more particularly a linear or branched alkyl a degree of substitution between 0.1 to 3, preferably between group, preferably a C-C alkyl. M can be Si, Ti, or Zr. 0.65 to 1.4, and more preferably between 0.8 to 1. 0078. A preferred sol/gel precursor is alkoxysilanes cor responding to the following general formula: (RO)(RO)Si 0068. The carboxymethyl cellulose polymer is present in (X)(X'), wherein each of X, X', R, and R are defined above. the capsule slurry at a level from 0.1 to 2% and preferably 0079 Particularly preferred compounds are the silicic acid from 0.3 to 0.7%. esters such as tetramethyl orthosilicate (TMOS) and tetra 0069. In some embodiments, capsules formed in presence ethyl orthosilicate (TEOS). A preferred compound includes of a capsule aid may unexpectedly provide a perceived fra Dynasylan R (organofunctional silanes commercially avail grance intensity increase of greater than 15%, and preferably able from Degussa Corporation, Parsippany N.J., USA). an increase of greater than 25% as compared to capsules Other sol-gel precursors suitable for the purposes of the formed without a capsule formation aid. invention are described, for example, in German Patent US 2016/0158121 A1 Jun. 9, 2016

Application DE 10021165. These sol-gel precursors are vari I0083. The monomer is polymerized in the presence of an ous hydrolyzable organosilanes such as, for example, alkyl activation agent (e.g., an initiator) at a raised temperature silanes, alkoxysilanes, alkyl alkoxysilanes and organoalkox (e.g., 30-90° C.) or under UV light. Exemplary initiators are ysilanes. Besides the alkyl and alkoxy groups, other organic 2,2'-azobis(isobutyronitrile) (AIBN'), dicetyl peroxydicar groups (for example allyl groups, aminoalkyl groups, bonate, di(4-tert-butylcyclohexyl) peroxydicarbonate, dio hydroxyalkyl groups, etc.) may be attached as Substituents to ctanoyl peroxide, dibenzoyl peroxide, dilauroyl peroxide, the silicon. didecanoyl peroxide, tert-butyl peracetate, tert-butyl perlau rate, tert-butyl perbenzoate, tert-butyl hydroperoxide, 0080 Recognizing that metal and semi metal alkoxide cumene hydroperoxide, cumene ethylperoxide, diisopropyl monomers (and their partially hydrolyzed and condensed hydroxy dicarboxylate, 2,2'-azobis(2,4-dimethyl Valeroni polymers) such as tetramethoxy silane (TMOS), tetraethoxy trile), 1,1'-azobis(cyclohexane-1-carbonitrile), dimethyl 2,2'- silane (TEOS), etc. are very good solvents for numerous aZobis(2-methylpropionate), 2,2'-azobis 2-methyl-N-(2- molecules and active ingredients is highly advantageous hydroxyethyl) propionamide, sodium persulfate, benzoyl since it facilitates dissolving the active materials at a high concentration and thus a high loading in the final capsules. peroxide, and combinations thereof. I0084 Emulsifiers used in the formation of polyacrylate/ 0081 Polyacrylate Microcapsules, Polyacrylamide polyacrylamide/poly(acrylate-co-acrylamide) capsule walls Microcapsules, and Poly(Acrylate-Co-Acrylamide) Micro are typically anionic emulsifiers including by way of illustra capsules. tion and not limitation, water-soluble salts of alkyl sulfates, 0082 Each of these microcapsules is prepared from a cor alkyl ether Sulfates, alkyl isothionates, alkyl carboxylates, responding precursor. Preferred precursors are bi- or poly alkyl Sulfo Succinates, alkyl Succinamates, alkyl Sulfate salts functional vinyl monomers including by way of illustration Such as Sodium dodecyl sulfate, alkyl sarcosinates, alkyl and not limitation, allyl methacrylate/acrylamide, triethylene derivatives of protein hydrolyzates, acyl aspartates, alkyl or glycol dimethacrylate/acrylamide, ethylene glycol alkyl ether or alkylaryl ether phosphate esters, sodium dode dimethacrylate? acrylamide, diethylene glycol dimethacry cyl Sulphate, phospholipids or lecithin, or Soaps, Sodium, late? acrylamide, triethylene glycol dimethacrylate? acryla potassium or ammonium Stearate, oleate or palmitate, alky mide, tetraethylene glycol dimethacrylate/acrylamide, pro larylsulfonic acid salts such as sodium dodecylbenzene pylene glycol dimethacrylate/acrylamide, glycerol Sulfonate, sodium dialkylsulfoSuccinates, dioctyl sulfo Succi dimethacrylate? acrylamide, neopentyl glycol dimethacry nate, Sodium dilaurylsulfo Succinate, poly(styrene Sulfonate) late? acrylamide, 1,10-decanediol dimethacrylate/acryla sodium salt, isobutylene-maleic anhydride copolymer, gum mide, pentaerythritol trimethacrylate/acrylamide, pen arabic, Sodium alginate, carboxymethylcellulose, cellulose taerythritol tetramethacrylate/acrylamide, dipentaerythritol Sulfate and pectin, poly(styrene Sulfonate), isobutylene-ma hexamethacrylate/acrylamide, triallyl-formal trimethacry leic anhydride copolymer, gum arabic, carrageenan, Sodium late? acrylamide, trimethylol propane trimethacrylate? acryla alginate, pectic acid, tragacanth gum, almond gum and agar, mide, tributanediol dimethacrylate/acrylamide, aliphatic or semi-synthetic polymers such as carboxymethyl cellulose, aromatic urethane diacrylates/acrylamides, difunctional ure sulfated cellulose, sulfated methylcellulose, carboxymethyl thane acrylates/acrylamides, ethoxylated aliphatic difunc starch, phosphated Starch, lignin Sulfonic acid; and synthetic tional urethane methacrylates/acrylamides, aliphatic or aro polymers such as maleic anhydride copolymers (including matic urethane dimethacrylates/acrylamides, epoxy hydrolyzates thereof), polyacrylic acid, polymethacrylic acrylates/acrylamides, epoxymethacrylates/acrylamides, acid, acrylic acid butyl acrylate copolymer or crotonic acid 1,3-butylene glycol diacrylate? acrylamide, 1,4-butanediol homopolymers and copolymers, vinylbenzenesulfonic acid dimethacrylate? acrylamide, 1,4-butaneidiol diacrylate? acry or 2-acrylamido-2-methylpropanesulfonic acid homopoly lamide, diethylene glycol diacrylate? acrylamide, 1.6-hex mers and copolymers, and partial amide or partial ester of anediol diacrylate/acrylamide, 1.6-hexanediol dimethacry Such polymers and copolymers, carboxymodified polyvinyl late? acrylamide, neopentyl glycol diacrylate/acrylamide, alcohol, Sulfonic acid-modified polyvinyl alcohol and phos polyethylene glycol diacrylate/acrylamide, tetraethylene gly phoric acid-modified polyvinyl alcohol, phosphated or Sul col diacrylate/acrylamide, triethylene glycol diacrylate? acry fated tristyrylphenol ethoxylates. The amount of anionic lamide, 1,3-butylene glycol dimethacrylate/acrylamide, emulsifier is anywhere from 0.1 to 40 percent by weight of all tripropylene glycol diacrylate/acrylamide, ethoxylated constitutents, more preferably from 0.5 to 10 percent, more bisphenol diacrylate/acrylamide, ethoxylated bisphenol dim preferably 0.5 to 5 percent by weight. ethylacrylate/acrylamide, dipropylene glycol diacrylate/ I0085 Aminoplasts and Gelatin. acrylamide, alkoxylated hexanediol diacrylate/acrylamide, I0086 A representative process used for aminoplast encap alkoxylated cyclohexane dimethanol diacrylate/acrylamide, sulation is disclosed in U.S. Pat. No. 3,516,941 and US 2007/ propoxylated neopentylglycol diacrylate/acrylamide, trim 0078071, though it is recognized that many variations with ethylol-propane triacrylate/acrylamide, pentaerythritol tria regard to materials and process steps are possible. Another crylate/acrylamide, ethoxylated trimethylolpropane triacry encapsulation process, i.e., gelatinencapsulation, is disclosed late? acrylamide, propoxylated trimethylolpropane in U.S. Pat. No. 2,800,457. Both processes are discussed in triacrylate/acrylamide, propoxylated glyceryl triacrylate/ the context of fragrance encapsulation for use in consumer acrylamide, ditrimethyloipropane tetraacrylate/acrylamide, products in U.S. Pat. Nos. 4,145,184 and 5,112,688 respec dipentaerythritol pentaacrylate/acrylamide, ethoxylated pen tively. Polymer systems are well-known in the art and non taerythritol tetraacrylate/acrylamide, PEG 200 dimethacry limiting examples of these include aminoplast capsules and late/acrylamide, PEG 400 dimethacrylate/acrylamide, PEG encapsulated particles as disclosed in GB 2006709 A; the 600 dimethacrylate/acrylamide, 3-acryloyloxy glycol production of micro-capsules having walls comprising Sty monoacrylate/acrylamide, triacrylformal, triallyl isocyanate, rene-maleic anhydride reacted with melamine-formaldehyde and triallyl isocyanurate. precondensates as disclosed in U.S. Pat. No. 4.396,670; an US 2016/0158121 A1 Jun. 9, 2016 acrylic acid-acrylamide copolymer, cross-linked with a Substituted acrylic acid polymer/co-polymer is in the range of melamine-formaldehyde resin as disclosed in U.S. Pat. No. from 9:1 to 1:9, preferably from 5:1 to 1:5 and most prefer 5,089,339; capsules composed of cationic melamine-formal ably from 2:1 to 1:2. dehyde condensates as disclosed in U.S. Pat. No. 5,401,577; 0090. In one embodiment of the invention, microcapsules melamine formaldehyde microencapsulation as disclosed in with polymer(s) composed of primary and/or secondary U.S. Pat. No. 3,074,845; amido-aldehyde resin in-situ poly amine reactive groups or mixtures thereof and cross-linkers merized capsules disclosed in EP 0 158 449 A1; etherified can also be used. See US 2006/024.8665. The amine polymers urea-formaldehyde polymer as disclosed in U.S. Pat. No. can possess primary and/or secondary amine functionalities and can be of either natural or synthetic origin. Amine-con 5,204,185; melamine-formaldehyde microcapsules as taining polymers of natural origin are typically proteins such described in U.S. Pat. No. 4,525,520; cross-linked oil-soluble as gelatin and albumen, as well as Some polysaccharides. melamine-formaldehyde precondensate as described in U.S. Synthetic amine polymers include various degrees of hydro Pat. No. 5,011,634; capsule wall material formed from a lyzed polyvinyl formamides, polyvinylamines, polyallyl complex of cationic and anionic melamine-formaldehyde amines and other synthetic polymers with primary and sec precondensates that are then cross-linked as disclosed in U.S. ondary amine pendants. Examples of Suitable amine poly Pat. No. 5,013,473; polymeric shells made from addition mers are the LUPAMIN series of polyvinyl formamides avail polymers such as condensation polymers, phenolic alde able from BASF. The molecular weights of these materials hydes, urea aldehydes or acrylic polymeras disclosed in U.S. can range from 10,000 to 1,000,000 Da. Pat. No. 3,516,941; urea-formaldehyde capsules as disclosed 0091 Urea-formaldehyde or melamine-formaldehyde in EP 0 443 428 A2; melamine-formaldehyde chemistry as capsules can also include formaldehyde Scavengers, which disclosed in GB 2 062 570 A; and capsules composed of are capable of binding free formaldehyde. When the capsules polymer or copolymer of styrene Sulfonic acid in acid of salt are for use in aqueous media, formaldehyde Scavengers such form, and capsules cross-linked with melamine-formalde as Sodium sulfite, melamine, glycine, and carbohydrazine are hyde as disclosed in U.S. Pat. No. 4,001,140. suitable. When the capsules are aimed to be used in products having low pH, e.g., fabric care conditioners, formaldehyde 0087 Urea-Formaldehyde and Melamine Formaldehyde Scavengers are preferably selected from beta diketones, such Capsules. as beta-ketoesters, or from 1,3-diols, such as propylene gly 0088. Urea-formaldehyde and melamine-formaldehyde col. Preferred beta-ketoesters include alkyl-malonates, alkyl pre-condensate capsule shell wall precursors are prepared by acetoacetates and polyvinyl alcohol acetoacetates. means of reacting urea or melamine with formaldehyde 0092. The microcapsule composition of this invention where the mole ratio of melamine or urea to formaldehyde is optionally contains one or more additional microcapsules, in the range of from 10:1 to 1:6, preferably from 1:2 to 1:5. e.g., a third, fourth, fifth, or sixth microcapsules. Each of For purposes of practicing this invention, the resulting mate these microcapsules can be any of the microcapsule described rial has a molecular weight in the range of from 156 to 3000. above. The resulting material may be used 'as-is' as a cross-linking agent for the aforementioned substituted or un-substituted Active Materials acrylic acid polymer or copolymer or it may be further reacted 0093. The core of the capsules of the invention can include with a C-C alkanol, e.g., methanol, ethanol. 2-propanol, one or more active materials including, but not limited to, 3-propanol, 1-butanol. 1-pentanol or 1-hexanol, thereby flavors and/or fragrance ingredients such as fragrance oils. forming a partial ether where the mole ratio of melamine/ Individual perfume ingredients that can be encapsulated urea: formaldehyde:alkanol is in the range of 1:(0.1-6):(0.1- include: 6). The resulting ether moiety-containing product may be 0094) i) hydrocarbons, such as, for example, 3-carene, used 'as-is' as a cross-linking agent for the aforementioned C-pinene, B-pinene, C-terpinene, Y-terpinene, p-cymene, bis Substituted or un-substituted acrylic acid polymer or copoly abolene, camphene, caryophyllene, cedrene, farnesene, mer, or it may be self-condensed to form dimers, trimers limonene, longifolene, myrcene, Ocimene, Valencene, (E,Z)- and/or tetramers which may also be used as cross-linking 1.3.5-undecatriene, styrene, and diphenylmethane; agents for the aforementioned substituted or un-substituted 0.095 ii) aliphatic alcohols, such as, for example, hexanol, acrylic acid polymers or co-polymers. Methods for formation octanol, 3-octanol. 2,6-dimethyl-heptanol, 2-methyl-2-hep of such melamine-formaldehyde and urea-formaldehyde pre tanol, 2-methyl-2-octanol, (E)-2-hexenol, (E)- and (Z)-3- condensates are set forth in U.S. Pat. Nos. 3,516,846 and hexenol, 1-octen-3-ol, a mixture of 3,4,5,6,6-pentamethyl-3/ 6.261,483, and Lee et al. (2002) J. Microencapsulation 19, 4-hepten-2-ol and 3,5,6,6-tetramethyl-4-methyleneheptan-2- 559-569. ol, (E,Z)-2,6-nonadienol. 3,7-dimethyl-7-methoxyoctan-2- 0089. Examples of urea-formaldehyde pre-condensates ol, 9-decenol, 10-undecenol, 4-methyl-3-decen-5-ol. useful in the practice of this invention are URAC 180 and aliphatic aldehydes and their acetals such as for example URAC 186, trademarks of Cytec Technology Corp. of Wilm hexanal, heptanal, octanal, nonanal, decanal, undecanal, ington, Del. Examples of melamine-formaldehyde pre-con dodecanal, tridecanal, 2-methyloctanal, 2-methylnonanal, densates useful in the practice if this invention, include, but (E)-2-hexenal, (Z)-4-heptenal, 2,6-dimethyl-5-heptenal, are not limited to, CYMEL U-60, CYMEL U-64 and 10-undecenal, (E)-4-decenal, 2-dodecenal, 2,6,10-trimethyl CYMEL U-65, trademarks of Cytec Technology Corp. of 5.9-undecadienal, heptanal-diethylacetal, 1,1-dimethoxy-2, Wilmington, Del. It is preferable to use, as the precondensate 2.5-trimethyl-4-hexene, and citronellyl oxyacetaldehyde; for cross-linking, the Substituted or un-substituted acrylic 0096 iii) aliphatic ketones and oximes thereof, such as, acid polymer or co-polymer. In practicing this invention, the for example, 2-heptanone, 2-octanone, 3-octanone, range of mole ratios of urea-formaldehyde precondensate/ 2-nonanone, 5-methyl-3-heptanone, 5-methyl-3-heptanone melamine-formaldehyde pre-condensate to Substituted/un Oxime, 2.4.4.7-tetra-methyl-6-octen-3-one, aliphatic Sulfur US 2016/0158121 A1 Jun. 9, 2016 containing compounds, such as for example 3-methylthio methyl-3-cyclopent-1-yl)-2-buten-1-ol. 3-methyl-5-(2,2,3- hexanol, 3-methylthiohexyl acetate, 3-mercaptohexanol, trimethyl-3-cyclopent-1-yl)-pentan-2-ol, 3-methyl-5-(2,2,3- 3-mercaptohexyl acetate, 3-mercapto-hexyl butyrate, trimethyl-3-cyclopent-1-yl)-4-penten-2-ol. 3,3-dimethyl-5- 3-acetylthiohexyl acetate, 1-menthene-8-thiol, and aliphatic (2.2,3-trimethyl-3-cyclopent-1-yl)-4-penten-2-ol. 1-(2.2.6- nitriles (e.g., 2-nonenenitrile, 2-tridecenenitrile, 2, 12 trimethylcyclohexyl)pentan-3-ol, 1-(2.2.6- tridecenenitrile, 3,7-dimethyl-2,6-octalienenitrile, and 3.7- trimethylcyclohexyl)hexan-3-ol; dimethyl-6-octenenitrile); 0104 xi) cyclic and cycloaliphatic ethers, such as, for 0097 iv) aliphatic carboxylic acids and esters thereof, example, cineole, cedryl methyl ether, cyclododecyl methyl Such as, for example, (E)- and (Z)-3-hexenylformate, ethyl ether; acetoacetate, isoamyl acetate, hexyl acetate, 3.5.5-trimethyl 0105 xii) (ethoxymethoxy)cyclododecane; alpha-ce hexyl acetate, 3-methyl-2-butenyl acetate, (E)-2-hexenyl drene epoxide, 3a,6,6,9a-tetramethyl-do decahydronaphtho acetate, (E)- and (Z)-3-hexenyl acetate, octyl acetate, 3-octyl 2,1-bfuran, 3a-ethyl-6,6,9a-trimethyldodecahydro-naph acetate, 1-octen-3-yl acetate, ethylbutyrate, butylbutyrate, tho2.1-bfuran, 1.5.9-trimethyl-13-oxabicyclo10.1.0- isoamyl butyrate, hexylbutyrate, (E)- and (Z)-3-hexenyl trideca-4,8-diene, rose oxide, 2-(2,4-dimethyl-3-cyclohexen isobutyrate, hexylcrotonate, ethylisovalerate, ethyl-2-methyl 1-yl)-5-methyl-5-(1-methylpropyl)-1,3-dioxan-: pentanoate, ethyl hexanoate, allyl hexanoate, ethyl hep 010.6 xiii) cyclic ketones, such as, for example, 4-tert.- tanoate, allyl heptanoate, ethyl octanoate, ethyl-(E,Z)-2,4- butylcyclohexanone, 2.2.5-trimethyl-5-pentylcyclopen decadienoate, methyl-2-octinate, methyl-2-noninate, allyl-2- tanone, 2-heptylcyclopentanone, 2-pentylcyclopentanone, isoamyl oxyacetate, and methyl-3,7-dimethyl-2,6- 2-hydroxy-3-methyl-2-cyclopenten-1-one, 3-methyl-cis-2- octadienoate; penten-1-yl-2-cyclopenten-1-one, 3-methyl-2-pentyl-2-cy 0098 v) acyclic terpene alcohols, such as, for example, clopenten-1-one, 3-methyl-4-cyclopentadecenone, 3-me citronellol, geraniol, nerol, linalool, lavandulol, nerolidol. thyl-1-cyclopentadecenone, 3-methylcyclopentadecanone, farnesol, tetrahydrolinalool, tetrahydrogeraniol. 2,6-dim 4-(1-ethoxyvinyl)-3,3,5,5-tetra-methyl cyclohexanone, ethyl-7-octen-2-ol. 2,6-dimethyloctan-2-ol, 2-methyl-6-me 4-tert.-pentylcyclohexanone, 5-cyclohexadecen-1-one, 6.7- thylene-7-octen-2-ol. 2,6-dimethyl-5.7-octadien-2-ol. 2,6- dihydro-1,1,2,3,3-pentamethyl-4(5H)-indanone, 5-cyclo dimethyl-3,5-octadien-2-ol. 3,7-dimethyl-4,6-octadien-3-ol, hexadecen-1-one, 8-cyclohexadecen-1-one, 9-cycloheptade 3,7-dimethyl-1,5,7-octatrien-3-ol, 2,6-dimethyl-2.5.7-oc cen-1-one, cyclopentadecanone, cycloaliphatic aldehydes, tatrien-1-ol, as well as formates, acetates, propionates, isobu Such as, for example, 2,4-dimethyl-3-cyclohexene carbalde tyrates, butyrates, isovalerates, pentanoates, hexanoates, cro hyde, 2-methyl-4-(2,2,6-trimethyl-cyclohexen-1-yl)-2-bute tonates, tiglinates and 3-methyl-2-butenoates thereof. nal, 4-(4-hydroxy-4-methylpentyl)-3-cyclohexene carbalde 0099 vi) acyclic terpenealdehydes and ketones, such as, hyde, 4-(4-methyl-3-penten-1-yl)-3-cyclohexene for example, geranial, neral, citronellal, 7-hydroxy-3,7-dim carbaldehyde; ethyloctanal, 7-methoxy-3,7-dimethyloctanal, 2,6,10-trim 0107 xiv) cycloaliphatic ketones, such as, for example, ethyl-9-undecenal, C.-Sinensal, B-sinensal, geranylacetone, as 1-(3.3-dimethylcyclohexyl)-4-penten-1-one, 1-(5,5-dim well as the dimethyl- and diethylacetals of geranial, neral and ethyl-1-cyclohexen-1-yl)-4-penten-1-one, 2.3,8,8-tetram 7-hydroxy-3,7-dimethyloctanal; ethyl-1,2,3,4,5,6,7,8-octahydro-2-naphtalenyl methyl-ke 0100 vii) cyclic terpene alcohols, such as, for example, tone, methyl-2,6,10-trimethyl-2.5.9-cyclododecatrienyl menthol, isopulegol, alpha-terpineol, terpinen-4-ol, men ketone, tert-butyl-(2,4-dimethyl-3-cyclohexen-1-yl)ketone; than-8-ol, menthan-1-ol, menthan-7-ol, borneol, isoborneol. 0.108 xv) esters of cyclic alcohols, such as, for example, linalool oxide, nopol, cedrol, ambrinol, Vetiverol, guaiol, and 2-tert-butylcyclohexyl acetate, 4-tert-butylcyclohexyl the formates, acetates, propionates, isobutyrates, butyrates, acetate, 2-tert-pentylcyclohexyl acetate, 4-tert-pentylcyclo isovalerates, pentanoates, hexanoates, crotonates, tiglinates hexyl acetate, decahydro-2-naphthyl acetate, 3-pentyltet and 3-methyl-2-butenoates of alpha-terpineol, terpinen-4-ol. rahydro-2H-pyran-4-yl acetate, decahydro-2.5.5.8a-tetram methan-8-ol, methan-1-ol, methan-7-ol, borneol, isoborneol. ethyl-2-naphthyl acetate, 47-methano-3a,4,5,6,7,7a linalool oxide, nopol, cedrol, ambrinol, Vetiverol, and guaiol; hexahydro-5 or 6-indenyl acetate, 4.7-methano-3a,4,5,6,7, 0101 viii) cyclic terpene aldehydes and ketones, such as, 7a-hexahydro-5 or 6-indenyl propionate, 4.7-methano-3a.4. for example, menthone, isomenthone, 8-mercaptomenthan 5,6,7,7a-hexahydro-5 or 6-indenyl-isobutyrate, 4.7- 3-one, carvone, camphor, fenchone, C-ionone, B-ionone, methanooctahydro-5 or 6-indenyl acetate; C.-n-methylionone, B-n-methylionone, C-isomethylionone, 0109 xvi) esters of cycloaliphatic carboxylic acids, such B-isomethylionone, alpha-irone, C-damascone, B-dam as, for example, allyl 3-cyclohexyl-propionate, allyl cyclo ascone, 3-damascenone, Ö-damascone, y-damascone, 1-(2,4, hexyl oxyacetate, methyl dihydrojasmonate, methyl jas 4-trimethyl-2-cyclohexen-1-yl)-2-buten-1-one, 1,3,4,6,7,8a monate, methyl 2-hexyl-3-oxocyclopentanecarboxylate, hexahydro-1,1,5,5-tetra-methyl-2H-2,4a ethyl 2-ethyl-6,6-dimethyl-2-cyclohexenecarboxylate, ethyl methanonaphthalen-8(5H-)-one, nootkatone, 2.3.6.6-tetramethyl-2-cyclohexenecarboxylate, ethyl 2-me dihydronootkatone; acetylated cedarwood oil (cedryl methyl thyl-1,3-dioxolane-2-acetate; ketone); 0110 xvii) aromatic and aliphatic alcohols, such as, for 0102 ix) cyclic alcohols, such as, for example, 4-tert example, benzyl alcohol. 1-phenylethyl alcohol. 2-phenyl butylcyclohexanol. 3,3,5-trimethylcyclohexanol, 3-isocam ethyl alcohol, 3-phenylpropanol. 2-phenylpropanol, 2-phe phylcyclohexanol. 2.6.9-trimethyl-Z2.Z5.E9-cyclo-dodec noxyethanol. 2.2-dimethyl-3-phenylpropanol. 2,2-dimethyl atrien-1-ol, 2-iso-butyl-4-methyltetrahydro-2H-pyran-4-ol; 3-(3-methylphenyl)-propanol, 1,1-dimethyl-2-phenylethyl 0103 X) cycloaliphatic alcohols, such as, for example, alcohol, 1,1-dimethyl-3-phenylpropanol, 1-ethyl-1-methyl alpha, 3,3-trimethylcyclo-hexylmethanol, 2-methyl-4-(2.2, 3-phenylpropanol, 2-methyl-5-phenylpentanol, 3-methyl-5- 3-trimethyl-3-cyclopent-1-yl)butanol, 2-methyl-4-(2,2,3-tri phenylpentanol, 3-phenyl-2-propen-1-ol. 4-methoxybenzyl methyl-3-cyclopent-1-yl)-2-buten-1-ol, 2-ethyl-4-(2,2,3-tri alcohol. 1-(4-isopropylphenyl)ethanol; US 2016/0158121 A1 Jun. 9, 2016

0111. xviii) esters of aliphatic alcohols and aliphatic car rol, diphenyl ether, beta-naphthyl methyl ether, beta-naphthyl boxylic acids, such as, for example, benzyl acetate, benzyl ethyl ether, beta-naphthyl isobutyl ether, 1,4-dimethoxyben propionate, benzyl isobutyrate, benzyl isovalerate, 2-phenyl Zene, eugenyl acetate, 2-methoxy-4-methylphenol, 2-ethoxy ethyl acetate, 2-phenylethylpropionate, 2-phenylethyl isobu 5-(1-propenyl)phenol, p-cresyl phenylacetate; tyrate, 2-phenylethyl isovalerate, 1-phenylethyl acetate, 0117 xxiv) heterocyclic compounds, such as, for O-trichloromethylbenzyl acetate, C.C.-dimethylphenylethyl example, 2,5-dimethyl-4-hydroxy-2H-furan-3-one, 2-ethyl acetate, alpha, alpha-dimethylphenylethyl butyrate, cin 4-hydroxy-5-methyl-2H-furan-3-one, 3-hydroxy-2-methyl namyl acetate, 2-phenoxyethyl isobutyrate, 4-methoxyben 4H-pyran-4-one, 2-ethyl-3-hydroxy-4H-pyran-4-one; Zyl acetate, araliphatic ethers. Such as for example 2-phenyl 0118 XXV) lactones, such as, for example, 1,4-octanolide, ethyl methyl ether, 2-phenylethyl isoamyl ether, 3-methyl-1,4-octanolide, 1,4-nonanolide, 1,4-decanolide, 2-phenylethyl-1-ethoxyethyl ether, phenylacetaldehyde dim 8-decen-1,4-olide, 1,4-undecanolide, 1.4-dodecanolide, 1.5- ethyl acetal, phenylacetaldehyde diethyl acetal, hydratropaal decanolide, 1.5-dodecanolide, 1.15-pentadecanolide, cis dehyde dimethyl acetal, phenylacetaldehyde glycerol acetal, and trans-11-pentadecen-115-olide, cis- and trans-12-penta 2,4,6-trimethyl-4-phenyl-1,3-dioxane, 4.4a.5.9b-tetrahy decen-1, 15-olide, 1,16-hexadecanolide, 9-hexadecen-1, 16 droindeno1,2-d-m-dioxin, 4.4a.5.9b-tetrahydro-2,4-dim olide, 10-Oxa-1,16-hexadecanolide, 11-oxa-1,16-hexade ethylindeno1,2-d-m-dioxin; canolide, 12-Oxa-1,16-hexadecanolide, ethylene-1,12 0112 xix) aromatic and aliphatic aldehydes, such as, for dodecanedioate, ethylene-1,13-tridecanedioate, coumarin, example, benzaldehyde; phenylacet-aldehyde, 3-phenylpro 2,3-dihydrocoumarin, and octahydrocoumarin; panal, hydratropaldehyde, 4-methylbenzaldehyde, 4-meth 0119 xxvi) essential oils, concretes, absolutes, resins, res ylphenyl-acetaldehyde, 3-(4-ethylphenyl)-2,2-dimethylpro inoids, balsams, tinctures such as for example ambergristinc panal, 2-methyl-3-(4-iso-propylphenyl)propanal, 2-methyl ture, amyris oil, angelica seed oil, angelica root oil, aniseed 3-(4-tert-butylphenyl)propanal, 3-(4-tert.-butyl-phenyl) oil, Valerian oil, basil oil, tree moss absolute, bay oil, armoise propanal, cinnamaldehyde, alpha-butylcinnamaldehyde, oil, benzoe resinoid, bergamotoil, beeswax absolute, birchtar alpha-amylcinnam-aldehyde, alpha-hexylcinnamaldehyde, oil, bitter almond oil, savory oil, buchu leaf oil, cabreuva oil, 3-methyl-5-phenylpentanal, 4-methoxybenzaldehyde, 4-hy cade oil, calamus oil, camphor oil, cananga oil, cardamom oil, droxy-3-methoxybenzaldehyde, 4-hydroxy-3-ethoxybenzal cascarilla oil, cassia oil, cassie absolute, castoreum absolute, dehyde, 3.4-methylene-dioxybenzaldehyde, 3,4-dimethoxy cedar leaf oil, cedar wood oil, cistus oil, citronella oil, lemon benzaldehyde, 2-methyl-3-(4-methoxyphenyl)propanal, oil, copaibabalsam, copaibabalsam oil, coriander oil, costus 2-methyl-3-(4-methylendioxyphenyl)propanal; root oil, cumin oil, cypress oil, davana oil, dill weed oil, dill 0113 xx) aromatic and aliphatic ketones, such as, for seed oil, eau de brouts absolute, oakmoss absolute, elemi oil, example, acetophenone, 4-methylacetophenone, 4-methoxy estragon oil, eucalyptus citriodora oil, eucalyptus oil (cineole acetophenone, 4-tert.-butyl-2,6-dimethylacetophenone, type), fennel oil, fir needle oil, galbanum oil, galbanum resin, 4-phenyl-2-butanone, 4-(4-hydroxyphenyl)-2-butanone, geranium oil, grapefruit oil, guaiacwood oil, gurjun balsam, 1-(2-naphthalenyl)ethanone, benzophenone, 1.1.2.3.3.6- gurun balsam oil, helichrysum absolute, helichrysum oil, hexamethyl-5-indanyl methyl ketone, 6-tert-butyl-1,1-dim ginger oil, iris root absolute, iris root oil, jasmine absolute, ethyl-4-indanyl methyl ketone, 1-2,3-dihydro-1,1,2,6-tet calamus oil, blue camomile oil, Roman camomile oil, carrot ramethyl-3-(1-methylethyl)-1H-5-indenylethanone, 5'6'7", seed oil, cascarilla oil, pine needle oil, spearmint oil, caraway 8-tetrahydro-3',5',5'6",8,8-hexamethyl-2-acetonaphthone; oil, labdanum oil, labdanum absolute, labdanum resin, lavan 0114 XXi) aromatic and araliphatic carboxylic acids and din absolute, lavandin oil, lavender absolute, lavender oil, esters thereof. Such as, for example, benzoic acid, phenylace lemon-grass oil, lovage oil, lime oil distilled, lime oil tic acid, methyl benzoate, ethyl benzoate, hexyl benzoate, expressed, linaloe oil, Litsea cubeba oil, laurel leaf oil, mace benzyl benzoate, methyl phenylacetate, ethyl phenylacetate, oil, marjoram oil, mandarin oil, massoi (bark) oil, mimosa geranyl phenylacetate, phenylethyl phenylacetate, methyl absolute, ambrette seed oil, musk tincture, clary sage oil, cinnamate, ethyl cinnamate, benzyl cinnamate, phenylethyl nutmeg oil, myrrh absolute, myrrh oil, myrtle oil, clove leaf cinnamate, cinnamyl cinnamate, allyl phenoxyacetate, oil, clove bud oil, neroli oil, olibanum absolute, olibanum oil, methyl salicylate, isoamyl Salicylate, hexyl salicylate, cyclo opopanax oil, orange flower absolute, orange oil, origanum hexyl salicylate, cis-3-hexenyl salicylate, benzyl salicylate, oil, palmarosa oil, patchouli oil, perilla oil, Peru balsam oil, phenylethyl salicylate, methyl 2,4-dihydroxy-3,6-dimethyl parsley leafoil, parsley seed oil, petitgrain oil, peppermint oil, benzoate, ethyl 3-phenylglycidate, ethyl 3-methyl-3-phe pepper oil, pimento oil, pine oil, pennyroyal oil, rose abso nylglycidate; lute, rosewood oil, rose oil, rosemary oil, Dalmatian sage oil, 0115 XXii) nitrogen-containing aromatic compounds, Spanish sage oil, sandal-wood oil, celery seed oil: spike such as, for example, 2,4,6-trinitro-1,3-dimethyl-5-tert-bu lavender oil, staranise oil, storax oil, tagetes oil, fir needle oil, tylbenzene, 3,5-dinitro-2,6-dimethyl-4-tert-butylaceto-phe tea tree oil, turpentine oil, thyme oil, Tolubalsam, tonka bean none, cinnamonitrile, 5-phenyl-3-methyl-2-pentenonitrile, absolute, tuberose absolute, Vanilla extract, violet leaf abso 5-phenyl-3-methylpentano-nitrile, methyl anthranilate, lute, verbena oil, Vetiver oil, juniperberry oil, wine lees oil, methy-N-methylanthranilate, Schiffs bases of methyl wormwood oil, wintergreen oil, ylang-ylang oil, hyssop oil, anthranilate with 7-hydroxy-3,7-dimethyl-octanal, 2-methyl civet absolute, cinnamon leaf oil, cinnamon bark oil, and 3-(4-tert.-butylphenyl)-propanal or 2,4-dimethyl-3-cyclo fractions thereof or ingredients isolated therefrom: hexene carbaldehyde, 6-isopropylquinoline, 6-isobutyl I0120 (XXvii) flavors including, but are not limited to, quinoline, 6-sec-butylquinoline, indole, skatole, 2-methoxy acetaldehyde, dimethyl sulfide, ethyl acetate, ethyl propi 3-isopropylpyrazine, 2-isobutyl-3-methoxypyrazine; onate, methylbutyrate, and ethylbutyrate. Flavors containing 0116 xxiii) phenols, phenyl ethers and phenyl esters, such Volatile aldehydes or esters include, e.g., cinnamyl acetate, as, for example, estragole, anethole, eugenol, eugenyl methyl cinnamaldehyde, citral, diethylacetal, dihydrocarvyl acetate, ether, isoeugenol, isoeugenol methyl ether, thymol, carvac eugenyl formate, and p-methylanisole. Further examples of US 2016/0158121 A1 Jun. 9, 2016

Volatile compounds that may be present in the instant flavor olane: 4-methyl-2-(methylthiomethyl)-1,3-dithiolane, and oils include acetaldehyde (apple); benzaldehyde (cherry, the flavor ingredients described in U.S. Pat. Nos. 6,110,520 almond): cinnamic aldehyde (cinnamon); citral, i.e., alpha and 6,333,180; citral (lemon, lime); neral, i.e., beta citral (lemon, lime); 0121 (XXViii) taste masking agents, Substances for mask decanal (orange, lemon); ethyl Vanillin (vanilla, cream): ing one or more unpleasant taste sensations, in particular a heliotropine, i.e., piperonal (vanilla, cream); Vanillin (vanilla, bitter, astringent and/or metallic taste sensation or aftertaste. cream); alpha-amyl cinnamaldehyde (spicy fruity flavors); Examples include lactisol20-(4-methoxyphenyl) lactic acid butyraldehyde (butter, cheese); Valeraldehyde (butter, (cf. U.S. Pat. No. 5,045,336), 2,4-dihydroxybenzoic acid cheese); citronellal (modifies, many types); decanal (citrus potassium salt (cf U.S. Pat. No. 5,643,941), ginger extracts fruits); aldehyde C-8 (citrus fruits); aldehyde C-9 (citrus (cf GB 2.380.936), neohesperidine dihydrochalcone (cf fruits); aldehyde C-12 (citrus fruits): 2-ethylbutyraldehyde Manufacturing Chemist 2000, July issue, p. 16-17), specific (berry fruits); hexenal, i.e., trans-2 (berry fruits); tolyl alde flavones (2-phenylchrom-2-en-4-ones) (cf U.S. Pat. No. hyde (cherry, almond); Veratraldehyde (vanilla); 2,6-dim 5,580.545), specific nucleotides, for example cytidine-5'- ethyl-5-heptenal, i.e., melonal (melon); 2-6-dimethyloctanal monophosphates (CMP) (cf US 2002/0177576), specific (green fruit); and 2-dodecenal (citrus, mandarin); cherry; or Sodium salts, such as Sodium chloride, Sodium citrate, sodium grape and mixtures thereof. The composition may also con acetate and sodium lactate (cf Nature, 1997, Vol. 387, p. 563), tain taste modulators and artificial Sweeteners. As used a lipoprotein of..beta.-lactoglobulin and phosphatidic acid (cf herein, flavor is understood to include spice oleoresins EPA 635 218), neodiosmine 5,7-dihydroxy-2-(4-methoxy derived from allspice, basil, capsicum, cinnamon, cloves, 3-hydroxyphenyl)-7-O-neohespendosyl-chrom-2-en-4-one cumin, dill, garlic, marjoram, nutmeg, paprika, black pepper, (cf U.S. Pat. No. 4,154,862), preferably hydroxyflavanones rosemary, and turmeric, essential oils, anise oil, caraway oil, according to EP 1 258 200, in turn preferred in this respect clove oil, eucalyptus oil, fennel oil, garlic oil, ginger oil, 2-(4-hydroxyphenyl)-5,7-dihydroxychroman-4-one (narin peppermint oil, onion oil, pepper oil, rosemary oil, spearmint genin), 2-(3,4-dihydroxyphenyl)-5,7-dihydroxychroman-4- oil, citrus oil, orange oil, lemon oil, bitter orange oil, tanger one (eriodictyol), 2-(3,4-dihydroxyphenyl)-5-hydroxy-7- ine oil, alliaceous flavors, garlic, leek, chive, and onion, methoxychroman-4-one (eriodictyol-7-methylether), 2-(3,4- botanical extracts, arnica flower extract, chamomile flower dihydroxyphenyl)-7-hydroxy-5-methoxychroman-4-one, extract, hops extract, marigold extract, botanical flavor (eriodictyol-5-methylether) and 2-(4-hydroxy-3-methox extracts, blackberry, chicory root, cocoa, coffee, kola, licorice yphenyl)-5,7-dihydroxychroman-4-one (homoerio-dictyol), root, rose hips, sarsaparilla root, Sassafras bark, tamarind and the (2S)- or (2R)-enantiomers thereof or mixtures thereof as Vanilla extracts, protein hydrolysates, hydrolyzed vegetable well as the mono-or polyvalent phenolate salts thereof with proteins, meat protein hydrolyzes, milk protein hydrolyzates Na', K", NH4", Ca", Mg" or Al" as counter cations or and compounded flavors both natural and artificial including gamma.-aminobutyric acid (4-aminobutyric acid, as the neu those disclosed in S. Heath, Source Book of Flavors, Avi tral form (“inner salt) or in the carboxylate or ammonium Publishing Co., Westport Conn., 1981, pages 149-277. Spe form) according to WO 2005/09684; cific preferred flavor adjuvants include, but are not limited to, 0.122 (XXiX) taste sensates including hot tasting, saliva the following: anise oil; ethyl-2-methyl butyrate; Vanillin; tion-inducing Substances, Substances causing a warmth or cis-3-heptenol; cis-3-hexenol; trans-2-heptenal; butyl Valer tingling feeling, and cooling active ingredients. Examples of ate; 2,3-diethyl pyrazine; methylcyclo-pentenolone; benzal hot tasting and/or salivation-inducing Substances and/or Sub dehyde; Valerian oil: 3,4-dimeth-oxyphenol; amyl acetate; stances which cause a feeling of warmth and/or a tingling amyl cinnamate, y-butyryl lactone; furfural; trimethyl pyra feeling on the skin or on the mucous membranes and which zine:phenyl acetic acid; isovaleraldehyde; ethyl maltol; ethyl can be a constituent of the products according to the invention vanillin; ethyl Valerate; ethylbutyrate; cocoa extract; coffee are: capsaicin, dihydrocapsaicin, gingerol, paradol, shogaol. extract; peppermint oil; spearmint oil; clove oil; anethol; car piperine, carboxylic acid-N-Vanillylamides, in particular damom oil; wintergreen oil; cinnamic aldehyde; ethyl-2-me nonanoic acid-N-Vanillylamide, pellitorin or spilanthol, thyl Valerate; g-hexenyl lactone; 2,4-decadienal; 2.4-heptadi 2-nonanoic acid amides, in particular 2-nonanoic acid-N- enal; methyl thiazole alcohol (4-methyl-5-b-hydroxyethyl isobutylamide, 2-nonanoic acid-N-4-hydroxy-3-methox thiazole); 2-methyl butanethiol: 4-mercapto-2-butanone; yphenylamide, alkyl ethers of 4-hydroxy-3-methoxybenzyl 3-mercapto-2-pentanone; 1-mercapto-2-propane; benzalde alcohol, in particular 4-hydroxy-3-methoxybenzyl-n-bu hyde; furfural; furfuryl alcohol; 2-mercapto propionic acid; tylether, alkyl ethers of 4-acyloxy-3-methoxybenzyl alcohol, alkyl pyrazine; methyl pyrazine; 2-ethyl-3-methyl pyrazine; in particular 4-acetyloxy-3-methoxybenzyl-n-butylether and tetramethyl pyrazine; polysulfides; dipropyl disulfide; methyl 4-acetyloxy-3-methoxybenzyl-n-hexylether, alkyl ethers of benzyl disulfide; alkyl thiophene: 2,3-dimethyl thiophene: 3-hydroxy-4-methoxybenzyl alcohol, alkyl ethers of 3,4- 5-methylfurfural; acetyl furan; 2,4-decadienal; guiacol; phe dimethoxybenzyl alcohol, alkyl ethers of 3-ethoxy-4-hy nyl acetaldehyde; b-decalactone; d-limonene; acetoin: amyl droxybenzyl alcohol, alkyl ethers of 3.4-methylene dioxy acetate; maltol; ethylbutyrate; levulinic acid; piperonal; ethyl benzyl alcohol, (4-hydroxy-3-methoxyphenyl)acetic acid acetate; n-octanal; n-pentanal; n-hexanal; diacetyl; monoso amides, in particular (4-hydroxy-3-methoxyphenyl)acetic dium glutamate; monopotassium glutamate; Sulfur-contain acid-N-n-octylamide, Vanillomandelic acid alkylamides, ing amino acids, e.g., cysteine; hydrolyzed vegetable protein; ferulic acid-phenethylamides, nicotinaldehyde, methylnico 2-methylfuran-3-thiol: 2-methyldihydrofuran-3-thiol; 2.5- tinate, propylnicotinate, 2-butoxyethylnicotinate, benzylni dimethylfuran-3-thiol: hydrolyzed fish protein; tetramethyl cotinate, 1-acetoxychavicol, polygodial and isodrimeninol, pyrazine; propylpropenyl disulfide; propylpropenyl trisul further preferred cis- and/or trans-pellitorin according to WO fide; diallyl disulfide; diallyl trisulfide; dipropenyl disulfide: 2004/000787 or WO 2004/043906, alkenecarboxylic acid-N- dipropenyl trisulfide: 4-methyl-2-Rmethylthio)-ethyl-1,3- alkylamides according to WO 2005/044778, mandelic acid dithiolane; 4,5-dimethyl-2-(methylthiomethyl)-1,3-dithi alkylamides according to WO 03/106404 or alkyloxyal US 2016/0158121 A1 Jun. 9, 2016

kanoic acid amides according to WO 2006/003210. palmitate, retinoic acid, tretinoin, and iso-tretinoin, known Examples of preferred hot tasting natural extracts and/or collectively as retinoids), vitamin E (tocopherol and its natural extracts which cause a feeling of warmth and/or a derivatives), vitamin C (L-ascorbic acid and its esters and tingling feeling on the skin or on the mucous membranes and other derivatives), vitamin B3 (niacinamide and its deriva which can be a constituent of the products according to the tives), alpha hydroxy acids (such as glycolic acid, lactic acid, invention are: extracts of paprika, extracts of pepper (for tartaric acid, malic acid, citric acid, etc.) and beta hydroxy example capsicum extract), extracts of chili pepper, extracts acids (such as salicylic acid and the like); of ginger roots, extracts of Aframomum melgueta, extracts of 0.125 (XXXii) antibacterials including bisguanidines (e.g., Spilanthes-acmella, extracts of Kaempferia galangal or chlorhexidine digluconate), diphenyl compounds, benzyl extracts of Alpinia galanga. Suitable cooling active ingredi alcohols, trihalocarbanilides, quaternary ammonium com ents include the following: 1-menthol, d-menthol, racemic pounds, ethoxylated phenols, and phenolic compounds. Such menthol, menthone glycerol acetal (trade name: Frescolat(R) as halo-substituted phenolic compounds, like PCMX (i.e., MGA), menthyl lactate (trade name: FrescolatR ML, men p-chloro-m-Xylenol), triclosan (i.e., 2, 4,4'-trichloro-2 thyl lactate preferably being 1-menthyl lactate, in particular hydroxy-diphenylether), thymol, and triclocarban; 1-menthyl-1-lactate), substituted menthyl-3-carboxamides 0.126 (XXXiii) Sunscreen actives including oxybenzone, (for example menthyl-3-carboxylic acid-N-ethylamide), octylmethoxy cinnamate, butylmethoxy dibenzoyln ethane, 2-isopropyl-N-2,3-trimethyl-butanamide, substituted cyclo p-aminobenzoic acid and octyl dimethyl-p-aminobenzoic hexane carboxamides, 3-menthoxypropane-1,2-diol, 2-hy acid; droxyethyl menthyl carbonate, 2-hydroxypropyl menthyl I0127 (XXXiv) antioxidants such as beta-carotene, vitamin carbonate, N-acetylglycine menthyl ester, isopulegol, C (Ascorbic Acid) or an ester thereof, vitamin A or an ester hydroxycarboxylic acid menthyl esters (for example men thereof, vitamin E or an ester thereof, lutein or an ester thyl-3-hydroxybutyrate), monomenthyl Succinate, 2-mercap thereof, lignan, lycopene, selenium, flavonoids, vitamin-like tocyclo-decanone, menthyl-2-pyrrolidin-5-onecarboxylate, antioxidants such as coenzyme Q10 (CoQ10) and glu 2,3-dihydroxy-p-menthane, 3,3,5-trimethylcyclohexanone tathione, and antioxidant enzymes such as Superoxide dismu glycerol ketal, 3-menthyl-3,6-di- and -trioxaalkanoates, tase (SOD), catalase, and glutathione peroxidase; 3-menthyl methoxyacetate and icilin. Cooling active ingredi 0128 (XXXV) anti-inflammatory agents including, e.g., ents which are particularly preferred are as follows: 1-men methyl salicylate, aspirin, ibuprofen, and naproxen. Addi thol, racemic menthol, menthone glycerol acetal (trade name: tional anti-inflammatories useful in topical applications Frescolater MGA), menthyl lactate (preferably 1-menthyl include corticosteroids, such as, but not limited to, flurandre lactate, in particular 1-menthyl-1-lactate, trade name: Fres nolide, clobetasol propionate, halobetasol propionate, fluti colat RML), 3-menthoxypropane-1,2-diol, 2-hydroxyethyl casone propionate, betamethasone dipropionate, betametha menthyl carbonate, 2-hydroxypropyl menthyl carbonate. Sone benzoate, betamethasone Valerate, desoximethasone, 0123 (XXX) malodor counteracting agents including an dexamethasone, diflorasone diacetate, mometasone furoate, C.f3-unsaturated carbonyl compounds including but not lim amcinodine, halcinonide, fluocinonide, fluocinolone ited to those disclosed in U.S. Pat. No. 6,610,648 and EP acetonide, desonide, triamcinolone acetonide, hydrocorti 2.524,704, amyl cinnamaldehyde, benzophenone, benzyl Sone, hydrocortisone acetate, fluoromethalone, methylpred benzoate, benzyl isoeugenol, benzyl phenyl acetate, benzyl nisolone, and predinicarbate; salicylate, butyl cinnamate, cinnamyl butyrate, cinnamyl I0129 (XXXVi) anesthetics that can be delivered locally isovalerate, cinnamyl propionate, decyl acetate, ethyl including benzocaine, butamben, butamben picrate, cocaine, myristate, isobutyl cinnamate, isoamyl salicylate, phenethyl procaine, tetracaine, lidocaine and pramoxine hydrochloride; benzoate, phenethyl phenyl acetate, triethylcitrate, tripropy 0.130 (XXXVii) analgesics such as ibuprofen, diclofenac, lene glycol n-butyl ether, isomers of bicyclo[2.2.1]hept-5- capsaicin, and lidocaine; ene-2-carboxylic acid, ethyl ester, nano silver, Zinc undece nylate, B-naphthyl methyl ether, 0-naphthyl ketone, benzyl 0131 (XXXViii) antifungal agents. Non-limiting examples acetone. They may include mixture of hexahydro-4,7-metha are micanazole, clotrimazole, butoconazole, fenticonasole, noinden-5-yl propionate and hexahydro-4,7-methanoinden tioconazole, terconazole, Sulconazole, fluconazole, halopro 6-yl propionate: 4-(2,6,6-trimethyl-2-cyclohexen-1-yl)-3- gin, ketonazole, ketoconazole, OXinazole, econazole, itra methyl-3-buten-2-one; 3,7-dimethyl-2,6-nonadien-1-nitrile; conazole, torbinafine, nystatin and griseofulvin; dodeca-hydro-3a,6,6,9a-tetramethylnaphtho(2,1-b)furan: I0132 (XXXix) antibiotics such as erythromycin, clindamy ethylene glycol cyclic ester of n-dodecanedioic acid, 1-cyclo cin, synthomycin, tetracycline, metronidazole and the like; hexadecen-6-one: 1-cycloheptadecen-10-one; and corn mint 0.133 (x1) anti-viral agents including famcyclovir, Valacy oil. They may also include 1-cyclohexylethan-1-ylbutyrate; clovir and acyclovir, 1-cyclohexylethan-1-yl acetate: 1-cyclohexylethan-1-ol; 0.134 (Xli) anti-parasitic agents such as scabicedes, such 1-(4-methylethyl)cyclohexylethan-1-yl propionate; and as permethrin, crotamiton, lindane and ivermectin; 2'-hydroxy-1'-ethyl(2-phenoxy)acetate each of which com 0.135 (xlii) anti-infectious and anti-acne agents including pound is marketed under the trademark VEILEX by Interna benzoyl peroxide, Sulfur, resorcinol and Salicylic acid; tional Flavors & Fragrances Inc. More suitable malodor 0.136 (xliii) dermatological active ingredients useful in counteracting agents are polymers containing an O-keto, ben topical applications including, e.g., jojoba oil and aromatic Zaldehyde, or C.B-unsaturated carbonyl moiety, Such as those oils such as methyl salicylate, wintergreen, peppermint oil, described in US Application Publications 2012/0294821, bay oil, eucalyptus oil and citrus oils, as well as ammonium 2013/0101544 and 2013/0101545; phenolsulfonate, bismuth Subgallate, Zinc phenolsulfonate 0124 (XXXi) vitamins including any vitamin, a derivative and Zinc salicylate; thereof and a salt thereof. Examples areas follows: vitamin A 0.137 (xliv) enzymes and co-enzymes useful for topical and its analogs and derivatives (e.g., retinol, retinal, retinyl application including coenzyme Q10, papain enzyme, US 2016/0158121 A1 Jun. 9, 2016 lipases, proteases, Superoxide dismutase, fibrinolysin, desox 0145. In certain embodiments, it is preferred that greater yribonuclease, trypsin, collagenase and Sutilains; than 60 weight percent, preferably greater than 80 and more 0138 (xlv) skin whitening agents such as hydroquinone preferably greater than 90 weight percent of the fragrance and monobenzone; chemicals have C log P values of greater than 2, preferably 0139 (xlvi) anti-histamines including chlorpheniramine, greater than 3.3, more preferably greater than 4, and even brompheniramine, dexchlorpheniramine, tripolidine, clem more preferably greater than 4.5. astine, diphenhydramine, prometazine, piperazines, pip 0146 In other embodiments, the ingredients having a C eridines, astemizole, loratadine and terfonadine; log P value between 2 and 7 (e.g., between 2 and 6, and 0140 (xlvii) chemotherapeutic agents such as 5-fluorou between 2 and 5) are 25% or greater (e.g., 50% or greater and racil, masoprocol, mechlorethamine, cyclophosphamide, 90% or greater) by the weight of the fragrance. In still other Vincristine, chlorambucil, Streptozocin, methotrexate, bleo embodiments, it is preferred that greater than 60%, preferably mycin, dactinomycin, daunorubicin, coxorubicin and tamox greater than 80% and more preferably greater than 90% of the ifen, and fragrance chemicals have Clog P values of greater than 3.3, 0141 (xlviii) insect repellents including pediculicides for preferably greater than 4 and most preferably greater than 4.5. treatment of lice. Such as pyrethrins, permethrin, malathion, 0147 Those with skill in the art will appreciate that many lindane and the like. fragrances can be created employing various solvents and fragrance chemicals. The use of a relatively low to interme 0142. In addition to the active materials listed above, the diate C log P fragrance ingredients will result in fragrances products of this invention can also contain, for example, the that are Suitable for encapsulation. These fragrances are gen following dyes, colorants or pigments: lactoflavin (ribofla erally water-insoluble, to be delivered through the capsule vin), beta-carotene, riboflavin-5'-phosphate, alpha-carotene, systems of this invention onto consumer products in different gamma-carotene, cantaXanthin, erythrosine, curcumin, stages such as damp and dry fabric. Without encapsulation, quinoline yellow, yellow orange S., tartrazine, bixin, norbixin the free fragrances would normally have evaporated or dis (annatto, Orlean), capsanthin, capsorubin, lycopene, beta Solved in water during use, e.g., wash. Though high log P apo-8-carotenal, beta-apo-8-carotenic acid ethyl ester, Xan materials are generally well delivered from a regular (non tophylls (flavoxanthin, lutein, cryptoxanthin, rubixanthin, encapsulated) fragrance in a consumer product, they have violaxanthin, rodoxanthin), fast carmine (carminic acid, cochineal), azorubin, cochineal red A (Ponceau 4R), beetroot excellent encapsulation properties and are also suitable for red, betanin, anthocyanins, amaranth, patent blue V, indigo encapsulation for overall fragrance character purposes, very tine I (indigo-carmine), chlorophylls, copper compounds of long-lasting fragrance delivery, or overcoming incompatibil chlorophylls, acid brilliant green BS (lissamine green), bril ity with the consumer product, e.g., fragrance materials that liant black BN, vegetable carbon, titanium dioxide, iron would otherwise be instable, cause thickening or discolora oxides and hydroxides, calcium carbonate, aluminum, silver, tion of the product or otherwise negatively affect desired gold, pigment rubine BK (lithol rubine BK), methyl violet B, consumer product properties. victoria blue R, Victoria blue B, acilan brilliant blue FFR 0.148. In some embodiments, the amount of encapsulated (brilliant wool blue FFR), naphthol green B, acilan fast green active material is from 5 to 95% (e.g., 20 to 90% and 40 to 10G (alkali fast green 10 G), ceres yellow GRN, Sudan blue 85%) by weight of the capsule. The amount of the capsule II, ultramarine, phthalocyanine blue, phthalocayanine green, wall is from 0.5 to 25% (e.g., 1.5 to 15% and 2.5 to 10%) also fast acid violet R. Further naturally obtained extracts (for by weight of the capsule. In other embodiments, the amount example paprika extract, black carrot extract, red cabbage of the encapsulated active material is from 15 to 99.5% (e.g., extract) can be used for coloring purposes. Good results are 50 to 98% and 30 to 95%) by weight of the capsule, and the also achieved with the colors named in the following, the amount of the capsule wall is from 0.5 to 85% (e.g., 2 to 50% so-called aluminum lakes: FD & CYellow 5 Lake, FD & C and 5 to 70%) by weight of the capsule. Blue 2 Lake, FD&C Blue 1 Lake, Tartrazine Lake, Quinoline Yellow Lake, FD&C Yellow 6 Lake, FD&C Red 40 Lake, Adjunct Materials Sunset Yellow Lake, Carmoisine Lake, Amaranth Lake, Pon 0149. In addition to the active materials, the present inven ceau 4R Lake, Erythrosyne Lake, Red 2G Lake, Allura Red tion also contemplates the incorporation of adjunct materials Lake, Patent Blue V Lake, Indigo Carmine Lake, Brilliant (i.e., adjuvant) including solvent, emollients, and core modi Blue Lake, Brown HT Lake, Black PN Lake, Green S Lake fier materials in the core encapsulated by the capsule wall. and mixtures thereof Other adjunct materials are solubility modifiers, density 0143. When the active material is a fragrance, it is pre modifiers, stabilizers, viscosity modifiers, pH modifiers, or ferred that fragrance ingredients within a fragrance having a any combination thereof. These modifiers can be present in C log P of 0.5 to 15 are employed. For instance, the ingredi the wall or core of the capsules, or outside the capsules in ents having a Clog P value between 0.5 to 8 (e.g., 1 to 12, 1.5 delivery system. Preferably, they are in the core as a core to 8, 2 to 7, 1 to 6, 2 to 6, 2 to 5, and 3 to 7) are 25% or greater modifier. (e.g., 50% or greater and 90% or greater) by the weight of the 0150. The one or more adjunct material may be added in fragrance. the amount of from 0.01 to 25% (e.g., from 0.5 to 10%) by 0144. In some embodiments, it is preferred that a fra weight of the capsule. grance having a weight-averaged C log P of 2.5 and greater 0151 (i) Solvent. Preferable solvent materials are hydro (e.g., 3 or greater, 2.5 to 7, and 2.5 to 5) is employed. The phobic and miscible with the active materials. Solvents weight-averaged C log P is calculated as follows: increase the compatibility of various active materials, increase the overall hydrophobicity of the mixture containing the active materials, influence the vapor pressure, or serve to in which Wi is the weight fraction of each fragrance ingredi structure the mixture. Suitable solvents are those having rea ent and (C log P)i is the C log P of that fragrance ingredient. sonable affinity for the active materials and a C log P greater US 2016/0158121 A1 Jun. 9, 2016 than 2.5, preferably greater than 3.5 and more preferably invention are the fatty acid mono and polyesters such as cetyl greater than 5.5. In some embodiments, the solvent is com octanoate, octylisonanoanate, myristyl lactate, cetyl lactate, bined with the active materials that have C log P values as set isopropyl myristate, myristyl myristate, isopropyl palmitate, forth above. It should be noted that selecting a solvent and isopropyl adipate, butyl Stearate, decyl oleate, cholesterol active material with high affinity for each other will result in isostearate, glycerol monostearate, glycerol distearate, glyc improvement in stability. Exemplary solvents are triglyceride erol tristearate, alkyl lactate, alkyl citrate and alkyl tartrate. oil, mono and diglycerides, mineral oil, silicone oil, diethyl 0155 (iv) Ester oil as a liquid polyester formed from the phthalate, polyalpha olefins, castor oil, isopropyl myristate, reaction of a dicarboxylic acid and a diol. Examples of poly mono-, di- and tri-esters and mixtures thereof, fatty acids, and esters suitable for the present invention are the polyesters glycerine. The fatty acid chain can range from C-C and can marketed by ExxonMobil under the trade name PURESYN have any level of unsaturation. For instance, one of the fol ESTER(R), hydrophobic plant extracts. lowing solvents can be used: capric/caprylic triglyceride 0156 (v) Silicones include, for example, linear and cyclic known as NEOBEE M5 (Stepan Corporation); the CAPMUL polydimethylsiloxanes, amino-modified, alkyl, aryl, and series by Abitec Corporation (e.g., CAPMULMCM); isopro alkylaryl silicone oil. pyl myristate; fatty acid esters of polyglycerol oligomers, 0157 (vi) Low/non-volatile hydrocarbons e.g., RCO OCH-CH(OCOR') CH-O-, where R' 0158 (vii) Solid materials. Nanoscale solid particulate and R can be H or Ca-Caliphatic chains, or mixtures materials such as those disclosed in U.S. Pat. No. 7,833,960 thereof, and n ranges between 2 and 50, preferably 2 and 30: may also be incorporated into the core and may be selected nonionic fatty alcohol alkoxylates like the NEODOL surfac from, but not limited to, metal or metallic particles, metal tants by BASF; the dobanol surfactants by Shell Corporation alloys, polymer particles, wax particles, inorganic particu or the BIO-SOFT surfactants by Stepan, wherein the alkoxy lates, minerals and clay particles. group is ethoxy, propoxy, butoxy, or mixtures thereofand said 0159. The metal particles can be selected from a non Surfactants can be end-capped with methyl groups in order to limiting list of main group elements, transition metal and increase their hydrophobicity; di- and tri-fatty acid chain post-transition metal elements including aluminum (Al), containing nonionic, anionic and cationic Surfactants, and silica (Si), Titanium (Ti), chromium (Cr), manganese (Mn), mixtures thereof fatty acid esters of polyethylene glycol, iron (Fe), nickel (Ni), cobalt (Co), copper (Cu), gold (Au), polypropylene glycol, and polybutylene glycol, or mixtures silver (Ag), platinum (Pt) and palladium (Pd). thereof; polyalphaolefins such as the EXXONMOBIL PUR 0160 Polymer particles of any chemical composition and ESYM PAO line; esters such as the EXXONMOBIL PUR nature are suitable for the present invention as long as their ESYN esters; mineral oil; silicone oils such polydimethyl physical dimension falls into the prescribed region and a siloxane and polydimethylcyclosiloxane; diethyl phthalate; liquid core is generated. The polymer particles can be di-octyl adipate and di-isodecyl adipate. In certain embodi selected from a nonlimiting list of polymers and co-copoly ments, ester oils have at least one ester group in the molecule. mer based on polystyrene, polyvinyl acetate, polylactides, One type of common ester oil useful in the present invention polyglycolides, ethylene maleic anhydride copolymer, poly are the fatty acid mono and polyesters such as cetyl octanoate, ethylene, polypropylene, polyamide, polyimide, polycarbon octyl isonanoanate, myristyl lactate, cetyl lactate, isopropyl ate, polyester, polyurethane, polyurea, cellulose and cellu myristate, myristyl myristate, isopropyl palmitate, isopropyl lose, and combinations and mixture of Such polymers. adipate, butyl Stearate, decyl oleate, cholesterol isostearate, 0.161 The inorganic particulate can be selected from a glycerol monostearate, glycerol distearate, glycerol tristear non-limiting list including silica, titanium dioxide (TiO), ate, alkyl lactate, alkyl citrate and alkyl tartrate. Sucrose ester Zinc oxide (ZnO), FeOs, and other metal oxides Such as but and polyesters, Sorbitol ester, and the like. A second type of not limited to NiO, Al-O. SnO, SnO, CeO, ZnO, CdO, useful ester oil is predominantly composed of triglycerides RuO. FeC), CuO. AgO, MnO, as well as other transition and modified triglycerides. These include vegetable oils such metal oxides. as jojoba, soybean, canola, Sunflower, safflower, rice bran, avocado, almond, olive, sesame, persic, castor, coconut, and 0162 Examples of nanoscaled material include AEROSIL mink oils. Synthetic triglycerides can also be employed pro R812, which has a particle size of less than 25 nm according vided they are liquid at room temperature. Modified triglyc to the specification from the manufacture, Degussa Corp. erides include materials such as ethoxylated and maleated Other suitable materials from Degussa include, but not lim triglyceride derivatives provided they are liquids. Proprietary ited to, AEROSIL R972, AEROSIL R974, AEROSIL R104, AEROSIL R106, AEROSIL R202, AEROSIL R805, AERO ester blends such as those sold by FINETEX as FINSOLV are SIL R812, AEROSIL R812S, AEROSIL R816, AEROSIL also Suitable, as is ethylhexanoic acid glyceride. A third type R7200, AEROSIL R9200, and AEROXIDE TiO2 P25, of ester oil is liquid polyester formed from the reaction of a AEROXIDE T805, AEROXIDE LE1, AEROXIDE LE2, dicarboxylic acid and a diol. Examples of polyesters suitable AEROXIDE TiO2 NKT90, AEROXIDE Alu C805, titanium for the present invention are the polyesters marketed by EXX dioxide PF2, SIPERNAT D110, SIPERNAT D-380. The ONMOBIL under the trade name PURESYNESTER hydrophobic materials from Deguassa Corp. Such as includ 0152 While the core can be free of the solvent, it is pref ing AEROSILE R812 and R972 are especially preferred. erable that the levelofsolventis 80 wt % or less, preferably 50 0163 Nanoscaled materials such as UVINUL TiO, and wt % or less (e.g., 0-20 wt %) by weight of the core. Z-COTE HP1 manufactured by BASF can also be used as 0153 (ii) Triglycerides and modified triglycerides as well as and TI-PURE titanium dioxide, TI-PURE R-700, and emollients. These include vegetable oils such as jojoba, Soy TI-SELECT. Additional Suitable materials include TS-6200 bean, canola, Sunflower, safflower, rice bran, avocado, from Dupont and ZEROFREE 516, HUBERDERM 2000 and almond, olive, sesame, persic, castor, coconut, and mink oils. HUBERDERM 1000 from the J. M. Huber Corporation, 0154 (iii) Ester oils have at least one ester group in the Havre De Grace, MD. Silica products such as SYLOID 63, molecule. One type of common ester oil useful in the present 244, 72,63FP 244FP, 72FP, SYLOX 15, 2 and Zeolites such US 2016/0158121 A1 Jun. 9, 2016

as SYLOSIV A3, SYLOSIV A4 and SYLOSIV K300 from 0166 (x) Solubility modifiers. Nonlimiting examples of a Grace Davison can also be used. solubility modifier include surfactants (e.g., SLS and Tween 80), acidic compounds (e.g., mineral acids such as Sulfuric 0164 (viii) Polymeric core modifiers. Polymeric core acid, hydrochloric acid, nitric acid, and phosphoric acid, and modifiers are also contemplated. It has been found that the carboxylic acids such as acetic acid, citric acid, gluconic acid, addition of hydrophobic polymers to the core can also glucoheptonic acid, and lactic acid), basic compounds (e.g., improve stability by slowing diffusion of the fragrance from ammonia, alkali metal and alkaline earth metal hydroxides, the core. The level of polymer is normally less than 80% of the primary, secondary, or tertiary amines, and primary, second core by weight, preferably less than 50%, and most preferably ary, or tertiary alkanolamines), ethyl alcohol, glycerol, glu less than 20%. The basic requirement for the polymer is that it be miscible or compatible with the other components of the cose, galactose, inositol, mannitol, glactitol, adonitol, arabi core, namely the fragrance and other solvent. Preferably, the tol, and amino acids. polymer also thickens or gels the core, thus further reducing 0.167 (xi) Density modifiers. The density of the capsule diffusion. Polymeric core modifiers include copolymers of slurry and/or the oil core can be adjusted so that the capsule ethylene; copolymers of ethylene and vinyl acetate (ELVAX composition has a substantially uniform distribution of the polymers by DOW Corporation); copolymers of ethylene and capsules using known density modifiers or technologies Such vinyl alcohol (EVAL polymers by Kuraray); ethylene/acrylic as those described in Patent Application Publications WO elastomers such as VALNAC polymers by Dupont; polyvinyl 2000/059616, EP 1 502 646, and EP 2 204 155. Suitable polymers, such as polyvinyl acetate; alkyl-substituted cellu density modifiers include hydrophobic materials and materi lose, such as ethyl cellulose (ETHOCEL made by DOW als having a desired molecular weight (e.g., higher than Corporation) and hydroxypropyl celluloses (KLUCEL poly 12,000 Da), such as silicone oils, petrolatums, vegetable oils, mers by Hercules); cellulose acetate butyrate available from especially Sunflower oil and rapeseed oil, and hydrophobic Eastman Chemical; polyacrylates (e.g., AMPHOMER, solvents having a desired density (e.g., less than 1,000 Kg/m DEMACRYL LT and DERMACRYL 79, made by National at 25°C. Such as limonene and octane. Starch and Chemical Company, the AMERHOLD polymers 0168 (xii) Stabilizers. In some embodiments, a stabilizer by Amerchol Corporation, and ACUDYNE 258 by ISP Cor (e.g., a colloidal stabilizer) is added to a capsule delivery poration); copolymers of acrylic or methacrylic acid and fatty system to stabilize the emulsion and/or capsule slurry. esters of acrylic or methacrylic acid such as INTELIMER Examples of colloidal stabilizers are polyvinyl alcohol, cel POLYMERS made by Landec Corporation (see also U.S. Pat. lulose derivatives such hydroxyethyl cellulose, polyethylene Nos. 4,830,855, 5,665,822, 5,783,302, 6,255,367 and 6,492, oxide, copolymers of polyethylene oxide and polyethylene or 462); polypropylene oxide; polybutylene oxide of poly(tet polypropylene oxide, or copolymers of acrylamide and rahydrofuran); polyethylene terephthalate; polyurethanes acrylic acid. In other embodiments, a stabilizing agent (i.e., a (DYNAMX by National Starch); alkyl esters of poly(methyl stabilizer) is added to the capsule delivery system to improve vinyl ether); maleic anhydride copolymers, such as the GAN the stability of the delivery system for an extended period of TREZ copolymers and OMNIREZ 2000 by ISP Corporation: storage. When one of these delivery system is added to a carboxylic acid esters of polyamines, e.g., ester-terminated consumer product such as a liquid fabric softener/freshener polyamides (ETPA) made by Arizona Chemical Company; and liquid detergent, this delivery system will also improve polyvinyl pyrrolidone (LUVISKOL series of BASF); block the viscosity stability of the consumer product, thus extend copolymers of ethylene oxide, propylene oxide and/or buty the shelf life of the product. lenes oxide including, e.g., PLURONIC and SYNPERONIC 0169. Useful stabilizing agents include multi-functional polymers/dispersants by BASF. Another class of polymers amines, amino acids/peptides, mono-functional amines, include polyethylene oxide-co-propyleneoxide-co-butylene polymers, and a polymeric mixture. These stabilizing agents oxide polymers of any ethylene oxide/propylene oxide/buty are in presence in the compositions as free compounds, which lene oxide ratio with cationic groups resulting in a net theo are not covalently attached to the capsule walls, being part of retical positive charge or equal to Zero (amphoteric). The the capsule walls, or encapsulated in capsules. general structure is: 0170 Multi-functional amines are those having at least an amine group (primary, secondary, or tertiary) and one or more other functional groups such as an amine and hydroxyl group. Exemplary multi-functional amines include hexamethylene diamine, hexaethylenediamine, ethylenediamine, 1,3-diami nopropane, 1,4-diamino-butane, diethylenetriamine, penta ethylenehexamine, bis(3-aminopropyl)amine, bis(hexa A methylene)triamine, tris(2-aminoethyl)amine, triethylene -NH tetramine, N,N'-bis(3-aminopropyl)-1,3-propanediamine, V tetraethylenepentamine, amino-2-methyl-1-propanol branched polyethylenimine, chitosan, 1.3-diamino-guani dine, 1,1-dimethylbiguanide, and guanidine. Suitable amino acids/peptides include arginine, lysine, histidine, ornithine, where R1,R2, R3, and R4 are independently Horanyalkyl or nisin, and gelatin. Suitable stabilizing polymers include poly fatty alkyl chain group. Examples of Such polymers are the vinylpyrrolidone, polyvinylpyridine-N-oxide, and polyvinyl commercially known as TETRONICS by BASF Corporation. imidazolinium. These polymers sometimes are used in com 0.165 (ix) Sacrificial core ingredients. These ingredients bination with a second polymer (e.g., a block copolymer) can also be included in the core and are designed to be lost Such that the second polymer. during or after manufacture and include, but are not limited 0171 Monofunational amines have a single amine group. to, highly water soluble or volatile materials. Examples include C1-C20 primary, secondary, or tertiary US 2016/0158121 A1 Jun. 9, 2016

amines, each of which typically has a molecular weight of 30 Deposition Aids to 800 Da (e.g., 31 to 500 Da and 31 to 300 Da). They can be linear, branched, cyclic, acyclic, saturated, unsaturated, ali 0.178 A capsule deposition aid from 0.01 to 25%, more phatic, and/or aromatic. Nonlimiting examples are methy preferably from 5 to 20% can be included by weight of the lamine, dimethylamine, trimethylamine, ethylamine, diethy capsule. The capsule deposition aid can be added during the lamine, triethylamine, propylamine, isopropylamine, preparation of the capsules or it can be added after the cap butylamine, dodecylamine, tetradecylamine, aniline, 4-me Sules have been made. thylaniline, 2-nitroaniline, diphenyl amine, pyrrolidone, pip eridine, and morpholine. 0179 These deposition aids are used to aid in deposition 0172 The stabilizing agent in the capsule composition can of capsules to Surfaces such as fabric, hair or skin. These be present in an amount effective to stabilize the composition include anionically, cationically, nonionically, or amphoteric and/or the final consumer product containing the composi water-soluble polymers. Those skilled in the art would appre tion. This amount can be 1 ppm or greater (e.g., 20 ppm or ciate that the charge of these polymers can be adjusted by greater, 20 ppm to 20%, 50 ppm to 10%, 50 ppm to 2%, 50 changing the pH, depending on the product in which this ppm to 1%, 50 to 2000 ppm, and 50 to 1000 ppm). Its con technology is to be used. Any suitable method for coating the centration in a consumer product can be 20 ppm to 2% (e.g., deposition aids onto the encapsulated fragrance materials can 50 ppm to 2%, 50 ppm to 1%, 50 to 2000 ppm, and 50 to 1000 be used. The nature of suitable polymers for assisted capsule ppm). delivery to interfaces depends on the compatibility with the 0173 (xiii) Viscosity control agents. Viscosity control capsule wall chemistry since there has to be some association agents (e.g., Suspending agents), which may be polymeric or to the capsule wall. This association can be through physical colloidal (e.g., modified cellulose polymers such as methyl interactions, such as hydrogen bonding, ionic interactions, cellulose, hydoxyethylcellulose, hydrophobically modified hydrophobic interactions, electron transfer interactions or, hydroxyethylcellulose, and cross-linked acrylate polymers alternatively, the polymer coating could be chemically (co such as Carbomer, hydrophobically modified polyethers) can Valently) grafted to the capsule or particle Surface. Chemical be included in the capsule composition, in the capsule core or modification of the capsule or particle Surface is another way wall, or in the capsule slurry outside the capsules. Optionally, to optimize anchoring of the polymer coating to capsule or silicas, either hydrophobic or hydrophilic, can be included at particle Surface. Furthermore, the capsule and the polymer a concentration from 0.01 to 20%, more preferable from 0.5 need to be compatible with the chemistry (polarity, for to 5%, by the weight of the capsule composition. Examples of instance) of the desired interface. Therefore, depending on hydrophobic silicas include silanols, surfaces of which are which capsule chemistry and interface (e.g., cotton, polyes treated with halogen silanes, alkoxysilanes, silaZanes, and ter, hair, skin, wool), the polymer can be selected from one or siloxanes, such as SIPERNAT D17, AEROSIL R972 and more polymers with an overall Zero (amphoteric: mixture of R974 available from Degussa. Exemplary hydrophilic silicas cationic and anionic functional groups) or net positive charge, are AEROSIL 200, SIPERNAT 22S, SIPERNAT50S (avail based on the following polymer backbones: polysaccharides, able from Degussa), and SYLOID 244 (available from Grace polypeptides, polycarbonates, polyesters, polyolefinic (vinyl, Davison). acrylic, acrylamide, poly diene), polyester, polyether, poly 0.174 (xiv) Humectants. One or more humectants are urethane, polyoxazoline, polyamine, silicone, polyphosphaZ optionally included to hold water in the capsule composition ine, olyaromatic, poly heterocyclic, or polyionene, with for a long period of time. Examples include glycerin, propy molecular weight (MW) ranging from 1,000 to 1000,000,000 lene glycol, alkyl phosphate esters, quaternary amines, inor Da, preferably from 5,000 to 10,000,000 Da. As used herein, ganic salts (e.g., potassium polymetaphosphate, sodium chlo molecular weight is provided as weight average molecular ride, etc.), polyethylene glycols, and the like. weight. 0.175. Further suitable humectants, as well as viscosity 0180 Particular examples of cationic polymers that can be control/suspending agents, are disclosed in U.S. Pat. Nos. used to coat the polyurea or polyurethane capsule include, 4,428,869, 4,464,271, 4,446,032, and 6,930,078. Details of e.g., polysaccharides such as guar, alginates, starch, Xanthan, hydrophobic silicas as a functional delivery vehicle of active chitosan, cellulose, dextrans, arabic gum, carrageenan, and materials other thana free flow/anticaking agent are disclosed hyaluronates. These polysaccharides can be employed with in U.S. Pat. Nos. 5,500,223 and 6,608,017. cationic modification and alkoxy-cationic modifications such 0176 (XV) pH modifiers. In some embodiments, one or as cationic hydroxyethyl or cationic hydroxypropyl. For more pH modifiers are included in the capsule composition to example, cationic reagents of choice are 3-chloro-2-hydrox adjust the pH value of the capsule slurry and/or the capsule ypropyl trimethylammonium chloride or its epoxy version. cores. The pH modifiers can also assist in the formation of Another example is graft-copolymers of polyDADMAC on capsule walls by changing the reaction rate of the crosslinking cellulose. Alternatively, polysaccharides can be employed reactions that form the capsule walls. Exemplary pH modifi with aldehyde, carboxyl. Succinate, acetate, alkyl, amide, ers include metal hydroxides (e.g., LiOH, NaOH, KOH, and Sulfonate, ethoxy, propoxy, butoxy, and combinations of Mg(OH)), metal carbonates and bicarbonates (CSCO these functionalities; or any hydrophobic modification (com LiCO, KCO, NaHCO, and CaCO), metal phosphates/ pared to the polarity of the polysaccharide backbone). The hydrogen phosphates/dihydrogen phosphates, metal Sulfates, above modifications can be in any ratio and the degree of ammonia, mineral acids (HCl, HSO, HPO, and HNO), functionalization can be up to complete Substitution of all carboxylic acids (e.g., acetic acid, citric acid, lactic acid, functionalizable groups, as long as the theoretical net charge benzoic acid, and Sulfonic acids), and amino acids. of the polymer is Zero (mixture of cationic and anionic func 0177. The level of the adjunct materials can be presentata tional groups) or preferably positive. Furthermore, up to 5 level of 0.01 to 25% (e.g., from 0.5 to 10%) or greater than different types of functional groups may be attached to the 10% (e.g., greater than 30% and greater than 70%). polysaccharides. Also, polymer graft chains may be differ US 2016/0158121 A1 Jun. 9, 2016

ently modified to the backbone. The counterions can be any 0191 i) polyalkylene imines such as polyethylene imine, halide ion or organic counter ion. See U.S. Pat. Nos. 6.297, commercially available as LUPASOL from BASF. Any 203 and 6,200,554. molecular weight and any degree of crosslinking of this poly 0181 Another source of cationic polymers contain proto mer can be used in the present invention; natable amine groups so that the overall net charge is Zero (0192 ii) ionenes as disclosed in U.S. Pat. No. 4,395,541 (amphoteric: mixture of cationic and anionic functional and U.S. Pat. No. 4,597,962: groups) or positive. The pH during use will determine the 0193 iii) adipic acid/dimethyl amino hydroxypropyl diethylene triamine copolymers, such as CARTARETIN F-4 overall net charge of the polymer. Examples include silk and F-23, commercially available from Sandoz: protein, Zein, gelatin, keratin, collagen and any polypeptide, 0194 iv) polymers of the general formula: —N(CH)— Such as polylysine. (CH), NH (CO) NH-(CH2), N(CH),) (CH.) 0182 Further cationic polymers include polyvinyl poly -O-(-CH2)] , with x, y, z, p=1-12, and naccording to mers with up to 5 different types of monomers can be used. the molecular weight requirements. Examples are The monomers of such polymer have the generic formula: Polyduaternium-2 (MIRAPOL A-15), Polyduaternium-17 (MIRAPOL AD-1), and Polyguaternium-18 (MIRAPOL AZ-1). Other polymers include cationic polysiloxanes and wherein, R is H. C-C alkane, C-C alkene (in which the cationic polysiloxanes with carbon-based grafts with a net number of double bonds ranges from 1-5), C-C alkoxy theoretical positive charge or equal to Zero (mixture of cat lated fatty alcohol, or a liquid crystalline moiety that can ionic and anionic functional groups). This includes cationic provide the polymer with thermotropic liquid crystalline end-group functionalized silicones (i.e., Polyduaternium properties; 80). Silicones with general structure: —Si(R)(R)—O— 0183 R is H or CH; and Si(R)(R)-O-, - where R is any alkane from 0184 R is —Cl, NH. (i.e., polyvinyl amine or its C-Cs or H with number of double bonds from 0-5, aromatic copolymers with N-vinyl formamide. moieties, polysiloxane grafts, or mixtures thereof. R can also be a liquid crystalline moiety that can provide the polymer 0185. Such polyvinyl polymers are sold under the name with thermotropic liquid crystalline properties. R can be Hor LUPAMIN 9095 by BASF Corporation. Further suitable cat CH; and R can be —R-Ra, where R can be —NH ionic polymers containing hydroxylalkylvinylamine units, as —NHR, —NRR - NRRR (where R. R. R. or disclosed in U.S. Pat. No. 6,057,404. —CH-COOH or its salt), -NH C(O)-, -COOH, 0186. Another class of materials are polyacrylates with up —COO— alkali salt, any C-C alcohol, —C(O)—NH to 5 different types of monomers. Monomers of polyacrylates (amide), —C(O)—N(R)(R')(R"), sulfobetaine, betaine, have the generic formula: polyethylene oxide, poly(ethyleneoxide?propylene oxide/bu tylene oxide) grafts with any end group, H. —OH. Styrene Sulfonate, pyridine, quaternized pyridine, alkyl-substituted wherein, R is H. C-C alkane, C-C alkene (in which the pyrrolidone or pyridine, pyridine-N-oxide, imidazolinium number of double bonds ranges from 1-5), C-C alkoxy halide, imidazolium halide, imidazol, piperidine, pyrroli lated fatty alcohol, or a liquid crystalline moiety that can done, caprolactam, Sulfonate, ethoxysulphate phenyl-Rs or provide the polymer with thermotropic liquid crystalline naphthalene-R where Rs and Rare R. R. R. Sulfonic acid properties; or its alkali salt or organic counterion. R can also be —(CH) 0187 R is H or CH: O CH-CH(OH)-CH N(CH) CH-COOH 0188 R is a C-C alkyl alcohol or an alkylene oxide and its salts. Any mixture of these R groups can be selected. with any number of double bonds, or R may be absent such Xandy can be varied as long as the theoretical net charge of that the C=O bond is (via the C-atom) directly connected to the polymer is Zero (amphoteric) or positive. In addition, Ra; and polysiloxanes containing up to 5 different types of mono (0189 R is NH, -NHR, NRR, NRRR meric units may be used. Examples of suitable polysiloxanes (where R. R. R., or —CH2—COOH or its salt). —NH are found in U.S. Pat. Nos. 4,395,541 4,597,962 and 6,200, C(O)—, sulfobetaine, betaine, polyethylene oxide, poly(eth 554. Another group of polymers that can be used to improve yleneoxide/propylene oxide/butylene oxide) grafts with any capsule/particle deposition are phospholipids that are modi end group, H, OH. Styrene Sulfonate, pyridine, quaternized fied with cationic polysiloxanes. Examples of these polymers pyridine, alkyl-substituted pyrrolidone or pyridine, pyridine are found in U.S. Pat. No. 5,849,313, WO Patent Application N-oxide, imidazolinium halide, imidazolium halide, imida 95/18096A1 and European Patent No. 0737.183B1. Zol, piperidine. —OR, —OH, -COOH alkali salt, sul 0.195. Furthermore, copolymers of silicones and polysac fonate, ethoxy Sulphate, pyrrolidone, caprolactam, phenyl-Ra charides and proteins can be used (e.g., those commercially or naphthalene-Rs, where R and Rs are R. R. R. Sulfonic available as CRODASONE brand products). acid or its alkali Salt or organic counterion. Also, glyoxylated 0196. Another class of polymers includes polyethylene cationic polyacrylamides can be used. Typical polymers of oxide-co-propyleneoxide-co-butylene oxide polymers of any choice are those containing the cationic monomer dimethy ethylene oxide?propylene oxide/butylene oxide ratio with laminoethyl methacrylate (DMAEMA) or methacrylami cationic groups resulting in a net theoretical positive charge dopropyl trimethyl ammonium chloride (MAPTAC). or equal to Zero (amphoteric). Examples of such polymers are DMAEMA can be found in GAFOUAT and GAFFIX the commercially available TETRONIC brand polymers. VC-713 polymers from ISP. MAPTAC can be found in (0197) Suitable polyheterocyclic (the different molecules BASF's LUVIQUAT PQ11 PN and ISP's GAFQUAT appearing in the backbone) polymers include the piperazine HS10O. alkylene main chain copolymers disclosed by Kashiki and 0190. Another group of polymers that can be used are Suzuki (1986) Ind. Eng. Chem. Fundam. 25:120-125. those that contain cationic groups in the main chain or back 0198 Table 2 below shows polyduaternium polymers that bone. Included in this group are: can be used as deposition aids in this invention. US 2016/0158121 A1 Jun. 9, 2016 20

TABLE 2 Deposition Aids - Cationic Polyduaternium Polymers Polyduaternium Description Commercial Products 1 Ethanol, 2,2'2"-nitrilotris-, polymer with Polyguad (Alcon) 1,4-dichloro-2-butene and N,N,N',N'- tetramethyl-2-butene-1,4-diamine Polybis(2-chloroethyl) ether-alt-1,3-bis(3- Mirapol A-15 (dimethylamino)propylurea Hydroxyethyl cellulose dimethyl Celaquat L-200, H-100, L-200 diallylammonium chloride copolymer; Diallyldimethylammonium chloride hydroxyethyl cellulose copolymer Copolymer of acrylamide and quaternized Merquat 5, RETEN (Hercules) dimethylammoniumethyl methacrylate 6 Poly(diallyldimethylammonium chloride) Merquat 100, 106, Mirapol 100 Copolymer of acrylamide and Merquat 550, 550L, 55OPR, S, diallyldimethylammonium chloride 7SPR, 740, 2200, Mirapol 550, Polyguart 770/NA, Conditioneze 7 Methyl and Stearyl Dimethylaminoethyl Methacrylate Quaternized with Dimethyl Sulfate Polydimethylaminoethyl Methacrylate Quaternized with Methyl Bromide 10 Quaternized hydroxyethyl cellulose Merquat 10, Celguat SC-230M, SC-240C, SC-140C, Ucare Polymer 11 Copolymer of vinylpyrrollidone and Luviguat PQ 11PN, Gafquat quaternized dimethylaminoethy 775N, 440, 734, 775 methacrylate 12 2-Propenoic Acid, 2-Methyl-, Decahydro 1,4-Dimethyl-7-(1-Methylethyl)-1- Phenanthrenyl)Methyl Ester, Polymer with 2-(Diethylamino)Ethyl 2-Methyl-2- Propenoate and Ethyl 2-Methyl-2- Propenoate, compol. with Dimethyl Sulfate 13 2-Propenoic Acid, 2-Methyl-, 2-(Diethyl amino)Ethyl Ester, Polymer with Ethyl 2 Methyl-2-Propenoate and 9-Octadecenyl 2-Methyl-2-Propenoate, compa. with Dimethyl Sulfate 14 Ethanaminium, N.N.N-Trimethyl-2-(2- Methyl-1-Oxo-2-Propenyl)Oxy-, Methyl Sulfate, Homopolymer 15 Ethanaminium, N.N.N-Trimethyl-2-(2- Rohagit KF 720F (Rohm Methyl-1-Oxo-2-Propenyl)Oxy-Chloride, GmbH) Polymer with 2-Propenamide 16 Copolymer of vinylpyrrollidone and Luviguat FC 370, HIM 552, quaternized vinylimidazole Style, FC 550, Excellence 17 Poly(Oxy-1,2-Ethanediyl (Dimethyl Mirapol AD iminio)-1,3-Propanediylimino(1,6-Dioxo ,6-Hexanediyl)Imino-1,3-Propanediyl (Dimethyliminio)-1,2-Ethanediyl Dichloride 18 Polyoxy-1,2-ethanediyl (dimethyliminio)- Luviguat 500 ,3-propanediylimino-(1,6-dioxo-1,6- heptanediyl)imino-1,3-propanediyl (dimethyliminio)-1,2-ethanediyl dichloride 19 Ethenol, polymer with Arlatone PQ-220 (ICI aminomethyloxirane Americas) Ethenyl octadecyl ether, polymer with Arlatone PQ-225 aminomethyloxirane 22 Copolymer of Acrylic Acid and Merquat 280, 281, 280SD, 295 Diallyldimethylammonium Chloride 24 Cellulose, 2-2-Hydroxy-3-(Trimethyl Quatrisoft Polymer LM-200 ammonio)Propoxy]Ethyl Ether, Chloride (Dow Chemical) (Similar to PQ-10) 27 Hexanediamide, N,N'-bis(3-(Dimethyl amino)Propyl)-, Polymer with N,N'-bis(3- Dimethylamino)Propyl Urea and 1,1'- Oxybis(2-Chloroethane), Block 28 Copolymer of vinylpyrrollidone and methacrylamidopropyl Gafquat HS-100, Conditioneze trimethylammonium NT-10 29 Chitosan, 2,3-Dihydroxypropyl-2- Quatemized Chitosan Hydroxy-3-(Trimethylammonio)Propyl Ether, Chloride US 2016/0158121 A1 Jun. 9, 2016 21

TABLE 2-continued Deposition Aids - Cationic Polyduaternium Polymers Polyduaternium Description Commercial Products 30 Ethanaminium, NCarboxymethyl)-N,N- Mexomere PX (Chimex) Dimethyl-2-((2-Methyl-1-Oxo-2- Propenyl)Oxy)-, Inner Salt, Polymer with Methyl 2-Methyl-2-Propenoate 31 2-Propenenitrile, Homopolymer, Hypan QT100 (Lipo) Hydrolyzed, Block, Reaction Products with N,N-Dimethyl-1,3-Propanediamine, Di-Et Sulfate-Quaternized 32 Poly(acrylamide 2-methacryloxyethyl Cosmedia CTC (Cognis trimethyl ammonium chloride) GmbH)-PQ-32 + other, Salcare SC92 (Ciba Corp.) PQ 32 + other 33 Ethanaminium, N.N.N-Trimethyl-2-1- Lanoquat DES-50, Ultimer Oxo-2-Propenyl)Oxy-, Chloride, Polymer CG-200 (Nalco), Sepigel with 2-Propenamide Quat33 (Seppic)-PQ-33 + other 34 Poly(diethyliminio-1,3-propanediyldi Mexomere PAK (Chimex) methyliminio-1,3-propanediyl dibromide) 35 Ethanaminium, N-carboxymethyl-N,N- Plex 3074 L (Rohm GmbH) dimethyl-2-(2-methyl-1-oxo-2- propenyloxy)-, inner salt, polymer with N.N.N-trimethyl-2-(2-methyl-1-oxo-2- propenyloxy)ethanaminium methylsulfate 36 2-Propenoic Acid, 2-Methyl-2- Plex 4739L (Rohm GmbH) (Dimethylamino)Ethyl Ester, Polymer with Methyl 2-Methyl-2-Propenoate, compa. with Dimethyl Sulfate 37 N.N.N-Trimethyl-2-(Methyl-1-Oxo-2- Ultragel 300 (Cognis), Propenyl)Oxy|Ethanaminium Chloride, Synthalen CN CRCU (3V Homopolymer Group), Syntran PC 5320 (Interpolymer) 39 2-Propen-1-aminium, N.NDimethyl-N-2- Merquat 3940, PLUS-3330, Propenyl-, Chloride, Polymer with 2 PLUS-3331,3331PR Propenamide and 2-Propenoic Acid 42 Polyoxyethylene(dimethyliminio)ethylene Busan 1507 (Buckman Labs) (dimethylimino)ethylene dichloride 43 polymeric quaternary ammonium salt Genamin PQ 43 (Clariant formed from acrylamide, Functional Chemicals), acrylamidopropyltrimonium chloride, 2 Bozequat 4000 (Clariant) amidopropylacrylamide Sulfonate, and DMAPA monomers 44 Poly(2-oxopyrrollidin-1-ylethylene, 3 Luviguat Ultracare, MS 370 methylimidazolium-1-ylethylene methyl (BASF), Softenol PQ44 Sulfate) (Zdchimmer & Schwarz Italianat S.p.A) 45 Glycine, N-methyl-N-(2-(2-methyl-1-oxo Plex 3073L (Rohm GmbH) 2-propenyl)oxyethyl-, polymer with 2 (dimethylamino)ethyl 2-methyl-2- propenoate, compound with dimethyl sulfate 46 H-Imidazolium, 1-Ethenyl-3-Methyl-, Luviduat Hold Methyl Sulfate, Polymer with 1-Ethenyl hexahydro-2H-Azepin-2-one and 1 Ethenyl-2-Pyrrolildinone 47 -Propanaminium, N.N.NTrimethyl-3-((2- Merquat 2001, 2001N Methyl-1-Oxo-2-Propenyl)Amino)-, Chloride, Polymer with Methyl 2 Propenoate and 2-Propenoic Acid 48 Polymeric quaternary ammonium salt of Plascize L-450 (Goo Chemical) ormed from methacryloyl ethyl betaine, 2 hydroxyethyl methacrylate and methacryloyl ethyl trimethyl ammonium chloride 49 polymeric quaternary ammonium salt Plascize L-440 ormed by the reaction of methacryloyl (Goo Chemical) ethyl betaine, PEG-9 methacrylate and methacryloyl ethyl trimethyl ammonium chloride 50 Carboxylatoethyldimethylammonioethyl 2 Plascize L-401 (Goo Chemical) methyl-2-propenoate homopolymer 51 3,5,8-Triox-4-Phosphaundec-10-en-1- Lipidure PMB aminium, 4-Hydroxy-N,N.N.10 (NOF) US 2016/0158121 A1 Jun. 9, 2016 22

TABLE 2-continued Deposition Aids - Cationic Polyduaternium Polymers Polyduaternium Description Commercial Products Tetramethyl-9-Oxo, Inner Salt, 4-Oxide, Polymer with Butyl 2-Methyl-2- Propenoate 53 Acrylic Acid. Acrylamide/Methacryl Merquat 2003PR amidopropyltrimonium Chloride Copolymer S4 Aspartic acid, polymer with C6-18 Quilty-Hy (Mitsui) alkylamine, 3-dimethylaminopropylamine and Sodium chloroacetate 55 1-Dodecanaminium, N,NDimethyl-N-3- Styreze W (2-Methyl-1-Oxo-2-Propenyl)-Amino Propyl-, Chloride, Polymer with N-3- (Dimethylamino)Propyl)-2-Methyl-2- Propenamide and 1-Ethenyl-2- Pyrrollidinone 56 5-Isocyanato-1-(isocyanatomethyl)-1,3,3- Hairrol UC-4 (Sanyo trimethylcyclohexane, polymer with 1,3- Chemical) butanediol and bis(2-hydroxyethyl)di methylammonium methylsulfate 57 12-Hydroxy-9(Z)-octadecenamidopropyl Zenigloss Q (Zenitech) trimethylammonium chloride, polymers with ricinus communis (castor) oil, isooctolecanoic acid and butandioic acid 58 2-Propenoic Acid, Methyl Ester, Polymer Loweno Conditioner PWW with 2.2-Bis(2-Propenyloxy)Methyl)-1- (Lowenstein)-PQ-58 and Butanol and Diethenylbenzene, Reaction Wheat Protein Products with N.NDimethyl-1,3-Propane diamine, Chloromethane-Quaternized 59 Poly(20.25-dioxo-2,5,10,15,18-penta Crodasorb UV-HPP (Croda, methyl-10-(2-hydroxy-3-(3-(3-phenyl-2- Inc.) - PQ-59 and Butylene propenamido)propyldimethylammonio)propyl)- Glycol O-azonia-1,4,7,13,16,19-hexaoxa pentacosanediyl) chloride 60 9-Octadecenoic Acid, 12-Hydroxy-, (2- Polylipid PPI-RC Hydroxyethyl)-IminoDi-2,1-Ethanediyl (Alzo/Bernel) - PQ-60 and Ester, Polymer with 5-Isocyanato-1- Propylene Glycol (Isocyanatomethyl)-1,3,3-Trimethyl cyclohexane, Compd. with Diethyl Sulfate 61 2-Methyl-2-propenoyloxyethyl N,N.N- Lipidure-S (NOF) trimethylammonioethyl phosphate inner salt, polymer with octadecyl 2-methyl-2- robenoate 62 Polymeric quaternary ammonium salt of NanoaquaSome (Amore butyl methacrylate, polyethylene glycol Pacific/Kyung-do) methyl ether methacrylate, ethylene glycol dimethacrylate and 2-methacryloylethyl trimonium chloride with 2,2'-azobis(2- methyl propionamidine)dihydrochloride 63 polymeric quaternary ammonium salt Finquat (Innospec), Octacare ormed by acrylamide, acrylic acid and PQ63 (Innospec Edison, NJ), ethyltrimonium chloride acrylate OF-308 (WSP Chemical & Technology) 64 2-Methyl-2-propenoyloxyethyl N,N.N- Lipidure-C (NOF) trimethylammonioethyl phosphate inner salt, polymer with 2-hydroxy-3-(2-methyl 2-propenoyl)oxypropyltrimethyl ammonium chloride 65 2-Methyl-2-propenoyloxyethyl N,N.N- Lipidure-A (NOF) trimethylammonioethyl phosphate inner salt, polymer with butyl 2-methyl-2- propenoate and sodium 2-methyl-2- propenoate 66 5-Isocyanato-1-(isocyanatomethyl)-1,3,3- WBR-2925C (Taisei) - PQ-66 trimethylcyclohexane, polymer with and Methyl Pyrrollidone di (hydroxypolymethylene) benzene dicarboxylate and ethylbis(2-hydroxy ethyl)methylammonium ethylsulfate 67 2-Hydroxyethyl cellulose ether, reaction Softcat (Dow Chemical) products with N.N.N-trimethyl-N- oxiranylmethylammonium chloride and N dodecyl-N,N-dimethyl-N- oxiranylmethylammonium chloride US 2016/0158121 A1 Jun. 9, 2016 23

TABLE 2-continued Deposition Aids - Cationic Polyduaternium Polymers Polyduaternium Description Commercial Products 68 1-Ethenyl-2-pyrrollidinone, polymer with Luviduat Supreme 1-ethenylimidazole and 1-ethenyl-3- methylimidazolium methylsulfate 69 polymeric quaternary ammonium salt Aquastyle 100, 300 (ISP) composed of vinyl caprolactam, vinylpyrrollidone, dimethylaminopropyl methacrylamide (DMAPA), and methacryloylaminopropyl lauryldimonium chloride 70 polymeric quaternary ammonium salt Lustreplex (Croda) consisting of an ethoxylated, propoxylated Stearylamine condensed with adipic acid and dilinoleic acid and quaternized with dimethylsulfate 71 Cola Moist 300P (Colonial Chemical Inc) 72 polymeric quaternary ammonium salt of Mirustyle CP (Croda) hydroxethylcellulose reacted with a coco alkyl dimethyl ammonium Substituted epoxide 73 polymeric quaternary ammonium salt Diaformer C-802, C-823 consisting of propyltrimonium chloride (Mitsubishi Chem), Diasleek acrylamide, ethyltrimonium chloride C-802, C-823 (Mitsubishi methacrylate and dimethylacrylamide Chem) monomers: Propanaminium, N.N.N- trimethyl-3-(2-propenamido)-, chloride, polymer with N.N.N-trimethyl-2-(2- methyl-2-propenoyloxy)ethanaminium chloride and N,N-dimethyl-2-propenamide 74 Mirapol PB20 (Rhodia) Polycare Boost (Rhodia) 75 O-(2-Hydroxy-2-trimethylammonio Amylomer Cat 220EMU propyl)starch chloride, reaction products (Grafe Chemie) with O-(3-dodecyldimethylammonio-2- hydroxypropyl)starch chloride 76 Mirapol AT-1 (Rhodia) 77 Cocoglucoside Crosspolymer Colonial Poly SugaQuat TM Hydroxypropyltrimonium Chloride 861OP (Colonial Chemical Inc) 78 Decylglucoside Crosspolymer Colonial Poly SugaQuat L Hydroxypropyl Laurdimonium Chloride 101OP (Colonial Chemical Inc) 79 Decylglucoside Crosspolymer Colonial Poly SugaQuat S Hydroxypropyl Steardimonium Chloride 101OP (Colonial Chemical Inc) Laurylglucoside Crosspolymer Colonial Poly SugaQuat L Hydroxypropyl Laurdimonium Chloride 1210P (Colonial Chemical Inc) 81 Laurylglucoside Crosspolymer Colonial Poly SugaQuat S Hydroxypropyl Steardimonium Chloride 1210P (Colonial Chemical Inc) 82 Laurylglucoside Crosspolymer Colonial Poly SugaQuat TM Hydroxypropyltrimonium Chloride 1218P (Colonial Chemical Inc) 84 polymeric quaternary ammonium salt of Diasleek C-824 (Mitsubishi acrylamidopropyltrimethylammonium Chemical) chloride, trimethylaminoethyl methacrylate, dimethylacrylamide and hydroxyethylmethacrylate 85 polymeric quaternary ammonium salt of Diasleek C-825 (Mitsubishi acrylamidopropyltrimethylammonium Chemical) chloride, dimethylacrylamide and hydroxyethylmethacrylate 86 polymeric quaternary ammonium salt of Luvigel Advanced (BASF) vinylpyrrollidone, 1-methyl-3- vinylimidazoline chloride, vinylimidazole and methacrylic acid 87 polymeric quaternary ammonium salt of Luviguat Sensation (BASF) vinylpyrrollidone, vinylimidazole and diallyldimethyl ammonium chloride 88 Poly(Dillinoleyldimonium Colaouat PDQ (Colonial hydroxypropyl)chlorides) Chemical Inc) 89 polymeric quaternary ammonium salt (BASF) prepared by the reaction of t-butyl acrylate, vinyl pyrollidone, dimethylaminopropyl methacrylamide, methacrylic acid and ethyldimethyl 2-(2-methyl-1- oxoallyl)oxylammonium ethylsulfate, neutralized with orthophosphoric acid US 2016/0158121 A1 Jun. 9, 2016 24

TABLE 2-continued Deposition Aids - Cationic Polyduaternium Polymers Polyduaternium Description Commercial Products 90 polymeric quaternary ammonium salt of Hymoquat AK325R (Hymo acrylamide and hydroxyethylcellulose Corporation) quaternized with diallyldimethyl ammonium chloride 91 polymeric quaternary ammonium salt of Syntran 5500 (Interpolymer) - hydroxypropyl methacrylate and PQ-91 and PA polyethylene glycol methacrylate quaternized with ethyltrimonium chloride methacrylate 92 GLYCERYLAMIDOETHYL Ceracute-G (NOF) METHACRYLATESTEARYL METHACRYLATE COPOLYMER 94 polymeric quaternary ammonium salt (Toho) consisting of acrylamide, dimethyl diallyl ammonium chloride and methacrylamidopropyltrimonium chloride OOCS 95 copolymer of Zea Mays (Corn) Starch, Polyguart Ecoclean (Cognis) Acrylic Acid and acrylamidopropyltrimethylammonium chloride monomers 98 (Cognis GmbH) 101 Deposilk Q1 (Air Products)

0199. Other suitable deposition aids include those DYLITE(R) of expandable polystyrene compositions described in US 2013/0330292, US 2013/0337023, US 2014/ (DYLITE(R) is a trademark of the Atlantic Richfield Company OO17278. of Los Angeles, Calif.), and SUPER DYLANR) of high den sity polyethylene (SUPER DYLANR) is a trademark of the Additional Components Atlantic Richfield Company of Los Angeles, Calif.) 0200. The microcapsule composition of this invention can 0206 Blended polyethylene and carbon black as specifi include one or more non-confined unencapsulated active cally taught in U.S. Pat. No. 4.369,267 issued on Jan. 18, materials from 0.01 to 50%, more preferably from 5 to 40%. 1983, the specification for which is incorporated by reference 0201 The microcapsule composition can also contain one herein. or more other delivery system such as polymer-assisted deliv 0207 Polystyrene as disclosed in U.S. Pat. No. 4,369,227 ery compositions (see U.S. Pat. No. 8,187.580), fiber-assisted issued on Jan. 18, 1983, the specification for which is incor delivery compositions (US 2010/0305021), cyclodextrinhost porated by reference herein. Polyene/alpha-olefin copoly guest complexes (U.S. Pat. No. 6,287.603 and US 2002/ mers as exemplified and disclosed in U.S. Pat. No. 4.369,291, 0019369), pro-fragrances (WO 2000/072816 and EP 0922 the specification for which is incorporated by reference 084), and any combination thereof. More exemplary delivery herein. Poly-alpha-olefins as exemplified in Canadian Letters systems that can be incorporated are coascervate capsules, Pat. No. 1,137,069 issued on Dec. 7, 1982, the specification cyclodextrin delivery systems, and pro-perfumes. for which is incorporated by reference herein. Polymeric 0202 (1) Melt extruded flavor/fragrance. Polymer compositions as disclosed in Canadian Letters Pat. No. 1,137. assisted delivery system include melt extruded flavor/fra 068 issued on Dec. 7, 1982, the specification for which is grance utilizing high molecular weight carbohydrates, low incorporated by reference herein. Poly-alpha-olefins dis molecular weight carbohydrates, or polymer. closed in Canadian Letters Pat. No. 1,137,067, the specifica 0203 (1.1) High molecular weight carbohydrate includ tion for which is incorporated by reference herein. ing starches, modified Starches. (0208 Polyolefins described in Canadian Letters Pat. No. 0204 (1.2) Low molecular weight carbohydrates of a low 1,137,066, the specification for which is incorporated by molecular weight carbohydrate or polyol, wherein said low reference herein. Polyethylene oxides as disclosed in Cana molecular weight carbohydrate or polyol is selected from the dian Letters Pat. No. 1,137,065 issued on Dec. 7, 1982, the group consisting of glucose. Sucrose, maltose, lactose, corn specification for which is incorporated by reference herein. syrup Solid, erythritol, lactitol, mannitol, Sorbitol, maltitol, 0209 Olefin polymers and co-polymers as disclosed in isomalt, Xylitol, trehalose, hydrogenated corn Syrup, hydro Canadian Letters Pat. No. 1,139,737, the disclosure of which genated glucose syrup, hydrogenated maltose syrup, hydro is incorporated by reference herein. Canadian Pat. No. 1,139. genated lactose syrup, starch hydrolysate, and a mixture 737 was issued on Jan. 18, 1983. Polyolefins disclosed in thereof, and wherein said glassy matrix has a glass transition Canadian Letters Pat. No. 1,139,738, the specification for temperature of greater than room temperature. which is incorporated by reference herein. Canadian Pat. No. 0205 (1.3) Polymers (various polymers are useful in the 1,139,738 was issued on Jan. 18, 1983. Chlorinated PVC as practice of our invention. Specific examples of polymers use disclosed in Polymer 1982, 23 (7. Suppl.), 1051-6 abstracted ful in the practice of our invention are as follows: DYLANR) at Chem. Abstracts 97:145570y, 1982. oflow density polyethylene (DYLANR) is a trademark owned 0210 Polyepsilon caprolactone co-polymers made by by the Atlantic Richfield Company of Los Angeles, Calif.), means of alcohol initiated polymerization as disclosed in J. US 2016/0158121 A1 Jun. 9, 2016

Polym. Sci. Polym. Chem. Ed. 1982, 20(2), pages 319-26, Solvents performing these functions are well known in the art abstracted at Chem. Abstracts, Volume 96: 123625x, 1982. and include mineral oils, triglyceride oils, silicone oils, fats, Styrene acrylonitrile co-polymers as disclosed in Diss. waxes, fatty alcohols, diisodecyl adipate, and diethyl phtha Abstracts, Int. B., 1982, 42(8), 3346 and abstracted at Chem. late among others. Abstracts 96:143750n (1982). Co-polymers of epsilon capro 0217 (2.3) emulsifiers including monoglycerides of fatty lactone with 1,4-butane diol as disclosed at Kauch. Rezine, acids, distilled Succinylated monoglycerides of fatty acids, 1982, (2), 8-9, abstracted at Chem. Abstracts, volume Sorbitan fatty acid esters; distilled acetylated monoglycerides 96:182506 g (1982). Polyesters as disclosed in U.S. Pat. No. offatty acids, monoglycerides of fatty acids. 4.326,010, the specification for which is incorporated by 0218 (3) Coascervate Capsules. reference herein. 0219 (3.1) Proteins useful in coacervation processes 0211 Chlorinated polyethylene as disclosed by Belorgey, include albumins, vegetable globulins and gelatines. The et. al. J. Polym. Sci. Polym. Phys. Ed. 1982, 20(2), 191-203. gelatine may be fish, pork, beef, and/or poultry gelatine, for Plasticized polyepsilon caprolactone co-polymers containing example. According to a preferred embodiment, the protein is dimethyl phthalate plasticizers as set forth in Japanese Pat. fish, beef or poultry gelatine. According to a more preferred No. J81/147844, abstracted at Chem. Abstracts, Volume embodiment, the protein is warm water fish gelatine. 96:69984y (1982), the specification for which is incorporated 0220 (3.2) Typical non-protein polymers useful in com by reference herein. Maleic anhydride modified adducts of plex coacervation methods include, in particular, negatively polyepsilon caprolactone polyols and ethylenically unsatur charged polymers. For example, they may be selected from ated monomeras disclosed in U.S. Pat. No. 4,137,279 issued gum arabic, Xanthan, agar, alginate salts, cellulose deriva on Jan. 30, 1979, the specification for which is incorporated tives, for example carboxymethyl cellulose, pectinate salts, by reference herein. Polyurethane polymers having lactone carrageenan, polyacrylic and methacrylic acid, and/or mix backbones as disclosed in U.S. Pat. No. 4,156,067 issued on tures thereof. Further suitable non-proteins can be derived May 22, 1979, the disclosure of which is incorporated by from the literature, for example from to WO 2004/022221, reference herein. Polyurethane polyether resins wherein the page 4, lines 27-29 resin is obtained by reacting a polyfunctional lactone with a 0221 (3.3) A cross-linking agent is typically used to long chain polyalkylene diol and a urethane precursor as harden the coating layer. Suitable cross-linking agents disclosed in U.S. Pat. No. 4,355,550 issued on Mar. 10, 1981, include formaldehyde, acetaldehyde, glutaraldehyde, gly the disclosure of which is incorporated by reference herein. oxal, chrome alum, or transglutaminase. Preferably, trans Resins having polyurethane backbones as disclosed in U.S. glutaminase is used at 10-100, preferably 30-60 activity units Pat. No. 3,975,350 issued on Aug. 17, 1976, the disclosure of per gram of gelatine. This enzyme is well described and which is incorporated by reference herein. commercially obtainable. 0212 (1.4) Suitable plasticizers include water; glycerol; 0222 (4) Cyclodextrin Delivery System propylene glycol; aqueous solutions of glycerol, propylene 0223 This technology approach uses a cyclic oligosac glycol, monosaccharides, and disaccharides; and invert and charide or cyclodextrin to improve the delivery of perfume. high fructose corn syrups. Typically, a perfume and cyclodextrin (CD) complex is 0213 (1.5) Emulsifier. Surface-active agent, i.e. an emul formed. Such complexes may be pre-formed, formed in-situ, sifier can be added to the dry blend, or preferably added to the or formed on or in the situs. See, e.g., WO 2013/109798 A2 liquid flavor mix which is ultimately injected into the meter and US 2011/0308556A1. ing Zone of the extruder. These emulsifiers can be from the 0224 (5) Pro-Perfume class of distilled monoglycerides, mono- and diglyceride 0225 (5.1) Michael Addition reaction products of a pri blends, propyleneglycol monoglycerides, lecithin, modified mary/secondary amine with an unsaturated ester, acid or lecithins, acetylated monoglycerides, lactylated monoglycer nitrile perfume compound such those described in U.S. Pat. ides, lactylated propyleneglycol monoglycerides, Sorbitan No. 6,858,575. esters, Sorbitan-polyoxyethylene 20 monoglycerides, 0226 (5.2) Reaction product between a primary/second polyglycerol esters, DATEMs (diacetyltartarate esters of ary amine compound/polymer and a ketone or aldehyde per monoglycerides). Succinylated esters of monoglycerides and fume compound such as those described in WO 2001/051599 polyoxyethylenepropylene copolymers and mixtures thereof. A1 and WO 2002/092746A1 Most preferred surfactants are the sorbitan-polyoxyethylene 0227 (5.3) other nonlimiting examples include aromatic 20 monoglycerides, lecithins, and polyglycerol esters. or non-aromatic imines (Schiff bases), oxazolidines, beta 0214 (2) Spray Dry Encapsulation. keto esters, orthoesters, compounds comprising one or more 0215 (2.1) The matrix is comprised of one or more of the beta-oxy or beta-thiocarbonyl moieties capable of releasing a following materials: Sugars Such as glucose, fructose, lactose, perfume (e.g., an alpha, beta-unsaturated ketone, aldehyde or galactose, ribose, Xylose, Sucrose, maltose; polyols such as carboxylic ester). The typical trigger for perfume release is glycerin and propylene glycol; corn Syrups, maltodextrin, exposure to water, although other triggers may include fats, silicone dioxide, polyhydric alcohols, corn Syrup Solids, enzymes, heat, light, pH change, autoxidation, a shift of equi starches, modified Starches, emulsifiers and food acids. The librium, change in concentration or ionic strength and others. level of maltodextrinused in the matrix, comprises from 25 to Suitable pro-perfumes and methods of making same can be 98 weight percent, preferably form 35 to 75 weight percent, found in U.S. Pat. Nos. 8,912,350 B2, 7,018,978 B2: 6,987, the maltodextrin 084 B2: 6,956,013 B2: 6,861,402 B1; 6,544,945 B1; 6,093, 0216 (2.2) Core modifiers: flavors and fragrance may also 691; 6,277,796 B1; 6,165,953; 6,316,397 B1; 6,437,150 B1; be combined with a variety of solvents which serve to 6,479,682 B1; 6,096,918; 6,218,355 B1; 6,133,228; 6,147, increase the compatibility of the various materials, increase 037: 7,109,153 B2; 7,071,151 B2: 6,987,084 B2: 6,916,769 the overall hydrophobicity of the blend, influence the vapor B2; 6,610,646 B2 and 5,958,870, as well as can be found in pressure of the materials, or serve to structure the blend. US 2005/OOO3980 A1 and US 2006/0223726A1. US 2016/0158121 A1 Jun. 9, 2016 26

0228. Any compound, polymer, or agent discussed above achieved, which is indicative of removal of unwanted impu can be the compound, polymer, or agent itself as shown rities and/or starting materials, e.g., polyisocyanate, cross above, or its salt, precursor, hydrate, or Solvate. A salt can be linking agent and the like. formed between an anion and a positively charged group on 0233. In certain embodiments of this invention, the puri the compound, polymer, or agent. Suitable anions include fication of the capsules includes the additional step of adding chloride, bromide, iodide, Sulfate, nitrate, phosphate, citrate, a salt to the capsule Suspension prior to the step of washing the methanesulfonate, trifluoroacetate, acetate, malate, tosylate, capsule Suspension with water. Exemplary salts of use in this tartrate, fumurate, glutamate, glucuronate, lactate, glutarate, step of the invention include, but are not limited to, sodium and maleate. Likewise, a salt can also be formed between a chloride, potassium chloride or bi-sulphite salts. See US cation and a negatively charged group on the compound, 2014/OO17287. polymer, or agent. Suitable cations include Sodium ion, potas 0234. The microcapsule composition of this invention can sium ion, magnesium ion, calcium ion, and an ammonium also be spray dried to a solid form. In a spray drying process, cation (e.g., tetramethylammonium ion). A precursor can be a spray dry carrier is added to a microcapsule composition to ester and another suitable derivative, which, during the pro assist the removal of water from the slurry. cess of preparing a polyurea or polyurethane capsule compo 0235 According to one embodiment, the spray dry carri sition of this invention, is capable of converting to the com ers can be selected from the group consisting of carbohy pound, polymer, or agent and being used in preparing the drates such as chemically modified Starches and/or hydro polyurea or polyurethane capsule composition. A hydrate lyZed Starches, gums such as gum arabic, proteins such as refers to the compound, polymer, or agent that contains water. whey protein, cellulose derivatives, clays, synthetic water A solvate refers to a complex formed between the compound, soluble polymers and/or copolymers such as polyvinyl pyr polymer, or agent and a suitable solvent. A Suitable solvent rolidone, polyvinyl alcohol. The spray dry carriers may be can be water, ethanol, isopropanol, ethyl acetate, acetic acid, present in an amount from 1 to 50%, more preferably from 5 and ethanolamine. to 20%. 0229 Certain compounds, polymers, and agents have one 0236. Optionally, a free flow agent (anticaking agent) of or more stereocenters, each of which can be in the R configu silicas which may be hydrophobic (i.e. silanol surface treated ration, the S configuration, or a mixture. Further, some com with halogen silanes, alkoxysilanes, silaZanes, siloxanes, etc. pounds, polymers, and agents possess one or more double such as SipernatD17, Aerosil R972 and R974 (available from bonds wherein each double bond exists in the E (trans) or Z Degussa), etc.) and/or hydrophilic such as Aerosil 200, Sip (cis) configuration, or combinations thereof. The compounds, ernat 22S, SipernatiS05, (available from Degussa), Syloid 244 polymers, and agents include all possible configurational Ste (available from Grace Davison), may be present from 0.01 to reoisomeric, regioisomeric, diastereomeric, enantiomeric, 10%, more preferable from 0.5 to 5%. and epimeric forms as well as any mixtures thereof. As such, 0237 Humectants and viscosity control/suspending lysine used herein includes L-lysine, D-lysine, L-lysine agents can also be added to facilitate spray drying. These monohydrochloride, D-lysine monohydrochloride, lysine agents are disclosed in U.S. Pat. Nos. 4,428,869, 4,464,271, carbonate, and so on. Similarly, arginine includes L-arginine, 4,446,032, and 6,930,078. Details of hydrophobic silicas as a D-arginine, L-arginine monohydrochloride, D-arginine functional delivery vehicle of active materials other than a monohydrochloride, arginine carbonate, arginine monohy free flow/anticaking agent are disclosed in U.S. Pat. Nos. drate, and etc. Guanidine includes guanidine hydrochloride, 5,500,223 and 6,608,017. guanidine carbonate, guanidine thiocyanate, and other guani 0238. The spray drying inlet temperature is in the range of dine salts including their hydrates. Ornithine include L-orni 150 to 240° C., preferably between 170 and 230° C., more thine and its salts/hydrates (e.g., monohydrochloride) and preferably between 190 and 220° C. D-ornithine and its salts/hydrates (e.g., monohydrochloride). 0239. As described herein, the spray-dried microcapsule composition is well suited for use in a variety of all dry 0230. The microcapsule composition of this invention can (anhydrous) products: powder laundry detergent, fabric Soft be a slurry containing in a solvent (e.g., water) the capsule at ener dryer sheets, household cleaning dry wipes, powder dish a level of 0.1 to 80% (preferably 1 to 65% and more preferably detergent, floor cleaning cloths, or any dry form of personal 5 to 45%) by weight of the capsule delivery system. care products (e.g. shampoo powder, deodorant powder, foot 0231. In some embodiments, the microcapsule composi powder, Soap powder, baby powder), etc. Because of high tion slurry is purified by washing the capsule slurry with fragrance and/or active agent concentration in the spray-dried water, e.g., deionized or double deionized water, until a neu products of the present invention, characteristics of the afore tral pH is achieved. For the purposes of the present invention, mentioned consumer dry products will not be adversely the capsule Suspension can be washed using any conventional affected by a small dosage of the spray-dried products. method including the use of a separatory funnel, filter paper, 0240. The microcapsule composition can also be sprayed centrifugation and the like. The capsule Suspension can be as a slurry onto a consumer product, e.g., a fabric care prod washed one, two, three, four, five, six, or more times until a uct. By way of illustration, a liquid delivery system contain neutral pH, e.g., pH 6-8 and 6.5-7.5, is achieved. The pH of ing capsules is sprayed onto a detergent powder during blend the purified capsules can be determined using any conven ing to make granules. See US 2011/0190191. In order to tional method including, but not limited to pH paper, pH increase fragrance load, water-absorbing material. Such as indicators, or a pH meter. Zeolite, can be added to the delivery system. 0232 A capsule suspension of this invention is “purified’ 0241 Alternatively, granulates in a consumer product are in that it is 80%, 90%, 95%, 97%, 98% or 99% homogeneous prepared in a mechanical granulator in the presence of a to capsules. In accordance with the present invention, purity granulation auxiliary such as non-acid water-soluble organic is achieved by washing the capsules until a neutral pH is crystalline solids. See WO 2005/097962. US 2016/0158121 A1 Jun. 9, 2016 27

Zeta Potentials and Rupture Forces used in a context whereby the composition is ultimately rinsed or washed from the hair either after or during the 0242. The first microcapsule of this invention is positively application of the product. charged as indicated by a Zeta potential of at least 10 mV. 0251 Conditioning agents include any material which is preferably at least 25 mV (e.g., 25 to 200 mV), and more used to give a particular conditioning benefit to hair. Suitable preferably at least 40 mV (e.g., 40 to 100 mV.). The second conditioning agents are those which deliver one or more microcapsule is either neutral (having a Zeta potential of 5 to benefits relating to shine, softness, comb ability, antistatic -5 mV) or negatively charged (having a Zeta potential of -10 properties, wet-handling, damage, manageability, body, and mV or less). greasiness. Examples include silicones (e.g. silicone oils, 0243 Zeta potential is a measurement of electrokinetic cationic silicones, silicone gums, high refractive silicones, potential in the microcapsule slurry. From a theoretical view silicone quaternary compounds, and silicone resins), organic point, Zeta potential is the potential difference between the conditioning oils (e.g., hydrocarbon oils, polyolefins, fatty water phase (i.e., the dispersion medium) and the stationary acids, fatty alcohols, and fatty esters), alkyl quaternaries, and layer of water attached to the surface of the microcapsule. combinations thereof. See U.S. Pat. No. 6,696,053 and WO 0244. The Zeta potential is a key indicator of the stability 2017/127494. of the microcapsule in the microcapsule compositions or in 0252. The concentration of the conditioning agent in the consumer products. Typically, a microcapsule having a Zeta hair conditioner products should be sufficient to provide the potential of 10 to 25 mV shows a moderate stability. Simi desired conditioning benefits, and as will be apparent to one larly, a microcapsule having a Zeta potential of 25 to 40 mV. of ordinary skill in the art (e.g., 0.1 to 30%, 0.1 to 20%, 0.1 to shows a good stability and a microcapsule having a Zeta 10%, and 0.1 to 6%). potential of 40 to 100 mV shows excellent stability. Not to be 0253) The microcapsule composition can be present at a bound by any theory, the microcapsule of this invention has a level of 0.02 to 15% (e.g., 0.05 to 10%, 0.1 to 5%, and 0.5 to desirable Zeta potential making it Suitable for use in consumer 3%) so that the hair conditioning composition has a fragrance products with improved stability. load of 0.01 to 5% (e.g., 0.02 to 3%, 0.05 to 2%, and 0.1 to 0245 Zeta potential is calculated using theoretical models 1%). The term “fragrance load’ refers to the percentage of the and an experimentally-determined electrophoretic mobility fragrance by weight of the consumer product, e.g., the hair or dynamic electrophoretic mobility. For more detailed dis conditioning composition. cussion on measurement of Zeta potential, see Dukhin, A. S. 0254 The hair care products of this invention contain any and Goetz, P. J. “Ultrasound for characterizing colloids, one of the microcapsule described above and a conditioning Elsevier, 2002. agent. Optional additional components that can be included in 0246 The first and second microcapsules of this invention the hair care products are cationic thickeners, carriers, emol each independently can have a fracture strength of 0.2 to 80 lients, moisturizing agents, hair soothing agents, anti-oxi MPa (e.g., 0.5 to 60 MPa, 1 to 50 MPa, and 5 to 30 MPa). The dants/radical scavengers, chelators or chelating agents, anti fracture strength of each microcapsule is calculated by divid inflammatory agents antimicrobial actives, Sunscreenactives, ing the rupture force (in Newtons) by the cross-sectional area antidandruff agents, styling agents, hair bodying and Volu of the respective microcapsule (Cr2, where r is the radius of mizing agents, and combinations thereof. See U.S. Pat. No. the particle before compression). The measurement of the 6,696,053 and WO 2017/127494. rupture force and the cross-sectional area is performed fol lowing the methods described in Zhang et al., J. Microencap Fabric Conditioning Products sulation 18(5), 593-602 (2001). 0255. The microcapsule composition of this invention is 0247 The first and second microcapsules each can have a also suitable for use in fabric care products such as fabric rupture force of less than 10 mN (e.g., 0.1 to 10 mN, 0.2 to 8 conditioning products. mN, 0.3 to 5 mN, and 0.1 to 2 mN). The rupture force is the 0256 The fabric conditioning compositions having the force needed to rupture the microcapsules. Its measurement is microcapsule composition contains at least one fabric condi based on a technique known in the art as micro-manipulation. tioning agent, preferably at a concentration of 1 to 30% (e.g., See Zhang et al., Journal of Microencapsulation 16(1), 117 4 to 20%, 4 to 10%, and 8 to 15%). It would be obvious to a 124 (1999). skilled person in the art to determine the concentration of a fabric conditioning agent while keeping its conditioning ben Hair Care Products efits and also maintaining a reasonable stability and shelflife. 0248. The microcapsule composition of this invention is 0257 Suitable fabric conditioning agents include cationic especially suitable for use in hair care products including hair Surfactants. Non-limiting examples are quaternary ammo conditioning products. nium compounds such as alkylated quaternary ammonium compounds, ring or cyclic quaternary ammonium com 0249 Hair conditioner products includes hair condition pounds, aromatic quaternary ammonium compounds, didua ers, leave-on hair conditioner, leave-in conditioner, rejuve ternary ammonium compounds, alkoxylated quaternary nating conditioner, creme rinse, oil-free hair conditioners, ammonium compounds, amidoamine quaternary ammonium rinse-off hair conditioner, conditioning rinse, foaming con compounds, ester quaternary ammonium compounds, and ditioner, conditioning styling gel, conditioning mousse, spay mixtures thereof. Fabric softening compositions, and compo on conditioner, hair dressing creme and hair repairspray. nents thereof, are generally described in US 2004/0204337 0250. The term “leave-on” refers to a hair care composi and US 2003/0060390. Suitable softening agents include tion that is applied to the hair and not further subjected to a esterquats such as Rewoquat WE 18 commercially available rinsing step. The term “rinse-out' as contrasted with the term from Evonik Industries and Stepantex SP-90 commercially “leave on is used herein to mean compositions which are available from Stepan Company. US 2016/0158121 A1 Jun. 9, 2016 28

0258. The microcapsule composition can be present at a ternary ammonium compounds such as alkylated level of 0.02 to 15% (e.g., 0.05 to 10%, 0.1 to 5%, and 0.5 to quaternary ammonium compounds, ring or cyclic 3%) so that the fabric conditioning composition has a fra quaternary ammonium compounds, aromatic qua grance load of 0.01 to 5% (e.g., 0.02 to 3%, 0.05 to 2%, and ternary ammonium compounds, diguaternary 0.1 to 1%). ammonium compounds, alkoxylated quaternary ammonium compounds, amidoamine quaternary Applications. ammonium compounds, ester quaternary ammo 0259. The microcapsule composition of the present inven nium compounds, and mixtures thereof. Fabric tion are well-suited for use, without limitation, in the follow softening compositions, and components thereof, ing products: are generally described in US 2004/0204337 and 0260 a) Household products US 2003/0060390. Suitable softening agents 10261) i. Liquid or Powder Laundry Detergents which include esterquats such as Rewoquat WE 18 com can use the present invention include those systems mercially available from Evonik Industries and described in U.S. Pat. Nos. 5,929,022, 5,916,862. Stepantex SP-90 commercially available from 5,731.278, 5,565,145, 5,470,507, 5,466,802, 5,460, Stepan Company. 752, 5,458,810, 5,458.809, 5,288,431, 5,194,639, 0266 v. Liquid dish detergents such as those 4,968,451, 4,597,898, 4,561,998, 4.550,862, 4,537, described in U.S. Pat. Nos. 6,069,122 and 5,990.065 707, 4,537,706, 4,515,705, 4,446,042, and 4,318,818 0267 vi. Automatic Dish Detergents such as those 0262 ii. Unit Dose Pouches, Tablets and Capsules described in U.S. Pat. Nos. 6,020,294, 6,017,871, such as those described in EP 1 431 382 A1, US 5,968,881, 5,962,386, 5,939,373, 5,914,307, 5,902, 2013/021999.6 A1, US 2013/0284637 A1, and U.S. 781, 5,705,464, 5,703,034, 5,703,030, 5,679,630, Pat. No. 6,492.315. These unit dose formulations can 5,597,936, 5,581,005, 5,559,261, 4,515,705, 5,169, contain high concentrations of a functional material 552, and 4,714,562 (e.g., 5-100% fabric softening agent or detergent 0268 vii. All-purpose Cleaners including bucket active), fragrance (e.g., 0.5-100%, 0.5-40%, and 0.5- dilutable cleaners and toilet cleaners 15%), and flavor (e.g., 0.1-100%, 0.1-40%, and 0269 viii. Bathroom Cleaners 1-20%). They can contain no water to limit the water 0270 ix. Bath Tissue content as low as less than 30% (e.g., less than 20%. 0271 x. Rug Deodorizers less than 10%, and less than 5%). 0272 xi. Candles 0263 iii. Scent Boosters such as those described in 0273 xii. Room Deodorizers U.S. Pat. No. 7,867,968, U.S. Pat. No. 7,871,976, 0274 xiii. Floor Cleaners U.S. Pat. No. 8,333,289, US 2007/0269651 A1, and (0275 xiv. Disinfectants US2014/0107010 A1. 0276 xv. Window Cleaners 0264) iv. Fabric Care Products such as Rinse Condi (0277 xvi. Garbage bags/trash can liners tioners (containing 1 to 30 weight% of a fabric con 0278 xvii. Air Fresheners including room deodorizer ditioning active), Fabric Liquid Conditioners (con and car deodorizer, scented candles, sprays, scented taining 1 to 30 weight % of a fabric conditioning oil air freshener, Automatic spray air freshener, and active), Tumble Drier Sheets, Fabric Refreshers, Fab neutralizing gel beads ric Refresher Sprays, Ironing Liquids, and Fabric 0279 xviii. Moisture absorber Softener Systems such as those described in U.S. Pat. 0280 xix. Household Devices such as paper towels Nos. 6,335,315, 5,674,832, 5,759,990, 5,877,145, and disposable Wipes 5,574,179, 5,562,849, 5,545,350, 5,545,340, 5,411, (0281 XX. Moth balls/traps/cakes 671, 5,403,499, 5,288,417, 4,767,547 and 4,424,134 0282 b) Baby Care Products Liquid fabric softeners/fresheners contains at least (0283) i. Diaper Rash Cream/Balm one fabric softening agent present, preferably at a 0284) ii. Baby Powder concentration of 1 to 30% (e.g., 4 to 20%, 4 to 10%. 0285) c) Baby Care Devices and 8 to 15%). The ratio between the active material 0286) i. Diapers and the fabric softening agent can be 1:500 to 1:2 (0287 ii. Bibs (e.g., 1:250 to 1:4 and 1:100 to 1:8). As an illustration, 0288 iii. Wipes when the fabric softening agent is 5% by weight of the 0289 d) Oral Care Products. Tooth care products (as an fabric softener, the active material is 0.01 to 2.5%, example of preparations according to the invention used preferably 0.02 to 1.25% and more preferably 0.1 to for oral care) generally include anabrasive system (abra 0.63%. As another example, when the fabric softening sive or polishing agent), for example silicic acids, cal agent is 20% by weight of the fabric softener, the cium carbonates, calcium phosphates, aluminum oxides active material is 0.04 to 10%, preferably 0.08 to 5% and/or hydroxylapatites, surface-active substances, for and more preferably 0.4 to 2.5%. The active material example sodium lauryl sulfate, sodium lauryl sarcosi is a fragrance, malodor counteractant or mixture nate and/or cocamidopropylbetaine, humectants, for thereof. The liquid fabric softener can have 0.15 to example glycerol and/or sorbitol, thickening agents, for 15% of capsules (e.g., 0.5 to 10%, 0.7 to 5%, and 1 to example carboxymethyl cellulose, polyethylene gly 3%). When including capsules at these levels, the neat cols, carrageenan and/or Laponite R, Sweeteners, for oil equivalent (NOE) in the softener is 0.05 to 5% example saccharin, taste correctors for unpleasant taste (e.g., 0.15 to 3.2%, 0.25 to 2%, and 0.3 to 1%). sensations, taste correctors for further, normally not 0265 Suitable fabric softening agents include cat unpleasant taste sensations, taste-modulating Sub ionic surfactants. Non-limiting examples are qua stances (for example inositol phosphate, nucleotides US 2016/0158121 A1 Jun. 9, 2016 29

Such as guanosine monophosphate, adenosine mono 0318 ix. Deodorants and Antiperspirants including phosphate or other substances such as Sodium glutamate aerosol and pump spray antiperspirant, Stick antiperspi or 2-phenoxypropionic acid), cooling active ingredients, rant, roll-on antiperspirant, emulsion spray antiperspi for example menthol derivatives, (for example L-men rant, clear emulsion Stick antiperspirant, Soft Solid anti thylactate, L-menthylalkylcarbonates, menthone ket perspirant, emulsion roll-on antiperspirant, clear als, menthane carboxylic acid amides), 2.2.2-trialky emulsion Stick antiperspirant, opaque emulsion Stick lacetic acid amides (for example 2.2- antiperspirant, clear gel antiperspirant, clear Stick diisopropylpropionic acid methyl amide), icilin and deodorant, gel deodorant, spray deodorant, roll-on, and icilin derivatives, stabilizers and active ingredients, for cream deordorant. example sodium fluoride, sodium monofluorophos 0319 X. Wax-based Deodorant. An exemplary for phate, tin difluoride, quaternary ammonium fluorides, mulation as follows: Zinc citrate, Zinc sulfate, tin pyrophosphate, tin dichlo 0320) 1. Parafin Wax 10-20% ride, mixtures of various pyrophosphates, triclosan, 0321) 2. Hydrocarbon Wax 5-10% cetylpyridinium chloride, aluminum lactate, potassium 0322. 3. White Petrolatum 10-15% citrate, potassium nitrate, potassium chloride, strontium 0323 4. Acetylated Lanolin Alcohol 2-4% chloride, hydrogen peroxide, flavorings and/or sodium 0324 5. Diisopropyl Adipate 4-8% bicarbonate or taste correctors. 0325 6. Mineral Oil 40-60% 0290 i. Tooth Paste. An exemplary formulation as 0326 7. Preservative (as needed) follows: 0327. The formulation is prepared by (i) mixing 0291 1. calcium phosphate 40-55% the above ingredients, (ii) heating the resultant 0292) 2. carboxymethyl cellulose 0.8-1.2% composition to 75° C. until melted, (iii) with 0293 3. sodium lauryl sulfate 1.5-2.5% stirring, adding 4% cryogenically ground poly 0294 4. glycerol 20-30% mer containing a fragrance while maintaining 0295 5. Saccharin 0.1-0.3% the temperature 75° C., and (iv) stirring the 0296 6. flavor oil 1.0-2.5% resulting mixture in order to ensure a uniform 0297 7. water q.s. to 100% Suspension while a composition of this invention 0298. A typical procedure for preparing the for is added to the formulation. mulation includes the steps of (i) mixing by a 0328. xi. Glycol/Soap Type Deodorant. An exem blender according to the foregoing formulation plary formulation as follows: to provide a toothpaste, and (ii) adding a com 0329. 1. Propylene Glycol 60-70% 0330 2. Sodium Stearate 5-10% position of this invention and blending the result 0331 3. Distilled Water 20-30% ant mixture till homogeneous. 0332 4.2,4,4-Trichloro-2'-Hydroxy Diphenyl 0299 ii. Tooth Powder Ether, manufactured by the Ciba-Geigy Chemical 0300 iii. Oral Rinse Company and a Trademark of the Ciba-Geigy 0301 iv. Tooth Whiteners Chemical Company) 0.01-0.5% 0302 v. Denture Adhesive 0333. The ingredients are combined and heated (0303 e) Health Care Devices to 75°C. with stirring until the sodium stearate 0304 i. Dental Floss has dissolved. The resulting mixture is cooled to 0305 ii. Toothbrushes 40° C. followed by addition of a composition of (0306 iii. Respirators this invention. 0307 iv. Scented/flavored condoms 0334 xii. Lotion including body lotion, faciallotion, 0308 f) Feminine Hygiene Products such as Tampons, and hand lotion Feminine Napkins and Wipes, and Pantiliners 0335 xiii. Body powder and foot powder 0309 g) Personal Care Products: Cosmetic or pharma 0336 xiv. Toiletries ceutical preparations, e.g., a “water-in-oil” (W/O) type 0337 xv. Body Spray emulsion, an “oil-in-water” (O/W) type emulsion or as 0338 xvi. Shave cream and male grooming products multiple emulsions, for example of the water-in-oil-in 0339 xvii. Bath Soak water (W/O/W) type, as a PIT emulsion, a Pickering (0340 xviii. Exfoliating Scrub emulsion, a micro-emulsion or nano-emulsion; and (0341 h) Personal Care Devices emulsions which are particularly preferred are of the 0342 i. Facial Tissues “oil-in-water (O/W) type or water-in-oil-in-water 0343 ii. Cleansing wipes (W/O/W) type. More specifically, (0344) i) Hair Care Products 0310 i. Personal Cleansers (bar soaps, body washes, 0345 i. Shampoos (liquid and dry powder) and shower gels) 0346) ii. Hair Conditioners (Rinse-out conditioners, 0311 ii. In-shower conditioner leave-in conditioners, and cleansing conditioners) 0312 iii. Sunscreenant tattoo color protection (sprays, 0347 iii. Hair Rinses lotions, and Sticks) 0348 iv. Hair Refreshers 0313 iv. Insect repellants (0349 v. Hair perfumes 0314 v. Hand Sanitizer 0350 vi. Hair straightening products 0315 vi. Antiinflammatory balms, ointments, and 0351 vii. Hair styling products, Hair Fixative and sprays styling aids 0316 vii. Antibacterial ointments and creams 0352 viii. Hair combing creams 0317 viii. Sensates 0353 ix. Hair wax US 2016/0158121 A1 Jun. 9, 2016 30

0354 x. Hair foam, hair gel, nonaerosol pump spray 0383 4. starch syrup 10-13% 0355 xi. Hair Bleaches, Dyes and Colorants 0384 5. plasticizer 0.1% 0356. xii. Perming agents 0385 6. flavor 0.8-1.2% 0357 xiii. Hair wipes 0386 The components described above were 0358 j) Beauty Care kneaded by a kneader according to the foregoing 0359 i. Fine Fragrance—Alcoholic. Compositions formulation to provide a chewing gum. Encap and methods for incorporating fragrance capsules into sulated Flavor or sensate is then added and alcoholic fine fragrances are described in U.S. Pat. blended till homogeneous. No. 4,428,869. Alcoholic fine fragrances may contain (0387 ii. Breath Fresheners the following: (0388 iii. Orally Dissolvable Strips 0360) 1. Ethanol (1-99%) (0389) iv. Chewable Candy 0361) 2. Water (0-99%) 0390 V. Hard Candy 0362. 3. A suspending aide including but not lim 0391 n) Baked products, preferably selected from the ited to: hydroxypropyl cellulose, ethyl cellulose, group consisting of bread, dry biscuits, cakes and other silica, microcrystalline cellulose, carrageenan, cookies; propylene glycol alginate, methyl cellulose, 0392 o) snack foods, preferably selected from the Sodium carboxymethyl cellulose or Xanthan gum group consisting of baked or fried potato chips or potato (0.1-1%) dough products, bread dough products and corn or pea 0363 4. Optionally an emulsifier or an emollient nut-based extrudates; may be included including but not limited to those 0393 i. Potato, tortilla, vegetable or multigrain chips listed above 0394 ii. Popcorn 0364 ii. Solid Perfume 0395 iii. Pretzels 0365 iii. Lipstick/lip balm 0396 iv. Extruded stacks 0366 iv. Make-up cleanser 0397) p) Cereal Products preferably selected from the 0367 v. Skin care cosmetic such as foundation, pack, group consisting of breakfast cereals, muesli bars and Sunscreen, skin lotion, milky lotion, skin cream, precooked finished rice products emollients, skin whitening 0398 q) Alcoholic and non-alcoholic beverages, pref 0368 vi. Make-up cosmetic including manicure, erably selected from the group consisting of coffee, tea, mascara, eyeliner, eye shadow, liquid foundation, wine, beverages containing wine, beer, beverages con powder foundation, lipstick and cheek rouge taining beer, liqueurs, Schnapps, brandies, sodas con 0369 k) Consumer goods packaging Such as fragranced taining fruit, isotonic beverages, soft drinks, nectars, cartons, fragranced plastic bottles/boxes fruit and vegetable juices and fruit or vegetable prepa 0370 l) Pet care products rations; instant beverages, preferably selected from the 0371) i. Cat litter group consisting of instant cocoa beverages, instant tea 0372 ii. Flea and tick treatment products beverages and instant coffee beverages 0373) iii. Pet grooming products 0399 i. Ready to drink liquid drinks 0374 iv. Pet shampoos 04.00 ii. Liquid Drink Concentrates 0375 v. Pet toys, treats, and chewables 04.01 iii. Powder Drinks 0376 vi. Pet training pads 0402 iv. Coffee: Instant Cappucino 0377 vii. Pet carriers and crates 0403 1. Sugar 30-40% 0378 m) Confectionaries confectionery, preferably 0404 2. Milk Powder 24-35% Selected from the group consisting of chocolate, choco 04.05 3. Soluble Coffee 20-25% late bar products, other products in bar form, fruitgums, 0406 4. Lactose 1-15% hard and soft caramels and chewing gum 0407 5. Food Grade Emulsifier 1-3% 0379 i. Gum 0408 6. Encapsulated Volatile Flavor 0.01-0.5% 0380) 1. Gum base (natural latex chicle gum, most 04.09 v. Tea current chewing gum bases also presently include 0410 vi. Alcoholic elastomers, such as polyvinylacetate (PVA), poly 0411 r) Spice blends and consumer prepared foods ethylene, (low or medium molecular weight) poly 0412 i. Powder gravy, sauce mixes isobutene (PIB), polybutadiene, isobutene-iso 0413 ii. Condiments prene copolymers (butyl rubber), 0414 iii. Fermented Products polyvinylethylether (PVE), polyvinylbutyether, 0415 s) Ready to heat foods: ready meals and soups, copolymers of vinyl esters and vinyl ethers, sty preferably selected from the group consisting of pow rene-butadiene copolymers (styrene-butadiene dered soups, instant soups, precooked soups rubber, SBR), or vinyl elastomers, for example 0416) i. Soups based on vinylacetate/vinyllaurate, vinylacetate/ 0417 ii. Sauces vinylstearate or ethylene/vinylacetate, as well as 0418 iii. Stews mixtures of the mentioned elastomers, as described 0419 iv. Frozen entrees for example in EP 0242325, U.S. Pat. No. 4,518, 0420 t) Dairy Products milk products, preferably 615, U.S. Pat. No. 5,093,136, U.S. Pat. No. 5,266, Selected from the group consisting of milk beverages, 336, U.S. Pat. No. 5,601,858 or U.S. Pat. No. 6,986, ice milk, yogurt, kefir, cream cheese, Soft cheese, hard 709.) 20-25% cheese, powdered milk, whey, butter, buttermilk and 0381 2. Powdered sugar 45-50% partially or fully hydrolyzed milk protein-containing 0382. 3. glucose 15-17% products Flavored milk beverages US 2016/0158121 A1 Jun. 9, 2016 31

0421) i. Yoghurt terms also refers to a compound containing one or more 0422 ii. Ice cream primary/secondary amine groups and one or more hydroxyl 0423 iii. Bean Curd groups (-OH). 0424 iv. Cheese 0437. The terms “polyethyleneimine.”99 “polyethylene&g 0425 u) Soya protein or other soybean fractions, pref imines.” “polyethylenimine.” and “polyethylenimines' are erably selected from the group consisting of soya milk used interchangeably. and products produced therefrom, Soyalecithin-contain 0438. The terms “polyfunctional alcohol.” “multifunc ing preparations, fermented products such as tofu or tional alcohol.” “poly alcohol.” and “polyol refer to a com tempeh or products produced therefrom and soy sauces: pound having two or more hydroxyl groups. 0426 v) Meat products, preferably selected from the 0439. The term “degree of polymerization” refers to the group consisting of ham, fresh or raw sausage prepara number of repeat units in a polymer. tions, and seasoned or marinated fresh or salt meat prod 0440 The term “degree of crosslinking refers to percent lucts of interconnecting units over the total repeat unit. It is gener 0427 w) Eggs or egg products, preferably selected from ally measured by swelling experiments. See ASTM Standard the group consisting of dried egg, egg white and egg yolk Test Method ASTM D2765-11: Lange, Colloid & Polymer 0428 x) Oil-based products or emulsions thereof, pref Science 264, 488-93 (1986). erably selected from the group consisting of mayon 0441 The terms “multi-functional nucleophile' and naise, remoulade, dressings and seasoning preparations "polyfunctional nucleophile are used herein interchange 0429 y) fruit preparations, preferably selected from the ably. They both refer to an aliphatic or aromatic hydrocarbon group consisting of jams, Sorbets, fruit sauces and fruit onto which is attached two or more nucleophilic groups such fillings; vegetable preparations, preferably selected as primary/secondary amine groups and the hydroxyl group. from the group consisting of ketchup, sauces, dried veg 0442. The term “multi-functional electrophile' and “poly etables, deep-frozen vegetables, precooked vegetables, functional electrophile' are used interchangeably and refer to Vegetables in vinegar and preserved vegetables an aliphatic or aromatic hydrocarbon, onto which is attached 0430 z) Flavored pet foods. two or more electrophilic groups reactive towards the nucleo 0431. The above-listed applications are all well known in philic group. Examples of an electrophilic group include: the art. For example, fabric softener systems are described in aldehydes, halide, Sulfate esters, Sulphonate esters, epoxide, U.S. Pat. Nos. 6,335,315, 5,674,832, 5,759,990, 5,877,145, chlorohydrins as well as terminal olefins conjugated with a 5,574, 179; 5,562,849, 5,545,350, 5,545,340, 5,411,671, carbonyl group including ketone, amide, or ester. 5,403,499, 5,288,417, and 4,767.547, 4,424,134. Liquid 0443) The invention is described in greater detail by the laundry detergents include those systems described in U.S. following non-limiting examples. Without further elabora Pat. Nos. 5,929,022, 5,916,862, 5,731,278, 5,565,145, 5,470, tion, it is believed that one skilled in the art can, based on the 507, 5,466,802, 5,460,752, 5,458,810, 5,458,809, 5,288,431, description herein, utilize the present invention to its fullest 5,194,639, 4,968,451, 4,597,898, 4,561,998, 4.550,862, extent. All publications cited herein are incorporated by ref 4,537,707, 4,537,706, 4,515,705, 4,446,042, and 4,318,818. erence in their entirety. Liquid dish detergents are described in U.S. Pat. Nos. 6,069, 122 and 5.990.065. Shampoo and conditioners that can Example 1 employ the present invention include those described in U.S. Pat. Nos. 6,162,423, 5,968,286, 5,935,561, 5,932,203, 5,837, 0444. A microcapsule composition of this invention (i.e., 661, 5,776,443, 5,756,436,5,661,118, 5,618,523, 5,275,755, Composition 1), was prepared following the procedure 5,085,857, 4,673,568, 4,387,090 and 4,705,681. Automatic below. Dish Detergents are described in U.S. Pat. Nos. 6,020,294, 6,017,871, 5,968,881, 5,962,386, 5,939,373, 5,914,307, Preparation of a Cationic Microcapsule 5,902,781, 5,705,464, 5,703,034, 5,703,030, 5,679,630, 0445. A cationic microcapsule (Microcapsule 1) was pre 5,597,936, 5,581,005, 5,559,261, 4,515,705, 5,169,552, and pared as a first microcapsule following the procedure below 4,714,562. using polystyrene Sulfonate and CMC as the capsule forma 0432 All parts, percentages and proportions refer to tion aid. Ninety-six grams of a fragrance accord (Interna herein and in the claims are by weight unless otherwise indi tional Flavors and Fragrance, Union Beach, N.J.) was cated. weighed out and combined with 24 g of NEOBEE oil M-5 0433. The values and dimensions disclosed herein are not (caprylic/capric triglyceride, Stepan, Chicago, Ill.) and 9.6 g. to be understood as being strictly limited to the exact numeri of isocyanate monomer, TAKENATE D110-N(trimethylol cal values recited. Instead, unless otherwise specified, each propane-adduct of xylylene diisocyanate, Mitsui Chemicals such value is intended to mean both the recited value and a Corporation, Rye Brook, N.Y.), to form the oil phase. In a functionally equivalent range Surrounding that value. For separate beaker, a solution (130 g) containing 1.0% of example, a value disclosed as “50%' is intended to mean FLEXAN II (polystyrene sulfonate, Akzo Nobel, Bridgewa about 50%. ter, N.J.) was mixed with a solution (30 g) of 1% CMC 0434. The terms “capsule' and “microcapsule' herein are (carboxymethyl cellulose, WALOCEL CRT 50000 PA 07, used interchangeably. Dow, Midland, Mich.) in water to form the aqueous phase. 0435 The terms “polyfunctional isocyanate.” “multifunc The oil phase was then emulsified into the aqueous phase to tional isocyanate.” and “polyisocyanate' all refer to a com form the fragrance emulsion under shearing (ULTRATUR pound having two or more isocyanate ( NCO) groups. RAX, T25 Basic, IKAWERKE) at 6500rpm for two minutes. 0436 The terms “polyfunctional amine,”“multifunctional 0446 Formation of Fragrance Capsules. The fragrance amine and “polyamine” refers to a compound containing emulsion was heated to 35° C. in a round bottom vessel and one, two or more primary or secondary amine groups. These 10.4 g of 49% branched polyethylenimine (Sigma-Aldrich, US 2016/0158121 A1 Jun. 9, 2016 32

St. Louis, Mo.) was added under constant mixing with an rubbing swatches together clockwise & counterclockwise 10 overhead mixer. Formation of capsules was immediately vis times each. After the shampoo was set on the Swatch for 15 ible by optical microscopy. The mixer speed was reduced seconds, the swatch was washed in a water flow (37° C. 1 after the addition of branched polyethylenimine was com gallon/min) for 45 seconds. Subsequently, the Swatch was plete. The capsule slurry was cured at 55° C. for two hours to washed with the hair conditioner containing Composition 1 obtain Microcapsule 1. using the same protocol as the shampoo. After washing, the 0447 Microcapsule 1 thus prepared had a Zeta potential of swatch was hang-dried for 16 hours before being evaluated by 51.5 mV. apanel of 12 judges. Before and after brushing the Swatch, the fragrance intensity was rated from a scale ranging from 0 to Preparation of an Anionic Microcapsule 10. A numerical value of 2 would suggest the hair only pro 0448. An anionic microcapsule (Microcapsule 2) was pre duce weak intensity while a value of 10 a very strong smell. pared as a second microcapsule following the procedure 0455 Microcapsules 1 and 2 were used as comparative below. This second microcapsule contains a microcapsule samples following the same blending and hair washing as wall formed of a reaction product of hexamethylene diamine Composition 1. and a polyisocyanate using a mixture of naphthalene Sul 0456. The results showed that Composition 1 had a pre fonate condensate salt and polyvinylpyrrolidone as the cap brush fragrance intensity of 3 before the hair swatch was Sule formation aid. brushed and a post-brush fragrance intensity of 5.8 after the 0449 Ninety six grams of a fragrance accord (Interna hair swatch was brushed. tional Flavors and Fragrance, Union Beach, N.J.) was 0457. By contrast, Microcapsule 1 had a pre-brush fra weighed out and combined with 24 g of Neobee oil (commer grance intensity of 2.3 and a post-brush fragrance intensity of cially available from Stepan, Chicago, Ill., USA) and 9.6 g of 5.6; Microcapsule 2 had a pre-brush fragrance intensity of 1.9 isocyanate monomer, Lupranate RM20 (BASF corporation, and a post-brush fragrance intensity of 3. Wyandotte, Mich., USA) to form the oil phase. In a separate beaker, a solution (160 g) containing 1% Morwet D-425 (a Other Embodiments Sodium salt of naphthalene Sulfonate condensate, commer 0458 All of the features disclosed in this specification cially available from AkzoNobel, Fort Worth, Tex., USA) and may be combined in any combination. Each feature disclosed 1% polyvinylpyrrolidone aqueous solution (Luviskol(RK90, in this specification may be replaced by an alternative feature commercially available from BASF, Ludwigshafen, Ger serving the same, equivalent, or similar purpose. Thus, unless many) was used as the aqueous phase. The oil phase was then expressly stated otherwise, each feature disclosed is only an emulsified into the aqueous phase to form the fragrance emul example of a generic series of equivalent or similar features. sion under shearing (Ultra Turrax(R), T25 Basic, IKAR 0459 Indeed, to achieve the purpose of encapsulating an WERKE) at 9500 rpm for two minutes. active material, one skilled in the art can design and prepare a 0450. The fragrance emulsion was then placed in a round capsule composition by using different microcapsules, poly bottom vessel and to which 10.8 g of 40% hexamethylene functional nucleophiles and/or electrophiles, Suitable encap diamine aqueous solution (HMDA) (commercially available Sulating polymers, and/or capsule formation aids, varying the from INVISTA, Wichita, Kans., USA) was added under con concentrations of these wall-forming materials and/or cata stant mixing with an overhead mixer. Formation of capsule lysts to achieve desirable organoleptic or release profiles in a was immediately visible by optical microscopy. The mixer consumable product. Further, the ratios among microcap speedwas reduced after the addition of HMDA was complete. Sules, encapsulating polymers, capsule forming aids, adju The capsule slurry was cured at 55° C. for two hours to obtain vents, core modifiers, active materials, and catalysts can also Microcapsule 2. be determined by a skilled artisan through assays known in 0451 Microcapsule 2 thus prepared had a Zeta potential of the art to prepare capsule compositions with desirable prop -26 mV. erties. 0460 From the above description, a skilled artisan can Preparation of Composition 1 easily ascertain the essential characteristics of the present 0452 Microcapsule 1 (30 g) was mixed with Microcap invention, and without departing from the spirit and scope sule 2 (30 g) at room temperature for 1 hour to obtain a thereof, can make various changes and modifications of the microcapsule composition of this invention, i.e., Composi invention to adapt it to various usages and conditions. Thus, tion 1. other embodiments are also within the claims. What is claimed is: Example 2 1. A microcapsule composition comprising a first micro capsule and a second microcapsule, Performance of Composition 1 in a Hair Conditioner wherein Base the first microcapsule has a Zeta potential of 10 mV or 0453 To evaluate the performance of Composition 1, it greater, was blended with a model hair conditioner base at a level of the second microcapsule has a Zeta potential of 5 mV or 1% by weight of the hair conditioner base. The fragrance load less, and was 0.3% neat equivalent. the weight ratio of the first microcapsule and the second 0454. The perfumery benefit of Composition 1 was evalu microcapsule is between 1:10 and 10:1. ated by conducting a personal wash experiment using the 2. The microcapsule composition of claim 1, wherein standard protocol below. Four hair swatches were washed per the first microcapsule contains a first oil core and a first sample. For each hair Swatch, 1 g an unfragranced shampoo microcapsule wall encapsulating the first oil core; was applied on Swatch. The shampoo is lathered into hair by the first oil core contains a first active material; US 2016/0158121 A1 Jun. 9, 2016 33

the first microcapsule wall is formed of a first encapsulat 9. The microcapsule composition of claim 8, wherein the ing polymer that is the reaction product of a multi branched polyethyleneimine has a molecular weight of 750 to functional nucleophile and a multi-functional electro 50000 Da; the polyisocyanate is a polymeric methylene phile; diphenyl diisocyanate, hydrogenated polymeric methylene the multi-functional nucleophile is a branched polyethyl diphenyl diisocyanate, methylene diphenyl diisocyanate, eneimine, a mixture of the branched polyethyleneimine hydrogenated methylene diphenyl diisocyanate, a trimer of and a polyfunctional amine, or a mixture of the branched hexamethylene diisocyanate, a trimer ofisophorone diisocy polyethyleneimine and a polyfunctional alcohol; anate, a biuret of hexamethylene diisocyanate, a polyisocya the multi-functional electrophile has a first functional nurate of toluene diisocyanate, a trimethylol propane-adduct group and a second functional group, each of which, of toluene diisocyanate, a trimethylol propane-adduct of independently, is an electrophilic group reactive towards Xylylene diisocyanate, or a combination thereof, and the sec the multi-functional nucleophile; ond encapsulating polymer is a polyurea that is the reaction the second microcapsule contains a second oil core and a product of a polyisocyanate and hexamethylenediamine. second microcapsule wall encapsulating the second oil 10. The microcapsule composition of claim 4, wherein core; the first microcapsule contains a first oil core and a first the second oil core contains a second active material; and microcapsule wall encapsulating the first oil core; the second microcapsule wall is formed of a second encap the first oil core contains a first active material; Sulating polymer. the first microcapsule wall is formed of a first encapsulat 3. The microcapsule composition of claim 2, wherein the ing polymer that is a reaction product of a multi-func first encapsulating polymer is the reaction product of a tional nucleophile and an multi-functional electrophile; branched polyethyleneimine and a polyisocyanate; and the the multi-functional nucleophile is a branched polyethyl second encapsulating polymer is a melamine-formaldehyde eneimine, a mixture of the branched polyethyleneimine polymer, polyurea, polyurethane, gelatin, or aurea formalde and a polyfunctional amine, or a mixture of the branched hyde polymer. polyethyleneimine and a polyfunctional alcohol; 4. The microcapsule composition of claim 1, wherein the the multi-functional electrophile has a first functional first microcapsule has a Zeta potential of 25 mV or greater, group and a second functional group, each of which is an and the second microcapsule has a Zeta potential of 5 mV to electrophilic group reactive towards the multi-func -5 mV. tional nucleophile; 5. The microcapsule composition of claim 1, wherein the the second microcapsule contains a second oil core and a first microcapsule has a Zeta potential of 25 mV or greater, second microcapsule wall encapsulating the second oil and the second microcapsule has a Zeta potential of -10 mV. core; or less. the second oil core contains a second active materials; and 6. The microcapsule composition of claim 5, wherein the the second microcapsule wall is formed of a second encap first microcapsule has a Zeta potential of 40 mV or greater, Sulating polymer selected from the group consisting of and the second microcapsule has a Zeta potential of -20 mV. Solgel polymers, starch polymers, carbohydrates, poly or less. ureas, and combinations thereof. 7. The microcapsule composition of claim 6, wherein 11. The microcompoisiton of claim 2, wherein the multi the first microcapsule contains a first oil core and a first functional nucleophile is a mixture of a branched polyethyl microcapsule wall encapsulating the first oil core; eneimine and a polyamine selected from the group consisting of hexamethylenediamine, ethylenediamine, 1,3-diamino the first oil core contains a first active material; propane, 1,4-diamino-butane, diethylenetriamine, pentaeth the first microcapsule wall is formed of a first encapsulat ylenehexamine, bis(3-aminopropyl)amine, bis(hexanethyl ing polymer that is a reaction product of a multi-func ene)triamine, tris(2-aminoethyl)amine, triethylene tional nucleophile and an multi-functional electrophile; tetramine, N,N'-bis(3-aminopropyl)-1,3-propanediamine, the multi-functional nucleophile is a branched polyethyl tetraethylenepentamine, penta-ethylenehexamine, chitosan, eneimine, a mixture of the branched polyethyleneimine nisin, gelatin, 1.3-diamino-guanidine, 1,1-dimethylbigu and a polyfunctional amine, or a mixture of the branched anide, guanidine, arginine, lysine, ornithine, and combina polyethyleneimine and a polyfunctional alcohol; tions thereof. the multi-functional electrophile has a first functional 12. The microcapsule composition of claim 1, wherein group and a second functional group, each of which is an each of the first and second active materials, independently, is electrophilic group reactive towards the multi-func a fragrance, pro-fragrance, flavor, vitamin or derivative tional nucleophile; thereof, malodor counteractive agent, anti-inflammatory the second microcapsule contains a second oil core and a agent, fungicide, anesthetic, analgesic, antimicrobial active, second microcapsule wall encapsulating the second oil anti-viral agent, anti-infectious agent, anti-acne agent, skin core; lightening agent, insect repellant, emollient, skin moisturiz the second oil core contains a second active material; and ing agent, wrinkle control agent, UV protection agent, fabric the second microcapsule wall is formed of a second encap softener active, hard Surface cleaning active, skin or hair Sulating polymer. conditioning agent, insect repellant, animal repellent, Vermin 8. The microcapsule composition of claim 7, wherein the repellent, flame retardant, antistatic agent, nanometer to first encapsulating polymer is the reaction product of a micron size inorganic Solid, polymeric or elastomeric par branched polyethyleneimine and a polyisocyanate, and the ticle, or combination thereof. second encapsulating polymer is a melamine-formaldehyde 13. The microcapsule composition of claim 1, further com polymer, polyurea, polyurethane, gelatin, a urea formalde prising a deposition aid selected from the group consisting of hyde polymer. polyduaternium-4, polyduaternium-5, polyduaternium-6, US 2016/0158121 A1 Jun. 9, 2016 34 polyduaternium-7, polyduaternium-10, polyduaternium-16, 15. The microcapsule composition of claim 1, further com polyduaternium-22, polyduaternium-24, polyduaternium prising a third, fourth, fifth, or sixth delivery system. 28, polyduaternium-39, polyduaternium-44, polyduater nium-46, polyduaternium-47, polyduaternium-53, 16. The microcapsule composition of claim 1, wherein the polyduaternium-55, polyduaternium-67, polyduaternium microcapsule composition is in the form of a solid or liquid. 68, polyguaternium-69, polyduaternium-73, polyduater 17. A consumer product comprising the microcapsule nium-74, polyduaternium-77, polyduaternium-78, composition of claim 1. polyduaternium-79, polyduaternium-80, polyduaternium 81, polyguaternium-82, polyduaternium-86, polyduater 18. The consumer product of claim 17, wherein the con nium-88, polyduaternium-101, polyvinylamine, polyethyl Sumer product is a hair care product, a personal care product, eneimine, polyvinylamine and vinylformamide copolymer, a fabric care product, or a home care product. and combinations thereof. 19. The consumer product of claim 17, wherein the con 14. The microcapsule composition of claim 1, further com Sumer product is a shampoo, hair conditioner, personal wash, prising a capsule formation aid selected from the group con shower gel, bar Soap, liquid detergent, powder detergent, sisting of a polyvinyl alcohol, polystyrene Sulfonate, car fabric conditioner, fabric softener, or fabric refresher. boxymethyl cellulose, naphthalene Sulfonate condensate salt, polyvinylpyrrolidone, copolymer of vinyl pyrrolidone and 20. A hair care product comprising the microcapsule com quaternized dimethylaminoethyl methacrylate, and combina position of claim 1 and a hair conditioning agent. tion thereof. k k k k k