Microcapsules made from proteins

Abstract

A microcapsule composition comprising microcapsules dispersed in an aqueous phase is disclosed. The microcapsule has a microcapsule core and a microcapsule wall. The microcapsule core contains an active material. The microcapsule wall encapsulates the microcapsule core and is formed from a polymer network having a protein moiety, a polyfunctional electrophile moiety, and a third moiety derived from chaotropic agents, polyfunctional nucleophiles, or a combination thereof. Methods of making the microcapsule compositions and consumer products containing the microcapsule compositions are also disclosed.

Description

[0001] This application is a divisional application of an application filed on December 17, 2019, with application number 2019800924212 and invention name “Microcapsules prepared from proteins”.

[0002] CROSS-REFERENCE TO RELATED APPLICATIONS

[0003] This application claims priority to U.S. Application Serial No. 62 / 834,356, filed April 15, 2019, U.S. Application Serial No. 62 / 834,373, filed April 15, 2019, and U.S. Application Serial No. 62 / 781,162, filed December 18, 2018. The contents of all applications are incorporated by reference in their entirety. background

[0004] Microcapsules are used in a variety of consumer products where it is desired to deliver, apply, or release active materials, including fragrances, flavors, and malodor counteractants, to a target area in a delayed or controlled manner.

[0005] Conventional microcapsules generally have microcapsule walls formed of synthetic polymers such as melamine formaldehyde polymer, polyurea or polyacrylate. Consumers prefer environmentally friendly natural materials to synthetic polymers and demand the development of green, sustainable products and technologies.

[0006] Mint et al., WO 2016 / 185171 A1 report microcapsules made from natural materials, including fungal chitosan. Silk fibroin particles have been found to be suitable for encapsulating fragrance oils. See Kaplan et al., US 2015 / 0164117 A1. Biomolecules have been used as emulsifiers in microcapsule preparations. See WO 2016 / 193435 A1, WO 2017 / 102812 A1, US 2018 / 0078468 A1, WO 2018 / 019894 A1, WO 2018 / 019896 A1, and WO 2017 / 102812 A1. Multilayer coacervate capsules are typically conventional microcapsules coated with a coacervate between gelatin and gum arabic. See US 4,946,624, WO 2012 / 001604 A1, US 2015 / 0250689 A1, and WO 2018 / 002214 A1. Chitosan and other biomolecules have also been explored and used to prepare microcapsule compositions. See WO 2015 / 023961 A1, WO 2018 / 077578 A1, and EP 2934464 B1. Proteins have been used to coat microcapsules to improve deposition. See US 2017 / 0189283 A1.

[0007] US2017 / 0360676 A1 describes an environmentally biodegradable polysaccharide delivery particle.

[0008] However, none of these microcapsules and particles exhibit high performance and environmental degradability that meet consumer demands.

[0009] There is a need to develop environmentally friendly microcapsules with high fragrance performance for laundry, washing, cleaning, surface care, and personal and skin care applications. Summary of the Invention

[0010] The present invention is based on the discovery that certain capsule compositions have unexpectedly desirable properties, such as high perceived olfactory intensity, high stability, and are environmentally friendly.

[0011] Thus, one aspect of the present invention relates to a microcapsule comprising a microcapsule core and a microcapsule wall encapsulating the microcapsule core, wherein the microcapsule core contains an active material, preferably selected from a fragrance, a cosmetic active agent, a malodor counteractant, and the microcapsule wall is formed by a polymer network comprising a first portion derived from a protein, a second portion derived from a multifunctional electrophile (e.g., polyisocyanate, glutaraldehyde, and glyoxal), and a third portion derived from a chaotrope, a multifunctional nucleophile, or any combination thereof.

[0012] In one embodiment, the microcapsule wall comprises from 2% to 20% of the first fraction, from 0.1% to 3% of the second fraction, and from 0.1% to 10% of the third fraction, based on the weight of the microcapsule.

[0013] Preferably, the first part is a denatured protein selected from the group consisting of whey protein, pea protein, rice protein, wheat protein, egg protein, barley protein, brown rice protein, pumpkin seed protein, oat protein, potato protein, almond protein, and any combination thereof.

[0014] Suitable polyisocyanates include trimer of hexamethylene diisocyanate, trimer of isophorone diisocyanate, biuret of hexamethylene diisocyanate, polyisocyanurate of toluene diisocyanate, trimethylolpropane adduct of toluene diisocyanate, trimethylolpropane adduct of xylylene diisocyanate, and combinations thereof.

[0015] In one embodiment, the third part is a polyfunctional nucleophilic reagent, such as polyphenols, maltodextrin, polyamines, and combinations thereof. In another embodiment, the third part is a chaotropic agent. In yet another embodiment, the third part is a combination of a chaotropic agent and a polyfunctional nucleophilic reagent. Suitable chaotropic agents include guanidine salts (such as guanidine hydrochloride and guanidine carbonate), ethyl acetate, urea, polysorbate, sodium benzoate, vanillin, o-cresol, phenol, propanol, formamide, ethanol, fructose, ammonium sulfate, ammonium chloride, ammonium nitrate, ammonium phosphate, potassium sulfate, potassium chloride, potassium nitrate, potassium phosphate, sodium sulfate, sodium chloride, sodium nitrate, sodium phosphate, guanidine thiocyanate, xylose, glycerol, benzyl alcohol, potassium iodide, triton X-100, ethyl acetate, hexadecyltrimethylammonium halide, acetone, sodium lauryl sulfate (SDS), sodium bromide, hydrochloric acid, sulfuric acid, polyethylene glycol, glutaraldehyde, and combinations thereof.

[0016] The active material may further comprise a pro-fragrance, a vitamin or derivative thereof, an anti-inflammatory agent, a fungicide, an anesthetic, an analgesic, an antimicrobial active agent, an antiviral agent, an anti-infective agent, an anti-acne agent, a skin lightening agent, an insect repellent, an object repellent, a pest repellent, an emollient, a skin moisturizer, an anti-wrinkle agent, a UV protectant, a fabric softener active agent, a hard surface cleaning active agent, a skin or hair conditioner, a flame retardant, an antistatic agent, a nano to micron sized inorganic solid, a polymer or elastomeric particle, a taste modifier, a cell, a probiotic, or a combination thereof. In one embodiment, the active material is a high performance fragrance.

[0017] The microcapsules of the present invention may have a deposition polymer The deposition polymer is selected from the group consisting of trimethylammonium, methacrylamidopropyltrimethylammonium, acrylamidopropyltrimethylammonium, acrylamide, acrylic acid, dimethylammonium, xylose, galactose, hydroxypropylated glucose, hydroxyethylated glucose, hydroxymethylated glucose, vinylamine, ethyleneimine, functionalized branched polyethyleneimine, vinylformamide, vinylpyrrolidone, chitosan, caprolactone, catechol, vinyl alcohol, polyquaternium-4, polyquaternium-5, polyquaternium-6, polyquaternium-7, polyquaternium-10, polyquaternium-11, polyquaternium-16, polyquaternium-22, polyquaternium-24, polyquaternium-28, polyquaternium-37, polyquaternium-39, polyquaternium-44, polyquaternium-46, polyquaternium-47, polyquaternium-53, polyquaternium-54, polyquaternium-55, polyquaternium-56, polyquaternium-57, polyquaternium-58, polyquaternium-59, polyquaternium-60, polyquaternium-61, polyquaternium-62, polyquaternium-63, polyquaternium-64, polyquaternium-65, polyquaternium-66, polyquaternium-67, polyquaternium-68, polyquaternium-69 ... Quaternium-55, polyquaternium-67, polyquaternium-68, polyquaternium-69, polyquaternium-73, polyquaternium-74, polyquaternium-77, polyquaternium-78, polyquaternium-79, polyquaternium-79 and hydrolyzed keratin copolymer, polyquaternium-80, polyquaternium-81, polyquaternium-82, polyquaternium-86, polyquaternium-88, polyquaternium-101, polyethyleneamine, polyethyleneimine, copolymers of vinylamine and vinylformamide, copolymers of acrylamide and 3-methacrylamidopropyltrimonium, 3-acrylamidotrimonium polymer or copolymers thereof, diallyldimethylammonium chloride polymer and copolymers thereof, polysaccharides having sugar units functionalized with hydroxypropyltrimonium, ethyltrimonium chloride methacrylate / hydrolyzed wheat protein copolymer, alkylammonium hydroxypropyl hydrolyzed protein, and combinations thereof.

[0018] The diameter of the microcapsules is usually 0.2 μm to 100 μm. The microcapsule shell accounts for 10% to 90% of the weight of the microcapsule, and the microcapsule core accounts for 90% to 10% of the weight of the microcapsule.

[0019] Another aspect of the present invention relates to a method for preparing a microcapsule composition comprising the steps of: (i) providing an oil-in-water emulsion having a plurality of oil droplets dispersed in an aqueous phase, wherein the oil-in-water emulsion comprises a polyfunctional electrophile (e.g., a polyisocyanate), the oil phase comprises an active material, and the aqueous phase comprises a protein and optionally a chaotropic agent, (ii) optionally adding a polyfunctional nucleophile to the oil-in-water emulsion, and (iii) providing conditions sufficient to initiate interfacial polymerization in the oil-in-water emulsion mixture to form microcapsules having a microcapsule wall encapsulating a microcapsule core, thereby obtaining the microcapsule composition. Optionally, the method further comprises the steps of: (iv) curing the microcapsules at a temperature of 0° C. to 125° C. or (iv) after the curing step, adding an aqueous chitosan solution to 0.5% to 5% by weight of the microcapsule composition at a pH of 1 to 5, and heating the resulting mixture to 35° C. to 95° C. (e.g., 45° C. to 75° C. for 10 minutes to 10 hours).

[0020] In one embodiment, the oil-in-water emulsion further contains a surfactant selected from the group consisting of polyvinyl alcohol, ethyleneamine / vinyl alcohol copolymers, polystyrene sulfonate, carboxymethyl cellulose, naphthalene sulfonate, polyvinyl pyrrolidone, copolymers of vinyl pyrrolidone and quaternized dimethylaminoethyl methacrylate, OSA-modified starch, OSA-modified gum arabic, gum arabic, alginate, carboxymethyl cellulose, carrageenan, xanthan gum, gellan gum, lecithin, modified lecithin, protein, modified protein, pectin, modified pectin, lignin, modified lignin, and combinations thereof.

[0021] Preferably, the polyfunctional electrophile (e.g., polyisocyanate) is present in each oil droplet or aqueous phase at a level of 0.1% to 5% (e.g., 0.2% to 3% and 0.5% to 2%), the chaotrope or polyfunctional nucleophile is added to the oil-in-water emulsion at a level of 0.1% to 10% (e.g., 0.2% to 5% and 0.2% to 2%), and the protein is present at a level of 2% to 20% (e.g., 3% to 18% and 5% to 15%), all by weight of the microcapsule composition. Preferred polyfunctional nucleophiles are polyphenols, which can be added to the oil-in-water emulsion at a level of 0.1% to 2.5% by weight of the microcapsule composition. Preferred chaotropes include guanidine salts and glutaraldehyde. When present, the combined levels of the chaotrope and polyfunctional nucleophile are 1% to 10% (e.g., 2% to 8% and 3% to 7%) of the weight of the microcapsule.

[0022] Each oil droplet may have a size of 0.1 μm to 100 μm in diameter, resulting in a microcapsule size of 0.2 μm to 100 μm in diameter.

[0023] Also within the scope of the present invention is a microcapsule composition comprising a plurality of the above-described microcapsules in a slurry, wherein the microcapsules are dispersed in an aqueous phase. The microcapsule composition may also be in dry form.

[0024] The microcapsules and compositions thereof can be used to impart fragrance to consumer products, such as baby care products, diaper rash creams or balms, baby powders, diapers, bibs, baby wipes, cosmetic preparations, powder foundations, liquid foundations, eye shadows, lipsticks or lip balms, home care products, all-purpose cleaners, scent drop products, bathroom cleaners, floor cleaners, window cleaners, plastic polishes, bleach, toilet bowl cleaners, toilet seats, toilet paper, paper towels, disposable wipes, liquid air fresheners, air freshener sprays, spray dispenser products, incense sticks, carpet deodorizers, candles, room deodorizers, liquid dishwashing detergents, dishwasher detergents, powder dishwashing detergents, leather detergents, tablet dishwashing detergents, paste dishwashing detergents, unit dose tablets or capsules, flavorings, beverage flavorings, dairy flavorings, fruit flavorings, mixed flavorings, dessert flavorings, tobacco flavorings, toothpaste flavorings, chewing gum, breath fresheners, anorally dissolvable tablets, strips), chewable candies, hard candies, oral care products, toothpaste, toothbrushes, dental floss, mouthwash, teeth whiteners, denture adhesives, hygiene products, tampons, sanitary napkins, anti-inflammatory balms, anti-inflammatory ointments, anti-inflammatory sprays, disinfectants, personal care products, soap, bar soap, liquid soap, a bath fragrance, a bodywash, a non-aerosol body spray, body lotion, cleansers, body creams, hand sanitizers, hand soaps, functional product bases, sunscreen lotions, sunscreen sprays, deodorants, antiperspirants, roll-on products, aerosol products, natural spray products, wax-based deodorants, glycol-based deodorants, soap-based deodorants, facial lotions, body lotions, hand lotions, miscellaneous lotions, body powder, shaving cream, shaving gel, shaving butter, a bath soak, a shower gel gel), exfoliating scrubs, foot creams, facial tissues, cleansing wipes, talc products, hair care products, ammonia-containing hair care products, shampoo, conditioner, a hair rinse, a hair refresher, hair styling or styling aids, hair bleach, hair dye or colorant, fabric care products, fabric softener, liquid fabric softener, fabric softener tablets, dryer sheets, fabric refreshers, ironing water, detergent, laundry detergent, liquid laundry detergent, laundry powder, laundry tablets, laundry bars, laundry cream, hand laundry detergent, scent enhancers, fragrance, cologne, compound, encapsulated fragrance, fine fragrance, men's fragrance, women's fragrance, perfume, solid fragrance, Eau De ToiletteToilette products, natural spray products, perfume spray products, insect repellent products and wildlife scents.

[0025] The details of one or more embodiments of the invention are set forth in the description below. Other features, objects, and advantages of the invention will be apparent from the description and claims. Detailed Description of the Invention

[0026] Certain protein microcapsules have been found to have unexpectedly high fragrance properties and are environmentally friendly. These protein microcapsule compositions have been successfully incorporated into many consumer product applications.

[0027] The microcapsules of the present invention can be prepared by printing the microcapsule shell and microcapsule core using a printing system, such as a 3D printer. See WO2016172699A1. Suitable active materials for printing include fragrances, flavorings, malodor counteractants, cosmetic actives, and nutrients. The printing step typically involves depositing the active material and microcapsule shell material in a layer-by-layer arrangement, preferably using separate print heads. The microcapsule shell material can be a polymer or an oil-in-water emulsion, as described below.

[0028] Conveniently, the microcapsule composition of the present invention is prepared by the following steps: (i) providing an oil-in-water emulsion having a plurality of oil droplets dispersed in an aqueous phase, wherein the oil-in-water emulsion comprises a polyfunctional electrophile (e.g., polyisocyanate, glutaraldehyde, and glyoxal) in the aqueous phase or the oil phase, the oil phase contains the active material, and the aqueous phase contains a protein and optionally a chaotropic agent, (ii) optionally adding a polyfunctional nucleophile to the oil-in-water emulsion, and (iii) providing conditions sufficient to initiate interfacial polymerization in the oil-in-water emulsion mixture to form a microcapsule slurry, the microcapsule slurry containing microcapsules, each microcapsule having a microcapsule wall encapsulating a microcapsule core, thereby obtaining a microcapsule composition. Interfacial polymerization can be initiated by heating the oil-in-water emulsion to an elevated temperature (e.g., at least 35° C., at least 45° C., at least 55° C., and 35° C. to 95° C.).

[0029] Optionally, the preparation method further comprises one or more additional steps: (iib) adding a catalyst (e.g., 1,4-diazabicyclo[2.2.2]octane) to the oil-in-water emulsion after step (ii) to promote polymerization and (iv) curing the microcapsule slurry at a temperature of 0° C. to 125° C. (e.g., 15° C. to 110° C., 25° C. to 100° C., 45° C. to 95° C., and 50° C. to 90° C.) for 10 minutes to 48 hours (e.g., 15 minutes to 24 hours, 30 minutes to 10 hours, and 30 minutes to 6 hours). The catalyst initiates interfacial polymerization with or without heating the oil-in-water emulsion.

[0030] Oil-in-water emulsions can be prepared using conventional emulsion technology by emulsifying the oil phase into the aqueous phase with or without additional capsule-forming aids. Protein can be used as both an emulsifier and a cross-linking agent. In one embodiment, the oil phase contains an active material (e.g., spices), a polyfunctional electrophilic reagent (e.g., polyisocyanate), and a core solvent (e.g., caprylic / capric triglyceride). The aqueous phase contains water and protein, with or without an emulsifier. In another embodiment, the oil phase contains an active material and a core solvent. The aqueous phase contains water, a polyfunctional electrophilic reagent (e.g., polyisocyanate, glutaraldehyde, and glyoxal), a protein, and an optional capsule-forming aid. In yet another embodiment, the polyfunctional electrophilic reagent is added to a preformed oil-in-water emulsion, rather than being added to the oil phase or the aqueous phase before the emulsion is formed.

[0031] In some embodiments, the method includes the step of denaturing the protein prior to adding the protein to the oil-in-water emulsion by adjusting the pH, heating, or adding a chaotropic agent to the oil-in-water emulsion or the protein.

[0032] The pH of the microcapsule composition thus prepared is generally 3 to 12, preferably 3 to 10, more preferably 4 to 9 (eg, 5 and 9).

[0033] Each microcapsule of the present invention has a core-shell structure, comprising a single microcapsule core and a single microcapsule wall encapsulating the single microcapsule core. The microcapsule wall has an inner surface and an outer surface. The inner surface contacts the microcapsule core. The outer surface contacts the environment in which the microcapsule is located (e.g., an aqueous phase, skin, or hair).

[0034] The microcapsule wall is formed by a polymer network containing at least three different parts: (i) a first part derived from a protein, (ii) a second part derived from a multifunctional electrophile (e.g., polyisocyanate, glutaraldehyde, and glyoxal), and (iii) a third part derived from a chaotropic agent or a multifunctional nucleophile. The first part is connected to the second part by a covalent bond. When the third part is a chaotropic agent, it is connected to the first part by a covalent or non-covalent bond (e.g., hydrogen bond) when the chaotropic agent has an amine (-NH2) or alcohol (-OH) functional group, or is connected to the second part by a covalent bond. When the third part is a multifunctional nucleophile, it is connected to the first part by a covalent bond (e.g., urea bond (-NHCONH-), urethane bond (-OCONH-), imine bond (-OH-), or polyfunctional nucleophile (-NHCONH-). or a C-N bond as found in Michael-type adducts) to the second moiety.

[0035] In a preferred embodiment, the polymer network contains four parts: a first part derived from a protein, a second part derived from a multifunctional electrophile (e.g., polyisocyanate, glutaraldehyde, and glyoxal), a third part derived from a multifunctional nucleophile (e.g., polyamines and polyphenols), and a fourth part derived from a chaotrope (e.g., guanidine and its salts).

[0036] The microcapsules thus prepared each have a particle size (in terms of diameter) ranging from 0.1 μm to 1000 μm (e.g., 0.5 μm to 500 μm, 1 μm to 200 μm, and 1 μm to 100 μm), with a lower limit of 0.1 μm, 0.5 μm, 1 μm, 2 μm, or 5 μm, and an upper limit of 1000 μm, 500 μm, 200 μm, 100 μm, 75 μm, 50 μm, or 30 μm.

[0037] The microcapsules can be positively or negatively charged with a zeta potential of -200 mV to +200 mV (e.g., 10 mV or higher, 25 mV or higher, 40 mV or higher, 25 mV to 200 mV, and 40 mV to 100 mV), with a lower limit of -200 mV, -150 mV, -100 mV, -50 mV, -25 mV, -10 mV, 0 mV, 10 mV, 20 mV, or 40 mV, and an upper limit of 200 mV, 150 mV, 100 mV, 50 mV, 40 mV, 20 mV, 10 mV, 0 mV, -10 mV, and -25 mV. Preferably, each microcapsule is positively charged. Without being bound by theory, the positively charged microcapsules have a strong affinity for certain animate and inanimate surfaces, such as hair and fabrics, and are unexpectedly stable in certain consumer product bases, such as conditioners, shampoos, body washes, and fabric conditioners.

[0038] The microcapsules of the present invention are biodegradable and therefore environmentally friendly. As used herein, "biodegradable" in relation to materials (e.g., biopolymers of the microcapsules and / or microcapsule shells as a whole) has no actual or perceived health and / or environmental issues and is capable of and / or does undergo physical, chemical, thermal, microbial and / or biological degradation. Ideally, microcapsules and / or biopolymers are considered to be "biodegradable" when they pass one or more of the following tests: Organisation for Economic Co-operation and Development (OECD) tests, including but not limited to OECD 301 / 310 (rapid biodegradation), OECD 302 (intrinsic biodegradation), International Organization for Standardization (ISO) 17556 (solid stimulation studies), ISO 14851 (fresh water stimulation studies), ISO 18830 (marine sediment stimulation studies), OECD 307 (soil stimulation studies), OECD 308 (sediment stimulation studies) and OECD 309 (water stimulation studies). In certain embodiments, the microcapsules are readily biodegradable as determined using the OECD 310 test. The passing level for ready biodegradability under OECD 310 is a 60% CO2 production within 60 days of testing.

[0039] Peptide biopolymers and proteins

[0040] Proteins suitable for use in the present invention include whey protein, pea protein, rice protein, wheat protein (e.g., concentrate or isolate), egg protein, and plant storage proteins (e.g., concentrate or isolate), such as barley protein, brown rice protein, pumpkin seed protein, oat protein, potato protein, almond protein, or any combination thereof.

[0041] As conventional in the art, a "polypeptide" or "protein" is a linear organic polymer composed of amino acid residues bonded together in a chain to form a portion (or all) of a protein molecule. As used herein, "polypeptide" or "protein" refers to a natural polypeptide, a polypeptide derivative and / or a modified polypeptide. The average molecular weight of a polypeptide can be expressed as 1,000 Da to 40,000,000 Da and / or greater than 10,000 Da and / or greater than 100,000 Da and / or greater than 1,000,000 Da and / or less than 3,000,000 Da and / or less than 1,000,000 Da and / or less than 500,000 Da, or a range defined by any of these molecular weights.

[0042] As used herein, "whey protein" refers to the protein contained in whey, which is a liquid dairy product obtained as the supernatant of the curd when milk or a liquid dairy product containing milk components is processed into cheese curd to obtain semi-solid cheese curd. Whey protein is generally understood in principle to include the globular proteins β-lactoglobulin and α-lactalbumin in various ratios (e.g., 1:1 to 5:1 (e.g., 2:1)). It may also include lower amounts of serum albumin, immunoglobulins, and other globulins. The term "whey protein" is also intended to include partially or completely modified or denatured whey proteins. Purified β-lactoglobulin and / or α-lactalbumin polypeptides can also be used to prepare the microcapsules of the present invention.

[0043] Plant storage proteins are proteins that accumulate in various plant tissues and serve as biological reserves for metal ions and amino acids. Plant storage proteins can be divided into two categories: seed or grain storage proteins and vegetative storage proteins. Seed / grain storage proteins are a group of proteins that accumulate to a high level in seeds / grains during the later stages of seed / grain development, while vegetative storage proteins are proteins that accumulate in vegetative tissues such as leaves, stems, and (depending on the plant) tubers. During germination, seed / grain storage proteins are degraded, and the amino acids produced are used as a source of nutrition by the developing seedling. In some embodiments, the plant storage protein for the preparation of microcapsules of the present invention is seed or grain storage protein, vegetative storage protein, or a combination thereof. In certain embodiments, seed storage protein is a leguminous storage protein. In a specific embodiment, the seed / grain storage protein is extracted from legumes, in particular from soybeans, lupins, peas, chickpeas, alfalfa, horse beans, lentils and lentils; from oilseed plants, such as rapeseed, cottonseed and sunflower; from cereals, such as wheat, corn, barley, malt, oats, rye and rice (e.g., brown rice protein); or a combination thereof. In other embodiments, the plant storage protein is a nutritional protein extracted from potato or sweet potato tubers.

[0044] In a particular embodiment, plant storage proteins are intended to include plant protein isolates, plant protein concentrates, or combinations thereof. Plant storage protein isolates and concentrates are generally understood to be composed of several proteins. For example, pea protein isolates and concentrates can include legumin, vicilin, and convicilin. Similarly, brown rice protein isolates can include albumin, globulin, and gluten proteins. The term "plant storage protein" is also intended to include partially or completely modified or denatured plant storage proteins. Separate storage polypeptides (e.g., legumin, vicilin, convicilin, albumin, globulin, or gluten) can also be used to prepare microcapsules of the present invention.

[0045] "Gelatin" refers to a protein mixture produced by partial hydrolysis of collagen extracted from the skin, bones, and connective tissue of animals. Gelatin can be derived from any type of collagen, such as type I, II, III, or IV collagen. This type of protein is characterized by the presence of Gly-Xaa-Yaa triplets, where Gly is the amino acid glycine and Xaa and Yaa can be the same or different and can be any known amino acid. At least 40% of the amino acids are preferably present as consecutive Gly-Xaa-Yaa triplets.

[0046] The whey protein or plant storage protein of the present invention may be native, partially or completely denatured by any suitable method, preferably without causing gelation of the whey protein or plant storage protein.The protein is used in the form of a protein isolate or concentrate.

[0047] Commercially available proteins include whey protein concentrate (from Glanbia Nutritionals 282 and from Wheyco ), whey protein isolate (from Glanbia Nutritionals 195), pea protein (from Roquette S85XF, Organic Pea Protein from Z Natural Foods TM ), potato protein (from Roquette GP), brown rice protein (Ingredients Inc. and Oryzatein from Z Natural Foods 90BR), white rice protein (from Roquette ), rice protein from Kerry, wheat protein from Scoular, egg protein from Henningsen Food, barley rice protein from Beretein, pumpkin seed protein Acetar.

[0048] Denaturation is the process of causing proteins (polypeptides) to lose their native quaternary, tertiary, and secondary structures through the application of denaturing conditions. During denaturation, proteins change their conformational structure by unfolding, making amine (-NH2) and hydroxyl (-OH) groups available for cross-linking with polyisocyanates to form the microcapsule wall. Denaturation can be reversible (the protein can return to its native state when the denaturing influence is removed) or irreversible.

[0049] Exemplary conditions for protein denaturation include, but are not limited to, radiation, exposure to heat or cold, alteration of pH with acid or base, exposure to denaturing agents such as detergents, inorganic salts, organic solvents (e.g., alcohols, ethyl acetate, and chloroform), urea or other chaotropic agents, or mechanical stress including shear. In certain embodiments, a chaotropic agent having a positive chaotropic activity value (kJ kg -1 , on the Hallsworth scale).

[0050] Exemplary chaotropic agents are guanidine salts (e.g., guanidine hydrochloride and guanidine carbonate), urea, polysorbate, sodium benzoate, vanillin, o-cresol, phenol, propanol, formamide, ethanol, fructose, ammonium sulfate, ammonium chloride, ammonium nitrate, ammonium phosphate, potassium sulfate, potassium chloride, potassium iodide, potassium nitrate, potassium phosphate, sodium sulfate, sodium chloride, sodium bromide, sodium nitrate, sodium phosphate, guanidine thiocyanate, xylose, glycerol, benzyl alcohol, ethyl acetate, triton X-100, ethyl acetate, hexadecyltrimethylammonium halide, acetone, sodium dodecyl sulfate (SDS), hydrochloric acid, sulfuric acid, polyethylene glycol, glutaraldehyde, and combinations thereof. Any amount of chaotropic agent can be used. The preferred weight ratio of protein to guanidine salt (guanidine carbonate or guanidine hydrochloride) is 1:1 to 15:1, more preferably 2:1 to 10:1.

[0051] For example, when an 8% pea storage protein solution (w / v) is used, the solution can be treated at a temperature of 80-90° C. for 20-30 minutes (or preferably at 85° C. for 25 minutes) to produce denatured pea storage protein. However, it should be understood that higher temperatures and shorter times can also be used. In a specific embodiment, whey protein or plant storage protein is partially or completely denatured using, for example, guanidine carbonate. It is worth noting that it has been found that the degree and method of protein denaturation can have a significant impact on performance. Therefore, in certain embodiments, whey protein or plant storage protein is denatured with a chaotropic agent to denature 20% to 100% (e.g., at least 20%, at least 40%, at least 60%, at least 90%, 95% or 99%, w / w) of the whey protein or plant storage protein used to prepare the microcapsules.

[0052] The proteins used in the microcapsules can also be derivatized or modified (e.g., derivatized or chemically modified). For example, the proteins can be modified by covalently attaching sugars, lipids, cofactors, peptides, or other chemical groups, including phosphates, acetates, methyl groups, and other natural or non-natural molecules.

[0053] The microcapsule wall contains protein at a level of 20 wt% to 98 wt% (e.g., 30 wt% to 95 wt%, 40 wt% to 90 wt%, 50 wt% to 90 wt%, and 60 wt% to 85 wt%) based on the weight of the microcapsule wall. The microcapsule wall having a high protein content is readily biodegradable while effectively encapsulating the fragrance with a satisfactory release profile.

[0054] Multifunctional nucleophiles

[0055] The term "polyfunctional nucleophile" refers to an aliphatic or aromatic hydrocarbon to which two or more nucleophilic groups, such as primary / secondary amine groups and hydroxyl groups, are attached. Preferred polyfunctional nucleophiles include tannic acid ( -02, Ajinomoto), triethyl citrate ( IFF)、BPEI( BASF), itaconic acid (Sigma Aldrich, St. Louis, Missouri), citric acid (Sigma Aldrich), malic acid (Sigma Aldrich), maleic acid (Sigma Aldrich), dibutyl itaconate (Sigma Aldrich), cysteamine (Sigma Aldrich), lysine (Sigma Aldrich), maltodextrin (Sigma Aldrich), glutaraldehyde (Sigma Aldrich).

[0056] Suitable polyfunctional nucleophiles include polyfunctional amines (ie, polyamines) and polyfunctional alcohols (ie, polyols).

[0057] These agents typically contain multiple (i.e., two or more) functional groups (e.g., -NH-, -NH2, and -OH) that can react with polyisocyanates to form polyureas or polyurethanes. Examples include polyfunctional amines (e.g., polyamines) and polyfunctional alcohols (e.g., polyols).

[0058] Suitable polyamines contain two or more amine groups, including –NH2 and –R*NH, where R* is a substituted or unsubstituted C1-C 20 Alkyl, C1-C 20 Heteroalkyl, C1-C 20 cycloalkyl, 3- to 8-membered heterocycloalkyl, aryl, and heteroaryl.

[0059] Two such classes of polyamines include the polyalkylene polyamines having the following structure:

[0060]

[0061] wherein R is hydrogen or -CH3; m, n, x, y, and z are each an integer from 0 to 2000 (e.g., 1, 2, 3, 4, and 5). Examples include ethylenediamine, 1,3-diaminopropane, diethylenetriamine, triethylenetetramine, 1,4-diaminobutane, hexylenediamine, hexamethylenediamine, pentaethylenehexamine, and the like.

[0062] Another class of polyamines are the polyalkylene polyamines of the following types:

[0063]

[0064] Wherein R is equal to hydrogen or -CH3, m is 1-5 and n is 1-5, for example, diethylenetriamine, triethylenetetramine, etc. Exemplary amines of this type also include diethylenetriamine, bis(3-aminopropyl)amine, bis(hexylene)triamine.

[0065] Another class of amines useful in the present invention is polyetheramines. These contain primary amino groups attached to the ends of a polyether backbone. The polyether backbone is typically based on propylene oxide (PO), ethylene oxide (EO), or a mixed PO / EO. Based on this core structure, etheramines can be monoamines, diamines, or triamines. An example is:

[0066]

[0067] Exemplary polyetheramines include 2,2'-ethylenedioxy)bis(ethylamine) and 4,7,10-trioxa-1,13-tridecanediamine.

[0068] Other suitable amines include, but are not limited to, hexamethylenediamine, ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, diethylenetriamine, pentaethylenehexamine, bis(3-aminopropyl)amine, bis(hexylene)triamine, tris(2-aminoethyl)amine, triethylene-tetramine, N,N'-bis(3-aminopropyl)-1,3-propylenediamine, tetraethylenepentamine, pentaethylenehexamine, chitosan, nisin, gelatin, 1,3-diaminoguanidine, 1,1-dimethylbiguanidine, guanidine, arginine, lysine, ornithine, 1,2-diaminopropane, N,N,N',N'-tetrakis(2-hydroxyethyl)ethylenediamine, N,N,N',N'-tetrakis(2-hydroxypropyl)ethylenediamine, branched polyethyleneimine, 2,4-diamino-6-hydroxypyrimidine and 2,4,6-triaminopyrimidine, and combinations thereof. For further examples, see WO 2015 / 023961 A1.

[0069] Amphoteric amines, i.e., amines that can react as both an acid and a base, are another class of amines useful in the present invention. Examples of amphoteric amines include proteins and amino acids, such as gelatin, L-lysine, D-lysine, L-arginine, D-arginine, L-lysine monohydrochloride, D-lysine monohydrochloride, L-arginine monohydrochloride, D-arginine monohydrochloride, L-ornithine monohydrochloride, D-ornithine monohydrochloride, or mixtures thereof.

[0070] Guanamines and guanidine salts are another class of polyfunctional amines useful in the present invention. Exemplary guanamines and guanidine salts include, but are not limited to, 1,3-diaminoguanidine monohydrochloride, 1,1-dimethylbiguanidine hydrochloride, guanidine carbonate, and guanidine hydrochloride.

[0071] Examples of commercially available amines include products under the following trade names: EDR-148 (where x=2), EDR-176 (where x=3), ED series, TRIAMINES (from Huntsman); polyethyleneimines from BASF (Ludwigshafen, Germany) under the following trade names: (For example, FG, G20 anhydrous, PR 8515, WF, FC, G20, G35, G100, G500, HF, PS, HEO 1, PN50, PN60, PO 100 and SK). Other commercially available polyethyleneimines include those from NIPPON SHOKUBAI (New York, NY) under the following trade names: P-1000, P-1050, RP18W and PP-061. Polyvinylamines, such as those available from BASF as A wide range of polyetheramines can be selected by those skilled in the art.

[0072] Preferred polyfunctional alcohols are polyphenols, including those having 3,4,5-trihydroxyphenyl or 3,4-dihydroxyphenyl groups, such as tannic acid, which has a typical chemical structure as shown below:

[0073]

[0074] The above chemical formula is often referred to as C 76 H 52 O 46 Given, which corresponds to decamalloylglucose. However, commercially available tannic acid typically comprises a mixture of polygalloylglucose or polygalloyquinate, with the number of galloyl moieties per molecule ranging from 2 to 20 (e.g., 2 to 15 and 2 to 12) and a molecular weight of 400 to 3500 Daltons (e.g., 496 to 3232 Daltons, 496 to 2472 Daltons, 180+152n Daltons, and 192+152n Daltons, where n is 2 to 13). Tannic acid has a weak acidity (e.g., pKa of around 6) and a pH of 2 to 5 (e.g., 3-4 and 2.5 to 3.5) in an aqueous solution containing 1% tannic acid. The water solubility of tannic acid at 25°C is 100 g / L to 2850 g / L (e.g., 250 g / L).

[0075] Tannic acid is typically extracted from any of the following plant parts: Tara pods (Caesalpinia spinosa), gallnuts from Rhus semialata or Quercus infectoria, or Sicilian sumac leaves (Rhus coriaria). Tannic acid is commercially available from suppliers such as Sigma-Aldrich (St Louis) and Ajinomoto OmniChem (Wetteren, Belgium) under the following trade names: 01 (polygalloyl glucose, molecular weight 1440 Daltons), 02 (polygalloyl glucose, molecular weight 1040 Daltons) and 04 (polygalloylquinate, molecular weight 860 Daltons).

[0076] In addition to polyphenols, other polyols can also be used. Referring to the polyols described in WO 2015 / 023961. Examples include pentaerythritol, dipentaerythritol, glycerol, polyglycerol, ethylene glycol, polyethylene glycol, trimethylolpropane, neopentyl glycol, sorbitol, erythritol, threitol, arabitol, xylitol, ribitol, mannitol, galactitol, fucitol, iditol, inositol, heptyl alcohol, isomalt, maltitol, lactitol, maltotriitol, maltotetraitol, polysaccharide alcohol (polyglycitol), polyphenols, and combinations thereof.

[0077] Multifunctional aldehydes, such as glutaraldehyde and glyoxal, form derivatives such as monohydrates, dehydrates, acetals or hemiacetals in aqueous solution within certain pH ranges (i.e., under acidic conditions). These multifunctional aldehyde derivatives have hydroxyl (-OH) groups that are reactive toward polyisocyanates, forming polyurethane bonds. Therefore, multifunctional aldehydes act as multifunctional nucleophiles under certain conditions (e.g., at a pH of 3 to 8).

[0078] The polyfunctional nucleophile may be present at a level of 0 to 40% (eg, 1% to 35%, 5% to 35%, and 10% to 30%) by weight of the microcapsule wall.

[0079] Carbonyl crosslinkers

[0080] One class of multifunctional electrophiles are carbonyl crosslinkers, each having at least two functional groups, eg, a first functional group and a second functional group.

[0081] The first functional group is an electrophilic group that is reactive toward proteins, polyamines, polyols, and other electron-rich groups. Examples include formyl, keto, carboxyl, carboxylate, acyl halide, amide, carboxylic anhydride, alkyl halide, epoxy, aziridine, oxetane, azetidine, sulfonyl halide, chlorophosphate, isocyanate, α,β-unsaturated carbonyl, α,β-unsaturated nitrile, or α,β-unsaturated methanesulfonyl. Preferably, the first functional group is a carbonyl electrophilic group containing a carbonyl group, such as formyl, keto, carboxyl, carboxylate, acyl halide, amide, carboxylic anhydride, α,β-unsaturated carbonyl, trifluoromethanesulfonate, and p-toluenesulfonate.

[0082] The second functional group is an electrophilic group reactive toward proteins, polyamines, polyols, and other electron-rich groups. Examples include formyl, keto, carboxyl, carboxylate, acyl halide, amide, carboxylic anhydride, alkyl halide, epoxy, aziridine, oxetane, azetidine, sulfonyl halide, chlorophosphate, isocyanate, α,β-unsaturated carbonyl, α,β-unsaturated nitrile, α,β-unsaturated methanesulfonyl, trifluoromethanesulfonate, or p-toluenesulfonate. The first and second functional groups may be the same or different.

[0083] Examples of carbonyl crosslinking agents include glutaraldehyde, succinaldehyde, and glyoxal; as well as compounds such as glyoxyl trimer and paraformaldehyde, bis(dimethyl)acetal, bis(diethyl)acetal, polymeric dialdehydes such as oxidized starch. Preferably, the crosslinking agent is a low molecular weight difunctional aldehyde such as glyoxal, 1,3-propanedial, 1,4-succinaldehyde, 1,5-glutaredial, or 1,6-hexanedialdehyde.

[0084] The carbonyl crosslinker may be present at a level of 0.5% to 40% (eg, 0.5% to 35% and 1% to 30%) by weight of the microcapsule wall.

[0085] polyisocyanate

[0086] Another class of polyfunctional electrophiles is polyisocyanates, each of which has at least two isocyanate (-NCO) groups reactive toward proteins or polyfunctional nucleophiles. Polyisocyanates can be aromatic, aliphatic, linear, branched, or cyclic. They can be water-soluble or water-dispersible. Alternatively, they can be soluble in organic solvents or aromatic oils. In some embodiments, polyisocyanates contain an average of 2 to 4 isocyanate groups. In particular embodiments, polyisocyanates contain at least three isocyanate functional groups. In certain embodiments, polyisocyanates are water-insoluble.

[0087] In specific embodiments, the polyisocyanate used in the present invention is an aromatic polyisocyanate. Desirably, the aromatic polyisocyanate comprises phenyl, tolyl, xylyl, naphthyl or diphenyl moieties as aromatic components. In certain embodiments, the aromatic polyisocyanate is a trimethylolpropane adduct of a polyisocyanurate of toluene diisocyanate, a toluene diisocyanate or a xylylene diisocyanate.

[0088] One class of suitable aromatic polyisocyanates has the general structure shown below and its structural isomers

[0089]

[0090] Wherein n can vary between zero and a desired value (e.g., 0-50, 0-20, 0-10, and 0-6), depending on the type of cross-linking agent used. Preferably, the number of n is limited to less than 6. The starting polyisocyanate can also be a mixture of polyisocyanates in which the value of n can vary between 0 and 6. In the case where the starting polyisocyanate is a mixture of various polyisocyanates, the average value of n preferably falls between 0.5 and 1.5. Commercially available polyisocyanates include products under the following trade names: M20 (chemical name: polymeric methylene diphenyl diisocyanate, i.e., "PMDI"; commercially available from BASF, containing 31.5 wt% of isocyanate groups "NCO"), wherein the average n is 0.7; PAPI TM 27 (PMDI commercially available from Dow Chemical, having an average molecular weight of 340 and containing 31.4 wt% NCO), wherein the average n is 0.7; MR (PMDI, containing 31 wt% or more NCO, commercially available from Covestro, Pittsburgh, PA), where the average n is 0.8; MR Light (PMDI, containing 31.8 wt% NCO, commercially available from Covestro), where the average n is 0.8; 489 (PMDI, commercially available from Covestro, containing 30-31.4 wt% NCO), where the average n is 1; poly[(phenyl isocyanate)-co-formaldehyde] (Aldrich Chemical, Milwaukee, WI), other isocyanate monomers, e.g. N3200 (poly(hexamethylene diisocyanate), commercially available from Covestro) and Takenate TM D-110N (trimethylolpropane adduct of xylylene diisocyanate, Mitsui Chemicals America, Inc., Rye Brook, NY, containing 11.5 wt% NCO), L75 (a polyisocyanate based on toluene diisocyanate, commercially available from Covestro), and IL (another toluene diisocyanate-based polyisocyanate, commercially available from Covestro).

[0091] The structures of certain commercially available polyisocyanates of the present invention are shown below:

[0092]

[0093] or its structural isomers. R can be C1-C 10 Alkyl, C1-C 10 Ester or isocyanurate. Representative polyisocyanates of this structure can be traded under the name TAKENATE TM D-110N (Mitsui), L75 (Covestro) and IL (Covestro) was purchased commercially.

[0094] Polyisocyanate Takenate TM D-110N and other polyisocyanates are typically available as solutions in ethyl acetate. Preferably, the ethyl acetate is replaced with a solvent having a high flash point (e.g., at least 100°C, at least 120°C, and at least 150°C). Suitable solvents include triacetin, triethyl citrate, ethylene glycol diacetate, benzyl benzoate, and combinations thereof.

[0095] As an example, Takenate TMD-110N (an ethyl acetate solution of a trimethylolpropane adduct of xylylene diisocyanate) is mixed with benzyl benzoate, and the ethyl acetate is removed by vacuum distillation to yield a polyisocyanate solution containing 59% trimethylolpropane adduct of xylylene diisocyanate and 41% benzyl benzoate. This polyisocyanate solution has a flash point of at least 60°C. This benzyl benzoate solution of a polyisocyanate can be used in conjunction with PVP / PQ-11 or Flexan / CMC to prepare microcapsule compositions.

[0096] Other examples of aromatic polyisocyanates include 1,5-naphthylene diisocyanate, 4,4′-diphenylmethane diisocyanate (MDI), hydrogenated MDI, xylylene diisocyanate (XDI), tetramethylxylene diisocyanate, 4,4′-diphenyldimethylmethane diisocyanate, di- and tetraalkyl-diphenylmethane diisocyanates, 4,4′-dibenzyl diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, isomers of tolylene diisocyanate (TDI), 4,4′-diisocyanatophenyl-perfluoroethane, diisocyanatoethyl phthalate, and polyisocyanates having reactive halogen atoms, such as 1-chloromethylphenyl 2,4-diisocyanate, 1-bromomethyl-phenyl 2,6-diisocyanate, and 3,3-bischloromethyl ether 4,4′-diphenyl diisocyanate, and combinations thereof.

[0097] In other specific embodiments, the polyisocyanate is an aliphatic polyisocyanate, such as trimer of hexamethylene diisocyanate, trimer of isophorone diisocyanate, and biuret of hexamethylene diisocyanate. Exemplary aliphatic polyisocyanates include commercial products, such as, N302, N303, N304 and N305, which are aliphatic water-dispersible products based on hexamethylene diisocyanate; N3600, N3700 and N3900, which are low viscosity, multifunctional aliphatic polyisocyanates based on hexamethylene diisocyanate; and 3600 and N100, which are aliphatic polyisocyanates based on hexamethylene diisocyanate, each available from Covestro, Pittsburgh, PA. Further examples include 1-methyl-2,4-diisocyanatocyclohexane, 1,6-diisocyanato-2,2,4-trimethyl-hexane, 1,6-diisocyanato-2,4,4-trimethylhexane, 1-isocyanatomethyl-3-isocyanato-1,5,5-trimethylcyclohexane, chlorinated and brominated diisocyanates, phosphorus-containing diisocyanates, tetramethoxybutane 1,4-diisocyanate, butane 1,4-diisocyanate, hexane 1,6-diisocyanate (HDI), dicyclohexylmethane diisocyanate, cyclohexane 1,4-diisocyanate, ethylene diisocyanate, and combinations thereof. Sulfur-containing polyisocyanates are obtained, for example, by reacting hexamethylene diisocyanate with thiodiglycol or dihydroxydihexyl sulfide. Other suitable diisocyanates are trimethylhexamethylene diisocyanate, 1,4-diisocyanatobutane, 1,2-diisocyanatododecane, dimer fatty acid diisocyanates, and combinations thereof.

[0098] The weight average molecular weight of useful polyisocyanates varies between 200 Da and 2500 Da, 250 Da and 1000 Da and preferably between 275 Da and 500 Da.

[0099] The polyisocyanate content can range from 1% to 30% (eg, 2% to 25%, 3% to 20%, and 5% to 15%) by weight of the microcapsule wall.

[0100] During the preparation of the microcapsule composition of the present invention, the polyisocyanate can be added to the water phase, the oil phase or the oil-in-water emulsion.

[0101] In some embodiments, the polyfunctional isocyanate used to prepare the microcapsules of the present invention is a single polyisocyanate. In other embodiments, the polyisocyanate is a mixture of polyisocyanates. In some embodiments, the mixture of polyisocyanates includes an aliphatic polyisocyanate and an aromatic polyisocyanate. In a specific embodiment, the mixture of polyisocyanates is a trimethylolpropane adduct of hexamethylene diisocyanate and a biuret of xylylene diisocyanate. In certain embodiments, the polyisocyanate is an aliphatic isocyanate or a mixture of aliphatic isocyanates, without any aromatic isocyanate. In other words, in these embodiments, no aromatic isocyanate is used to prepare the encapsulating polymer as the capsule wall material. More examples of polyisocyanates can be found in WO 2004 / 054362 and WO 2017 / 192648.

[0102] Capsule forming aids

[0103] Microcapsule compositions are typically prepared in the presence of a capsule-forming aid, which can be a surfactant or dispersant. Capsule-forming aids also improve the performance of the microcapsule composition. Performance is measured by the intensity of the fragrance released during certain stages, such as the pre-rub and post-rub stages in laundry applications. The pre-rub stage is when the capsules have already deposited on the fabric, for example, after a wash cycle using a fabric softener or detergent containing the capsules. The post-rub stage occurs after the capsules have been deposited and ruptured by rubbing or other mechanisms.

[0104] In some embodiments, the capsule forming aid is a protective colloid or emulsifier, including, for example, maleic acid-vinyl copolymers, such as copolymers of vinyl ether and maleic anhydride or acid, sodium lignin sulfonate, maleic anhydride / styrene copolymers, ethylene / maleic anhydride copolymers, and copolymers of propylene oxide and ethylene oxide, polyvinyl pyrrolidone (PVP), polyvinyl alcohol (PVA), sodium salts of naphthalenesulfonic acid condensates, carboxymethyl cellulose (CMC), fatty acid esters of polyoxyethylated sorbitol, sodium lauryl sulfate, and combinations thereof. The concentration of the capsule forming aid (e.g., surfactants and dispersants) varies between 0.1% and 5% (e.g., 0.2% to 4%, 0.5% to 4%, 0.5% to 2.5%, and 1% to 2%) by weight of the capsule composition.

[0105] Commercially available surfactants include, but are not limited to, sulfonated naphthalene-formaldehyde condensates, e.g. D-425 (alkylnaphthalenesulfonate formaldehyde condensate, commercially available from Akzo Nobel, Fort Worth, TX); Partially hydrolyzed polyvinyl alcohol, such as 3-83 (commercially available from Kuraray, Houston, TX); ethylene oxide-propylene oxide block copolymers or poloxamers, such as or (BASF); sulfonated polystyrenes, e.g. II (Akzo Nobel); ethylene-maleic anhydride polymers, e.g. (Vertellus Specialties Inc., Indianapolis, IN); and the polyquaternium series, such as Polyquaternium 11 ("PQ11"; a copolymer of vinyl pyrrolidone and quaternized dimethylaminoethyl methacrylate; marketed by BASF as PQ11AT 1 sales).

[0106] Processing aids may also be used as capsule forming aids. They include hydrocolloids, which improve the colloidal stability of the slurry against coagulation, sedimentation and creaming. The term "hydrocolloid" refers to a large class of water-soluble or water-dispersible polymers having anionic, cationic, zwitterionic or nonionic properties. Hydrocolloids that can be used in the present invention include, but are not limited to, polycarbohydrates such as starch, modified starches, dextrins, maltodextrins and cellulose derivatives, and their quaternized forms; natural gums such as alginates, carrageenan, xanthan gum, agar, pectin, pectic acid, and natural gums such as gum arabic, tragacanth and karaya, guar gum and quaternized guar gum; gelatin, protein hydrolysates and their quaternized forms; synthetic polymers and copolymers such as poly(vinyl pyrrolidone-co-vinyl acetate) , poly(vinyl alcohol-co-vinyl acetate), poly((meth)acrylic acid), poly(maleic acid), poly(alkyl(meth)acrylate-co-(meth)acrylic acid), poly(acrylic acid-co-maleic acid) copolymers, poly(alkylene oxide), poly(vinyl-methyl ether), poly(vinyl ether-co-maleic anhydride), and the like, as well as poly(ethyleneimine), poly((meth)acrylamide), poly(alkylene oxide-co-dimethylsiloxane), poly(aminodimethylsiloxane), and the like, and their quaternized forms.

[0107] Capsule forming aids may also be used in combination with carboxymethyl cellulose ("CMC"), polyvinyl pyrrolidone, polyvinyl alcohol, alkyl naphthalene sulfonate formaldehyde condensate and / or surfactants during processing to facilitate capsule formation. Examples of these surfactants include cetyl trimethyl ammonium chloride (CTAC), (For example F127), (For example F127) or MIRANET- Poloxamers, saponins such as (National Starch Food Innovation); or gum arabic, such as Seyal or Senegal. In certain embodiments, the molecular weight (e.g., weight average molecular weight) of the CMC polymer ranges from 90,000 Daltons to 1,500,000 Daltons, preferably from 250,000 Daltons to 750,000 Daltons, more preferably from 400,000 Daltons to 750,000 Daltons. The degree of substitution of the CMC polymer is from 0.1 to 3, preferably from 0.65 to 1.4, more preferably from 0.8 to 1. The CMC polymer is present in the capsule slurry at a level of 0.1% to 2%, preferably from 0.3% to 0.7%. In other embodiments, the polyvinyl pyrrolidone used in the present invention is a water-soluble polymer and has a molecular weight (e.g., weight average molecular weight) of 1,000 Daltons to 10,000,000 Daltons. Suitable polyvinylpyrrolidone is polyvinylpyrrolidone K12, K15, K17, K25, K30, K60, K90 or a mixture thereof. The amount of polyvinylpyrrolidone is 2% to 50%, 5% to 30% or 10% to 25% by weight of the microcapsule composition.

[0108] catalyst

[0109] In some embodiments, a catalyst is added to initiate interfacial polymerization in the formation of the capsule wall. Examples include metal carbonates, metal hydroxides, amino or organometallic compounds and include, for example, sodium carbonate, cesium carbonate, potassium carbonate, lithium hydroxide, 1,4-diazabicyclo[2.2.2]octane (i.e., DABCO), N,N-dimethylaminoethanol, N,N-dimethylcyclohexylamine, bis-(2-dimethylaminoethyl) ether, N,N-dimethylacetamide, stannous octoate, and dibutyltin dilaurate.

[0110] Other encapsulating polymers

[0111] The microcapsule composition of the present invention optionally comprises a second, third, fourth, fifth, or sixth microcapsule, each microcapsule being composed of a polymer selected from the group consisting of a sol-gel polymer (e.g., silica), polyacrylates, polyacrylamides, poly(acrylate-co-acrylamide), polyureas, polyurethanes, starches, gelatin, gum arabic, poly(melamine-formaldehyde), poly(urea-formaldehyde), and combinations thereof. Branched polyethyleneimine and its derivatives may also be coated on the microcapsule wall to prepare microcapsules with a positive zeta potential.

[0112] These encapsulating polymers are described in detail below.

[0113] Sol-gel microcapsules. These microcapsules have a microcapsule wall formed from a sol-gel polymer, which is the reaction product of a sol-gel precursor by polymerization (e.g., hydrolysis). Suitable sol-gel precursors are compounds capable of forming a gel, such as compounds containing silicon, boron, aluminum, titanium, zinc, zirconium, and vanadium. Preferred precursors are organosilicon, organoboron, and organoaluminum, including metal alkoxides and b-diketonates.

[0114] Sol-gel precursors suitable for the purposes of the present invention are chosen in particular from di-, tri- and / or tetrafunctional silicic acid, boric acid and aluminum esters, more particularly alkoxysilanes (alkyl orthosilicates), and their precursors.

[0115] One example of a sol-gel precursor suitable for the purposes of the present invention is an alkoxysilane corresponding to the following general formula:

[0116] (R1O)(R2O)M(X)(X'),

[0117] wherein X can be hydrogen or -OR3; X' can be hydrogen or -OR4; and R1, R2, R3 and R4 independently represent an organic group, more particularly a straight chain or branched alkyl group, preferably C1-C 12 M can be Si, Ti or Zr.

[0118] Preferred sol / gel precursors are alkoxysilanes corresponding to the following general formula: (R1O)(R2O)Si(X)(X'), wherein each of X, X', R1 and R2 are as defined above.

[0119] Particularly preferred compounds are silicates, such as tetramethyl orthosilicate (TMOS) and tetraethyl orthosilicate (TEOS). Preferred compounds include (Organofunctional silanes are commercially available from Degussa Corporation, Parsippany, New Jersey, USA). Other sol-gel precursors suitable for the purposes of the present invention are described, for example, in German patent application DE 10021165. These sol-gel precursors are various hydrolyzable organosilanes, such as alkylsilanes, alkoxysilanes, alkylalkoxysilanes, and organoalkoxysilanes. In addition to alkyl and alkoxy groups, other organic groups (e.g., allyl, aminoalkyl, hydroxyalkyl, etc.) can be attached to the silicon as substituents.

[0120] The recognition that metal and semi-metal alkoxide monomers (and their partially hydrolyzed and condensed polymers) such as tetramethoxysilane (TMOS), tetraethoxysilane (TEOS), etc. are very good solvents for many molecules and active ingredients is very advantageous as it helps in solubilizing high concentrations of active materials and hence high loading in the final capsule.

[0121] Polyacrylate microcapsules, polyacrylamide microcapsules and poly(acrylate-co-acrylamide) microcapsules. These microcapsules are prepared from the corresponding precursors that form the microcapsule wall.Preferred precursors are difunctional or multifunctional vinyl monomers including, for example, but not limited to, allyl methacrylate / acrylamide, triethylene glycol dimethacrylate / acrylamide, ethylene glycol dimethacrylate / acrylamide, diethylene glycol dimethacrylate / acrylamide, triethylene glycol dimethacrylate / acrylamide, tetraethylene glycol dimethacrylate / acrylamide, propylene glycol dimethacrylate / acrylamide, glycerol dimethacrylate / acrylamide, neopentyl glycol dimethacrylate / acrylamide, 1,10-decanediol dimethacrylate / acrylamide, pentaerythritol trimethacrylate / acrylamide, pentaerythritol tetra ... tetramethacrylate / acrylamide, pentaerythritol tetramethacrylate / acrylamide, pentaerythritol tetramethacrylate / acrylamide, pentaerythritol tetramethacrylate / acrylamide, pentaerythritol tetramethacrylate / acrylamide, pentaerythritol tetramethacrylate / acrylamide, pentaerythritol tetramethacrylate / acryl Methacrylates / acrylamides, dipentaerythritol hexamethacrylate / acrylamide, triallyl formaldehyde trimethacrylate / acrylamide, trimethylolpropane trimethacrylate / acrylamide, tributylene glycol dimethacrylate / acrylamide, aliphatic or aromatic urethane diacrylate / acrylamide, difunctional urethane acrylate / acrylamide, ethoxylated aliphatic difunctional urethane methacrylate / acrylamide, aliphatic or aromatic urethane dimethacrylate / acrylamide, epoxy acrylate / acrylamide, epoxy methacrylate / acrylamide, 1,3-butylene glycol diacrylate / acrylamide, 1,4-butylene glycol dimethacrylate Acrylates / Acrylamide, 1,4-Butanediol Diacrylate / Acrylamide, Diethylene Glycol Diacrylate / Acrylamide, 1,6-Hexanediol Diacrylate / Acrylamide, 1,6-Hexanediol Dimethacrylate / Acrylamide, Neopentyl Glycol Diacrylate / Acrylamide, Polyethylene Glycol Diacrylate / Acrylamide, Tetraethylene Glycol Diacrylate / Acrylamide, Triethylene Glycol Diacrylate / Acrylamide, 1,3-Butanediol Dimethacrylate / Acrylamide, Tripropylene Glycol Diacrylate / Acrylamide, Ethoxylated Bisphenol Diacrylate / Acrylamide, Ethoxylated Bisphenol Dimethacrylate / Acrylamide, Dipropylene Glycol Diacrylate / Acrylamide Acrylates / acrylamide, alkoxylated hexanediol diacrylate / acrylamide, alkoxylated cyclohexanedimethanol diacrylate / acrylamide, propoxylated neopentyl glycol diacrylate / acrylamide, trimethylolpropane triacrylate / acrylamide, pentaerythritol triacrylate / acrylamide, ethoxylated trimethylolpropane triacrylate / acrylamide, propoxylated trimethylolpropane triacrylate / acrylamide, propoxylated glyceryl triacrylate / acrylamide, ditrimethylolpropane tetraacrylate / acrylamide, dipentaerythritol pentaacrylate / acrylamide, ethoxylated pentaerythritol tetraacrylate / acrylamide, PEG 200 dimethacrylate / acrylamide, PEG 400 dimethacrylate / acrylamide, PEG 600 dimethacrylate / acrylamide, 3-acryloyloxy glycol monoacrylate / acrylamide, triacryl formal, triallyl isocyanate, and triallyl isocyanurate.

[0122] The monomers are typically polymerized in the presence of an activator (eg, an initiator) at elevated temperature (eg, 30-90°C) or under ultraviolet light. Exemplary initiators are 2,2′-azobis(isobutyronitrile) (“AIBN”), dihexadecyl peroxydicarbonate, di(4-tert-butylcyclohexyl) peroxydicarbonate, dioctanoyl peroxide, dibenzoyl peroxide, dilauroyl peroxide, didecanoyl peroxide, tert-butyl peracetate, tert-butyl perlaurate, tert-butyl perbenzoate, tert-butyl hydroperoxide, cumene hydroperoxide, ethylcumene peroxide, diisopropyl hydroxydicarboxylate, 2,2′-azobis(2,4-dimethylvaleronitrile), 1,1′-azobis-(cyclohexane-1-carbonitrile), dimethyl 2,2′-azobis(2-methylpropionate), 2,2′-azobis[2-methyl-N-(2-hydroxyethyl)propionamide, sodium persulfate, benzoyl peroxide, and combinations thereof.

[0123] The emulsifiers used to form these capsule walls are typically anionic emulsifiers and include, but are not limited to, alkyl sulfates, alkyl ether sulfates, alkyl isosulfonates, alkyl carboxylates, alkyl sulfosuccinates, alkyl succinates, alkyl sulfates such as sodium lauryl sulfate, alkyl sarcosinates, alkyl derivatives of protein hydrolysates, acyl aspartates, alkyl or alkyl ether or alkyl aryl ether phosphates, sodium lauryl sulfate, phospholipids or lecithin, or soap, sodium, potassium or ammonium stearic acid, oleic acid or palmitic acid, alkylaryl sulfonates such as sodium dodecylbenzenesulfonate, sodium dialkylsulfosuccinate, dioctylsulfosuccinate, sodium dilaurylsulfosuccinate, sodium salt of poly(styrenesulfonic acid), isobutylene-maleic anhydride copolymer, gum arabic, sodium alginate, carboxymethyl cellulose, cellulose sulfate and pectin, Poly(styrene sulfonate), isobutylene-maleic anhydride copolymer, gum arabic, carrageenan, sodium alginate, pectic acid, tragacanth gum, almond gum and agar; semisynthetic polymers such as carboxymethyl cellulose, sulfated cellulose, sulfated methyl cellulose, carboxymethyl starch, phosphorylated starch, lignin sulfonic acid; and synthetic polymers such as maleic anhydride copolymers (including hydrolyzates thereof), polyacrylic acid, polymethacrylic acid, butyl acrylate copolymers or crotonic acid homopolymers and copolymers, vinylbenzenesulfonic acid or 2-acrylamido-2-methylpropanesulfonic acid homopolymers and copolymers, and partial amides or partial esters of such polymers and copolymers, carboxyl-modified polyvinyl alcohol, sulfonic acid-modified polyvinyl alcohol and phosphoric acid-modified polyvinyl alcohol, phosphorylated or sulfated tristyrylphenol ethoxylate. The amount of anionic emulsifier is 0.1% to 40% by weight, more preferably 0.5% to 10%, more preferably 0.5% to 5% by weight, based on the weight of all ingredients.

[0124] Aminoplasts and gelatin. Representative methods for aminoplast encapsulation are disclosed in US Pat. Nos. 3,516,941 and 2007 / 0078071, although it is recognized that many variations in materials and process steps are possible. Another encapsulation method, gelatin encapsulation, is disclosed in US Pat. Nos. 2,800,457. These two methods are discussed in the context of fragrance encapsulation for consumer products in US Pat. Nos. 4,145,184 and 5,112,688, respectively. Polymer systems are well known in the art, and non-limiting examples of these systems include aminoplast capsules and encapsulated particles as disclosed in GB 2006709 A; microcapsules having a wall comprising styrene-maleic anhydride reacted with a melamine-formaldehyde precondensate as disclosed in US 4,396,670; acrylic acid-acrylamide copolymers crosslinked with a melamine-formaldehyde resin as disclosed in US 5,089,339; capsules composed of cationic melamine-formaldehyde condensates as disclosed in US 5,401,577; melamine-formaldehyde microencapsulation as disclosed in US 3,074,845; amide-formaldehyde resin in situ polymerization capsules as disclosed in EP 0158449 A1; etherified urea-formaldehyde polymers as disclosed in US 5,204,185; melamine-formaldehyde microcapsules as described in US 4,525,520; 5,011,634; capsule wall materials formed from a complex of cationic and anionic melamine-formaldehyde precondensates which are then crosslinked as disclosed in US 5,013,473; polymer shells made from addition polymers such as condensation polymers, phenolic, urea-formaldehyde or acrylic polymers as disclosed in US 3,516,941; urea-formaldehyde capsules as disclosed in EP 0 443 428 A2; melamine-formaldehyde chemistry as disclosed in GB 2 062 570 A; and capsules composed of polymers or copolymers of styrene sulfonic acid in the form of an acid salt, and capsules crosslinked with melamine-formaldehyde as disclosed in US 4,001,140.

[0125] Urea-formaldehyde and melamine-formaldehyde capsules. Urea-formaldehyde and melamine-formaldehyde precondensate capsule shell wall precursors are prepared by reacting urea or melamine with formaldehyde, wherein the molar ratio of melamine or urea to formaldehyde is in the range of 10:1 to 1:6, preferably in the range of 1:2 to 1:5. For the practice of the present invention, the molecular weight of the resulting material is in the range of 156 Da to 3000 Da. The resulting material can be used "as is" as a crosslinker for the above-mentioned substituted or unsubstituted acrylic polymers or copolymers, or it can be further reacted with a C1-C6 alkanol (e.g., methanol, ethanol, 2-propanol, 3-propanol, 1-butanol, 1-pentanol, or 1-hexanol) to form a partial ether, wherein the molar ratio of melamine / urea:formaldehyde:alkanol is in the range of 1:(0.1-6):(0.1-6). The resulting product containing ether moieties can be used "as is" as a crosslinking agent for the above-mentioned substituted or unsubstituted acrylic polymers or copolymers, or it can self-condense to form dimers, trimers and / or tetramers, which can also be used as crosslinking agents for the above-mentioned substituted or unsubstituted acrylic polymers or copolymers. Methods for forming such melamine-formaldehyde and urea-formaldehyde precondensates are described in U.S. Patent No. 6,261,483 and Lee et al. (2002) J. Microencapsulation 19, 559-569.

[0126] An example of a urea-formaldehyde precondensate useful in the practice of this invention is URAC TM 180 and URAC TM 186, a trademark of Cytec Technology Corp. (Wilmington, DE). Examples of melamine-formaldehyde precondensates useful in the practice of the present invention include, but are not limited to U-60\ U-64 and U-65 is a trademark of Cytec Technology Corp. (Wilmington, DE). Preferably, a substituted or unsubstituted acrylic acid polymer or copolymer is used as the precondensate for crosslinking. In the practice of the present invention, the molar ratio of urea-formaldehyde precondensate / melamine-formaldehyde precondensate to substituted / unsubstituted acrylic acid polymer / copolymer ranges from 9:1 to 1:9, preferably from 5:1 to 1:5, and most preferably from 2:1 to 1:2.

[0127] In one embodiment of the present invention, microcapsules having polymers composed of primary and / or secondary amine reactive groups or mixtures thereof and crosslinking agents may also be used. See US2006 / 0248665. Amine polymers may have primary and / or secondary amine functional groups and may be of natural or synthetic origin. Amine-containing polymers of natural origin are typically proteins, such as gelatin and albumin, and some polysaccharides. Synthetic amine polymers include polyvinylformamide, polyvinylamine, polyallylamine and other synthetic polymers having primary and secondary amine side groups, which are hydrolyzed to varying degrees. Examples of suitable amine polymers are available from BASF A series of polyvinyl formamides. These materials can have molecular weights ranging from 10,000 Da to 1,000,000 Da.

[0128] The capsules may also include a formaldehyde scavenger capable of binding free formaldehyde. When the capsules are used in aqueous media, formaldehyde scavengers such as sodium sulfite, melamine, glycine, and carbohydrazine are suitable. When the capsules are used in products with a low pH (e.g., fabric conditioners), the formaldehyde scavenger is preferably selected from beta-diketones, such as beta-ketoesters, or from 1,3-diols, such as propylene glycol. Preferred beta-ketoesters include alkyl malonates, alkyl acetoacetates, and polyvinyl acetoacetate.

[0129] The microcapsule composition of the present invention optionally contains one or more additional microcapsules, such as a second, third, fourth, fifth or sixth microcapsule. Each of these microcapsules can be any of the microcapsules described above.

[0130] These additional microcapsules can be any of the microcapsules described above, but differ from one another in microcapsule size, degree of polymerization, degree of crosslinking, encapsulating polymer, wall thickness, active material, ratio between wall material and active material, rupture force or breaking strength, etc.

[0131] Active Materials

[0132] The microcapsule core may contain one or more active materials, including flavoring and / or fragrance ingredients, such as fragrance oils. Individual active materials that can be encapsulated include those listed in WO 2016049456, pages 38-50. These active materials include flavor or fragrance ingredients, taste masking agents, taste sensates, malodor counteractants, vitamins or their derivatives, antimicrobial agents, sunscreen actives, antioxidants, anti-inflammatory agents, antifungals, anesthetics, analgesics, antifungals, antibiotics, antivirals, antiparasitics, anti-infectives, anti-acne agents, dermatological actives, enzymes and coenzymes, skin whitening agents, antihistamines, chemotherapeutic agents, insect repellents, emollients, skin moisturizers, anti-wrinkle agents, UV protectants, fabric softener actives, hard surface cleaning actives, skin or hair conditioners, deflectants, pest repellents, flame retardants, antistatic agents, nano to micron sized inorganic solids, polymeric or elastomeric particles, and combinations thereof.

[0133] High performance, high impact spices are envisioned. A class of high performance spices is described in WO 2018 / 071897. These spices have high intensity accords and contain (i) at least 7 wt% (e.g., 7 to 95 wt%) of Class 1 spices, (ii) 5 to 95 wt% (e.g., 5 to 80 wt%, 10 to 80 wt%, and 10 to 70 wt%) of Class 2 spices, and (iii) 0 to 80 wt% of Class 3 spices, wherein each of the Class 1 spices has an experimental velocity of 8.5 cm / second or greater, each of the Class 2 spices has an experimental velocity of less than 8.5 cm / second and greater than 5 cm / second, and each of the Class 3 spices has an experimental velocity of 5 cm / second or less. In some embodiments, the sum of the Class 1 spices, the Class 2 spices, and the Class 3 spices is 100%. In other embodiments, the sum of the Class 1 and Class 2 ingredients is 20% to 100 wt%. Other high impact fragrances suitable for use in the present invention are those described in WO 1999 / 065458, US 9,222,055, US 2005 / 0003975 and WO 1997 / 034987.

[0134] In addition to the active ingredients listed above, the products of the present invention may also contain dyes, colorants or pigments such as lactoflavin (riboflavin), beta-carotene, riboflavin-5'-phosphate, alpha-carotene, gamma-carotene, cantharellin, erythrosine, curcumin, quinoline yellow, yellow orange S, tartrazine, annatto, norbixin (annatto, orlean), capsanthin, capsanthin, lycopene, beta-apo-8'-carotenal, beta-apo-8'-carotenic acid ethyl ester, xanthophylls (xanthophylls, lutein, cryptoxanthin, rubaxanthin, violaxanthin, rodoxanthin), permanent carmine (carminic acid, cochineal), azoin, cochineal red A (Ponceau TM 4R), beetroot red, betanin, anthocyanin, amaranth, patent blue V, indigo I (indigo carmine), chlorophylls, chlorophyllin copper compounds, acid brilliant green BS (lissamine green), brilliant black BN, vegetable carbon, titanium dioxide, iron oxides and hydroxides, calcium carbonate, aluminum, silver, gold, pigments ruby ​​red BK (litsol ruby ​​BK), methyl violet B, Victoria Blue R, Victoria Blue B, acid brilliant blue FFR (brilliant wool blue FFR), naphthol green B, acid fast green 10G (basic fast green 10G), ceres yellow GRN (ceres yellow GRN), Sudan blue II, ultramarine, phthalocyanine blue, phthalocyanine green, acid fast violet R. Other naturally obtained extracts (e.g., paprika extract, black carrot extract, red cabbage extract) can be used for coloring purposes. Good results can also be obtained with the following named colors (the so-called aluminum lakes): FD&C Yellow No. 5 Lake, FD&C Blue No. 2 Lake, FD&C Blue No. 1 Lake, Tartar Yellow Lake, Quinoline Yellow Lake, FD&C Yellow No. 6 Lake, FD&C Red No. 40 Lake, Sunset Yellow Lake, Red Acid Dye Lake (Carmoisine Lake), Amaranth Lake, Ponceau 4R Lake, Erythrosyne Lake, Red 2G Lake, Allura Red Lake, Patent Blue V Lake, Indigo Carmine Lake, Brilliant Blue Lake, Brown HT Lake, Black PN Lake, Green S Lake, and mixtures thereof.

[0135] When the active material is a fragrance, it is preferred to use fragrance ingredients having a ClogP in the fragrance of 0.5 to 15. For example, ingredients having a ClogP value between 0.5 and 8 (e.g., between 1 and 12, between 1.5 and 8, between 2 and 7, between 1 and 6, between 2 and 6, between 2 and 5, between 3 and 7) are present at 25% or more (e.g., 50% or more and 90% or more) by weight of the fragrance.

[0136] It is preferred to use fragrances having a weight average ClogP of 2.5 or higher (e.g., 3 or higher, 2.5 to 7, 2.5 to 5). The weight average ClogP is calculated as follows:

[0137] ClogP={Sum[(Wi)(ClogP)i]} / {Sum Wi},

[0138] Where Wi is the weight fraction of each fragrance ingredient and (ClogP)i is the ClogP of that fragrance ingredient.

[0139] For example, preferably greater than 60 wt% (preferably greater than 80 wt%, more preferably greater than 90 wt%) of the fragrance chemicals have a ClogP value greater than 2 (preferably greater than 3.3, more preferably greater than 4, even more preferably greater than 4.5).

[0140] Those skilled in the art will appreciate that various solvents and perfume chemicals can be used to form many spices. Use relatively low to medium ClogP perfume ingredients to obtain spices suitable for encapsulation. These spices are normally water-insoluble and are delivered to the consumer's products at different stages, such as moist and dry fabrics, by the capsule system of the present invention. When not encapsulated, free spices evaporate or are dissolved in water during use (such as washing). Although high ClogP materials can be discharged well from conventional (non-encapsulated) spices in consumer's products usually, they have outstanding encapsulation properties and are also suitable for encapsulation to realize the purpose of overall fragrance characteristics, very lasting fragrance transmission or to overcome incompatibility with consumer's products (such as otherwise unstable, causing product thickening or discoloration or otherwise having a negative impact on required consumer's product properties).

[0141] In some embodiments, the amount of encapsulated active material is 5% to 95% (e.g., 10% to 90%, 15% to 90%, and 20% to 80%) by weight of the microcapsule composition. The amount of capsule wall is also 0.5% to 30% (e.g., 1% to 25%, 2 to 20%, and 5 to 15%) by weight of the microcapsule composition. In other embodiments, the amount of encapsulated active material is 15% to 99.5% (e.g., 20% to 98% and 30% to 90%) by weight of the microcapsule, and the amount of capsule wall is 0.5% to 85% (e.g., 2 to 50% and 5 to 40%) by weight of the microcapsule.

[0142] Supplementary Materials

[0143] In addition to the active material, the present invention also contemplates that the auxiliary materials including solvents, emollients and core modifier materials will be incorporated into the core of the capsule wall package. Other auxiliary materials are solubility modifiers, density modifiers, stabilizers, viscosity modifiers, pH regulators or any combination thereof. These modifiers can be present in the wall or core of the capsule, or outside the capsule in the delivery system. Preferably, they are used as core modifiers in the core.

[0144] One or more auxiliary materials may be added in an amount of 0.01% to 40% (eg, 0.5% to 30%) by weight of the microcapsule.

[0145] Suitable examples include those described in WO 2016 / 049456 pp. 55-57 and US 2016 / 0158121 pp. 15-18.

[0146] Deposition aids

[0147] An exemplary deposition aid useful in the microcapsule compositions of the present invention is a copolymer of acrylamide and acrylamidopropyltrimethylammonium chloride. This copolymer facilitates deposition of the microcapsules on hard surfaces such as hair, skin, fabrics, furniture, and floors. The average molecular weight of the copolymer (e.g., weight average molecular weight (Mw) as determined by size exclusion chromatography) is typically from 2,000 Da to 10,000,000 Da, with a lower limit of 2,000 Da, 5,000 Da, 10,000 Da, 20,000 Da, 50,000 Da, 100,000 Da, 250,000 Da, 500,000 Da, or 800,000 Da, and an upper limit of 10,000,000 Da, 5,000,000 Da, 2,000,000 Da, 1,000,000 Da, or 500,000 Da (e.g., from 500,000 Da to 2,000,000 Da and from 800,000 Da to 1,500,000 Da). The charge density of the copolymers ranges from 1 meq / g to 2.5 meq / g, preferably from 1.5 meq / g to 2.2 meq / g. Acrylamide and acrylamide-propyltrimethylammonium chloride copolymers are available from various suppliers such as Ashland as N- SP-100 and Ciba SC60 was purchased commercially.

[0148] Other suitable deposition aids include anionic, cationic, nonionic or zwitterionic water-soluble polymers. Suitable deposition aids include trimethylammonium, methacrylamidopropyltrimethylammonium, acrylamidopropyltrimethylammonium, acrylamide, acrylic acid, dimethylammonium, xylose, galactose, hydroxypropylated glucose, hydroxyethylated glucose, chitosan, hydroxymethylated glucose, vinylamine, ethyleneimine, functionalized branched polyethyleneimine, vinylformamide, vinylpyrrolidone, caprolactone, catechol, vinyl alcohol, polyquaternium-4, polyquaternium Polyquaternium-5, Polyquaternium-6, Polyquaternium-7, Polyquaternium-10, Polyquaternium-11, Polyquaternium-16, Polyquaternium-22, Polyquaternium-24, Polyquaternium-28, Polyquaternium-37, Polyquaternium-39, Polyquaternium-44, Polyquaternium-46, Polyquaternium-47, Polyquaternium-53, Polyquaternium-55, Polyquaternium-67, Polyquaternium-68, Polyquaternium- 69, polyquaternium-73, polyquaternium-74, polyquaternium-77, polyquaternium-78, polyquaternium-79, polyquaternium-79 and hydrolyzed keratin copolymer, polyquaternium-80, polyquaternium-81, polyquaternium-82, polyquaternium-86, polyquaternium-88, polyquaternium-101, polyethyleneamine, polyethyleneimine, copolymer of vinylamine and vinylformamide, copolymer of methacrylamidopropyltrimonium chloride and acrylamide, copolymer of acrylamide and acrylamidopropyltrimonium chloride, 3-acrylamidopropyltrimonium polymer or copolymers thereof, diallyldimethylammonium chloride polymer and copolymers thereof, polysaccharides having sugar units functionalized with hydroxypropyltrimonium, ethyltrimonium chloride methacrylate / hydrolyzed wheat protein copolymer, alkylammonium hydroxypropyl hydrolyzed protein, and combinations thereof. Further examples of deposition aids are described in WO 2016049456, pages 13-27; US 2013 / 0330292; US 2013 / 0337023; and US 2014 / 0017278.

[0149] Additional deposition aids are cationic polymers such as those described in WO2016032993. These cationic polymers are typically characterized by a relatively high charge density (e.g., from 4 meq / g, or from 5 meq / g, or from 5.2 meq / g to 12 meq / g, or to 10 meq / g, or to 8 meq / g, or to 7 meq / g, or to 6.5 meq / g. The cationic polymer comprises structural units that are nonionic, cationic, anionic, or mixtures thereof. In some aspects, the cationic polymer comprises 5 mol% to 60 mol% or 15 mol% to 30 mol% of nonionic structural units derived from monomers selected from the group consisting of (meth)acrylamide, vinylformamide, N,N-dialkylacrylamide, N,N-dialkylmethacrylamide, C1-C12 Alkyl acrylate, C1-C 12 Hydroxyalkyl acrylate, polyalkylene glycol acrylate, C1-C 12 Alkyl methacrylate, C1-C 12 Hydroxyalkyl methacrylates, polyalkylene glycol methacrylates, vinyl acetate, vinyl alcohol, vinyl formamide, vinyl acetamide, vinyl alkyl ethers, vinyl pyridine, vinyl pyrrolidone, vinyl imidazole, vinyl caprolactam, and mixtures thereof.

[0150] In some aspects, the cationic polymer comprises cationic structural units at a level of 30 mol% to 100 mol% or 50 mol% to 100 mol% or 55 mol% to 95 mol% or 70 mol% to 85 mol% by mass of the cationic polymer. Cationic structural units are typically derived from cationic monomers, such as N,N-dialkylaminoalkyl methacrylates, N,N-dialkylaminoalkyl acrylates, N,N-dialkylaminoalkyl acrylamides, N,N-dialkylaminoalkyl methacrylamides, methacrylamidoalkyl trialkylammonium salts, acrylamidoalkyl trialkylammonium salts, vinylamines, vinylimines, vinylimidazoles, quaternized vinylimidazoles, diallyldialkylammonium salts, and mixtures thereof. Preferably, the cationic monomer is selected from diallyldimethylammonium salt (DADMAS), N,N-dimethylaminoethyl acrylate, N,N-dimethylaminoethyl methacrylate (DMAM), [2-(methacryloylamino)ethyl]trimethylammonium salt, N,N-dimethylaminopropylacrylamide (DMAPA), N,N-dimethylaminopropylmethacrylamide (DMAPMA), acrylamidopropyltrimethylammonium salt (APTAS), methacrylamidopropyltrimethylammonium salt (MAPTAS), quaternized vinylimidazole (QVi), and mixtures thereof.

[0151] In some aspects, the cationic polymer comprises anionic structural units at a level of 0.01 mol% to 15 mol%, 0.05 mol% to 10 mol%, or 0.1 mol% to 5 mol%, based on the mass of the cationic polymer. In some aspects, the anionic structural units are derived from anionic monomers selected from the group consisting of acrylic acid, methacrylic acid, maleic acid, vinyl sulfonic acid, styrene sulfonic acid, acrylamidopropylmethanesulfonic acid (AMPS), and salts and mixtures thereof.

[0152] Exemplary cationic polymers are polyacrylamide-co-DADMAS, polyacrylamide-co-DADMAS-co-acrylic acid, polyacrylamide-co-APTAS, polyacrylamide-co-MAPTAS, polyacrylamide-co-QVi, polyvinylformamide-co-DADMAS, poly(DADMAS), polyacrylamide-co-MAPTAS-co-acrylic acid, polyacrylamide-co-APTAS-co-acrylic acid, and mixtures thereof.

[0153] Deposition aids are typically present at a level of from 0.01% to 50% (with a lower limit of 0.01%, 0.05%, 0.1%, 0.5%, 1%, 2% or 5% and an upper limit of 50%, 40%, 30%, 20%, 15% or 10%, for example, from 0.1% to 30%, from 1% to 20%, from 2% to 15% and from 5% to 10%) by weight of the microcapsule composition. In consumer products such as shampoo, deposition aids are typically present at a level of from 0.001% to 20% (with a lower limit of 0.001%, 0.005%, 0.01%, 0.02% or 0.05% and an upper limit of 20%, 15%, 10%, 5%, 2% or 1%, for example, from 0.005% to 10%, from 0.01% to 5% and from 0.02% to 0.5%) by weight of the shampoo composition. The capsule deposition aid may be added during the preparation of the microcapsules, or may be added after the microcapsules have been formed.

[0154] From 0.01% to 25%, more preferably from 5% to 20%, of a second capsule deposition aid may be added to the microcapsule composition.The second capsule-forming deposition aid may be selected from the deposition aids described above.

[0155] Additional components

[0156] The microcapsule compositions of the present invention may comprise from 0.01 to 50%, more preferably from 5 to 40%, of one or more non-enclosed or unencapsulated active materials.

[0157] The capsule delivery system may also contain one or more other delivery systems, such as polymer-assisted delivery compositions (see US 8,187,580), fiber-assisted delivery compositions (US 2010 / 0305021), cyclodextrin host-guest inclusion complexes (US 6,287,603 and US 2002 / 0019369), pro-fragrances (WO 2000 / 072816 and EP 0922084), and any combination thereof. More exemplary delivery systems that may be incorporated are coacervate capsules, cyclodextrin delivery systems, and pro-perfumes.

[0158] Examples of additional components include those described in US 2016 / 0158121.

[0159] Any compound, polymer or reagent discussed above can be the compound, polymer or reagent itself as shown above, or a salt, precursor, hydrate or solvate thereof. Salts can be formed between anions and positively charged groups on compounds, polymers or reagents. Suitable anions include chloride, bromide, iodide, sulfate, nitrate, phosphate, citrate, methanesulfonate, trifluoroacetate, acetate, malate, toluenesulfonate, tartrate, fumarate, glutamate, glucuronide, lactate, glutarate and maleate. Similarly, salts can also be formed between cations and negatively charged groups on compounds, polymers or reagents. Suitable cations include sodium, potassium, magnesium, calcium and ammonium cations (e.g., tetramethylammonium ion). Precursors can be esters and another suitable derivative that can be converted into compounds, polymers or reagents and used to prepare capsule compositions during the preparation of the capsule compositions of the present invention. Hydrates refer to compounds, polymers or reagents containing water. Solvates refer to complexes formed between compounds, polymers or reagents and suitable solvents. Suitable solvents may be water, ethanol, isopropanol, ethyl acetate, acetic acid and ethanolamine.

[0160] Some compounds, polymers and reagents have one or more stereocenters, each of which can be an R configuration, an S configuration or a mixture. In addition, some compounds, polymers and reagents have one or more double bonds, each of which exists in an E (trans) or Z (cis) configuration or a combination thereof. Compounds, polymers and reagents include all possible configurational stereoisomers, regioisomers, diastereomers, enantiomers and epimeric forms, and any mixture thereof. Therefore, lysine used herein includes L-lysine, D-lysine, L-lysine monohydrochloride, D-lysine monohydrochloride, lysine carbonate, etc. Similarly, arginine includes L-arginine, D-arginine, L-arginine monohydrochloride, D-arginine monohydrochloride, arginine carbonate, arginine monohydrate, etc. Guanidine includes guanidine hydrochloride, guanidine carbonate, guanidine thiocyanate and other guanidine salts, including their hydrates. Ornithine includes L-ornithine and salts / hydrates thereof (eg, monohydrochloride) and D-ornithine and salts / hydrates thereof (eg, monohydrochloride).

[0161] The microcapsule composition of the present invention can be a slurry containing 0.1% to 80% (preferably 1% to 65%, more preferably 5% to 45%) capsules by weight of the capsule delivery system in a solvent (e.g., water). Exemplary microcapsule compositions of the present invention contain a plurality of microcapsules, each microcapsule dispersed in an aqueous phase and stable at 40° C. for at least 7 days (e.g., at least 10 days, at least 30 days, and at least 60 days).

[0162] It is known that microcapsule compositions have a tendency to form gels, which are not suitable for use in many consumer products. The viscosity of the gelled-out composition increases to at least 3000 centipoise (cP) (e.g., at least 6000 cP). It can be easily measured on a rheometer such as a RheoStress TM 1 instrument (commercially available from ThermoScientific) using a rotating disk at 21 s -1 The viscosity is measured at a shear rate of 1000 s and a temperature of 25° C. In certain embodiments, the microcapsule composition of the present invention has a viscosity of 1000 s at a shear rate of 1000 s and a temperature of 25° C. -1 The viscosity at a shear rate of 1000 cP and a temperature of 25°C is less than 3000 cP.

[0163] The stability of the microcapsules can be assessed using a variety of different methods, including physical stability and / or storage stability. When assessing physical stability, exemplary microcapsule compositions can be dispersed in aqueous phase and shown to be stable for at least 7 days (e.g., at least 10 days, at least 30 days, and at least 60 days) at 40°C. Stability is measured (e.g., in a graduated cylinder) by separating a clear aqueous phase from the microcapsule composition. If, by the volume of the microcapsule composition, less than 10% of the clear aqueous phase is separated, the microcapsule composition is considered to be stable. When (i) the viscosity of the composition is 3000 cP or less (e.g., 2000 cP or less) and (ii) 20% or less (e.g., 15% or less and 10% or less) of water by volume of the composition is separated from the composition, the microcapsule composition is considered to be stable. The volume of the separated water can be easily measured by conventional methods such as a graduated cylinder.

[0164] When evaluating storage stability, the fragrance retention can be measured directly within the microcapsules after storage in the consumer product base at a desired temperature and time period, such as four weeks, six weeks, two months, three months or longer. A preferred approach is to measure the total headspace of the consumer product at a specified time and compare the result with the headspace of a control consumer product representing 0% fragrance retention, made by directly adding the existing total amount of fragrance. Alternatively, the consumer product can be tested for performance after the storage period and the performance compared with the fresh product by analysis or sensory evaluation. Such measurements often involve measuring the fragrance headspace above the substrate used with the product, or performing an odor evaluation on the same substrate. In certain embodiments, the fragrance retention of the active material in the microcapsule core of the present invention is evaluated in the consumer product base, for example, under storage conditions, such as at a temperature in the range of 25°C to 40°C, or more preferably in the range of 30°C to 37°C, or most preferably at 37°C for an extended period of at least 2 weeks, 4 weeks, 6 weeks, 8 weeks, 16 weeks or 32 weeks. In certain embodiments, the microcapsules of the present invention retain at least 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, or 99% of the active material when added to a consumer product base. In specific embodiments, the microcapsules of the present invention, when added to a consumer product base, retain between 40% and 90% of the active material after storage at 37°C for at least 4 weeks, 8 weeks, or 12 weeks. Alternatively, the microcapsules of the present invention lose less than 50% of the active material due to leakage when added to a consumer product base and stored at 37°C for 8 weeks.

[0165] Using the methods of the present invention, relatively high encapsulation efficiencies are achieved. "Encapsulation efficiency" or "microencapsulation efficiency" or "MEE" represents the proportion of active material cores that are not captured by the extraction solvent under specified test conditions. Using the methods of the present invention, microencapsulation efficiencies of 50% to 99.9%, or more preferably 60% to 99.7%, can be achieved. In particular, encapsulation efficiencies of at least 90%, 92%, 94%, 96%, 98%, or 99% have been achieved.

[0166] In some embodiments, the microcapsule composition is purified by washing the capsule slurry with water until a neutral pH (pH 6 to 8) is reached. For the purposes of the present invention, the capsule suspension can be washed using any conventional method, including the use of a separatory funnel, filter paper, centrifugation, and the like. The capsule suspension can be washed one, two, three, four, five, six, or more times until a neutral pH is reached, such as pH 6-8 and 6.5-7.5. The pH of the purified capsules can be determined using any conventional method, including but not limited to pH paper, a pH indicator, or a pH meter.

[0167] The capsule composition is "purified" if it is 80%, 90%, 95%, 97%, 98%, or 99% homogeneous with the capsule. Purity is achieved according to the present invention by washing the capsules until a neutral pH is reached, which indicates the removal of unwanted impurities and / or starting materials, such as polyisocyanates, crosslinking agents, etc.

[0168] In certain embodiments of the present invention, the purification of the capsules includes an additional step of adding a salt to the capsule suspension prior to the step of washing the capsule suspension with water. Exemplary salts used in this step of the present invention include, but are not limited to, sodium chloride, potassium chloride, or bisulfite. See US 2014 / 0017287.

[0169] The microcapsule compositions of the present invention can also be dried (e.g., spray drying, heat drying, and belt drying) to a solid form. During the spray drying process, a spray drying carrier is added to the microcapsule composition to assist in removing water from the slurry. See US20120151790, US20140377446, US20150267964, US20150284189, and US20160097591.

[0170] According to one embodiment, the spray drying carrier can be selected from carbohydrates such as chemically modified starch and / or hydrolyzed starch, gums such as gum arabic, proteins such as whey protein, cellulose derivatives, clays, synthetic water-soluble polymers and / or copolymers such as polyvinyl pyrrolidone, polyvinyl alcohol. The spray drying carrier can be present in an amount of 1% to 50%, more preferably 5% to 20%, by weight of the microcapsule composition in the slurry.

[0171] Optionally, there may be present from 0.01% to 10%, more preferably from 0.5% to 5%, by weight of the microcapsule composition in the slurry, of a silica free-flow agent (anti-caking agent), which may be hydrophobic (i.e., a silanol surface treated with a halogen silane, alkoxysilane, silazane, siloxane, etc., e.g. D17, R972 and R974 (available from Degussa), etc.) and / or hydrophilic, e.g. 200, 22S, 50S, (available from Degussa); 244 (available from Grace Davison).

[0172] Humectants and viscosity control / suspending agents may also be added to facilitate spray drying. These agents are disclosed in U.S. Patent Nos. 4,446,032 and 6,930,078. Detailed information on hydrophobic silica as a functional delivery vehicle for active materials rather than a free-flowing / anti-caking agent is disclosed in U.S. Patent Nos. 5,500,223 and 6,608,017.

[0173] The spray drying inlet temperature is in the range of 150°C to 240°C, preferably between 170°C to 230°C, more preferably between 190°C to 220°C.

[0174] As described herein, the spray-dried microcapsule compositions are well suited for use in a variety of completely dry (water-free) products: powdered laundry detergents, fabric softener dry tablets, household cleaning dry wipes, powdered dishwashing detergents, floor cleaning cloths, or any dry form of personal care products (e.g., shampoo powder, deodorant powder, foot powder, soap powder, baby powder), etc. Due to the high fragrance and / or active agent concentration in the spray-dried products of the present invention, small doses of the spray-dried products do not adversely affect the properties of the aforementioned dry consumer products.

[0175] The microcapsule composition can also be sprayed as a slurry onto consumer products such as fabric care products. For example, the liquid capsule slurry is sprayed onto detergent powder during mixing to form granules. See US2011 / 0190191. To increase the perfume loading, a water-absorbing material (e.g., zeolite) can be added to the delivery system.

[0176] Alternatively, the granules in the consumer product are prepared in a mechanical granulator in the presence of a granulation aid such as a non-acidic water-soluble organic crystalline solid. See WO 2005 / 097962.

[0177] Zeta potential and rupture force

[0178] The microcapsules of the present invention can be positively or negatively charged, with a zeta potential in the range of -200 mV to +200 mV, such as at least 10 mV, at least 25 mV, at least 40 mV, 25 mV to 200 mV, and 40 mV to 100 mV.

[0179] The zeta potential is a measure of the zeta potential in a microcapsule. From a theoretical point of view, the zeta potential is the potential difference between the aqueous phase (i.e., the dispersion medium) and the stable layer of water attached to the surface of the microcapsule.

[0180] Zeta potential is an important indicator of the stability of microcapsules in compositions or consumer products. Typically, microcapsules with a zeta potential of 10 to 25 mV exhibit moderate stability. Similarly, microcapsules with a zeta potential of 25 to 40 mV exhibit good stability, while microcapsules with a zeta potential of 40 to 100 mV exhibit excellent stability. Without being bound by any theory, the microcapsules of the present invention have an ideal zeta potential, making them suitable for consumer products with improved stability.

[0181] Zeta potential can be calculated using theoretical models and experimentally determined electrophoretic mobility or dynamic electrophoretic mobility. Zeta potential is typically measured by methods such as microelectrophoresis or electrophoretic light scattering or electroacoustic phenomena. For a more detailed discussion of zeta potential measurements, see Dukhin and Goetz, "Ultrasound for characterizing colloids," Elsevier, 2002.

[0182] The microcapsules of the present invention have a breaking strength of 0.2 MPa to 80 MPa (e.g., 0.5 MPa to 60 MPa, 1 MPa to 50 MPa, and 5 MPa to 30 MPa). The breaking strength of each microcapsule is calculated by dividing the breaking force (in Newtons) by the cross-sectional area (πr 2 , where r is the radius of the particle before compression). The rupture force and cross-sectional area were measured according to the method described in Zhang et al., J. Microencapsulation 18(5), 593-602 (2001).

[0183] The rupture force of the microcapsules of the present invention is less than 10 millinewtons ("mN"), for example, 0.1 mN to 10 mN, 0.2 mN to 8 mN, 0.3 mN to 5 mN, 0.1 mN to 2 mN, 0.1 mN, 0.5 mN, 1 mN, 2 mN, 5 mN, and 8 mN. The rupture force is the force required to rupture the microcapsule. Its measurement is based on a technique known in the art as micromanipulation. See Zhang et al., Journal of Microencapsulation 16(1), 117-124 (1999).

[0184] application

[0185] The microcapsule composition of the present invention can be directly added to a consumer product base or printed onto a product base or a movable product conveyor (e.g., a non-stick tape) for drying. See International Application Publication WO2019212896A1. In a typical printing system, the microcapsule composition is printed onto a movable product conveyor, which directly receives the printed microcapsules, which are then dried on the movable product conveyor to produce a dried product. Additional carriers and solvents may be added to the microcapsule composition before printing. In some embodiments, the viscosity of the microcapsule composition is adjusted to greater than 500 cP or greater than 1000 cP with a viscosity modifier. With regard to the printing assembly, the printing assembly may include a print head or a nozzle array, and is optionally suitable for printing microcapsules in a dot pattern (e.g., arranged to promote drying, post-processing, and product quality). Optional features of the system include a dehumidifier configured to supply dry air to the drying component; a supplemental energy source (e.g., a radiant heat source) for promoting drying of the printed microcapsules; and / or a product discharge component for removing the dried product from the movable product conveyor.

[0186] The microcapsules of the present invention are well suited for use in, but not limited to, the following additional products:

[0187] a) Household products

[0188] i. Liquid or powder laundry detergents that can use the present invention include those systems described in U.S. Patent Nos. 5,929,022, 5,916,862, 5,731,278, 5,565,145, 5,470,507, 5,466,802, 5,460,752, 5,458,810, 5,458,809, 5,288,431, 5,194,639, 4,968,451, 4,597,898, 4,561,998, 4,550,862, 4,537,707, 4,537,706, 4,515,705, 4,446,042, and 4,318,818

[0189] ii. Unit dose capsules, tablets and capsules, such as those described in EP 1431382A1, US 2013 / 0219996 A1, US 2013 / 0284637 A1 and US 6,492,315. These unit dose formulations may contain high concentrations of functional materials (e.g., 5-100% fabric softener or detergent active materials), fragrances (e.g., 0.5-100%, 0.5-40% and 0.5-15%) and flavors (e.g., 0.1-100%, 0.1-40% and 1-20%). They may be free of water to limit the water content to less than 30% (e.g., less than 20%, less than 10% and less than 5%).

[0190] iii. Odor enhancers, such as those described in US 7,867,968, US 7,871,976, US 8,333,289, US 2007 / 0269651 A1, and US 2014 / 0107010 A1.

[0191] iv. Fabric care products, such as rinse conditioners (containing 1-30% by weight of fabric conditioning active materials), fabric liquid conditioners (containing 1 to 30% by weight of fabric conditioning active materials), tumble dryer sheets, fabric refreshers, fabric refresher sprays, ironing water, and fabric softener systems, such as those described in U.S. Pat. Nos. 6,335,315;

[0192] Liquid fabric softeners / fresheners contain at least one fabric softener, preferably present in a concentration of 1-30% (e.g., 4-20%, 4-10%, and 8-15%). The ratio between active material and fabric softener can be 1:500 to 1:2 (e.g., 1:250 to 1:4 and 1:100 to 1:8). For example, when the fabric softener is 5% by weight of the fabric softener, the active material is 0.01-2.5%, preferably 0.02-1.25%, and more preferably 0.1-0.63%. As another example, when the fabric softener is 20% by weight of the fabric softener, the active material is 0.04-10%, preferably 0.08-5%, and more preferably 0.4-2.5%. The active material is a fragrance, a malodor counteractant, or a mixture thereof. The liquid fabric softener may have 0.15-15% of capsules (e.g., 0.5-10%, 0.7-5%, and 1-3%). When these levels of capsules are included, the net oil equivalent (NOE) in the softener is 0.05-5% (eg, 0.15-3.2%, 0.25-2%, and 0.3-1%).

[0193] Suitable fabric softening agents include cationic surfactants. Non-limiting examples are quaternary ammonium compounds, such as alkylated quaternary ammonium compounds, ring or cyclic quaternary ammonium compounds, aromatic quaternary ammonium compounds, diquaternary ammonium compounds, alkoxylated quaternary ammonium compounds, amidoamine quaternary ammonium compounds, ester quaternary ammonium compounds, and mixtures thereof. Fabric softening compositions and components thereof are generally described in US2004 / 0204337 and US2003 / 0060390. Suitable softening agents include ester quaternary ammonium salts such as Rewoquat WE 18 commercially available from Evonik Industries and Stepantex SP-90 commercially available from Stepan Company.

[0194] v. Liquid dishwashing detergents, such as those described in U.S. Patent Nos. 6,069,122 and 5,990,065

[0195] vi. Dishwasher detergents such as those described in U.S. Pat. Nos. 6,020,294, 6,017,871, 5,968,881, 5,962,386, 5,939,373, 5,914,307, 5,902,781, 5,705,464, 5,703,034, 5,703,030, 5,679,630, 5,597,936, 5,581,005, 5,559,261, 4,515,705, 5,169,552, and 4,714,562.

[0196] vii. All-purpose cleaners, including dilutable bucket cleaners and toilet bowl cleaners

[0197] viii.Bathroom cleaner

[0198] ix. Toilet paper

[0199] x. Carpet deodorizer

[0200] xi. Candle

[0201] xii.Room deodorizer

[0202] xiii. Floor cleaner

[0203] xiv. Disinfectants

[0204] xv.Window cleaner

[0205] xvi.Garbage bags / trash can liners

[0206] xvii. Air fresheners including room and car deodorizers, scented candles, sprays, scented oil air fresheners, automatic spray air fresheners, and neutralizing gel beads

[0207] xviii. Hygroscopic agent

[0208] xix. Household equipment, such as paper towels and disposable wipes

[0209] xx. Mothballs / rings / cakes

[0210] xxi. The liquid fragrance compositions each comprise: (i) 3 to 40 wt% (e.g., 5 to 35 wt%, preferably 8 to 30 wt%, and more preferably 10 to 3 wt%) of fragrance in the form of a neat oil or encapsulated in microcapsules, (ii) 0.5 to 5 wt% (preferably 0.2 to 3 wt%, more preferably 0.5 to 2.5 wt%) of ricinoleyl glyceride, and (iii) 60 to 95 wt% of water. All amounts are based on the weight of the liquid fragrance composition.

[0211] b) Baby care products

[0212] i. Diaper rash cream / balm

[0213] ii. Baby powder

[0214] c) Baby care equipment

[0215] i. Diapers

[0216] ii. Bib

[0217] iii. Wet wipes

[0218] d) Oral care products. Tooth care products (as an example of a preparation according to the invention for oral care) generally include an abrasive system (abrasive or polishing agent), such as silicic acid, calcium carbonate, calcium phosphate, aluminum oxide and / or hydroxyapatite; surface-active substances, such as sodium lauryl sulfate, sodium lauryl sarcosinate and / or cocamidopropyl betaine; humectants, such as glycerol and / or sorbitol; thickeners, such as carboxymethylcellulose, polyethylene glycol, carrageenan and / or Sweeteners, such as saccharin; flavorings for an unpleasant taste; flavorings for a further generally unpleasant taste; taste-modifying substances (e.g. inositol phosphates, nucleotides such as guanosine monophosphate, adenosine monophosphate or other substances such as sodium glutamate or 2-phenoxypropionic acid); cooling active ingredients, such as menthol derivatives (e.g. L-menthyl lactate, L-menthyl alkyl carbonate, menthone ketal, menthanecarboxylic acid amide), 2,2,2-trialkylacetic acid amides (e.g. 2,2-diisopropylpropionic acid methylamide); icilin and icilin derivatives; stabilizers and active ingredients, such as sodium fluoride, sodium monofluorophosphate, tin difluoride, quaternary ammonium fluorides, zinc citrate, zinc sulfate, tin pyrophosphate, tin dichloride, mixtures of various pyrophosphates, triclosan, cetylpyridinium chloride, aluminum lactate, potassium citrate, potassium nitrate, potassium chloride, strontium chloride, hydrogen peroxide, flavorings and / or sodium bicarbonate or flavorings.

[0219] i. Toothpaste. An exemplary formula is as follows:

[0220] 1. Calcium phosphate 40-55%

[0221] 2. Carboxymethyl cellulose 0.8-1.2%

[0222] 3. Sodium lauryl sulfate 1.5-2.5%

[0223] 4. Glycerol 20-30%

[0224] 5. Saccharin 0.1-0.3%

[0225] 6. Flavor oil 1-2.5%

[0226] 7. Add water to 100%

[0227] A typical procedure for preparing the formulation comprises the following steps: (i) mixing by a mixer according to the aforementioned recipe to provide a toothpaste, and (ii) adding the composition of the present invention and mixing the resulting mixture until homogeneous.

[0228] ii. Tooth powder

[0229] iii. Mouthwash

[0230] iv. Teeth whitening agents

[0231] v. Denture adhesive

[0232] e) Medical care equipment

[0233] i. Dental floss

[0234] ii. Toothbrush

[0235] iii. Respirator

[0236] iv. Scented / flavored condoms

[0237] f) Feminine hygiene products, such as tampons, sanitary napkins and wipes, and panty liners

[0238] g) Personal care products: cosmetic or pharmaceutical preparations, for example "water-in-oil" (W / O) emulsions, "oil-in-water" (O / W) emulsions or multiple emulsions, for example water-in-oil-in-water (W / O / W) emulsions, such as PIT emulsions, Pickering emulsions, microemulsions or nanoemulsions; and particularly preferred emulsions are "oil-in-water" (O / W) or water-in-oil-in-water (W / O / W) emulsions. More specifically,

[0239] i. Personal cleansers (bar soap, body wash, and shower gel)

[0240] ii.Shower Conditioner

[0241] iii. Sunscreen Ant Tattoo Color Protection (Spray, Lotion and Stick)

[0242] iv. Insect repellent

[0243] v.Disinfectant hand sanitizer

[0244] vi. Anti-inflammatory balms, ointments and sprays

[0245] vii. Antibacterial ointments and creams

[0246] viii. Sensible things

[0247] ix. Deodorants and antiperspirants including aerosol and pump spray antiperspirants, stick antiperspirants, roll-on antiperspirants, emulsion spray antiperspirants, clear emulsion stick antiperspirants, soft solid antiperspirants, emulsion roll-on antiperspirants, clear emulsion stick antiperspirants, opaque emulsion stick antiperspirants, clear gel antiperspirants, clear stick deodorants, gel deodorants, spray deodorants, roll-on deodorants, and ointment deodorants

[0248] x. Wax-based deodorant. An exemplary formula is as follows:

[0249] 1. Paraffin wax 10-20%

[0250] 2. Hydrocarbon wax 5-10%

[0251] 3. White petrolatum 10-15%

[0252] 4. Acetylated lanolin alcohol 2-4%

[0253] 5. Diisopropyl adipate 4-8%

[0254] 6. Mineral oil 40-60%

[0255] 7. Preservatives (as needed)

[0256] The formulation is prepared by (i) mixing the above ingredients, (ii) heating the resulting composition to 75°C until melted, (iii) adding 4% cryogenically ground polymer containing fragrance under stirring while maintaining the temperature at 75°C, and (iv) stirring the resulting mixture while adding the composition of the present invention to the formulation to ensure a uniform suspension.

[0257] xi. Glycol / soap type deodorant. An exemplary formula is as follows:

[0258] 1. Propylene glycol 60-70%

[0259] 2. Sodium stearate 5-10%

[0260] 3. Distilled water 20-30%

[0261] 4. 2,4,4-Trichloro-2'-hydroxydiphenyl ether (produced by Ciba-Geigy Chemical Company and a trademark of Ciba-Geigy Chemical Company) 0.01-0.5%

[0262] The ingredients were mixed and heated to 75°C with stirring until the sodium stearate dissolved. The resulting mixture was cooled to 40°C before adding the composition of the present invention.

[0263] xii. Lotions include body lotion, facial lotion, and hand lotion

[0264] xiii. Body powder and foot powder

[0265] xiv. Cosmetics

[0266] xv.Body spray

[0267] xvi. Shaving cream and male grooming products

[0268] xvii. Bath soaker

[0269] xviii. Exfoliating scrubs h) Personal care equipment

[0270] i.Facial tissue

[0271] ii. Cleansing wipes

[0272] i) Hair care products

[0273] i. Shampoo (liquid and dry powder)

[0274] ii. Conditioners (rinse-out conditioners, leave-in conditioners, and cleansing conditioners)

[0275] iii. Conditioner

[0276] iv. Hair water

[0277] v. Hair perfume

[0278] vi. Hair straightening products

[0279] vii. Hair styling products, hair styling and styling aids

[0280] viii. Comb Cream

[0281] ix. Hair wax

[0282] x. Foam, hair spray, non-aerosol pump spray

[0283] xi. Hair bleaches, dyes and colorants

[0284] xii.Perm

[0285] xiii. Hair wipes

[0286] j)Beauty treatments

[0287] i. Perfume-Alcohol. US 4,428,869 describes compositions and methods for incorporating fragrance capsules into alcohol perfumes. Alcohol perfumes may contain the following ingredients:

[0288] 1. Ethanol (1-99%)

[0289] 2. Water (0-99%)

[0290] 3. Suspending agents, including but not limited to: hydroxypropyl cellulose, ethyl cellulose, silicon dioxide, microcrystalline cellulose, carrageenan, propylene glycol alginate, methyl cellulose, sodium carboxymethyl cellulose or xanthan gum (0.1%)

[0291] 4. Optionally, an emulsifier or moisturizer may be included, including but not limited to those listed above.

[0292] ii. Solid flavor

[0293] iii. Lipstick / Lip Balm

[0294] iv. Makeup remover

[0295] v. Skin care cosmetics, such as foundation, facial mask, sunscreen, skin lotion, lotion, skin cream, moisturizer, skin whitening agent

[0296] vi. Makeup products, including nail polish, mascara, eyeliner, eye shadow, liquid foundation, powder foundation, lipstick, and blush

[0297] k) Consumer goods packaging, such as scented cartons, scented plastic bottles / boxes

[0298] l)Pet care products

[0299] i.Cat litter

[0300] ii. Flea and tick treatment products

[0301] iii.Pet grooming products

[0302] iv.Pet shampoo

[0303] v.Pet toys, treats and chews

[0304] vi.Pet training mat

[0305] vii. Pet cages and crates

[0306] m) confectionery, preferably selected from chocolate, chocolate bar products, other bar products, fruit gummies, hard and soft caramels and chewing gum

[0307] i. Glue

[0308] 1. Gum base (natural latex gum, most chewing gum bases currently also include elastomers such as polyvinyl acetate (PVA), polyethylene, (low or medium molecular weight) polyisobutylene (PIB), polybutadiene, isobutylene-isoprene copolymer (butyl rubber), polyvinyl ethyl ether (PVE), polyvinyl butyl ether, copolymers of vinyl esters and vinyl ethers, styrene-butadiene copolymers (styrene-butadiene rubber, SBR) or vinyl elastomers, such as those based on vinyl acetate / vinyl laurate, vinyl acetate / vinyl stearate or ethylene / vinyl acetate, and mixtures of the above elastomers, such as those described in EP 0 242 325, U.S. Pat. No. 4,518,615, U.S. Pat. No. 5,093,136, U.S. Pat. No. 5,266,336, U.S. Pat. No. 5,601,858 or U.S. Pat. No. 6,986,709) 20-25%

[0309] 2. Powdered sugar 45-50%

[0310] 3. Glucose 15-17%

[0311] 4. Starch syrup 10-13%

[0312] 5. Plasticizer 0.1%

[0313] 6. Flavoring 0.8-1.2%

[0314] The above components are kneaded by a kneader according to the above formulation to provide a chewing gum. The encapsulated flavoring or sensate is then added and mixed until uniform.

[0315] ii. Breath freshener

[0316] iii. Orally dissolving strips

[0317] iv. Chewing candy

[0318] v.Hard candy

[0319] n) baked products, preferably selected from bread, dry biscuits, cakes and other biscuits;

[0320] o) snack foods, preferably selected from baked or fried potato chips or potato dough products, bread dough products and corn or peanut based extrudates;

[0321] i. Potato, tortilla, vegetable or multigrain chips

[0322] ii. Popcorn

[0323] iii. Pretzels

[0324] iv. Extrusion stack

[0325] p) Cereal products are preferably selected from breakfast cereals, muesli bars and pre-cooked rice products

[0326] q) alcoholic and non-alcoholic beverages, preferably selected from coffee, tea, wine, wine-containing beverages, beer, beer-containing beverages, liqueurs, gin, brandy, fruit-containing sodas, isotonic beverages, soft drinks, nectars, fruit and vegetable juices and fruit or vegetable products; instant beverages, preferably selected from instant cocoa drinks, instant tea drinks and instant coffee drinks

[0327] i. Ready-to-drink liquid beverages

[0328] ii. Liquid beverage concentrates

[0329] iii. Powdered drinks

[0330] iv.Coffee: Instant Cappuccino

[0331] 1. Sugar 30-40%

[0332] 2. Milk powder 24-35%

[0333] 3. Soluble coffee 20-25%

[0334] 4. Lactose 1-15%

[0335] 5. Food grade emulsifier 1-3%

[0336] 6. Encapsulated volatile flavors 0.01-0.5%

[0337] v.Tea

[0338] vi. Alcohol

[0339] r) Spice mixtures and consumable prepared foods

[0340] i. Powdered gravy, sauce mixture

[0341] ii. Seasoning

[0342] iii. Fermented products

[0343] s) Ready-to-heat foods: ready-to-eat foods and soups, preferably selected from soup powder, instant soup, pre-cooked soup

[0344] i. Soup

[0345] ii. Sauce

[0346] iii. Stew

[0347] iv. Frozen entrees

[0348] t) Dairy products, preferably selected from milk drinks, ice milk, yogurt, goat cheese, cream cheese, soft cheese, hard cheese, milk powder, whey, butter, buttermilk and partially or completely hydrolyzed milk protein-containing products flavored milk drinks

[0349] i. Yogurt

[0350] ii. Ice cream

[0351] iii. Tofu

[0352] iv. Cheese

[0353] u) soy protein or other soy parts, preferably selected from soy milk and products produced therefrom, products containing soy lecithin, fermented foods such as tofu or tempeh or products produced therefrom, and soy sauce;

[0354] v) Meat products, preferably selected from ham, fresh or raw sausage products, and seasoned or cured fresh or salted meat products

[0355] w) eggs or egg products, preferably selected from dried eggs, egg whites and egg yolks

[0356] x) Oil-based products or emulsions thereof, preferably selected from mayonnaise, mayonnaise, dressings and condiments

[0357] y) Fruit products, preferably selected from jams, sorbets, fruit spreads and fruit fillings; Vegetable products, preferably selected from ketchup, sauces, dried vegetables, deep-frozen vegetables, pre-cooked vegetables, pickled vegetables and pickled vegetables

[0358] z) Flavored pet food.

[0359] The applications listed above are all well known in the art. For example, fabric softener systems are described in U.S. Patent Nos. 6,335,315, 5,674,832, 5,759,990, 5,877,145, 5,574,179; 5,562,849, 5,545,350, 5,545,340, 5,411,671, 5,403,499, 5,288,417 and 4,767,547, 4,424,134. Liquid laundry detergents include those systems described in U.S. Patent Nos. 5,929,022, 5,916,862, 5,731,278, 5,565,145, 5,470,507, 5,466,802, 5,460,752, 5,458,810, 5,458,809, 5,288,431, 5,194,639, 4,968,451, 4,597,898, 4,561,998, 4,550,862, 4,537,707, 4,537,706, 4,515,705, 4,446,042, and 4,318,818. Liquid dishwashing detergents are described in U.S. Patent Nos. 6,069,122 and 5,990,065. Shampoos and conditioners to which the present invention can be applied include those described in U.S. Patent Nos. 6,162,423, 5,968,286, 5,935,561, 5,932,203, 5,837,661, 5,776,443, 5,756,436, 5,661,118, 5,618,523, 5,275,755, 5,085,857, 4,673,568, 4,387,090, and 4,705,681. Dishwasher detergents are described in U.S. Patent Nos. 6,020,294, 6,017,871, 5,968,881, 5,962,386, 5,939,373, 5,914,307, 5,902,781, 5,705,464, 5,703,034, 5,703,030, 5,679,630, 5,597,936, 5,581,005, 5,559,261, 4,515,705, 5,169,552, and 4,714,562.

[0360] Consumer product bases

[0361] The microcapsules of the present invention are suitable for incorporation into consumer product bases in slurry or dry form. As used herein, "consumer product base" refers to a composition used as a consumer product to achieve a specific effect, such as cleaning, softening, and conditioning. The components of the consumer product base can include any suitable additives that produce the desired effect under the expected use conditions of the consumer product. For example, the consumer product base ingredients can be selected from personal cleansers and / or conditioners, such as hair care agents, including shampoos and / or hair dyes, hair conditioners, skin care agents, sunscreens, and skin conditioners; laundry care and / or conditioning agents, such as fabric care agents, fabric conditioners, fabric softeners, fabric wrinkle removers, fabric care antistatic agents, fabric care soil removers, soil removers, dispersants, foam suppressors, foam boosters, defoamers, fabric refreshers; liquid and / or powder dishwashing agents (for hand dishwashing and / or automatic dishwasher applications), hard surface care and / or conditioners and / or polishes; other cleaning and / or conditioning agents, such as antimicrobial agents, fragrances, bleaches (e.g., oxygen bleaches, hydrogen peroxide, percarbonate bleaches, perborate bleaches, chlorine bleaches) , bleach activators, chelating agents, builders, detergents, whitening agents, air care agents, carpet care agents, dye transfer inhibitors, water softeners, water hardeners, pH adjusters, enzymes, flocculants, effervescent agents, preservatives, cosmetic agents, makeup removers, foaming agents, deposition aids, coacervate formers, clays, thickeners, latex, silica, desiccants, odor control agents, antiperspirants, cooling agents, warming agents, absorbent gelling agents, anti-inflammatory agents, dyes, pigments, acids and bases; liquid treatment actives; agricultural actives; industrial actives; ingestible actives, such as pharmaceuticals, tooth whitening agents, tooth care agents, mouthwashes, periodontal and gum care agents, edibles, dietary agents, vitamins, minerals; water treatment agents, such as water clarifiers and / or water disinfectants, and mixtures thereof. Non-limiting examples of suitable cosmetics, skin care agents, skin conditioning agents, hair care agents, and hair conditioning agents are described in the CTFA Cosmetic Ingredient Handbook, Second Edition, The Cosmetic, Toiletries, and Fragrance Association, Inc. 1988, 1992.

[0362] One or more classes of compounds can be used for one or more reagents listed above. For example, surfactants can be used for many of the above-mentioned reagents. Similarly, bleaching agents can be used for fabric care, hard surface cleaning, dishwashing and even tooth whitening. Therefore, it will be understood by those skilled in the art that these reagents will be selected based on the required intended use of the consumer's goods. For example, if the consumer's goods are used for hair care and / or conditioning, one or more suitable surfactants, such as foaming surfactants, can be selected to provide the consumer with required benefit. Similarly, if the consumer's goods are used for washing clothes in a laundry operation, one or more suitable surfactants and / or enzymes and / or builders and / or essences and / or foam suppressants and / or bleaching agents can be selected to provide the consumer with required benefit.

[0363] In one embodiment, the agent is a non-perfume ingredient. In another embodiment, the agent is a non-surfactant ingredient. In yet another embodiment, the agent is a non-ingestible ingredient, that is, an agent other than an ingestible ingredient.

[0364] In certain embodiments, the consumer product base comprises one or more bleach-activators, surfactants, builders, chelating agents, dye transfer inhibitors, dispersants, enzymes and enzyme stabilizers, catalytic metal complexes, polymeric dispersants, sedimentation agents, clay and soil removers / anti-redeposition agents, brighteners, suds suppressors, dyes, other essences and essence delivery systems (perfume delivery systems), structural elastic agents, fabric softeners, carriers, hydrotropes, processing aids, structurants, anti-caking agents, coatings, formaldehyde scavengers and / or pigments, and combinations thereof. The exact nature of these compositions and the level of incorporation thereof will depend on the physical form of the composition and the nature of the operation using it. However, when there are one or more compositions, such one or more compositions may be present as described in detail below.

[0365] Surfactants. Surfactants can be anionic, nonionic, zwitterionic, amphoteric or cationic, or can include compatible mixtures of these types. If the product is a laundry detergent, anionic and nonionic surfactants are typically used. Conversely, if the product is a fabric softener, cationic surfactants are typically used. In addition to anionic surfactants, the product may also contain nonionic surfactants. The product may contain up to 0.01% to 30%, or 0.01% to 20%, or more or 0.1% to 10% of nonionic surfactants by weight of the product. In some examples, the nonionic surfactant may include an ethoxylated nonionic surfactant. Suitable for use herein is a surfactant of the formula R(OC2H4) nOH ethoxylated alcohols and ethoxylated alkylphenols wherein R is selected from aliphatic hydrocarbon groups containing 8 to 20 carbon atoms and alkylphenyl groups wherein the alkyl group contains 8 to 12 carbon atoms, and wherein the average value of n is 5 to 15.

[0366] Suitable nonionic surfactants are of formula R 1 (OC2H4) n Those of OH, where R 1 C 10 -C 16 Alkyl or C8-C 12 Alkylphenyl, n is 3 to 80. In one aspect, particularly useful materials are C9-C 15 The condensation products of alcohols with 5 to 20 moles of ethylene oxide per mole of alcohol.

[0367] The fabric and home care compositions may contain up to 30%, alternatively from 0.01% to 20%, more alternatively from 0.1% to 20%, of a cationic surfactant by weight of the product. Cationic surfactants include those that can provide fabric care benefits, non-limiting examples of which include: fatty amines; quaternary ammonium surfactants; and imidazoline quaternary ammonium salt materials.

[0368] Builder. The product may also contain 0.1% to 80% builder by weight of the product. Liquid compositions typically contain 1% to 10% builder components by weight of the product. Granular compositions typically contain 1% to 50% builder components by weight of the product. Detergent builders are well known in the art and may contain, for example, phosphates and various organic and inorganic non-phosphate builders. Water-soluble, non-phosphate organic builders that can be used in the present invention include alkali metal salts, ammonium salts, and substituted ammonium salts of various polyacetic acids, carboxylic acids, polycarboxylic acids, and polyhydroxysulfonic acids. Examples of polyacetate and polycarboxylate builders are sodium, potassium, lithium, ammonium, and substituted ammonium salts of ethylenediaminetetraacetic acid, nitrilotriacetic acid, oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids, and citric acid. Other polycarboxylate builders are oxydisuccinates and ether carboxylate builder compositions consisting of a combination of tartrate monosuccinate and tartrate disuccinate. Builders for liquid detergents include citric acid. Suitable phosphate-free, inorganic builders include silicates, aluminosilicates, borates and carbonates (e.g., sodium carbonate and potassium carbonate), bicarbonates, sesquicarbonates, tetraborate decahydrate, and silicates in which the weight ratio of SiO2 to alkali metal oxide is from 0.5 to 4 or from 1 to 2.4. Aluminosilicates, including zeolites, are also useful.

[0369] Dispersants. The product may contain from 0.1% to 10% of a dispersant by weight of the product. Suitable water-soluble organic materials are homo- or co-polymeric acids or their salts, in which the polycarboxylic acid may contain at least two carboxyl groups separated from each other by not more than two carbon atoms. Dispersants may also be alkoxylated and / or quaternized derivatives of polyamines.

[0370] Enzymes. The composition can contain one or more detergent enzymes that provide cleaning performance and / or fabric care benefits. Examples of suitable enzymes include hemicellulases, peroxidases, proteases, cellulases, xylanases, lipases, phospholipases, esterases, cutinases, pectinases, keratinase, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, beta-glucanases, arabinosidases, hyaluronidase, chondroitinase, laccases, and amylases, or mixtures thereof. Typical combinations can be mixtures of conventionally used enzymes such as proteases, lipases, cutinases, and / or cellulases with amylases. The enzyme can be used at levels taught in its field, for example, at levels recommended by suppliers such as Novozymes and Genencor. Typical levels in the product are 0.0001% to 5% by weight of the product. When enzymes are present, they can be used at very low levels, e.g., 0.001% or less, or they can be used at higher levels (e.g., 0.1% or more) in heavy-duty laundry detergent formulations. Products can be enzyme-containing or enzyme-free, or both, in accordance with some consumers' preference for "non-biological" detergents.

[0371] Dye transfer inhibitors. The product may also include from 0.0001%, 0.01%, 0.05% by weight of the product to 10%, 2% or even 1% by weight of the product of one or more dye transfer inhibitors such as polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinyloxazolidones and polyvinylimidazoles, or mixtures thereof.

[0372] Chelating agents. The product may contain less than 5% or 0.01% to 3% by weight of the product of chelating agents such as citrates; nitrogen-containing, P-free aminocarboxylates such as EDDS, EDTA, and DTPA; aminophosphonates such as diethylenetriaminepentamethylenephosphonic acid and ethylenediaminetetramethylenephosphonic acid; nitrogen-free phosphonates such as HEDP; and nitrogen- or oxygen-containing, P-free carboxylate chelating agents such as certain compounds of the general class of macrocyclic N-ligands, such as those known for use in bleach catalyst systems.

[0373] Whitening agent. The product may also include a whitening agent (also called an "optical brightener"), and may include any compound that exhibits fluorescence, including compounds that absorb ultraviolet light and re-emit it as "blue" visible light. Non-limiting examples of useful whitening agents include derivatives of stilbene or 4,4'-diaminostilbene, biphenyl, five-membered heterocycles such as triazole, pyrazoline, oxazole, imidazole, etc., or six-membered heterocycles (coumarins, naphthalamide, s-triazine, etc.). Cationic, anionic, nonionic, amphoteric and zwitterionic whitening agents may be used. Suitable whitening agents include those sold by Ciba Specialty Chemicals Corporation (High Point, NC) under the trademark Tinopal-UNPA- Those that are sold.

[0374] Bleaching System. Suitable bleaching systems for use herein contain one or more bleaching agents. Non-limiting examples of suitable bleaching agents include catalytic metal complexes; activated peroxygen sources; bleach activators; bleach boosters; photobleaches; bleaching enzymes; free radical initiators; H2O2; hypohalite bleaches; peroxygen sources including perborates and / or percarbonates, and combinations thereof. Suitable bleach activators include perhydrolyzable esters and perhydrolyzable imides, such as tetraacetylethylenediamine, octanoylcaprolactam, benzoyloxybenzenesulfonate, nonanoyloxybenzenesulfonate, benzoylvalerolactam, and dodecyloxybenzenesulfonate. Other bleaching agents include metal complexes of transition metals with ligands having defined stability constants.

[0375] Stabilizers. The product may contain one or more stabilizers and thickeners. Any suitable level of stabilizer may be used; exemplary levels include 0.01% to 20%, 0.1% to 10%, or 0.1% to 3% by weight of the product. Non-limiting examples of stabilizers suitable for use herein include crystalline, hydroxyl-containing stabilizers, trihydroxystearin, hydrogenated oils or variants thereof, and combinations thereof. In some aspects, the crystalline, hydroxyl-containing stabilizer can be a water-insoluble waxy substance, including fatty acids, fatty esters, or fatty soaps. In other aspects, the crystalline, hydroxyl-containing stabilizer can be a derivative of castor oil, such as a hydrogenated castor oil derivative, such as castor wax. Hydroxyl-containing stabilizers are disclosed in US 6,855,680 and US 7,294,611. Other stabilizers include thickening stabilizers, such as gums and other similar polysaccharides, such as gellan gum, carrageenan, and other known types of thickeners and rheological additives. Exemplary stabilizers in this class include gum-type polymers (e.g., xanthan gum), polyvinyl alcohol and its derivatives, cellulose and its derivatives, including cellulose ethers and cellulose esters, and tamarind gum (e.g., including xyloglucan polymers), guar gum, locust bean gum (including galactomannan polymers in certain aspects), and other industrial gums and polymers.

[0376] Deposition Aid. In some examples, the fabric and home care product may include 0.01% to 10%, 0.05% to 5%, or 0.15% to 3% of a deposition aid, by weight of the product. In some examples, the deposition aid may be a cationic or amphoteric polymer. In some examples, the cationic polymer may have a cationic charge density of 0.005 to 23 meq / g, 0.01 to 12 meq / g, or 0.1 to 7 meq / g at the pH of the composition. For amine-containing polymers, where the charge density depends on the pH of the composition, the charge density is measured at the product's intended use pH. This pH typically ranges from 2 to 11, more typically from 2.5 to 9.5. The charge density is calculated by dividing the net charge per repeat unit by the molecular weight of the repeat unit. The positive charges may be located on the polymer backbone and / or on the side chains of the polymer.

[0377] In some examples, the deposition aid can include a cationic acrylic acid-based polymer. In another aspect, the deposition aid can include a cationic polyacrylamide. In another aspect, the deposition aid can include a polymer composed of polyacrylamide and polymethacrylamidopropyltrimethylammonium cations. In another aspect, the deposition aid can be composed of poly(acrylamide-N-dimethylaminoethyl acrylate) and its quaternized derivatives.

[0378] In some examples, the deposition aid can be selected from cationic or amphoteric polysaccharides. In some examples, the deposition aid can be selected from cationic and amphoteric cellulose ethers, cationic or amphoteric galactomannans, cationic guar gum, cationic or amphoteric starches, and combinations thereof.

[0379] Another group of suitable cationic polymers may include alkylamine-epichlorohydrin polymers, which are reaction products of amines and oligoamines with epichlorohydrin. Another group of suitable synthetic cationic polymers may include polyamidoamine-epichlorohydrin (PAE) resins of polyalkylene polyamines with polycarboxylic acids. The most common PAE resins are condensation products of diethylenetriamine and adipic acid, followed by reaction with epichlorohydrin.

[0380] The weight average molecular weight of the polymer can be 500 Daltons to 5,000,000 Daltons, for example 1,000 Daltons to 2,000,000 Daltons and 2,500 Daltons to 1,500,000 Daltons, as determined by size exclusion chromatography relative to polyethylene oxide standards using RI detection. In some examples, the cationic polymer can have a MW of 500 Daltons to 37,500 Daltons.

[0381] Silicone. Suitable silicones include Si—O moieties and can be selected from (a) non-functionalized siloxane polymers, (b) functionalized siloxane polymers, and combinations thereof. The molecular weight of an organosilicon is often expressed by reference to the material's viscosity. In one aspect, the organosilicon can have a viscosity of 10 to 2,000,000 centistokes at 25°C. In another aspect, suitable organosilicones can have a viscosity of 10 to 800,000 centistokes at 25°C.

[0382] Suitable organosilicones can be linear, branched or cross-linked. In some examples, the organosilicon can be a cyclic silicone. The cyclic silicone can be of the formula [(CH3)2SiO] n wherein n is an integer which may be from 3 to 7 or from 5 to 6.

[0383] In some instances, the organosilicone can include a functionalized siloxane polymer. The functionalized siloxane polymer can include one or more functional moieties selected from amino, amido, alkoxy, hydroxyl, polyether, carboxyl, hydride, sulfhydryl, sulfate phosphate and / or quaternary ammonium moieties. These moieties can be directly attached to the siloxane backbone via a divalent alkylene group (i.e., a "side chain"), or can be part of the backbone. Suitable functionalized siloxane polymers include materials selected from the group consisting of aminosilicones, amidosilicones, silicone polyethers, silicone-urethane polymers, quaternary ABn silicones, aminoABn silicones, and combinations thereof.

[0384] In some examples, the functionalized silicone polymer can include a silicone polyether, also known as a "dimethicone copolyol." Generally speaking, a silicone polyether comprises a polydimethylsiloxane backbone with one or more polyoxyalkylene chains. The polyoxyalkylene moieties can be incorporated into the polymer as side chains or as end blocks. In some examples, the functionalized silicone polymer can include an aminosilicone.

[0385] In some examples, organosilicones may include amine ABn silicones and quaternary ammonium ABn silicones. Such organosilicones are typically produced by reacting a diamine with an epoxide.

[0386] Fabric softening active agents. Non-limiting examples of fabric softening active agents are N,N-bis(stearoyl-oxy-ethyl) N,N-dimethylammonium chloride, N,N-bis(tallowoyl-oxy-ethyl) N,N-dimethylammonium chloride, N,N-bis(stearoyl-oxy-ethyl) N-(2-hydroxyethyl) N-methylammonium methylsulfate; dialkylene dimethylammonium salts, such as dicanoladimethylammonium chloride; chloride), di(hard) tallow dimethyl ammonium chloride, dirape dimethyl ammonium methyl sulfate; 1-methyl-1-stearoylamidoethyl-2-stearoyl imidazoline methyl sulfate; 1-tallowamidoethyl-2-tallowyl imidazoline; N,N"-dialkyldiethylenetriamines; the reaction products of N-(2-hydroxyethyl)-1,2-ethylenediamine or N-(2-hydroxyisopropyl)-1,2-ethylenediamine with glycolic acid esterified with a fatty acid, wherein the fatty acid is (hydrogenated) tallow fatty acid, palm fatty acid, hydrogenated palm fatty acid, oleic acid, rapeseed fatty acid, hydrogenated rapeseed fatty acid; polyglycerol esters (PGE), oily sugar derivatives and wax emulsions, and mixtures thereof. It will be understood that combinations of the softener actives disclosed above are suitable for use herein.

[0387] Fabric hueing agents. The product may also include a fabric hueing agent (sometimes referred to as a shade changer, bluing agent, or brightener). Typically, hueing agents provide a blue or purple hue to the fabric. Hueing agents can be used alone or in combination to create a specific hue and / or to provide hue changes for different types of fabrics. This can be achieved, for example, by mixing red and green-blue dyes to create a blue or purple hue. Toners can be selected from dyes of any known chemical class, including but not limited to acridines, anthraquinones (including polycyclic quinones), azine, azos (e.g., monoazo, disazo, triazo, tetrakis azo, polyazo), including premetallated azos, benzodifurans and benzodifuranones, carotenoids, coumarins, cyanines, diaza semicyanines, diphenylmethanes, formazans, semicyanines, indigos, methanes, naphthalimides, naphthoquinones, nitro and nitroso groups, oxazines, phthalocyanines, pyrazoles, diphenylethylenes, styryls, triarylmethanes, triphenylmethanes, xanthenes, and mixtures thereof. Suitable fabric hueing agents include dyes, dye-clay conjugates, and organic and inorganic pigments. Suitable dyes include small molecule dyes and polymeric dyes. Suitable small molecule dyes include small molecule dyes selected from the group consisting of dyes that fall into the Color Index (CI) classification of acid, direct, basic, reactive or hydrolytically reactive, solvent or disperse dyes, for example classified as blue, violet, red, green or black, and provide the desired hue alone or in combination.

[0388] Suitable polymeric dyes include polymeric dyes selected from the group comprising a covalently bound (sometimes referred to as conjugated) chromogen to a polymer (dye-polymer conjugate), for example polymers having a chromogen copolymerized into the polymer backbone, and mixtures thereof. Polymeric dyes include those described in US 7,686,892 B2.

[0389] Suitable dye-clay conjugates include dye-clay conjugates selected from the group consisting of at least one cationic / basic dye and montmorillonite clay, and mixtures thereof.

[0390] Toners can be incorporated into the product as part of a reaction mixture that is the result of an organic synthesis of the dye molecule, with an optional purification step. Such a reaction mixture typically includes the dye molecule itself and may also include unreacted starting materials and / or by-products of the organic synthesis route.

[0391] Pigments. Suitable pigments include those chosen from the group consisting of flavanthrones, indanthrone, chlorinated indanthrone containing 1 to 4 chlorine atoms, pyranthrone, dichloropyranthrone, monobromodichloropyranthrone, dibromodichloropyranthrone, tetrabromo-pyranthrone, perylene-3,4,9,10-tetracarboxylic acid diimides, where the imide groups may be unsubstituted or substituted by C1-C3-alkyl or phenyl or heterocyclic groups, and where the phenyl and heterocyclic groups may additionally carry substituents that do not impart water solubility, anthrapyrimidinecarboxylic acid amides, anthrone violet, isoanthrone violet, dioxazine pigments, copper phthalocyanines which may contain up to 2 chlorine atoms per molecule, polychlorocopper phthalocyanines or polybromochlorocopper phthalocyanines containing up to 14 bromine atoms per molecule, and mixtures thereof.

[0392] Structuring agents. Useful structurants that can be added to adequately suspend the beneficial agent or microcapsules include polysaccharides such as gellan gum, waxy or dent corn starch, octenylsuccinate starch, derivatized starches such as hydroxyethylated or hydroxypropylated starch, carrageenan, guar gum, pectin, xanthan gum, and mixtures thereof; modified celluloses such as hydrolyzed cellulose acetate, hydroxypropyl cellulose, methyl cellulose, and mixtures thereof; modified proteins such as gelatin; hydrogenated and non-hydrogenated polyolefins, and mixtures thereof; inorganic salts such as magnesium chloride, calcium chloride, calcium formate, magnesium formate, aluminum chloride, potassium permanganate, laponite clay, bentonite clay, and mixtures thereof; polysaccharides in combination with inorganic salts; quaternized polymeric materials such as polyetheramines, alkyltrimethylammonium chloride, diester ditallow ammonium chloride; imidazoles; nonionic polymers having a pKa less than 6.0 such as polyethyleneimine, polyethyleneimine ethoxylates; and polyurethanes. Such materials are available from CP Kelco Corp., San Diego, CA; Degussa AG, Düsseldorf, Germany; BASF AG, Ludwigshafen, Germany; Rhodia Corp., Cranbury, NJ; Baker Hughes Corp., Houston, TX; Hercules Corp., Wilmington, DE; Agrium Inc., Calgary, Alberta, Canada; and ISP, NJ.

[0393] Anti-caking agents. Useful anti-caking agents include divalent salts, such as magnesium salts, such as magnesium chloride, magnesium acetate, magnesium phosphate, magnesium formate, magnesium boride, magnesium titanate, magnesium sulfate heptahydrate; calcium salts, such as calcium chloride, calcium formate, calcium acetate, calcium bromide; trivalent salts, such as aluminum salts, such as aluminum sulfate, aluminum phosphate, aluminum chloride hydrate, and polymers capable of suspending anionic particles, such as suspending polymers, such as polyethyleneimine, alkoxylated polyethyleneimine, polyquaternium-6, and polyquaternium-7.

[0394] Unless otherwise indicated, all parts, percentages and ratios referred to herein and in the claims are by weight.

[0395] The values ​​and dimensions disclosed herein should not be understood as being strictly limited to the exact numerical values ​​recited. Instead, unless otherwise specified, each such value is intended to represent both the recited value and a functionally equivalent range surrounding that value. For example, a value disclosed as "50%" is intended to mean "about 50%."

[0396] The term "including" is intended to be non-limiting.

[0397] The terms "capsule" and "microcapsule" are used interchangeably herein.

[0398] The term "curing" as used in polymer chemistry and process engineering refers to the process of toughening or hardening a polymer by cross-linking of polymer chains, induced by heat, chemical additives, or light radiation.

[0399] As used herein, "core-shell microcapsules," or more generally "microcapsules" or "capsules," are substantially spherical structures having a well-defined core and a well-defined envelope or wall. Ideally, the wall protects the core from degradation due to the action of oxygen, moisture, light, and other compounds, or other factors; limits the loss of volatile core materials; and releases the core materials under desired conditions. In this regard, the core-shell microcapsules of the present invention provide controlled release of the active material. As used herein, "controlled release" means that the active material is retained in the core until a specific trigger condition occurs. Such triggers include, for example, friction, swelling, pH change, enzymes, temperature change, ionic strength change, or a combination thereof.

[0400] The present invention is described in more detail by the following non-limiting examples. Without further elaboration, it is believed that one skilled in the art can utilize the present invention to its fullest extent based on the description herein. All publications cited herein are incorporated by reference in their entirety.

[0401] Example 1: Microcapsules 1 prepared from moderately denatured brown rice protein

[0402] Microcapsules 1 were prepared according to the following procedure. First, 28.6 grams (g) of a model fragrance and 7.15 g of caprylic / capric triglyceride (core solvent, sold under the trade name Oil M-5( oil M-5) commercially available from Stepan, Chicago, IL) and aliphatic polyisocyanate (0.7 g) (a polyisocyanate based on hexamethylene diisocyanate (HDI) that can be The oil phase was prepared by mixing an aqueous solution (46 g) containing 10% denatured brown rice protein solution, 10% polystyrene sulfonate sodium salt (a capsule forming aid available under the trade name II was obtained commercially from AkzoNobel Surface Chemistry, Ossining, NY) in aqueous solution (5.8 g), 1% carboxymethyl cellulose (encapsulation aid, An aqueous solution (10 g) of CRT50000 (commercially available from Dow Chemical Company, Midland, MI) and 0.14 g of 20% DABCO crystals (a catalyst, 1,4-diazabicyclo[2.2.2]octane, Evonik, Essen, Germany) were mixed to form an oil-in-water emulsion. The oil phase was then emulsified into the aqueous phase, shearing at 7200 rpm (ULTRA TURRAX™, T25 Basic, IKA WERKE) for 5 minutes to form an oil-in-water emulsion. The formulation of Microcapsule 1 is shown in Table 1 below.

[0403] Table 1.

[0404]

[0405] After stirring the oil-in-water emulsion at 25°C for 0.5 hours, 2 g of a 25% aqueous glutaraldehyde solution (Sigma-Aldrich, St. Louis, MO) and 5 g of a 30% aqueous tannic acid solution (Sigma-Aldrich, St. Louis, MO) were added with continued stirring. The mixture was allowed to cure at room temperature for 1 hour. The pH was then adjusted to 8. After heating to 55°C, the resulting capsule slurry was stirred for 1 hour and then at 80°C for 3 hours. The encapsulation efficiency was 99.9%.

[0406] Packaging efficiency

[0407] Encapsulation efficiency (EE) was calculated as: EE = [1 - (free oil / total oil)] x 100%. Analysis of free oil and total oil was performed according to the method described in WO 2017 / 161364, page 21.

[0408] Sensory performance evaluation

[0409] The microcapsule compositions of the present invention were used in fabric conditioner bases and their fragrance intensity was evaluated on an LMS scale of 0 to 30, with 1 being a weak odor, 5 being a moderate odor, and 15 being a strong odor. Each microcapsule was incorporated into a model unscented fabric conditioner base at 0.6% neat oil equivalent. A representative fabric conditioner base contains 1-20% quaternary ammonium surfactant (active), <1% stabilizer, <1% pH buffer, <1% salt, <0.1% preservative, and <0.1% defoamer, all by weight of the base.

[0410] Headspace gas chromatography (GC) after kneading

[0411] The microcapsules of the present invention were also evaluated using headspace GC on Tenax tubes, where fragrance intensity was measured in ppb. A washed and dried towel was placed in a plastic bag, sealed, and rubbed. The headspace was collected through a nozzle.

[0412] Examples 2-6

[0413] Microcapsules 2 were prepared following the procedure described in Example 1, except that the brown rice protein was slightly denatured by treating the protein dispersion at 80°C for 1 hour without any pH adjustment.

[0414] Microcapsules 3 were prepared according to the procedure described in Example 1, except that the brown rice protein was not denatured.

[0415] Microcapsules 4 were prepared according to the procedure described in Example 1, except that glutaraldehyde was not added to the slurry mixture for cross-linking.

[0416] Microcapsule 5 was prepared in a similar manner to microcapsule 1, except that 1.25 g of 40% glyoxal solution was added to the slurry mixture instead of glutaraldehyde solution.

[0417] Microcapsules 6 were prepared according to the procedure described in Example 1 except that 1% trimethylolpropane adduct of xylylene diisocyanate (as Takenate TM D-110N was purchased from Mitsui Chemicals Inc., Japan) instead of N100A.

[0418] Example 7

[0419] Microcapsules 7 were prepared according to the following procedure. A mixture containing 3 wt% whey protein concentrate (trade name: Hydrovon TM 282 commercially available from Glanbia Nutritionals, Chicago, IL), 1.3 wt% aqueous guanidine carbonate solution, 0.5% polystyrene sulfonate ( II, from AkzoNobel, Union, NJ) and 1% OSA modified starch (available under the trademark Purity An aqueous dispersion of an aqueous solution of 1% xylylene diisocyanate (available as Takenate Ultra from Ingredion, Bridgewater, NJ) was added to the dispersion. TM D-110N (commercially available from Mitsui Chemicals Inc., Japan), 32% model fragrance and caprylic / capric triglyceride in oil. The mixture was homogenized at 7400 rpm for 3 minutes, at which time 0.5% tannic acid (Sigma Aldrich) was added, mixed for an additional 15 minutes and cured at 55°C for 4 hours.

[0420] Examples 8-11: Denatured hydrolyzed whey protein concentrate microcapsules

[0421] Microcapsules 8 were prepared according to the same procedure as in Example 1, except that 1.3% guanidine hydrochloride (Sigma Aldrich) was used instead of guanidine carbonate. In addition, the pH was adjusted to 9 with 10% sodium hydroxide before solidification.

[0422] Microcapsules 9 were prepared as in Example 7 except that whey protein isolate (Hydrovon TM 195, Glanbia Nutritionals) instead of whey protein concentrate.

[0423] Microcapsules 10 were prepared as in Example 8, except that no guanidine salt was added.

[0424] Microcapsules 11 were prepared as in Example 10, except that 0.5% glutaraldehyde was used instead of tannic acid.

[0425] Examples 12-20: Protein Microcapsules

[0426] Microcapsules 12-21 were prepared according to the same procedure as in Example 7, except that a different protein was used in each example.

[0427] Microcapsules 12, pea protein (Naturals S85XF, from Roquette),

[0428] Microcapsule 13, rice protein ( 5312, from Kerry),

[0429] Microcapsule 14, oat protein ( from Tate and Lyle),

[0430] Microcapsules 15, potato protein (Meelunie BV, The Netherlands),

[0431] Microcapsule 16: Wheat protein ( 500, from Scoular),

[0432] Microcapsule 17: Egg protein (P110, from Henningsen Food),

[0433] Microcapsule 18: Barley / Rice Protein TM , Zea10 LLC),

[0434] Microcapsule 19: Brown Rice Protein (Naked Nutrition), and

[0435] Microcapsule 20: Pumpkin seed protein (Acetar Bio-Tech Inc.)

[0436] Table 2 below summarizes each example and the headspace GC readings after rubbing. In each example, the microcapsules were dispersed in the aqueous phase as a microcapsule composition. Based on the weight of the microcapsule composition, 3% protein, 1.3% guanidine carbonate as a chaotropic agent, 1% trimethylolpropane adduct of xylylene diisocyanate (Takenate TM D-110N) as a multifunctional electrophilic reagent, 0.5% tannic acid as a multifunctional nucleophilic reagent, 0.5% polystyrene sulfonate ( II) as an emulsifier, 1% OSA modified starch (Purity Each microcapsule composition was prepared with PEG-100 Ultra) as a co-emulsifier, 32% of a model fragrance, and caprylic / capric triglyceride.

[0437] Table 2.

[0438]

[0439] Examples 21-24: Whey protein capsules

[0440] Microcapsule compositions 21-24 were prepared according to the same procedure as described in Example 7, except that different proteins or chaotropic agents were used. Based on the weight of the microcapsule composition, 3% denatured protein, 1.3% chaotropic agent, 1% trimethylolpropane adduct of xylylene diisocyanate (Takenate TM D-110N) as a multifunctional electrophile, 0.5% tannic acid as a multifunctional nucleophile, 0.5% polystyrene sulfonate ( II) as an emulsifier, 1% OSA modified starch (Purity Each microcapsule composition was prepared using 1% of a trimethylolpropane adduct of xylylene diisocyanate (Takenate TM D-110N), 0.5% glutaraldehyde as a multifunctional nucleophile, 0.5% polystyrene sulfonate ( II), 1% OSA modified starch (Purity Ultra) as a co-emulsifier, 32% of a model fragrance, and caprylic / capric triglyceride were prepared in a similar manner. Table 3 below shows the free oil % and post-rubbing headspace GC readings for each microcapsule composition.

[0441] Microcapsule composition 21 was cured at either 55° C. or 25° C. In headspace GC analysis, the GC readings after rubbing were similar.

[0442] Table 3

[0443]

[0444] Examples 25-40: Capsule compositions prepared from various polyfunctional nucleophiles

[0445] The same procedure as described in Example 7 was followed using denatured protein (whey protein concentrate, potato protein or pea protein), 1.3% guanidine carbonate, trimethylolpropane adduct of xylylene diisocyanate (polyisocyanate, Takenate TM D-110N), multifunctional nucleophile, 0.5% sulfonated polystyrene ( II), 1% OSA modified starch (Purity Microcapsule compositions 25-40 were prepared using 1% PEG-100 Ultra, 32% model fragrance, and caprylic / capric triglyceride. See Table 4 below for composition, % free oil, and post-rub fragrance intensity from sensory evaluation.

[0446] Table 4.

[0447]

[0448]

[0449] 1 BPEI, branched polyethyleneimine, is available from BASF as Commercially available.

[0450] 2 TEC, triethyl citrate, IFF, Union Beach, NJ.

[0451] 3 DBI, dibutyl itaconate (Sigma-Aldrich, St. Louis, MO).

[0452] 4 Headspace GC readings.

[0453] Examples 41-43

[0454] The same procedure as described in Example 7 was followed using 3% denatured whey protein concentrate, various concentrations of guanidine carbonate, 0.5% (Example 41) or 1% (Examples 42-44) trimethylolpropane adduct of xylylene diisocyanate (Takenate TM D-110N), 0.5% tannic acid, 0.5% polystyrene sulfonate ( II) as emulsifier, 1% OSA modified starch (Purity Microcapsule compositions 41-43 were prepared using 1% PEG-100 Ultra as a co-emulsifier, 32% model fragrance, and caprylic / capric triglyceride. Comparative composition 2C was prepared in the same manner as Example 42, except that guanidine carbonate was omitted. See Table 5 below for composition, free oil percentage, and post-rub aroma intensity from sensory evaluation.

[0455] The pH of the oil-in-water in Example 41 was 7 without adjustment. It was adjusted to a pH < 7 (e.g., 3) with citric acid or to a pH > 7 (e.g., 9) with sodium hydroxide. The aroma intensity was approximately 4.7, with no significant change with pH adjustment.

[0456] Table 5

[0457]

[0458] 1 Trimethylolpropane adduct of xylylene diisocyanate (Takenate TM D-110N).

[0459] Examples 44 and 45: Conditioner

[0460] In Example 44, Conditioner 1 was obtained by adding Microcapsule Composition 25 to a conditioner base at a level of 0.25% neat oil equivalent. The conditioner base contained 4% fatty alcohol, 0.7% behentrimonium chloride, 1% terminal amino silicone, 2.5% silicone, and 0.5% preservative in water.

[0461] In Example 45, Conditioner 2 was obtained by adding microcapsule composition 22 at 0.25% neat oil equivalent to a conditioner base together with 2% chitosan (commercially available from Glentham Life Sciences, Corsham, UK) as a deposition aid.

[0462] Hair samples were washed with both conditioners and, after combing, rated on a fragrance intensity scale of 0 to 10 (5 being a strong odor).

[0463] The post-comb fragrance intensities for hair swatches treated with Conditioner 1 and 2 were 5.6 and 4.3, respectively.

[0464] Examples 46-48: Shampoo

[0465] In Example 46, Shampoo 1 was obtained by adding microcapsule composition 22 to a shampoo base at a level of 0.25% absolute oil equivalent. The shampoo base contained 12% sodium lauryl ether sulfate, 1.6% cocamidopropyl betaine, 0.2% nonionic guar gum, 2-3% silicone, and 0.5% preservative in water.

[0466] In Example 47, Shampoo 2 was obtained by adding Microcapsule Composition 25 to a conditioner base at 0.25% neat oil equivalent.

[0467] In Example 48, Shampoo 3 was obtained by adding Microcapsule Composition 22 at 0.25% neat oil equivalent to a conditioner base along with 2% chitosan as a deposition aid.

[0468] Hair swatches were washed with the three shampoos and, after combing, rated on a fragrance intensity scale of 0 to 10 (5 being strong).

[0469] The post-comb fragrance intensities for hair swatches treated with Shampoos 1-3 were 7, 5.2, and 6.8, respectively.

[0470] Chitosan coating

[0471] To improve the deposition of encapsulated fragrances, any of the microcapsules of the present invention can be coated with chitosan as follows. A 3% aqueous solution of chitosan (extracted from fungi) is prepared by dissolving chitosan in water along with 1% acetic acid. The microcapsule composition is mixed with a dilute sulfuric acid solution until the pH reaches 2. The chitosan solution is added to the acidified microcapsule composition so that the chitosan is present at a level of 2%. The resulting microcapsule composition has a pH of 2 and is heated to a temperature of 60°C and maintained at this temperature for 4 hours to obtain a microcapsule composition having a chitosan coating on the microcapsules.

[0472] The chitosan-coated microcapsule composition can be further mixed with 0.25 wt % of a copolymer of acrylamide and acrylamidopropyltrimethylammonium chloride (ACM-APTAC, as a deposition aid) or a copolymer of acrylamide and methacrylamidopropyl-trimethylammonium chloride (ACM-MAPTAC, as a deposition aid) to obtain a microcapsule composition with a deposition aid.

[0473] The chitosan coated microcapsule compositions and the microcapsule compositions with a deposition aid exhibited higher fragrance intensity in the conditioner evaluation compared to microcapsule compositions without chitosan, ACM-APTAC, or ACM-MAPTAC.

[0474] Biodegradability

[0475] Biodegradability testing was performed according to OECD 310 protocol. Aliquots of the microcapsule slurry were placed in biological oxygen demand (BOD) bottles in water containing a microbial inoculum collected from a publicly owned treatment plant in Escatawpa, Mississippi. The bottles were checked at regular intervals for carbon dioxide evolution for 60 days. Intermittent points may also be used, as asymptotic values ​​may be reached much earlier than 60 days. Percent degradation was analyzed relative to a positive control starch.

[0476] Consumer Product Examples

[0477] The microcapsule compositions of the present invention can be added to a variety of consumer products. Non-limiting examples are shown in Table 6 below.

[0478] Table 6

[0479]

[0480]

[0481]

[0482] 1 All component percentages are shown by weight of the consumer product.

[0483] 2 NOE is net fragrance oil equivalent, which is equal to the weight percent of fragrance oil in a consumer product.

[0484] Other implementation plans

[0485] All features disclosed in this specification can be combined in any combination. Each feature disclosed in this specification can be replaced by an alternative feature used for the same, equivalent or similar purpose.

[0486] To achieve the goal of encapsulating the active material, one skilled in the art can design and prepare capsule compositions by using different encapsulating polymers, coatings, and capsule-forming aids, and varying the concentration of wall-forming materials or catalysts to achieve a desired release profile in a consumer product. Furthermore, the ratios of wall-forming materials, capsule-forming aids, adjuvants, core modifiers, active materials, and catalysts can also be determined by one skilled in the art using known assays.

[0487] Based on the above description, those skilled in the art can easily determine the essential characteristics of the present invention, and without departing from the spirit and scope of the present invention, various changes and modifications can be made to the present invention to adapt it to various uses and conditions. Therefore, other embodiments are also within the scope of the claims.

Claims

1. A microcapsule composition comprising microcapsules dispersed in an aqueous phase, wherein the microcapsules have a microcapsule core and a microcapsule wall encapsulating the microcapsule core, The microcapsule core contains the active material, The microcapsule wall is formed from a polymer network comprising a first portion derived from a protein, a second portion derived from a multifunctional electrophile, and a third portion derived from a chaotrope, a multifunctional nucleophile, or a combination thereof.

2. The microcapsule composition of claim 1, wherein the microcapsule wall comprises 2% to 20% of the first portion, 0.1% to 3% of the second portion, and 0.1% to 10% of the third portion, based on the weight of the microcapsule.

3. The microcapsule composition according to claim 1 or 2, wherein the first part is a native or denatured protein.

4. The microcapsule composition according to any one of the preceding claims, wherein the protein is whey protein, pea protein, soy protein, rice protein, wheat protein, egg protein, barley protein, brown rice protein, pumpkin seed protein, oat protein, potato protein, almond protein, or any combination thereof.

5. The microcapsule composition according to any one of the preceding claims, wherein the polyfunctional electrophile is a polyisocyanate selected from the group consisting of trimers of hexamethylene diisocyanate, trimers of isophorone diisocyanate, biuret of hexamethylene diisocyanate, polyisocyanurates of toluene diisocyanate, trimethylolpropane adducts of toluene diisocyanate, trimethylolpropane adducts of xylylene diisocyanate, and combinations thereof.

6. The microcapsule composition of any preceding claim, wherein the active material comprises a fragrance, a cosmetic active and malodor counteractant, a fragrance precursor, a vitamin or derivative thereof, an anti-inflammatory agent, a fungicide, an anesthetic, an analgesic, an antimicrobial active, an antiviral agent, an anti-infective agent, an anti-acne agent, a skin lightening agent, an insect repellent, an insect repellent, a pest repellent, an emollient, a skin moisturizer, an anti-wrinkle agent, a UV protectant, a fabric softener active, a hard surface cleaning active, a skin or hair conditioning agent, a flame retardant, an antistatic agent, a nano to micron sized inorganic solid, a polymer or elastomeric particle, a taste modifier, a cell, a probiotic, or a combination thereof.

7. The microcapsule composition according to claim 6, wherein the active material is a high performance fragrance.

8. A microcapsule composition according to any one of the preceding claims, wherein the third moiety is a polyfunctional nucleophile.

9. The microcapsule composition according to any one of claims 1 to 7, wherein the third part is a combination of a chaotropic agent and a multifunctional nucleophilic agent.

10. The microcapsule composition of any one of the preceding claims, wherein the polyfunctional nucleophile is a polyphenol, maltodextrin, a polyamine, or a combination thereof.

11. The microcapsule composition according to any one of claims 1 to 7, wherein the third part is a chaotropic agent selected from the group consisting of guanidine salts, urea, polysorbate, sodium benzoate, vanillin, o-cresol, phenol, propanol, formamide, ethanol, fructose, ammonium sulfate, ammonium chloride, ammonium nitrate, ammonium phosphate, potassium sulfate, potassium chloride, potassium nitrate, potassium phosphate, sodium sulfate, sodium chloride, sodium nitrate, sodium phosphate, guanidine thiocyanate, xylose, glycerol, benzyl alcohol, potassium iodide, ethyl acetate, triton X-100, ethyl acetate, hexadecyltrimethylammonium halide, acetone, SDS, sodium bromide, hydrochloric acid, sulfuric acid, polyethylene glycol, glutaraldehyde, glyoxal, and combinations thereof.

12. A microcapsule composition as claimed in any one of the preceding claims, wherein the microcapsules have a deposition polymer coating selected from the group consisting of trimethylammonium, methacrylamidopropyltrimethylammonium, acrylamidopropyltrimethylammonium, acrylamide, acrylic acid, dimethylammonium, xylose, galactose, hydroxypropylated glucose, hydroxyethylated glucose, hydroxymethylated glucose, vinylamine, ethyleneimine, functionalized branched polyethyleneimine, vinylformamide, vinylpyrrolidone, caprolactone, catechol, vinyl alcohol, chitosan, polyquaternium-4, polyquaternium-5, polyquaternium-6, polyquaternium-7, polyquaternium-10, polyquaternium-11, polyquaternium-16, polyquaternium-22, polyquaternium-24, polyquaternium-28, polyquaternium-37, polyquaternium-39, polyquaternium-44, polyquaternium-46, polyquaternium-47, polyquaternium-50, polyquaternium-61, polyquaternium-72, polyquaternium-101, polyquaternium-111, polyquaternium-162, polyquaternium-22, polyquaternium-24, polyquaternium-28, polyquaternium-37, polyquaternium-39, polyquaternium-44, polyquaternium-46, polyquaternium-47, polyquaternium-48, polyquaternium-51, polyquaternium-62, polyquaternium-73, polyquaternium-102, polyquaternium-103, polyquaternium-104, polyquaternium-105, polyquaternium-106, polyquaternium-107, polyquaternium-108, polyquaternium-109, polyquaternium-1112, polyquaternium-113, polyquaternium- -53, Polyquaternium-55, Polyquaternium-67, Polyquaternium-68, Polyquaternium-69, Polyquaternium-73, Polyquaternium-74, Polyquaternium-77, Polyquaternium-78, Polyquaternium-79, Polyquaternium-79 / hydrolyzed keratin, Polyquaternium-80, Polyquaternium-81, Polyquaternium-82, Polyquaternium-86, Polyquaternium-88, Polyquaternium-101, polyethyleneamine, polyethyleneimine, copolymers of vinylamine and vinylformamide, copolymers of acrylamide and 3-methacrylamidopropyltrimonium, 3-acrylamidopropyltrimonium polymer or copolymers thereof, diallyldimethylammonium chloride polymer and copolymers thereof, polysaccharides having sugar units functionalized with hydroxypropyltrimonium, ethyltrimonium chloride methacrylate / hydrolyzed wheat protein copolymer, alkylammonium hydroxypropyl hydrolyzed protein, and combinations thereof.

13. The microcapsule composition according to any one of the preceding claims, wherein the microcapsules have a size of 0.2 μm to 100 μm in diameter.

14. A microcapsule composition according to any one of the preceding claims, wherein the microcapsule shell comprises 10% to 90% by weight of the microcapsule and the microcapsule core comprises 90% to 10% by weight of the microcapsule.

15. A method for preparing a microcapsule composition, comprising the following steps: (i) providing an oil-in-water emulsion having a plurality of oil droplets dispersed in an aqueous phase, wherein the oil-in-water emulsion contains a multifunctional electrophile, the oil phase contains an active material, and the aqueous phase contains a protein and optionally a chaotropic agent, (ii) optionally adding a polyfunctional nucleophile to the oil-in-water emulsion, and (iii) providing conditions sufficient to initiate interfacial polymerization in the oil-in-water emulsion mixture to form microcapsules having microcapsule walls encapsulating microcapsule cores to obtain a microcapsule composition.

16. The method according to claim 15, further comprising the steps of: (iv) curing the microcapsules at a temperature of 0°C to 125°C, or (v) after the curing step, adding an aqueous chitosan solution at a pH of 1 to 5 to 0.5% to 5% by weight of the microcapsule composition and heating the resulting mixture to 35°C to 95°C.

17. The method of claim 15 or 16, wherein the oil-in-water emulsion further comprises a surfactant selected from the group consisting of polyvinyl alcohol, ethyleneamine / vinyl alcohol copolymers, polystyrene sulfonates, carboxymethyl cellulose, naphthalene sulfonates, polyvinyl pyrrolidone, copolymers of vinyl pyrrolidone and quaternized dimethylaminoethyl methacrylate, OSA-modified starch, OSA-modified gum arabic, gum arabic, alginate, carboxymethyl cellulose, carrageenan, xanthan gum, gellan gum, lecithin, modified lecithin, protein, modified protein, pectin, modified pectin, lignin, modified lignin, and combinations thereof.

18. A method according to any one of claims 15 to 17, wherein the polyisocyanate is present in each oil droplet or aqueous phase at a level of from 0.1% to 3% by weight of the microcapsule composition.

19. A method according to any one of claims 15 to 18, wherein the chaotrope or multifunctional nucleophile is added to the oil-in-water emulsion at a level of from 0.1% to 5% by weight of the microcapsule composition.

20. The method of any one of claims 15-19, wherein the protein is present at a level of 0.5% to 10% by weight of the microcapsule composition.

21. The method according to any one of claims 15 to 20, wherein each oil droplet has a size of 0.1 to 100 μm in diameter, and each microcapsule has a size of 0.2 to 100 μm in diameter.

22. The method of any one of claims 15 to 21, wherein the polyfunctional nucleophile is a polyphenol added to the oil-in-water emulsion at a level of 0.1% to 2.5% by weight of the microcapsule composition.

23. The method according to any one of claims 15 to 22, wherein the chaotropic agent is a guanidine salt or glutaraldehyde.

24. A consumer product comprising the microcapsule composition of any one of claims 1-14.

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