阅读说明：本技术 由蛋白质制备的微胶囊 (Microcapsules prepared from proteins ) 是由 佐佐木隆 R·钦 J·A·维兰德 张毅 罗纳德·加巴德 雷亚斌 L·M·波普尔韦尔 C 于 2019-12-17 设计创作，主要内容包括：本发明公开了包含分散在水相中的微胶囊的微胶囊组合物。微胶囊具有微胶囊核和微胶囊壁。微胶囊核含有活性材料。微胶囊壁封装微胶囊核并由聚合物网络形成,所述聚合物网络具有蛋白质部分、多官能亲电试剂部分和衍生自离液剂、多官能亲核试剂,或它们的组合的第三部分。还公开了该微胶囊组合物的制备方法和含有该微胶囊组合物的消费品。(Microcapsule compositions comprising microcapsules dispersed in an aqueous phase are disclosed. The microcapsules have 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 multifunctional electrophile moiety, and a third moiety derived from a chaotropic agent, a multifunctional nucleophile, or a combination thereof. Also disclosed are processes for preparing the microcapsule compositions and consumer products containing the microcapsule compositions.)

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 an active material,

the microcapsule wall is formed from a polymer network comprising a first moiety derived from a protein, a second moiety derived from a multifunctional electrophile, and a third moiety derived from a chaotrope, a multifunctional nucleophile, or a combination thereof.

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

3. The microcapsule composition of claim 1 or 2, wherein the first portion is a native or denatured protein.

4. The microcapsule composition of 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 of any one of the preceding claims, wherein the polyfunctional electrophile is a polyisocyanate selected from the group consisting of a trimer of hexamethylene diisocyanate, a trimer of isophorone diisocyanate, a biuret of hexamethylene diisocyanate, a polyisocyanurate of toluene diisocyanate, a trimethylolpropane adduct of xylylene diisocyanate, and combinations thereof.

6. The microcapsule composition of any one of the preceding claims, wherein the active material comprises fragrances, cosmetic actives and malodor counteractants, fragrance precursors, vitamins or derivatives thereof, anti-inflammatory agents, fungicides, anesthetics, analgesics, antimicrobial actives, antivirals, anti-infective agents, anti-acne agents, skin lightening agents, insect repellents, drivers, pest repellents, emollients, skin moisturizers, anti-wrinkle agents, UV protectants, fabric softener actives, hard surface cleaning actives, skin or hair conditioners, flame retardants, antistatic agents, nano to micro sized inorganic solids, polymeric or elastomeric particles, taste modifiers, cells, probiotics, or combinations thereof.

7. The microcapsule composition of claim 6, wherein the active material is a high performance perfume.

8. The microcapsule composition of any one of the preceding claims, wherein the third moiety is a multifunctional nucleophile.

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

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

11. The microcapsule composition of any one of claims 1 to 7, wherein the third portion is a chaotropic agent selected from the group consisting of guanidinium salts, urea, polysorbates, 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, guanidinium thiocyanate, xylose, glycerol, benzyl alcohol, potassium iodide, ethyl acetate, triton X-100, ethyl acetate, cetyltrimethylammonium halide, acetone, SDS, sodium bromide, hydrochloric acid, sulfuric acid, polyethylene glycol, glutaraldehyde, glyoxal, and combinations thereof.

12. The microcapsule composition of any one of the preceding claims, wherein the microcapsules have a coating of a deposition polymer selected from 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-53, polyquaternium-55, polyquaternium-67, polyquaternium-68, polyquaternium-69, polyquaternium-73, polyquaternium-74, polyquaternium-77, polyquaternium-78, polyquaternium-79/hydrolyzed keratin, polyquaternium-80, polyquaternium-81, polyquaternium-82, polyquaternium-86, polyquaternium-88, polyquaternium-101, polyvinylamine, polyethyleneimine, a copolymer of vinylamine and vinylformamide, a copolymer of acrylamide and 3-methacryloylaminopropyltrimethylammonium, a copolymer of a mixture of a poly (A) and a copolymer of a poly (A) and a mixture (B) of a mixture (B) thereof, 3-acrylamidopropyltrimethylammonium polymer or copolymers thereof, diallyldimethylammonium chloride polymers and copolymers thereof, polysaccharides having saccharide units functionalized with hydroxypropyltrimethylammonium, ethyltrimethylammonium chloride methacrylate/hydrolyzed wheat protein copolymers, alkylammonium hydroxypropylated protein hydrolysates, and combinations thereof.

13. The microcapsule composition of any one of the preceding claims, wherein microcapsules have a size of from 0.2 μ ι η to 100 μ ι η in diameter.

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

15. A method of making 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 multifunctional electrophile, an oil phase comprises an active material, and the aqueous phase comprises a protein and optionally a chaotrope,

(ii) optionally adding a multifunctional nucleophile to the oil-in-water emulsion, and

(iii) providing conditions sufficient to initiate interfacial polymerization in an oil-in-water emulsion mixture to form microcapsules having microcapsule walls encapsulating a microcapsule core to obtain a microcapsule composition.

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

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, vinylamine/vinyl alcohol copolymer, polysulfonyl styrene, carboxymethyl cellulose, naphthalenesulfonate, polyvinylpyrrolidone, copolymers of vinylpyrrolidone and quaternized dimethylaminoethyl methacrylate, OSA modified starch, OSA modified 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. The method of any one of claims 15-17, 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. The method of any one of claims 15-18, wherein the chaotropic agent or multifunctional nucleophile is added to the oil-in-water emulsion at a level of 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 microcapsule composition.

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

22. The method of any one of claims 15-21, wherein the multifunctional 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 of any one of claims 15-22, wherein the chaotropic agent is a guanidinium salt or glutaraldehyde.

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

Background

Microcapsules are used in a variety of consumer products that require the delivery, application, or release of active materials (including perfumes, flavors, and malodor counteractants) in a time-delayed or controlled manner to a target area.

Conventional microcapsules typically have a microcapsule wall formed from a synthetic polymer such as a melamine formaldehyde polymer, polyurea or polyacrylate. Consumers prefer natural materials that are environmentally friendly relative to synthetic polymers and demand the development of green, sustainable products and technologies.

Mint et al, WO 2016/185171A 1, report microcapsules prepared from natural materials with fungal chitosan. It has been found that silk fibroin particles are suitable for encapsulating aromatic oils (fragance oil). See Kaplan et al, US 2015/0164117A 1. Biomolecules have been used in microcapsule preparation as emulsifiers. See WO 2016/193435 a1, WO 2017/102812 a1, US 2018/0078468a1, WO 2018/019894 a1, WO 2018/019896 a1 and WO 2017/102812 a 1. Multi-layer coacervate capsules are generally 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 WO2018/002214a 1. 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 2934464B 1. Proteins have been used to coat microcapsules to improve deposition. See US 2017/0189283 a 1.

US 2017/0360676 a1 describes an environmentally biodegradable polysaccharide delivery particle.

However, none of these microcapsules and granules exhibit high performance and environmental degradability to meet consumer needs.

There is a need to develop environmentally friendly microcapsules with high fragrance properties for laundry, washing, cleaning, surface care and personal and skin care.

Disclosure of Invention

The present invention is based on the following findings: certain capsule compositions have unexpectedly desirable properties such as high perceived olfactory intensity, high stability, and environmental friendliness.

Accordingly, 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 perfumes, cosmetic actives, malodor counteractants, the microcapsule wall being formed from a polymeric network comprising a first part derived from a protein, a second part derived from a multifunctional electrophile (e.g. polyisocyanate, glutaraldehyde and glyoxal) and a third part derived from a chaotropic agent, a multifunctional nucleophile or any combination thereof.

In one embodiment, the microcapsule wall comprises from 2% to 20% of the first part, from 0.1% to 3% of the second part, and from 0.1% to 10% of the third part, by weight of the microcapsule.

Preferably, the first portion 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.

Suitable polyisocyanates include trimers of hexamethylene diisocyanate, trimers of isophorone diisocyanate, biurets of hexamethylene diisocyanate, polyisocyanurates of toluene diisocyanate, trimethylolpropane adducts of xylylene diisocyanate, and combinations thereof.

In one embodiment, the third moiety is a multifunctional nucleophile, such as a polyphenol, maltodextrin, polyamine, and combinations thereof. In another embodiment, the third fraction is a chaotropic agent. In yet another embodiment, the third moiety is a combination of a chaotropic agent and a multifunctional nucleophile. Suitable chaotropic agents include guanidinium salts (e.g., 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, cetyltrimethylammonium halide, acetone, Sodium Dodecyl Sulfate (SDS), sodium bromide, hydrochloric acid, sulfuric acid, polyethylene glycol, glutaraldehyde, and combinations thereof.

The active material may further comprise a pro-fragrance precursor (pro-fragrance), 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, a driver, 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 conditioner, a flame retardant, an antistatic agent, nano-to micro-sized inorganic solids, polymeric or elastomeric particles, a taste modulator, cells, a probiotic, or a combination thereof. In one embodiment, the active material is a high performance perfume.

The microcapsules of the present invention may have a coating of a deposition polymer (deposition polymer) selected from trimethylammonium, methacrylamidopropyltrimethylammonium, acrylamide-propyltrimethylammonium, 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-4), polyquaternium-5, polyquaternium-6, polyquaternium-7, polyquaternium-10, polyquaternium-11, polyquaternium-16, polyquaternium-22, polyquaternium-24, polyquaternium-28, and mixtures thereof, 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 and hydrolyzed keratin copolymer, polyquaternium-80, polyquaternium-81, polyquaternium-82, polyquaternium-86, polyquaternium-88, polyquaternium-101, polyvinylamine, polyethyleneimine, copolymer of vinylamine and vinylformamide, copolymer of acrylamide and 3-methacrylamidopropyltrimethylammonium, polyquaternium-4, polyquaternium-A, polyquaternium-A, polyquaternium-A, polyquaternium, poly, 3-acrylamidotrimethylammonium polymers or copolymers thereof, diallyldimethylammonium chloride polymers and copolymers thereof, polysaccharides having saccharide units functionalized with hydroxypropyltrimethylammonium, ethyltrimethylammonium chloride methacrylate/hydrolyzed wheat protein copolymers, alkylammonium hydroxypropylated proteins, and combinations thereof.

The diameter size of the microcapsules is typically 0.2 μm to 100 μm. The microcapsule shell accounts for 10 to 90 percent of the weight of the microcapsule, and the microcapsule core accounts for 90 to 10 percent of the weight of the microcapsule.

Another aspect of the present invention relates to a method of 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, the aqueous phase comprises a protein and optionally a chaotrope, (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, thereby obtaining a microcapsule composition. Optionally, the method further comprises the steps of: (iv) (iii) curing the microcapsules at a temperature of from 0 ℃ to 125 ℃ 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 from 1 to 5, and heating the resulting mixture to from 35 ℃ to 95 ℃ (e.g., from 45 ℃ to 75 ℃ for from 10 minutes to 10 hours).

In one embodiment, the oil-in-water emulsion further contains a surfactant selected from the group consisting of polyvinyl alcohol, vinylamine/vinyl alcohol copolymers, polystyrene sulfonate, carboxymethyl cellulose, naphthalene sulfonate, polyvinylpyrrolidone, copolymers of vinylpyrrolidone and quaternized dimethylaminoethyl methacrylate, OSA modified starch, OSA modified gum arabic, alginates, carboxymethyl cellulose, carrageenans, xanthan gum, gellan gum, lecithin, modified lecithin, proteins, modified proteins, pectin, modified pectin, lignin, modified lignin, and combinations thereof.

Preferably, the multifunctional electrophile (e.g., polyisocyanate) is present at a level of 0.1% to 5% (e.g., 0.2% to 3% and 0.5% to 2%) per oil droplet or aqueous phase, the chaotrope or multifunctional 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 may be added to the oil-in-water emulsion at a level of from 0.1% to 2.5% by weight of the microcapsule composition. Preferred chaotropic agents include guanidinium salts and glutaraldehyde. When a chaotropic agent and a multifunctional nucleophile are present, the levels of these two agents sum to 1% to 10% (e.g., 2% to 8% and 3% to 7%) of the microcapsule weight.

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

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

The microcapsules and compositions thereof described above can be used to impart a fragrance in consumer products such as baby care products, diaper rash creams or balms, baby talcum powders, diapers, bibs, baby wipes, cosmetic formulations, powder foundations, liquid foundations, eye shadows, lipsticks or lip balms, home care products, multipurpose cleaners, fragrancing agent products (a moisture products), bathroom cleaners, floor cleaners, window cleaners, plastic polishes, bleaches, toilet bowl cleaners, toilet seat, toilet tissue, hand wipes, disposable, liquid air fresheners, air freshener sprays, spray dispenser products, line notes, carpet deodorants, candles, room deodorants, liquid wet wipes, dishwasher detergents, powder detergents, leather detergents, tablet dishwashing detergents, paste dishwashing detergents, unit dose tablets or capsules, Flavoring agents, beverage flavoring agents, dairy flavoring agents, fruit flavoring agents, hybrid flavoring agents, dessert flavoring agents, tobacco flavoring agents, toothpaste flavoring agents, chewing gum, breath freshening agents, oral solutions (an oral dispersible strips), chewing gum, hard candy, oral care products, toothpaste, toothbrush, dental floss, mouthwash, tooth whitener, denture adhesive, health care devices, tampons, sanitary napkins, anti-inflammatory creams, anti-inflammatory ointments, anti-inflammatory sprays, disinfectants, personal care products, soaps, bar soaps, liquid soaps, fragrance shower emulsions (a bath emulsions), bath liquids (a body wash), non-aerosol body sprays, body milks, cleansers, body creams, sanitizing hand washes, functional product bases, sun lotions, sun sprays, deodorants, roll ball products, aerosol products, natural spray products, body lotions, creams, lotions, creams, lotions, creams, lotions, creams, lotions, or lotions, creams, lotions, creams, lotions, creams, or lotions, creams, or a preparation for use to make-in the form a preparation for use, Wax-based deodorants, glycol deodorants, soap deodorants, facial lotions, body lotions, hand lotions, all-purpose lotions, talcum powders, shaving creams (shave creams), shaving gels, shaving creams (shave lotions), bath soaks (a bath soaks), body washes (a shower gels), exfoliating scrubs, foot creams, facial tissues, cleansing wipes, talc products, hair care products, ammonia-containing hair care products, shampoos, conditioners, rinses (a hair rinses), hair rinses (a hair refreshers), hair styling or styling aids, hair bleaches, hair dyes or colorants, fabric care products, fabric softeners, liquid fabric softeners, fabric softening tablets, desiccant tablets, fabric fresheners, ironing water, detergents, laundry detergents, liquid laundry detergents, laundry powders, laundry tablets, liquid laundry detergents, laundry detergents, Laundry bars, laundry creams, hand laundry detergents, odor enhancers, fragrances (a fragance), colognes, chemical compounds, encapsulated fragrances, perfumes (fine fragance), men's perfumes, women's perfumes, perfumes (perfume), solid perfumes, Eau De toilete products, natural spray products, perfume spray products (perfume spray products), insect repellent products and wildlife odors.

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 from the claims.

Detailed Description

It has been found that certain protein microcapsules have unexpectedly high flavour properties and are environmentally friendly. These protein microcapsule compositions have been successfully incorporated into many consumer product applications.

The microcapsules of the present invention may be prepared by printing the microcapsule shell and the microcapsule core using a printing system, such as a 3D printer. See WO2016172699a 1. Suitable active materials for printing include perfumes, flavors, malodor counteractants, cosmetic actives and nutrients. The printing step generally comprises depositing the active material and microcapsule shell material in a layer-by-layer arrangement, preferably by separate print heads. The microcapsule shell material may be a polymer or an oil-in-water emulsion as described below.

Conveniently, the microcapsule composition of the present invention is prepared according to 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 multifunctional electrophile (e.g., a polyisocyanate, glutaraldehyde, and glyoxal) in an aqueous phase or an oil phase, the oil phase comprising an active material, the aqueous phase comprising a protein and optionally a chaotrope, (ii) optionally adding a multifunctional 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 comprising microcapsules, each 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 ℃, at least 45 ℃, at least 55 ℃, and 35 ℃ to 95 ℃).

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 from 0 ℃ to 125 ℃ (e.g., from 15 ℃ to 110 ℃, from 25 ℃ to 100 ℃, from 45 ℃ to 95 ℃, and from 50 ℃ to 90 ℃) for from 10 minutes to 48 hours (e.g., from 15 minutes to 24 hours, from 30 minutes to 10 hours, and from 30 minutes to 6 hours).

Oil-in-water emulsions can be prepared using conventional emulsion techniques by emulsifying the oil phase into the aqueous phase with or without additional capsule forming aids. The protein can be used as an emulsifier and also can be used as a cross-linking agent. In one embodiment, the oil phase contains an active material (e.g., perfume), a polyfunctional electrophile (e.g., a polyisocyanate), and a core solvent (e.g., caprylic/capric triglyceride). The aqueous phase contains water and protein, with or without emulsifier. In another embodiment, the oil phase contains the active material and the core solvent. The aqueous phase contains water, a multifunctional electrophile (e.g., polyisocyanate, glutaraldehyde and glyoxal), protein, and optionally a capsule-forming aid. In yet another embodiment, the multifunctional electrophile is added to a preformed oil-in-water emulsion, rather than being added to the oil or water phase prior to emulsion formation.

In some embodiments, the method comprises the steps of: proteins are denatured by adjusting the pH, heating or adding chaotropes to the oil-in-water emulsion or to the protein prior to adding the protein to the oil-in-water emulsion.

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

The microcapsules of the present invention each have a core-shell structure with 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 is in contact with the microcapsule core. The outer surface is in contact with the environment in which the microcapsules are located (e.g., water phase, skin, and hair).

The microcapsule wall is formed from a polymer network containing at least three distinct moieties: (i) a first moiety derived from a protein, (ii) a second moiety derived from a multifunctional electrophile (e.g., polyisocyanate, glutaraldehyde, and glyoxal), and (iii) a third moiety derived from a chaotropic agent or a multifunctional nucleophile. The first moiety is covalently linked to the second moiety. When the third moiety is a chaotropic agent, the chaotropic agent has an amine (-NH)₂) Or an alcohol (-OH) functional group, it is attached to the first moiety by covalent or non-covalent bonding (e.g., hydrogen bonding), or to the second moiety by covalent bonding. When the third moiety is a multifunctional nucleophile, it is covalently bonded (e.g., urea linkage (-NHCONH-), urethane linkage (-OCONH-), imine linkage (-OCONH-), etc.)Or a C-N bond found in Michael-type adducts) to the second moiety.

In a preferred embodiment, the polymer network contains four moieties: a first moiety derived from a protein, a second moiety derived from a multifunctional electrophile (e.g., polyisocyanates, glutaraldehyde, and glyoxal), a third moiety derived from a multifunctional nucleophile (e.g., polyamines and polyphenols), and a fourth moiety derived from a chaotropic agent (e.g., guanidine and its salts).

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

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

The microcapsules of the present invention are biodegradable and thus environmentally friendly. As used herein with respect to materials (e.g., the microcapsules as a whole and/or the biopolymer of the microcapsule shell), "biodegradable" has no real or perceived health and/or environmental issues and is capable of undergoing and/or does undergo physical, chemical, thermal, microbial and/or biological degradation. Ideally, the microcapsules and/or biopolymers are considered "biodegradable" when they pass one or more of the following testsThe following components in percentage by weight: the economic cooperation and development Organization (OECD) tests include, but are not limited to, OECD 301/310 (rapid biodegradation), OECD 302 (intrinsic biodegradation), international organization for standardization (ISO)17556 (solid stimulation study), ISO 14851 (fresh water stimulation study), ISO 18830 (marine sediment stimulation study), OECD 307 (soil stimulation study), OECD 308 (sediment stimulation study), and OECD 309 (water stimulation study)). In certain embodiments, the microcapsules are readily biodegradable as determined using the OECD 310 test. The rapid biodegradability pass level under OECD 310 is to reach 60% CO within 60 days of the test₂And (4) yield.

Polypeptide biopolymers and proteins

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 protein (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.

As is conventional in the art, a "polypeptide" or "protein" is a linear organic polymer composed of amino acid residues bonded together in a chain, forming part (or all) of a protein molecule. As used herein, "polypeptide" or "protein" refers to a native polypeptide, a polypeptide derivative, and/or a modified polypeptide. The average molecular weight of the polypeptide may represent from 1,000Da to 40,000,000Da and/or more than 10,000Da and/or more than 100,000Da and/or more than 1,000,000Da and/or less than 3,000,000Da and/or less than 1,000,000Da and/or less than 500,000Da, or a range bounded by any of these molecular weights.

As used herein, "whey protein" refers to a protein contained in whey, which is a liquid milk product obtained as a supernatant of curd when milk or a liquid milk product containing a milk component is processed into cheese curd to obtain a semi-solid cheese-made curd. Whey protein is generally understood in principle to include the globular proteins beta-lactoglobulin and alpha-lactalbumin in various ratios, for example 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 fully modified or denatured whey proteins. Purified beta-lactoglobulin and/or alpha-lactalbumin polypeptides may also be used to prepare the microcapsules of the invention.

Plant storage proteins are proteins that accumulate in various plant tissues and act as biological stores for metal ions and amino acids. Plant storage proteins can be divided into two categories: seed or grain storage proteins (seed or grain storage proteins) and vegetative storage proteins (vegetative storage proteins). Seed/grain storage proteins are a group of proteins that accumulate to high levels in seeds/grains during later stages of seed/grain development, whereas 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 nutritional source by the developing seedling. In some embodiments, the plant storage protein used to prepare the microcapsules of the present invention is a seed or grain storage protein, a vegetative storage protein, or a combination thereof. In certain embodiments, the seed storage protein is a leguminous storage protein. In particular embodiments, the plant is selected from the group consisting of legumes, in particular from soybeans, lupins, peas, chickpeas, alfalfa, horse beans, lentils, and lentils; from oilseed plants, such as rape, cottonseed and sunflower; from cereals, such as wheat, maize, barley, malt, oats, rye and rice (e.g. brown rice protein); or a combination thereof. In other embodiments, the plant storage protein is a nutrient protein extracted from potato or sweet potato tubers.

In particular embodiments, the plant storage protein is intended to include a plant protein isolate, a plant protein concentrate, or a combination thereof. Plant storage protein isolates and concentrates are generally understood to be composed of several proteins. For example, pea protein isolates and concentrates may include soy protein, vicilin, and concilian. Similarly, the brown rice protein isolate may 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. Storage polypeptides alone (e.g., legumin, vicilin, concanavalin, albumin, globulin, or gluten) may also be used to prepare microcapsules of the invention.

"gelatin" refers to a protein mixture produced by partial hydrolysis of collagen extracted from the skin, bone and connective tissue of an animal. Gelatin may be derived from any type of collagen, such as collagen type I, II, III or IV. Such proteins are characterized as comprising a Gly-Xaa-Yaa triplet, wherein Gly is the amino acid glycine and Xaa and Yaa may be the same or different and may be any known amino acid. At least 40% of the amino acids are preferably present in the form of consecutive Gly-Xaa-Yaa triplets.

The whey protein or plant storage protein of the present invention may be native, partially or fully 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.

Commercially available proteins include whey protein concentrate (from Glanbia Nutritions)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 Foods90BR), polished 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.

Denaturation is the process by which a protein (polypeptide) loses the quaternary, tertiary and secondary structure present in its native state by applying denaturing conditions. During denaturation, proteins change their conformational structure by unfolding, thereby allowing amines (-NH)₂) And hydroxyl (-OH) groups can be crosslinked with polyisocyanates to form microcapsule walls. Denaturation is either reversible (a protein can revert to its native state when the denaturing effects are removed) or irreversible.

Exemplary conditions for protein denaturation include, but are not limited to, radiation, exposure to heat or cold, pH change with acids or bases, exposure to denaturing agents such as detergents, inorganic salts, organic solvents (e.g., alcohols, ethyl acetate, and chloroform), urea or other chaotropes, or mechanical stress including shear. In certain embodiments, a chaotropic agent (kJ kg) having a positive chaotropic activity value is used^-1On the Hallsworth scale).

Exemplary chaotropic agents are guanidinium salts (e.g., guanidinium hydrochloride and guanidinium 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, guanidinium thiocyanate, xylose, glycerol, benzyl alcohol, ethyl acetate, triton X-100, ethyl acetate, cetyltrimethylammonium halide, acetone, Sodium Dodecyl Sulfate (SDS), hydrochloric acid, sulfuric acid, polyethylene glycol, glutaraldehyde, and combinations thereof. Any amount of chaotropic agent may be used. The preferred weight ratio of protein to guanidinium salt (guanidine carbonate or guanidine hydrochloride) is from 1:1 to 15:1, more preferably from 2:1 to 10: 1.

For example, when an 8% pea storage protein solution (w/v) is used, the solution may be treated at a temperature of 80-90 ℃ for 20-30 minutes (or preferably at 85 ℃ for 25 minutes) to produce denatured pea storage protein. However, it should be understood that higher temperatures and shorter times may also be employed. In particular embodiments, whey proteins or plant storage proteins are partially or completely denatured using, for example, guanidine carbonate. Notably, it has been found that the degree and method of denaturing the protein can have a significant impact on performance. Thus, in certain embodiments, the 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.

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

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%) by weight of the microcapsule wall. Microcapsule walls with high protein content can be readily biodegradable while effectively encapsulating the perfume with a satisfactory release profile.

Multifunctional nucleophiles

The term "multifunctional 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 (A), (B), (C) and C)Ajinomoto), triethyl citrate (al) (m)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).

Suitable polyfunctional nucleophiles include polyfunctional amines (i.e., polyamines) and polyfunctional alcohols (i.e., polyols).

These agents typically contain multiple (i.e., two or more) functional groups (e.g., -NH-)₂and-OH) which can react with a polyisocyanate to form a polyurea or polyurethane. Examples include polyfunctional amines (e.g., polyamines) and polyfunctional alcohols (e.g., polyols).

Suitable polyamines contain two or more amine groups, including-NH₂and-R NH, R being substituted and unsubstituted C₁-C₂₀Alkyl radical, C₁-C₂₀Heteroalkyl group, C₁-C₂₀Cycloalkyl, 3-to 8-membered heterocycloalkyl, aryl, and heteroaryl.

Two such classes of polyamines include polyalkylene polyamines having the structure:

wherein R is hydrogen or-CH₃(ii) a m, n, x, y and z are each integers from 0 to 2000 (e.g., 1,2, 3,4 and 5). Examples include ethylenediamine, 1, 3-diaminopropane, diethylenetriamine, triethylenetetramine, 1, 4-diaminobutane, hexaethylenediamine, hexamethylenediamine, pentaethylenehexamine, and the like.

Another class of polyamines are the following classes of polyalkylene polyamines:

wherein R is equal to hydrogen or-CH₃M is 1 to 5 and n is 1 to 5, for example, diethylenetriamine, triethylenetetramine and the like. Exemplary amines of this type also include diethylenetriamine, bis (3-aminopropyl) amine, bis (hexaethylenetriamine).

Another class of amines useful in the present invention are polyetheramines. They contain primary amino groups attached to the ends of the polyether backbone. The polyether backbone is typically based on Propylene Oxide (PO), Ethylene Oxide (EO) or mixed PO/EO. Based on this core structure, the ether amine can be a monoamine, diamine, or triamine. One example is:

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

Other suitable amines include, but are not limited to, hexamethylenediamine, ethylenediamine, 1, 3-diaminopropane, 1, 4-diaminobutane, diethylenetriamine, pentaethylenehexamine, bis (3-aminopropyl) amine, bis (hexaethylene) triamine, tris (2-aminoethyl) amine, triethylenetetramine, N, N ' -bis (3-aminopropyl) -1, 3-propanediamine, tetraethylenepentamine, pentaethylenehexamine, chitosan, nisin, gelatin, 1, 3-diamino-guanidine, 1-dimethylbiguanide, guanidine, arginine, lysine, ornithine, 1, 2-diaminopropane, N, N, N ', N ' -tetrakis (2-hydroxyethyl) ethylenediamine, N, N, N ', N ' -tetrakis (2-hydroxypropyl) ethylenediamine, Branched polyethyleneimines, 2, 4-diamino-6-hydroxypyrimidines, and 2,4, 6-triaminopyrimidines, and combinations thereof. Further examples are described in WO 2015/023961A 1.

Amphoteric amines, i.e., amines that can react either as an acid or 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.

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-dimethylbiguanide hydrochloride, guanidine carbonate, and guanidine hydrochloride.

Examples of commercially available amines include products under the following trade names:EDR-148 (where x is 2),EDR-176 (where x is 3),ED series,TRIAMINES (from Huntsman); polyethyleneimines from BASF (ludwigshafen, germany) under the following trade names:(for example,FG、g20 is anhydrous,PR 8515、WF、FC、G20、G35、G100、G500、HF、PS、HEO 1、PN50、PN60、PO100 andSK). Other commercially available polyethyleneimines include the following trade names from NIPPON SHOKUBA (NY):P-1000、P-1050、RP18W andPP-061. Polyvinylamines, for example from BASF, may also be usedThose sold under the trade name of (1). A wide range of polyetheramines can be selected by those skilled in the art.

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

the above formula is often referred to as C₇₆H₅₂O₄₆Given, it corresponds to decagalloylglucose. However, commercially available tannic acids typically comprise a mixture of polygalloylglucose or polygalloylquinic acid esters, with the number of galloyl moieties per molecule ranging from 2 to 20 (e.g., from 2 to 15 and from 2 to 12), and molecular weights from 400 daltons to 3500 daltons (e.g., 496 to 3232 daltons, 496 daltons to 2472 daltons, 180+152n daltons, and 192+152n daltons, where n is from 2 to 13). Tannic acid has weak acidity (e.g., pKa of about 6) in an aqueous solution containing 1% tannic acid, and pH of 2 to 5 (e.g., 3-4 and 2.5 to 3.5). The tannin has a water solubility of 100g/L to 2850g/L (e.g., 250g/L) at 25 ℃.

Tannic acid is typically extracted from any of the following plant parts: tara legume (Caesalpinia spinosa), gallnut from Rhus chinensis (Rhus semiata) or Quercus biflora (Quercus inflctoria) or Rhus occidentalis (Sicilian Sumac) leaves (Rhus coriaria). Tannic acid is commercially available from suppliers such as Sigma-aldrich (st louis) and Ajinomoto OmniChem (wetter, belgium) under the following trade names:01 (polyglucosyl glucose, molecular weight 1440 Dalton),02 (poly galloyl glucose, molecular weight 1040 daltons)Dun) and04 (polygalloylquinic acid ester, molecular weight 860 daltons).

In addition to polyphenols, other polyols may also be used. See the polyol 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, heptatol, isomalt, maltitol, lactitol, maltotriose, maltotetraitol, polyglycitol (polyglycitol), polyphenols, and combinations thereof.

Multifunctional aldehydes, such as glutaraldehyde and glyoxal, form derivatives, such as monohydrate, anhydrate, acetal or hemiacetal, in aqueous solution at certain pH ranges (i.e., under acidic conditions). These polyfunctional aldehyde derivatives have hydroxyl (-OH) groups which are reactive with polyisocyanates to form urethane linkages. Thus, the multifunctional aldehyde acts as a multifunctional nucleophile under certain conditions (e.g., at a pH of 3 to 8).

The multifunctional nucleophile may be present at a level of 0 to 40% (e.g., 1% to 35%, 5% to 35%, and 10% to 30%) by weight of the microcapsule wall.

Carbonyl cross-linking agents

One class of polyfunctional electrophiles are carbonyl crosslinkers, each having at least two functional groups, e.g., a first functional group and a second functional group.

The first functional group is an electrophilic group reactive with proteins, polyamines, polyols and other electron rich groups. Examples include formyl, keto, carboxyl, carboxylate, acid halide, amide, carboxylic anhydride, haloalkyl, 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 a formyl group, a keto group, a carboxyl group, a carboxylate group, an acyl halide group, an amide group, a carboxylic anhydride group, an α, β -unsaturated carbonyl group, a triflate group, and a p-toluenesulfonate group.

The second functional group is an electrophilic group reactive with proteins, polyamines, polyols and other electron rich groups. Examples include formyl, keto, carboxyl, carboxylate, acid halide, amide, carboxylic anhydride, haloalkyl, 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 functional group and the second functional group may be the same or different.

Examples of carbonyl cross-linking agents include glutaraldehyde, succinaldehyde, and glyoxal; and compounds such as glyoxyl trimer and paraformaldehyde, bis (dimethyl) acetal, bis (diethyl) acetal, polymeric dialdehydes, for example oxidized starch. Preferably, the crosslinking agent is a low molecular weight difunctional aldehyde, such as glyoxal, 1, 3-malonaldehyde, 1, 4-succinaldehyde, 1, 5-glutaraldehyde or 1, 6-hexanedial.

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

Polyisocyanate

Another class of polyfunctional electrophiles are polyisocyanates, each of which has at least two isocyanate (-NCO) groups that are reactive with proteins or polyfunctional nucleophiles. The polyisocyanate may be aromatic, aliphatic, linear, branched or cyclic. It may be water soluble or water dispersible. Alternatively, it may be dissolved in an organic solvent or an aromatic oil. In some embodiments, the polyisocyanate contains an average of 2 to 4 isocyanate groups. In a particular embodiment, the polyisocyanate contains at least three isocyanate functional groups. In certain embodiments, the polyisocyanate is water insoluble.

In a particular embodiment, the polyisocyanate used in the present invention is an aromatic polyisocyanate. Desirably, the aromatic polyisocyanate includes a phenyl, tolyl, xylyl, naphthyl or diphenyl moiety as the aromatic component. In certain embodiments, the aromatic polyisocyanate is a polyisocyanurate of toluene diisocyanate, a trimethylolpropane adduct of toluene diisocyanate, or a trimethylolpropane adduct of xylylene diisocyanate.

One suitable class of aromatic polyisocyanates are those having the general structure shown below and structural isomers thereof

Where n can vary from zero to a desired value (e.g., 0-50, 0-20, 0-10, and 0-6), depending on the type of crosslinking agent used. Preferably, the number of n is limited to less than 6. The starting polyisocyanate may also be a mixture of polyisocyanates wherein the value of n may 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% by weight of isocyanate groups "NCO"), wherein the average n is 0.7; PAPI^TM27 (PMDI commercially available from Dow Chemical having an average molecular weight of 340 and 31.4 weight percent NCO) wherein the average n is 0.7;MR (PMDI, containing 31 wt% or more NCO, commercially available from Covestro, Pittsburgh, Pa.) with an average n of 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) wherein the average n is 1; poly [ (phenyl isocyanate) -co-formaldehyde](Aldrich Chemical, Milwaukee, Wis.) other isocyanate monomers, e.g.N3200 (poly (hexamethylene diisocyanate), commercially available from Covestro) and Takenate^TMD-110N (trimethylolpropane adduct of xylylene diisocyanate, Mitsui Chemicals America, Inc., Bluk rye, NY, containing 11.5% by weight of NCO),l75 (a polyisocyanate based on toluene diisocyanate, commercially available from Covestro), andIL (another polyisocyanate based on toluene diisocyanate, commercially available from Covestro).

The structures of some commercially available polyisocyanates of the present invention are shown below:

or a structural isomer thereof. R may be C₁-C₁₀Alkyl radical, C₁-C₁₀Esters or isocyanurates. Representative polyisocyanates of this structure may be sold under the tradename TAKENATE^TM D-110N(Mitsui)、L75(Covestro) andIL (covestro) is commercially available.

Polyisocyanate Takenate^TMD-110N and other polyisocyanates are generally obtained as ethyl acetate solutions. Preferably, the ethyl acetate is replaced by a solvent having a high flash point (e.g., at least 100 ℃, at least 120 ℃, and at least 150 ℃). Suitable solvents include triacetin, triethyl citrate, ethylene glycol diacetate, benzyl benzoate, and combinations thereof.

As an example, Takenate^TMD-110N (ethyl acetate solution of trimethylolpropane adduct of xylylenediisocyanate) was mixed with benzyl benzoate, and ethyl acetate was removed by vacuum distillation to obtain a trimethylolpropane adduct solution containing 59% of xylylenediisocyanate and a polyisocyanate solution containing 41% of benzyl benzoate. The polyisocyanate solution has a flash point of at least 60 ℃. This benzyl benzoate solution of polyisocyanate can be used to prepare microcapsule compositions together with PVP/PQ-11 or Flexan/CMC.

Other examples of the aromatic polyisocyanate include 1, 5-naphthylene diisocyanate, 4 '-diphenylmethane diisocyanate (MDI), hydrogenated MDI, Xylylene Diisocyanate (XDI), tetramethylxylene diisocyanate, 4' -diphenyldimethylmethane diisocyanate, di-and tetraalkyl-diphenylmethane diisocyanates, 4 '-dibenzyl diisocyanate, 1, 3-phenylene diisocyanate, 1, 4-phenylene diisocyanate, isomers of Tolylene Diisocyanate (TDI), 4' -diisocyanatophenyl-perfluoroethane, diisocyanatoethyl phthalate, and polyisocyanates having a reactive halogen atom, such as 1-chloromethylphenyl 2, 4-diisocyanate, diisocyanatodiphenylmethane, diphenylmethane diisocyanate, tolylene diisocyanate, and tolylene diisocyanate, 1-bromomethyl-phenyl 2, 6-diisocyanate and 3, 3-bischloromethyl ether 4,4' -diphenyl diisocyanate, and combinations thereof.

In other particular embodiments, the polyisocyanate is an aliphatic polyisocyanate, such as a trimer of hexamethylene diisocyanate, a trimer of isophorone diisocyanate, and a biuret of hexamethylene diisocyanate. Exemplary aliphatic polyisocyanates include commercial products such as, for example,N302、N303、n304 andn305, which are aliphatic water-dispersible products based on hexamethylene diisocyanate;N3600、n3700 andn3900, which are low-viscosity, polyfunctional aliphatic polyisocyanates based on hexamethylene diisocyanate; and3600 andn100, 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 polyisocyanatesFor 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 diisocyanate, and combinations thereof.

Useful polyisocyanates have a weight average molecular weight ranging from 200Da to 2500Da, 250Da to 1000Da and preferably between 275Da to 500 Da.

The polyisocyanate content may range between 1% to 30% (e.g., 2% to 25%, 3% to 20%, and 5% to 15%) by weight of the microcapsule wall.

In the process of preparing the microcapsule composition of the present invention, the polyisocyanate may be added to the water phase, the oil phase or the oil-in-water emulsion.

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 aliphatic polyisocyanates and aromatic polyisocyanates. In a particular embodiment, the mixture of polyisocyanates is a biuret of hexamethylene diisocyanate and a trimethylolpropane adduct of xylylene diisocyanate. In certain embodiments, the polyisocyanate is an aliphatic isocyanate or a mixture of aliphatic isocyanates, free of any aromatic isocyanates. In other words, in these embodiments, no aromatic isocyanate is used to prepare the encapsulating polymer as a capsule wall material. Further examples of polyisocyanates can be found in WO 2004/054362 and WO 2017/192648.

Capsule forming aid

Microcapsule compositions are typically prepared in the presence of a capsule forming adjuvant, which may be a surfactant or dispersant. The capsule forming aid also improves the performance of the microcapsule composition. Performance is measured by the intensity of the fragrance released at certain stages, for example, the pre-rub (pre-rub) and post-rub (post-rub) stages in laundry applications. The pre-rub stage is the stage when the capsules have been deposited on the cloth, for example, after a wash cycle using a fabric softener or detergent containing the capsules. The post-kneading stage is after the capsules are deposited and ruptured by kneading or other mechanisms.

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 ethers with maleic anhydride or acid, sodium lignosulfonates, maleic anhydride/styrene copolymers, ethylene/maleic anhydride copolymers, and copolymers of propylene oxide and ethylene oxide, polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), sodium salts of naphthalene sulfonic acid condensates, carboxymethylcellulose (CMC), fatty acid esters of polyoxyethylated sorbitol, sodium lauryl sulfate, and combinations thereof. The concentration of capsule forming aids (e.g., surfactants and dispersants) varies between 0.1% to 5% (e.g., 0.2% to 4%, 0.5% to 2.5%, and 1% to 2%) by weight of the capsule composition.

Commercially available surfactants include, but are not limited to, sulfonated naphthalene-formaldehyde condensates, e.g.D-425 (an alkylnaphthalene sulfonate formaldehyde condensate, commercially available from Akzo Nobel, Watsburg, Tex.); the name of the commodity isPartially hydrolyzed polyvinyl alcohols, e.g.3-83 (commercially available from Kuraray, Houston, Tex.); ethylene oxide-propylene oxide block copolymers or poloxamers, e.g.Or(BASF); sulfonated polystyrenes, e.g.II (Akzo Nobel); ethylene-maleic anhydride polymers, e.g.(Vertellus Specialties Inc., Indianapolis, Ind. Andean); and polyquaternium series, such as polyquaternium 11 ("PQ 11"; copolymers of vinylpyrrolidone and quaternized dimethylaminoethyl methacrylate; from BASF andPQ11 AT 1).

Processing aids may also be used as capsule forming aids. They include hydrocolloids, which improve the colloidal stability of the slurries against coagulation, sedimentation and creaming. The term "hydrocolloid" refers to a broad class of water-soluble or water-dispersible polymers having anionic, cationic, zwitterionic or nonionic character. Hydrocolloids useful in the present invention include, but are not limited to, polycarbohydrates such as starches, modified starches, dextrins, maltodextrins, and cellulose derivatives, and their quaternized forms; natural gums such as alginate esters, carrageenan, xanthan gum, agar, pectin, pectic acid, and natural gums such as gum arabic, gum tragacanth and gum karaya, guar gum and quaternized guar gum; gelatin, protein hydrolysates and their quaternized forms; synthetic polymers and copolymers such as poly (vinylpyrrolidone-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 oxides), 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 quaternized forms thereof.

The capsule forming aid can also be mixed with carboxymethyl cellulose ("CMC"), polyvinylpyrrolidone, polyethylene during processingThe enol, alkyl naphthalene sulfonate formaldehyde condensate and/or surfactant are used in combination to promote capsule formation. Examples of such surfactants include cetyltrimethylammonium chloride (CTAC), under the trade name CTAC(e.g. inF127)、(e.g. inF127) OrPoloxamers, 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 0.1 to 3, preferably 0.65 to 1.4, more preferably 0.8 to 1. The CMC polymer is present in the capsule slurry at a level of 0.1% to 2%, preferably 0.3% to 0.7%. In other embodiments, the polyvinylpyrrolidone 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 polyvinylpyrrolidones are polyvinylpyrrolidone K12, K15, K17, K25, K30, K60, K90 or mixtures thereof. The amount of polyvinylpyrrolidone is from 2% to 50%, from 5% to 30% or from 10% to 25% by weight of the microcapsule composition.

Catalyst and process for preparing same

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-dimethylaminoethanol, N-dimethylcyclohexylamine, bis- (2-dimethylaminoethyl) ether, N-dimethylacetamide, stannous octoate and dibutyltin dilaurate.

Other encapsulating polymers

The microcapsule composition of the present invention optionally has a second, third, fourth, fifth or sixth microcapsule, each microcapsule being made of a material selected from the group consisting of sol-gel polymers (e.g., silica), polyacrylates, polyacrylamides, poly (acrylate-co-acrylamide), polyureas, polyurethanes, starches, gelatin and gum arabic, poly (melamine-formaldehyde), poly (urea-formaldehyde), and combinations thereof. The branched polyethyleneimine and derivatives thereof can also be coated on the microcapsule wall to prepare the microcapsule with positive zeta potential.

These encapsulating polymers are described in detail below.

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 a polymerization reaction (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.

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

An example of a sol-gel precursor suitable for the purposes of the present invention is an alkoxysilane corresponding to the general formula:

(R₁O)(R₂O)M(X)(X’)，

wherein X may be hydrogen OR-OR₃(ii) a X' may be hydrogen OR-OR₄(ii) a And R is₁、R₂、R₃And R₄Independently represent an organic radical, more particularly a linear or branched alkyl radical, preferably C₁-C₁₂An alkyl group. M may be Si, Ti or Zr.

Preferred sol/gel precursors are alkoxysilanes corresponding to the general formula: (R)₁O)(R₂O) Si (X) (X '), wherein X, X' and R₁And R₂Each as defined above.

Particularly preferred compounds are silicates, such as tetramethyl orthosilicate (TMOS) and tetraethyl orthosilicate (TEOS). Preferred compounds include(an organofunctional silane, commercially available from Degussa Corporation, Parsippani, N.J., 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.) may be attached to the silicon as substituents.

Recognizing 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 molecular and active ingredients, it is highly advantageous because it helps to dissolve high concentrations of active material and therefore the loading in the final capsule is high.

Polyacrylate microcapsules, polyacrylamide microcapsules and poly (acrylate-co-acrylamide) microcapsules. These microcapsules are prepared from the corresponding precursors forming 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 tetramethacrylate/acrylamide, dipentaerythritol hexamethacrylate/acrylamide, mixtures thereof, and mixtures thereof, 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-butanediol diacrylate/acrylamide, 1, 4-butanediol dimethacrylate/acrylamide, 1, 4-butanediol diacrylate/acrylamide, diethylene glycol diacrylate/acrylamide, ethylene glycol diacrylate/acrylamide, propylene glycol diacrylate, ethylene glycol diacrylate, propylene glycol diacrylate, ethylene glycol diacrylate, propylene glycol diacrylate, and the like, 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 dimethacrylate/acrylamide, dipropylene glycol diacrylate/acrylamide, alkoxylated hexanediol diacrylate/acrylamide, alkoxylated cyclohexane dimethanol diacrylate/acrylamide, propoxylated neopentyl glycol diacrylate/acrylamide, poly (ethylene glycol) diacrylate/propylene glycol diacrylate, poly (ethylene glycol) diacrylate/acrylamide, poly (ethylene glycol) diacrylate/propylene glycol diacrylate/acrylamide), poly (ethylene glycol) diacrylate/propylene glycol diacrylate/acrylamide, poly (ethylene glycol) diacrylate/acrylamide), poly (ethylene glycol) acrylate), poly (ethylene glycol) acrylate, poly (ethylene glycol), and poly (ethylene glycol) acrylate), and poly (ethylene glycol) acrylate), and/acrylate), and poly (ethylene glycol) acrylate), and poly (ethylene glycol) and/or poly (ethylene glycol) and/bis (ethylene glycol) and/or poly (ethylene glycol) and/or a mixture, Trimethylolpropane triacrylate/acrylamide, pentaerythritol triacrylate/acrylamide, ethoxylated 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-acryloxy diol monoacrylate/acrylamide, triacrylaldehyde (triacryl formal), triallyl isocyanate and triallyl isocyanurate.

The monomers are typically polymerized in the presence of an activator (e.g., an initiator) at elevated temperatures (e.g., 30-90 ℃) or under ultraviolet light. Exemplary initiators are 2,2' -azobis (isobutyronitrile) ("AIBN"), dicetyl peroxydicarbonate, bis (4-tert-butylcyclohexyl) peroxydicarbonate, dioctanoyl peroxide, dibenzoyl peroxide, dilauroyl peroxide, didecanoyl peroxide, tert-butyl peracetate, tert-butyl perbenzoate, tert-butyl hydroperoxide, cumene ethylperoxide, diisopropylhydroxydicarboxylate, 2' -azobis (2, 4-dimethylvaleronitrile), 1' -azobis- (cyclohexane-l-carbonitrile), dimethyl 2,2' -azobis (2-methylpropionate), 2' -azobis [ 2-methyl-N- (2-hydroxyethyl) propionamide, Sodium persulfate, benzoyl peroxide, and combinations thereof.

The emulsifiers used to form these capsule walls are typically anionic emulsifiers including, but not limited to, alkyl sulfates, alkyl ether sulfates, alkyl isothionates, 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 alkylaryl ether phosphates, sodium lauryl sulfate, phospholipids or lecithin, or soaps, stearic acid, oleic acid or sodium palmitate, potassium or ammonium, alkylaryl sulfonates such as sodium dodecylbenzene sulfonate, dialkyl sulfosuccinates, dioctyl sulfosuccinates, sodium dilauryl sulfosuccinates, poly (styrene sulfonic acid) sodium salt, isobutylene-maleic anhydride copolymer, gum arabic, sodium alginate, carboxymethyl cellulose, cellulose sulfate and pectin, sodium lauryl sulfate, or sodium stearate, or sodium lauryl sulfate, or sodium, Poly (styrene sulfonate), isobutylene-maleic anhydride copolymer, gum arabic, carrageenan, sodium alginate, pectic acid, tragacanth, almond gum, and agar; semi-synthetic polymers such as carboxymethyl cellulose, sulfated methyl cellulose, carboxymethyl starch, phosphated starch, lignosulfonic acid; and synthetic polymers such as maleic anhydride copolymers (including hydrolysis products 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 alcohols, sulfonic acid-modified polyvinyl alcohols and phosphoric acid-modified polyvinyl alcohols, phosphorylated or sulfated tristyrylphenol ethoxylates. The amount of anionic emulsifier is from 0.1% to 40% by weight of all ingredients, more preferably from 0.5% to 10%, more preferably from 0.5% to 5% by weight.

Aminoplasts (aminoplasts) and gelatin. Representative methods for aminoplast encapsulation are disclosed in US 3,516,941 and US 2007/0078071, however it is recognized that many variations on materials and process steps are possible. Another encapsulation method, gelatin encapsulation, is disclosed in US2,800,457. These two methods are discussed in U.S. Pat. Nos. 4,145,184 and 5,112,688, respectively, for fragrance packaging for consumer products. Polymeric systems are well known in the art, and non-limiting examples of such systems include aminoplast capsules and encapsulated particles as disclosed in GB 2006709A; as disclosed in US 4,396,670, microcapsules are produced having a wall comprising styrene-maleic anhydride reacted with melamine-formaldehyde precondensate; acrylic acid-acrylamide copolymers crosslinked with melamine-formaldehyde resins as disclosed in US 5,089,339; capsules consisting of cationic melamine-formaldehyde condensates as disclosed in US 5,401,577; melamine formaldehyde microencapsulation as disclosed in US 3,074,845; amide aldehyde resins as disclosed in EP 0158449 a1 in situ polymerized capsules; etherified urea-formaldehyde polymers as disclosed in US 5,204,185; melamine-formaldehyde microcapsules as described in US 4,525,520; crosslinked oil-soluble melamine-formaldehyde precondensates as described in US 5,011,634; capsule wall materials formed from complexes of cationic and anionic melamine-formaldehyde precondensates which are then crosslinked as disclosed in US 5,013,473; polymeric shells made from addition polymers such as polycondensates, phenolic, urea-formaldehyde or acrylic polymers as disclosed in US 3,516,941; urea formaldehyde capsules as disclosed in EP 0443428 a 2; melamine-formaldehyde chemistry as disclosed in GB 2062570A; and capsules consisting of polymers or copolymers of styrene sulfonic acid in the acid salt form, and capsules crosslinked with melamine-formaldehyde as disclosed in US 4,001,140.

Urea-formaldehyde and melamine formaldehyde capsules. The urea-formaldehyde and melamine-formaldehyde precondensate capsule shell wall precursor is prepared by reacting urea or melamine with formaldehyde in a molar ratio of melamine or urea to formaldehyde in the range of 10:1 to 1:6, preferably in the range of 1:2 to 1: 5. To practice the invention, the molecular weight of the resulting material is in the range of 156Da to 3000 Da. The resulting material may be used "as is" as a crosslinking agent for the above substituted or unsubstituted acrylic polymer or copolymer, or it may be further reacted with C₁-C₆The alkanol (e.g., methanol, ethanol, 2-propanol, 3-propanol, 1-butanol, 1-pentanol, or 1-hexanol) is reacted to form a partial ether in which the ratio of melamine/urea: formaldehyde: the molar ratio of the alkanol is in the range of 1 (0.1-6) to (0.1-6). The resulting product containing ether moieties may be used "as is" as a crosslinking agent for the above substituted or unsubstituted acrylic polymers or copolymers, or it may self-condense to form dimers, trimers and/or tetramers, which may also be used as a crosslinking agent for the above substituted or unsubstituted acrylic polymers or copolymers. Methods for forming such melamine-formaldehyde and urea-formaldehyde precondensates are described in U.S. Pat. Nos. 6,261,483 and Lee et al (2002) J.Microencapsation 19,559-569.

An example of a urea-formaldehyde precondensate that can be used in the practice of the present invention is URAC^TM180 and URAC^TM186, Cytec Technology Corp (Wilmington, DE). Examples of melamine-formaldehyde precondensates that can be used in the practice of the present invention include, but are not limited to U-64 andu-65, trademark of Cytec Technology Corp. (Wilmington, DE). It is preferred to use a substituted or unsubstituted acrylic polymer or copolymer as precondensate for crosslinking. In the practice of the present invention, the molar ratio of urea-formaldehyde precondensate/melamine-formaldehyde precondensate to substituted/unsubstituted acrylic polymer/copolymer is in the range of from 9:1 to 1:9, preferably from 5:1 to 1:5, and most preferably from 2:1 to 1: 2.

In one embodiment of the invention, microcapsules having a polymer composed of primary and/or secondary amine reactive groups or mixtures thereof and a crosslinking agent may also be used. See US 2006/0248665. The amine polymer may have primary and/or secondary amine functional groups and may be of natural or synthetic origin. Amine-containing polymers of natural origin are generally proteins, such as gelatin and albumin, and some polysaccharides. Synthetic amine polymers include various degrees of hydrolyzed polyvinyl formamide, polyvinyl amine, polyallylamine, and other synthetic polymers having pendant primary and secondary amine groups. Examples of suitable amine polymers are available from BASFA series of polyvinyl formamides. The molecular weight of these materials may range from 10,000Da to 1,000,000 Da.

These capsules may also include a formaldehyde scavenger capable of binding free formaldehyde. Formaldehyde scavengers such as sodium sulfite, melamine, glycine and carbohydrazine are suitable when the capsules are used in an aqueous medium. When the capsules are used in products having a low pH (e.g. fabric conditioners), the formaldehyde scavenger is preferably selected from a beta diketone, such as a beta ketoester, or from a1, 3-diol, such as propylene glycol. Preferred beta-ketoesters include alkyl malonates, alkyl acetoacetates, and polyvinyl alcohol acetoacetates.

The microcapsule compositions of the present invention optionally contain one or more additional microcapsules, for example, a second, third, fourth, fifth, or sixth microcapsule. Each of these microcapsules may be any of those described above.

These additional microcapsules may be any of the microcapsules described above, but differ from each other in terms of microcapsule size, degree of polymerization, degree of crosslinking, encapsulating polymer, wall thickness, active material, ratio between wall material and active material, breaking force or breaking strength, etc.

Active material

The microcapsule core may comprise one or more active materials, including flavour and/or fragrance ingredients (fragrances), such as perfume oils. Individual active materials that can be encapsulated include those listed on pages 38-50 of WO 2016049456. These active materials include flavor or fragrance ingredients, taste masking agents, taste tastants (tast sensates), malodor counteractants, vitamins or derivatives thereof, antibacterial agents, sunscreen actives, antioxidants, anti-inflammatory agents, fungicides, anesthetics, analgesics, antifungal agents, antibiotics, antivirals, antiparasitics, anti-infective agents, anti-acne agents, dermatological actives, enzymes and coenzymes, skin lightening 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, drivers, pest repellents, flame retardants, antistatic agents, nano to micro sized inorganic solids, polymeric or elastomeric particles, and combinations thereof.

High performance, high impact (high impact) fragrances are contemplated. A class of high performance perfumes is described in WO 2018/071897. These perfumes have a high intensity accord (accord) comprising (i) at least 7 wt% (e.g., 7 to 95 wt%) of a class 1 perfume ingredient, (ii)5 to 95 wt% (e.g., 5 to 80 wt%, 10 to 80 wt%, and 10 to 70 wt%) of a class 2 perfume ingredient, and (iii)0 to 80 wt% of a class 3 perfume ingredient, wherein the class 1 perfume ingredients each have an experimental speed of 8.5 cm/sec or greater, the class 2 perfume ingredients each have an experimental speed of less than 8.5 cm/sec and greater than 5 cm/sec, and the class 3 perfume ingredients each have an experimental speed of 5 cm/sec or less. In some embodiments, the sum of the class 1 perfume ingredient, the class 2 perfume ingredient and the class 3 perfume ingredient is 100%. In other embodiments, the sum of the group 1 and group 2 ingredients is from 20% to 100% by weight. Other high impact perfumes 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.

In addition to the active materials listed above, the products of the invention may also contain, for example, the following dyes, colorants or pigments: lactoflavin (riboflavin), beta-carotene, riboflavin-5 '-phosphate, alpha-carotene, gamma-carotene, canthaxanthin, erythrosine, curcumin, quinoline yellow, yellow orange S, tartrazine, annatto, norbixin (annatto, orleans), capsaicin, capsanthin, lycopene, beta-apo-8' -carotenal ethyl ester, xanthophylls (xanthins, lutein, cryptoxanthin, rubixanthin, violaxanthin, rhodoxanthin (rodoxanthin)), permanent carmine (carminic acid, cochineal), azorubin, cochineal A (Ponceau)^TM4R), beet red, betanin, anthocyanins, amaranth, patent blue V, indigo I (indigo carmine), chlorophylls, copper chlorophyllins compounds, acid brilliant green BS (lissamine green), brilliant black BN, vegetable carbons, titanium dioxide, iron oxides and hydroxides, calcium carbonate, aluminum, silver, gold, pigment rubine BK (lithol rubine BK), methyl violet B, victoria blue R, victoria blue B, brilliant acid blue FFR (brilliant wool blue FFR), naphthol green B, acid fast green 10G (basic fast green 10G), god yellow grn (ceres yellow grn), sudan blue II, ultramarine, phthalocyanine blue, phthalocyanine green, fast acid violet R. Other naturally obtained extracts (e.g., paprika extract, black carrot extract, red cabbage extract) may be used for coloring purposes. Good results have also been obtained with the following named colorants (so-called aluminium lakes): FD&C yellow No. 5 lake, FD&C blue No. 2 lake, FD&C blue No. 1 lake, tartrazine 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), amaranthLakes, Ponceau 4R Lake, erythrosine Lake (erythrosine 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.

When the active material is a perfume, it is preferred to use perfume ingredients in the perfume having a ClogP of from 0.5 to 15. For example, ingredients having ClogP values 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 5, between 3 and 7) are 25% or more (e.g., 50% or more and 90% or more) by weight of the perfume.

Preferably, perfumes having a weight average ClogP of 2.5 or more (e.g., 3 or more, 2.5 to 7, 2.5 to 5) are used. The weight-averaged ClogP was calculated as follows:

ClogP＝{Sum[(Wi)(ClogP)i]}/{Sum Wi}，

where Wi is the weight fraction of each perfume ingredient, (ClogP) i is the ClogP of the perfume ingredient.

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

Those skilled in the art will appreciate that a variety of solvents and fragrance chemicals can be used to form a wide variety of fragrances. The use of relatively low to moderate ClogP perfume ingredients will result in a perfume suitable for encapsulation. These perfumes are generally water insoluble and are delivered by the capsule system of the present invention to consumer products at various stages, such as damp and dry fabrics. Free perfume, without encapsulation, is typically evaporated or dissolved in water during use (e.g., washing). While high ClogP materials generally release well from conventional (non-encapsulated) perfumes in consumer products, they have excellent encapsulation properties, are also suitable for encapsulation for the purpose of achieving overall perfume character, very long lasting perfume delivery, or to overcome incompatibilities with consumer products such as perfume materials that are otherwise unstable, cause thickening or discoloration of the product, or otherwise negatively impact desired consumer product properties.

In some embodiments, the amount of encapsulated active material is from 5% to 95% (e.g., from 10% to 90%, from 15% to 90%, and from 20% to 80%) by weight of the microcapsule composition. The amount of capsule wall is also from 0.5% to 30% (e.g., from 1% to 25%, from 2 to 20%, and from 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.

Auxiliary material

In addition to active materials, the present invention also contemplates the incorporation of auxiliary materials, including solvents, emollients, and core modifier materials, into the core of the capsule wall encapsulation. Other auxiliary materials are solubility modifiers, density modifiers, stabilizers, viscosity modifiers, pH modifiers, or any combination thereof. These modulators may be present in the wall or core of the capsule, or outside the capsule in a delivery system. Preferably, they act as nuclear modulators in the nucleus.

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

Suitable examples include those described in WO 2016/049456, pages 55-57 and US 2016/0158121, pages 15-18.

Deposition aid

An exemplary deposition aid useful in the microcapsule compositions of the present invention is a copolymer of acrylamide and acrylamidopropyltrimethylammonium chloride. Such copolymers facilitate deposition of microcapsules on hard surfaces (e.g., hair, skin, fibers, furniture, and floors). The average molecular weight (e.g., weight average molecular weight (Mw) as determined by size exclusion chromatography) of the copolymer is typically 2,000Da to 10,000,000Da, with a lower limit of 2,000Da, 5,000Da, 10,000Da, 20,000Da, 50,000Da, 100,000Da,250,000Da, 500,000Da, or 800,000Da and an upper limit of 10,000,000Da, 5,000,000Da, 2,000,000Da, 1,000,000Da, or 500,000Da (e.g., 500,000Da to 2,000,000Da and 800,000Da to 1,500,000 Da). The charge density of the copolymer is in the range of 1meq/g to 2.5meq/g, preferably 1.5meq/g to2.2 meq/g. Copolymers of acrylamide and acrylamide-propyltrimethylammonium chloride are available from various suppliers such as Ashland asSP-100 and CibaSC60 is commercially available.

Other suitable deposition aids include anionic, cationic, nonionic or zwitterionic water-soluble polymers. Suitable deposition aids trimethyl ammonium, methacrylamidopropyl trimethyl ammonium, acrylamidopropyl trimethyl ammonium, acrylamide, acrylic acid, dimethyl ammonium, xylose, galactose, hydroxypropylated glucose, hydroxyethylated glucose, chitosan, hydroxymethylated glucose, vinylamine, ethyleneimine, functionalized branched polyethyleneimine, vinylformamide, vinylpyrrolidone, 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, Polyquaternium-47, polyquaternium-53, polyquaternium-55, polyquaternium-67, polyquaternium-68, polyquaternium-69, polyquaternium-73, polyquaternium-74, polyquaternium-77, polyquaternium-78, polyquaternium-79 and hydrolyzed keratin copolymers, polyquaternium-80, polyquaternium-81, polyquaternium-82, polyquaternium-86, polyquaternium-88, polyquaternium-101, polyvinylamine, polyethyleneimine, copolymers of vinylamine and vinylformamide, copolymers of methacrylamidopropyltrimethylammonium chloride and acrylamide, copolymers of acrylamide and acrylamidopropyltrimethylammonium chloride, 3-acrylamidopropyltrimethylammonium polymer or copolymers thereof, Diallyl dimethyl ammonium chloride polymers and copolymers thereof, polysaccharides having saccharide units functionalized with hydroxypropyl trimethyl ammonium, ethyltrimethyl ammonium chloride methacrylate/hydrolyzed wheat protein copolymers, alkylammonium hydroxypropyl hydrolyzed proteins, and combinations thereof. Further examples of deposition aids are described on pages 13-27 of WO 2016049456; US 2013/0330292; US 2013/0337023; and US 2014/0017278.

Further deposition aids are those cationic polymers described in WO 2016032993. These cationic polymers are typically characterized by relatively high charge densities (e.g., from 4meq/g, or from 5meq/g, or from 5.2meq/g to 12meq/g, or to 10meq/g, or to 8meq/g or to 7meq/g, or to 6.5 meq/g. the cationic polymers comprise structural units that are nonionic, cationic, anionic, or mixtures thereof in some aspects the cationic polymers comprise from 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-dialkylacrylamide, N-dialkylmethacrylamide, C₁-C₁₂Alkyl acrylate, C₁-C₁₂Hydroxyalkyl acrylates, polyalkylene glycol acrylates, C₁-C₁₂Alkyl methacrylate, C₁-C₁₂Hydroxyalkyl methacrylates, polyalkylene glycol methacrylates, vinyl acetate, vinyl alcohol, vinyl formamide, vinyl acetamide, vinyl alkyl ether, vinyl pyridine, vinyl pyrrolidone, vinyl imidazole, vinyl caprolactam, and mixtures thereof.

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

In some aspects, the cationic polymer comprises anionic structural units at a level of 0.01 to 15 mol%, 0.05 to 10 mol%, or 0.1 to 5 mol% by 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, vinylsulfonic acid, styrenesulfonic acid, acrylamidopropylmethanesulfonic Acid (AMPS), and salts and mixtures thereof.

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.

The deposition aid is 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%, e.g., from 0.1% to 30%, 1% to 20%, 2% to 15%, and 5% to 10%) by weight of the microcapsule composition. In consumer products such as shampoos, the deposition aid is 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 made.

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.

Additional Components

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-encapsulated or unencapsulated active materials.

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

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

Any of the compounds, polymers or agents discussed above may be the compounds, polymers or agents themselves, or salts, precursors, hydrates or solvates thereof, as indicated above. Salts may be formed between an anion and a positively charged group on a compound, polymer or reagent. Suitable anions include chloride, bromide, iodide, sulfate, nitrate, phosphate, citrate, methanesulfonate, trifluoroacetate, acetate, malate, toluenesulfonate, tartrate, fumarate, glutamate, glucuronate, lactate, glutarate, and maleate. Likewise, salts may also be formed between cations and negatively charged groups on compounds, polymers, or agents. Suitable cations include sodium, potassium, magnesium, calcium, and ammonium cations (e.g., tetramethylammonium). The precursor may be an ester and another suitable derivative which can be converted to a compound, polymer or reagent during the preparation of the capsule composition of the present invention and used to prepare the capsule composition. Hydrate refers to a compound, polymer, or agent that contains water. Solvates refer to complexes formed between a compound, polymer or agent and a suitable solvent. Suitable solvents may be water, ethanol, isopropanol, ethyl acetate, acetic acid and ethanolamine.

Certain compounds, polymers, and agents have one or more stereocenters, each of which can be in the R configuration, S configuration, or mixtures. In addition, some compounds, polymers, and agents have one or more double bonds, where each double bond is present in either the E (trans) or Z (cis) configuration, or a combination thereof. The compounds, polymers and reagents include all possible configurational stereoisomeric, regioisomeric, diastereomeric, enantiomeric and epimeric forms, and any mixtures thereof. Thus, lysine as used herein includes L-lysine, D-lysine, L-lysine monohydrochloride, D-lysine monohydrochloride, lysine carbonate, and the like. Similarly, arginine includes L-arginine, D-arginine, L-arginine monohydrochloride, D-arginine monohydrochloride, arginine carbonate, arginine monohydrate, and the like. Guanidines include guanidine hydrochloride, guanidine carbonate, guanidine thiocyanate, and other guanidine salts, including hydrates thereof. Ornithine includes L-ornithine and salts/hydrates thereof (e.g., monohydrochloride) and D-ornithine and salts/hydrates thereof (e.g., monohydrochloride).

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

Microcapsule compositions are known to have a tendency to form gels, which are not suitable for many consumer products. The viscosity of the gelled composition (geled-out composition) increases to at least 3000 centipoise (cP) (e.g., at least 6000 cP). Can be easily used in rheometers such as RheoStress^TM1 Instrument (commercially available from Thermoscientific) using a rotating disk at 21s^-1And the viscosity was measured at a temperature of 25 ℃. In certain embodiments, the microcapsule compositions of the present invention are in 21s^-1And a viscosity at a temperature of 25 ℃ of less than 3000 cP.

The stability of the microcapsules can be evaluated using a variety of different methods, including physical stability and/or storage stability. When evaluating physical stability, exemplary microcapsule compositions can be dispersed in an aqueous phase and exhibit stability at 40 ℃ for at least 7 days (e.g., at least 10 days, at least 30 days, and at least 60 days). Stability is measured by separating a clear aqueous phase from the microcapsule composition (e.g., in a graduated cylinder). A microcapsule composition is considered stable if less than 10% of a clear aqueous phase separates out by volume of the microcapsule composition. The microcapsule composition is considered stable when (i) the viscosity of the composition is 3000cP or less (e.g., 2000cP 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 volume of separated water can be easily measured by conventional methods such as measuring cylinder.

When evaluating storage stability, fragrance retention (fragrance coverage) within the microcapsules can be measured directly after storage in the consumer product base at a desired temperature and time period, e.g., four weeks, six weeks, two months, three months, or longer. A preferred way is to measure the total headspace (total head space) of the consumer product at a given time and compare the result with the headspace of a control consumer product made by adding the total amount of perfume present directly, representing 0% fragrance. Alternatively, the consumer product may be tested for performance after a storage period and the performance compared to fresh product by analysis or by sensory evaluation. Such measurements often involve measuring the fragrance headspace above a substrate used with the product, or performing an odor assessment on the same substrate. In certain embodiments, the fragrance retention of an active material in a microcapsule core of the invention is assessed in a consumer product base, for example, under storage conditions, for example, for an extended period of at least 2 weeks, 4 weeks, 6 weeks, 8 weeks, 16 weeks, or 32 weeks, at a temperature in the range of 25 ℃ to 40 ℃, or more preferably in the range of 30 ℃ to 37 ℃, or most preferably at 37 ℃. In certain embodiments, 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 particular embodiments, the microcapsules of the present invention retain from 40% to 90% of the active material when added to a consumer product base after storage at 37 ℃ 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 for 8 weeks at 37 ℃.

Using the method of the invention, a relatively high encapsulation efficiency is achieved. "encapsulation efficiency" or "micro-encapsulation efficiency" or "MEE" represents the proportion of active material cores that is not obtained by the extraction solvent under the specified test conditions. According to the method of the present invention, a micro-encapsulation efficiency of 50% to 99.9% or more preferably 60% to 99.7% can be achieved. In particular, a packaging efficiency of at least 90%, 92%, 94%, 96%, 98% or 99% is achieved.

In some embodiments, the microcapsule composition is purified by washing the capsule slurry with water until a neutral pH is reached (pH 6 to 8). For the purposes of the present invention, the capsule suspension may be washed using any conventional method, including using a separatory funnel, filter paper, centrifugation, and the like. The capsule suspension may be washed once, twice, three times, four times, five times, six times or more until a neutral pH is reached, e.g., pH6-8 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, pH indicators, or pH meters.

The capsule composition is "purified" in that it has 80%, 90%, 95%, 97%, 98%, or 99% homogeneity with the capsule. According to the invention, purity is obtained by washing the capsules until a neutral pH is reached, which indicates the removal of unwanted impurities and/or starting materials, such as polyisocyanates, cross-linking agents, etc.

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

The microcapsule compositions of the present invention may also be dried (e.g., spray dried, heat dried, and belt dried) to solid form. During the spray drying process, a spray drying carrier is added to the microcapsule composition to aid in the removal of water from the slurry. See US20120151790, US20140377446, US20150267964, US20150284189, and US 20160097591.

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

Optionally, 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-blocking agent) may be present, which may be hydrophobic (i.e. silanol surface treated with halosilanes, alkoxysilanes, silazanes, siloxanes, etc., e.g. silanol surfaceD17、R972 and R974 (available from Degussa), etc.) and/or hydrophilic, e.g.200、22S、50S, (available from Degussa);244 (available from Grace Davison).

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

The spray drying inlet temperature is in the range of 150 ℃ to 240 ℃, preferably between 170 ℃ to 230 ℃, more preferably between 190 ℃ to 220 ℃.

As described herein, the spray-dried microcapsule compositions are well suited for use in various all-dry (anhydrous) products: powdered laundry detergents, fabric softener dry tablets, household cleaning dry wipes, powdered dish detergents, floor cleaning cloths, or any dry form of personal care product (e.g., shampoo, deodorant, foot powder, soap powder, baby powder), and the like. Due to the high perfume and/or active agent concentration in the spray-dried product of the invention, a small dose of the spray-dried product does not adversely affect the properties of the dried consumer product as described above.

The microcapsule composition may also be sprayed as a slurry onto consumer products such as fabric care products. For example, during mixing to make granules, the liquid capsule slurry is sprayed onto the detergent powder. See US 2011/0190191. To increase perfume loading, water absorbing materials (e.g., zeolites) can be added to the delivery system.

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.

Zeta potential and rupture force

The microcapsules of the present invention may be positively or negatively charged and have a zeta potential in the range of-200 mV to +200mV, for example at least 10mV, at least 25mV, at least 40mV, 25mV to 200mV, and 40mV to 100 mV.

The zeta potential is a measure of the electromotive potential in the microcapsules. From a theoretical point of view, the zeta potential is the potential difference between the aqueous phase (i.e. the dispersion medium) and the stabilizing layer of water attached to the surface of the microcapsules.

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

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 micro-electrophoresis or electrophoretic light scattering or electroacoustical phenomena. For a more detailed discussion of zeta potential measurements, see Dukhin and Goetz, "Ultrasound for chromatography colloids", Elsevier, 2002.

The microcapsules of the present invention have a breaking strength of 0.2 to 80MPa (e.g., 0.5 to 60MPa, 1 to 50MPa, and 5 to 30 MPa). The breaking strength of each microcapsule is determined by dividing the breaking force (in newtons) by the cross-sectional area (π r) of the corresponding microcapsule²Where r is the radius of the particles before compression). The fracture force and cross-sectional area were measured according to the method described in Zhang et al, J.Microencapsis 18(5),593-602 (2001).

The burst force of the microcapsules of the invention is less than 10 millinewtons ("mN"), e.g., 0.1mN to 10mN, 0.2mN to 8mN, 0.3mN to 5mN, 0.1mN to 2mN, 0.1mN, 0.5mN, 1mN, 2mN, 5mN, and 8 mN. The rupture force is the force required to rupture the microcapsules. The measurement is based on a technique known in the art as micromanipulation. See Zhang et al, Journal of Microencapsidation 16(1),117-124 (1999).

Applications of

The microcapsule compositions of the present invention may be added directly to a consumer product base or printed onto a product base or a removable product conveyor (e.g., non-stick tape) for drying. See international application publication WO2019212896a 1. In a typical printing system, the microcapsule composition is printed onto a movable product conveyor that 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 prior to printing. In some embodiments, the viscosity of the microcapsule composition is adjusted to greater than 500cP or greater than 1000cP with a viscosity modifier. With respect to the printing assembly, the printing assembly may include a printhead or nozzle array, and is optionally adapted to print microcapsules in a dot pattern (e.g., arranged to facilitate drying, post-processing, and product quality). Optional features of the system include a dehumidifier configured to supply drying air to the drying component; a supplemental energy source (e.g., a radiant heat source) for facilitating drying of the printed microcapsules; and/or a product discharge component for removing dried product from the movable product conveyor.

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

a) household product

i. Liquid or powder laundry detergents that may be used with the present invention include those systems described in the following documents: U.S. Pat. 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

Unit dose sachets, tablets and capsules, such as those described in the following references: EP 1431382 a1, 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 material), perfumes (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%).

Odor enhancers, such as those described in the following references: US 7,867,968, US 7,871,976, US 8,333,289, US 2007/0269651 a1 and US2014/0107010 a 1.

Fabric care products such as rinse conditioners (containing 1 to 30 wt% fabric conditioning active), fabric liquid conditioners (containing 1 to 30 wt% fabric conditioning active), tumble dryer sheets, fabric refreshers, fabric refresher sprays, ironing water and fabric softener systems such as those described in the following documents: U.S. Pat. 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.

The liquid fabric softener/refresher comprises at least one fabric softener, which is preferably present at a concentration of 1-30% (e.g., 4-20%, 4-10%, and 8-15%). The ratio between the active material and the fabric softener may 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 to 2.5%, preferably 0.02 to 1.25%, more preferably 0.1 to 0.63%. As another example, when the fabric softener is 20% by weight of the fabric softener, the active material is 0.04 to 10%, preferably 0.08 to 5%, more preferably 0.4 to 2.5%. The active material is a fragrance, malodor counteractant, or a mixture thereof. The liquid fabric softener may have 0.15-15% capsules (e.g., 0.5-10%, 0.7-5%, and 1-3%). When capsules are included at these levels, the Net Oil Equivalent (NOE) in the softener is 0.05-5% (e.g., 0.15-3.2%, 0.25-2%, and 0.3-1%).

Suitable fabric softeners include cationic surfactants. Non-limiting examples are quaternary ammonium compounds such as alkylated quaternary ammonium compounds, cyclic or cyclic quaternary ammonium compounds, aromatic quaternary ammonium compounds, bis-quaternary 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 US 2004/0204337 and US 2003/0060390. Suitable softeners include esterquats such as Rewoquat WE 18, commercially available from Evonik Industries, and Stepancex SP-90, commercially available from Stepan Company.

Liquid dishwashing detergents, such as those described in U.S. Pat. Nos. 6,069,122 and 5,990,065

Detergents for use in dishwashers, 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

Multipurpose cleaners, including bucket dilutable cleaners and toilet bowl cleaners

Bathroom cleaner

ix, toilet paper

x. carpet deodorant

xi. candle

xi. room deodorant

xiii. floor cleaner

xiv. disinfectant

xv. Window cleaning agent

xvi. garbage bag/can liner

xvii. air fresheners including room and car deodorants, fragranced candles, sprays, fragranced oil air fresheners, automatic spray air fresheners, and neutralizing gel beads

xviii. moisture absorbent

Household appliances, such as paper towels and disposable wipes

xx. Camphor ball/circle/cake

Liquid perfume 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 a perfume in the form of an neat oil or encapsulated in a microcapsule, (ii)0.5 to 5 wt% (preferably 0.2 to 3 wt%, more preferably 0.5 to 2.5 wt%) of glyceryl ricinoleate, and (iii)60 to 95 wt% of water. All amounts are based on the weight of the liquid perfume composition.

b) Baby care product

i. Diaper rash cream/balm

ii. baby talcum powder

c) Infant care apparatus

i. Diaper with a disposable absorbent article

ii. bib

iii wet wipes

d) An oral care product. Dental care products, as an example of a preparation according to the invention for oral care, generally comprise 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 glycerin and/or sorbitol; thickeners, e.g. carboxymethylcellulose, polyethylene glycol, carrageenan and/orSweetening agents, such as saccharin; unpleasant taste flavors; a flavoring agent for further, often unpleasant taste sensations; taste modulating 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, menthane carboxylic acid amide), 2,2, 2-trialkyl acetic acid amides (e.g., 2, 2-diisopropylpropionic acid methylamide); icilin and icilin derivatives; stabilizers and active ingredients, for example 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, flavors and/or sodium bicarbonate or flavors.

i. A toothpaste. An exemplary formulation is as follows:

1. 40-55% of calcium phosphate

2. Carboxymethyl cellulose 0.8-1.2%

3. Sodium dodecyl sulfate 1.5-2.5%

4. 20-30% of glycerin

5. Saccharin 0.1-0.3%

6. 1 to 2.5 percent of flavor oil

7. The proper amount of water is 100 percent

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

Tooth powder ii

Mouthwash

Tooth whitening agent

v. denture adhesive

e) Medical health-care apparatus

i. Dental floss

ii, toothbrushes

iii. respirator

Aroma/flavour condom

f) Feminine hygiene articles, such as tampons, sanitary napkins and wet wipes, and panty liners

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 of the "oil-in-water" (O/W) or water-in-oil-in-water (W/O/W) type. More specifically, the present invention is described in detail,

i. personal cleanser (soap bar, bath foam and shower gel)

Shower stall conditioner

Sunscreen ant tattoo color protection (spray, lotion and stick)

An insect repellent

v. disinfectant hand sanitizer

Anti-inflammatory balms, ointments and sprays

Antibacterial ointments and creams

Sensates

Deodorants and antiperspirants include aerosol and pump spray antiperspirants, stick antiperspirants, roll-on antiperspirant, emulsion spray antiperspirant, clear emulsion stick antiperspirant, soft solid antiperspirant, emulsion roll-on antiperspirant, clear emulsion stick antiperspirant, opaque emulsion stick antiperspirant, clear gel antiperspirant, clear stick deodorant, gel deodorant, spray deodorant, roll-on deodorant, and ointment deodorant

x. wax-based deodorant. An exemplary formulation is as follows:

1. 10 to 20 percent of paraffin

2. 5-10% of hydrocarbon wax

3. 10 to 15 percent of white vaseline

4. Acetylated lanolin alcohol 2-4%

5. Diisopropyl adipate 4-8%

6. Mineral oil 40-60%

7. Antiseptic (according to need)

The formulation was prepared by the following steps: (i) mixing the above ingredients, (ii) heating the resulting composition to 75 ℃ until molten, (iii) adding 4% cryogenically milled polymer containing perfume with stirring whilst maintaining the temperature at 75 ℃, and (iv) stirring the resulting mixture whilst adding the composition of the invention to the formulation to ensure a homogeneous suspension.

A glycol/soap deodorant. An exemplary formulation is as follows:

1. 60 to 70 percent of propylene glycol

2.5 to 10 percent of sodium stearate

3. 20 to 30 percent of distilled water

2,4, 4-trichloro-2' -hydroxydiphenyl ether manufactured by Ciba-Geigy Chemical Company under the trademark of Ciba-Geigy Chemical Company) 0.01 to 0.5%

The ingredients were mixed and heated to 75 ℃ with stirring until the sodium stearate dissolved. The resulting mixture was cooled to 40 ℃ and then the composition of the present invention was added.

Lotions include body lotions, face lotions and hand lotions

xiii. toilet powder and foot powder

xiv. cosmetic product

xv. body spray

Shaving cream and masculine cosmetic product

xvii bath soak

xviii. exfoliating scrub

h) Personal care apparatus

i. Face tissues

ii cleaning wet tissue

i) Hair care products

i. Shampoo (liquid and dry powder)

Conditioners (rinse conditioner, leave-on conditioner and cleaning conditioner)

iii, a wetting agent

Proofing water

v. hair perfume

Hair straightening products

Hair styling products, hair styling and styling aids

viii hair-combing cream

ix hair wax

x. foam, hair spray, non-aerosol pump spray

Hair bleaches, dyes and colorants

xii permanent waving agent

xiii wet towel for hair

j) Beauty care

i. Perfume-alcohol. Compositions and methods for incorporating perfume capsules into an alcohol perfume are described in US 4,428,869. The alcoholic perfume may contain the following ingredients:

1. ethanol (1-99%)

2. Water (0-99%)

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

4. Optionally, emulsifiers or emollients may be included, including but not limited to those listed above

Solid perfume

Lipstick/lip balm

Makeup remover

Skin care cosmetics, e.g. foundations, masks, sun creams, skin lotions, skin creams, emollients, skin whiteners

Make-up cosmetic including nail, mascara, eyeliner, eye shadow, liquid foundation, powder foundation, lipstick and blush

k) Consumer goods packaging, e.g. perfumed cartons, perfumed plastic bottles/boxes

l) Pet Care products

i. Cat litter

Flea and tick treatment product

Cosmetic pet products

Pet shampoo

Toy for pets, snacks and chews

vi. pet training mat

Pet cages and crates

m) confectionery, preferably selected from chocolate, chocolate bar products, other bar products, fruit gummies, hard and soft caramels and chewing gums

i. Glue

1. Gum bases (natural latex gums, most chewing gum bases today also include elastomers such as polyvinyl acetate (PVA), polyethylene, (low or medium molecular weight) Polyisobutylene (PIB), polybutadiene, isobutylene-isoprene copolymers (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, e.g. based on vinyl acetate/vinyl laurate, vinyl acetate/vinyl stearate or ethylene/vinyl acetate, as well as mixtures of the above elastomers, e.g. as described in EP 0242325, 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%.

2. Sugar powder 45-50%

3. 15 to 17 percent of glucose

4. Starch syrup 10-13%

5. 0.1 percent of plasticizer

6. 0.8 to 1.2 percent of flavoring agent

The above components were kneaded by a kneader according to the aforementioned formulation to provide chewing gum. The encapsulated flavor or sensate is then added and mixed until uniform.

Breath fresheners

Dissolving strip in mouth iii

Chewing gum

v. hard candy

n) baked products, preferably selected from bread, dried biscuits, cakes and other biscuits;

o) snack foods, preferably selected from the group consisting of baked or fried potato chips or potato dough products, bread dough products and corn or peanut based extrudates;

i. potato, corn cake, vegetable or coarse cereal chips

ii. popcorn

Pretzels and pretzels

Extruding the stack

p) the cereal product is preferably selected from breakfast cereals, cereal bars and precooked finished rice products

q) alcoholic and non-alcoholic beverages, preferably selected from coffee, tea, wine-containing beverages, beer-containing beverages, liqueurs, gin, brandy, fruit-containing sodas, isotonic drinks, soft drinks, nectars, fruit and vegetable juices and fruit or vegetable products; an instant beverage, preferably selected from the group consisting of an instant cocoa beverage, an instant tea beverage and an instant coffee beverage

i. Ready-to-drink liquid beverage

Liquid beverage concentrates

Powdered beverages

Coffee: instant cappuccino

1. Sugar 30-40%

2. 24-35% of milk powder

3. Soluble coffee 20-25%

4. 1-15% of lactose

5. 1 to 3 percent of food-grade emulsifier

6. Encapsulated volatile flavoring agent 0.01-0.5%

v. tea

vi alcohols

r) spice mix and consumable prepared food

i. Powdered gravy and sauce mixture

ii. seasoning

Fermentation products of iii

s) instant food: instant food and soup, preferably selected from soup powder, instant soup, pre-cooked soup

i. Soup

ii. sauce

iii stewing vegetables

Frozen entrees

t) Dairy milk product, preferably selected from the group consisting of milk drink, ice milk, yoghurt, goat cheese, cream cheese, soft cheese, hard cheese, milk powder, whey, butter, buttermilk and flavored milk drink containing partially or fully hydrolyzed milk protein product

i. Yoghurt

ii ice cream

iii, bean curd

iv. cheese

u) soy protein or other soy fractions, preferably selected from soy milk and products produced therefrom, soy phospholipid-containing products, fermented food products such as tofu or fermented beans or products produced therefrom, and soy sauce;

v) meat products, preferably selected from ham, fresh or raw sausage products, and seasoned or cured fresh or bacon products

w) eggs or egg products, preferably selected from the group consisting of dried eggs, egg whites and egg yolks

x) oil-based products or emulsions thereof, preferably selected from the group consisting of mayonnaise, dressings and condiment products

y) a fruit preparation, preferably selected from the group consisting of jams, sorbets, fruit sauces and fruit fillings; vegetable product, preferably selected from tomato sauce, dried vegetable, deep-frozen vegetable, pre-cooked vegetable, pickled vegetable and pickled vegetable

z) a flavored pet food.

The applications listed above are all well known in the art. For example, fabric softener systems are described in the following documents: 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 the following documents: U.S. Pat. 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 may be applied include those described in the following documents: 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. Detergents for use in dishwashers are described in the following documents: 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.

Consumer product base material

The microcapsules of the present invention are suitable for incorporation into consumer product bases in either slurry or dry form. As used herein, "consumer product base" refers to a composition used as a consumer product to achieve a particular effect, such as cleaning, softening, and care, and the like. The components of the consumer product base may include any suitable additive that produces the desired effect under the conditions of intended use of the consumer product. For example, the consumer product base ingredients may be selected from personal cleansers and/or conditioners, such as hair conditioners, 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 conditioning agents, fabric softeners, fabric anti-wrinkle agents, fabric care antistatic agents, fabric care detergents, soil release agents, dispersants, suds suppressors, suds boosters, antifoams, fabric fresheners; liquid and/or powder dishwashing agents (for hand dishwashing and/or automatic dishwasher applications), hard surface care agents and/or conditioning agents and/or polishing agents; other cleaning and/or conditioning agents, such as antimicrobial agents, perfumes, bleaching agents (e.g., oxygen bleaches, hydrogen peroxide, percarbonate bleaches, perborate bleaches, chlorine bleaches), bleach activators, chelants, builders, lotions, brighteners, air care agents, carpet care agents, dye transfer inhibitors, water softeners, water hardeners, pH adjusters, enzymes, flocculants, effervescing agents, preservatives, cosmetics, make-up removers, foaming agents, deposition aids, coacervate formers, clays, thickeners, latexes, silica, desiccants, odor control agents, antiperspirants, coolants, warming agents, absorbent gels, anti-inflammatory agents, dyes, pigments, acids, and bases; a liquid treatment active; an agricultural active agent; an industrial active agent; ingestible active agents such as medicaments, tooth whiteners, tooth care agents, mouth washes, periodontal gum care agents, food stuffs, dietary supplements, vitamins, minerals; water treatment agents, such as water clarifiers and/or water disinfectants, and mixtures thereof. Non-limiting examples of suitable cosmetic agents, skin care agents, skin conditioning agents, hair care agents and hair conditioning agents are described in the following documents: CTFA Cosmetic Ingredient Handbook, Second Edition, The Cosmetic, Toiletries, and Fragrance Association, Inc.1988, 1992.

One or more classes of compounds may be used for one or more of the agents listed above. For example, surfactants can be used for many of the above agents. Also, bleaching agents can be used for fabric care, hard surface cleaning, dishwashing, and even tooth whitening. Thus, one of ordinary skill in the art will appreciate that these agents will be selected based on the desired intended use of the consumer product. For example, if the consumer product is used for hair care and/or conditioning, one or more suitable surfactants, such as lathering surfactants, can be selected to provide the desired benefit to the consumer. Similarly, if the consumer product is to be used to wash laundry in a laundry operation, one or more suitable surfactants and/or enzymes and/or builders and/or perfumes and/or suds suppressors and/or bleaches may be selected to provide the desired benefit to the consumer.

In one example, the agent is a non-perfume ingredient (non-perfume ingredient). In another example, the agent is a non-surfactant component. In yet another example, the agent is a non-ingestible ingredient, in other words, an agent other than an ingestible ingredient.

In certain embodiments, the consumer product base comprises one or more bleach activators, surfactants, builders, chelating agents, dye transfer inhibiting agents, dispersants, enzymes, and enzyme stabilizers, catalytic metal complexes, polymeric dispersing agents, deposition agents, clay and soil removal/anti-redeposition agents, brighteners, suds suppressors, dyes, additional perfume and perfume delivery systems (perfume delivery systems), structure elasticizing agents, fabric softeners, carriers, hydrotropes, processing aids, structuring agents, anti-caking agents, coatings, formaldehyde scavengers, and/or pigments, and combinations thereof. The exact nature of these ingredients and the level of incorporation thereof will depend on the physical form of the composition and the nature of the operation in which it is used. However, when one or more ingredients are present, such one or more ingredients may be present as detailed below.

A surfactant. The surfactant may be anionic, nonionic, zwitterionic, amphoteric or cationic, or may comprise compatible mixtures of these types. If the product is a laundry detergent, anionic and nonionic surfactants are commonly 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%, alternatively 0.01% to 20%, more alternatively 0.1% to 10% by weight of the product of a nonionic surfactant. In some examples, the nonionic surfactant can include an ethoxylated nonionic surfactant. Suitable for use herein are compounds of formula R (OC)₂H₄)_nEthoxylated alcohols and ethoxylated alkylphenols of OH, wherein R is selected from the group consisting of aliphatic hydrocarbon radicals having 8 to 20 carbon atoms and alkylphenyl radicals wherein the alkyl radical has 8 to 12 carbon atoms, and n has an average value of 5 to 15.

Suitable nonionic surfactants are of the formula R¹(OC₂H₄)_nThose of OH, wherein R¹Is C₁₀-C₁₆Alkyl or C₈-C₁₂Alkylphenyl, n is 3 to 80. In one aspect, a particularly useful material is C₉-C₁₅Condensation products of alcohols with 5 to 20 mol of ethylene oxide per mol of alcohol.

Fabric and home care compositions may contain up to 30%, alternatively from 0.01% to 20%, more alternatively from 0.1% to 20% by weight of the product of a cationic surfactant. Cationic surfactants include those capable of providing fabric care benefits, non-limiting examples include: a fatty amine; a quaternary ammonium surfactant; and imidazoline quaternary ammonium salt materials.

A builder. The product may also contain from 0.1% to 80% by weight of the product of a builder. Compositions in liquid form typically contain from 1% to 10% by weight of the product of a builder component. Compositions in granular form typically contain from 1% to 50% by weight of the product of a builder component. Detergent builders are well known in the art and may contain, for example, phosphates as well as various organic and inorganic non-phosphate builders. Water-soluble, non-phosphorus organic builders useful herein include the alkali metal, ammonium and substituted ammonium salts of the various polyacetic acids, carboxylic acids, polycarboxylic acids and polyhydroxy sulfonic acids. Examples of polyacetate and polycarboxylate builders are the 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 monosuccinates and tartrate disuccinates. Builders for liquid detergents include citric acid. Suitable phosphorus-free, inorganic builders include silicates, aluminosilicates, borates and carbonates (e.g. sodium and potassium carbonate), bicarbonates, sesquicarbonates, decahydrate tetraborates and SiO therein₂Silicate in a weight ratio to alkali metal oxide of 0.5 to 4 or 1 to 2.4. Aluminosilicates, including zeolites, are also useful.

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

An enzyme. The composition may contain one or more detergent enzymes which provide cleaning performance and/or fabric care benefits. Examples of suitable enzymes include hemicellulases, peroxidases, proteases, cellulases, xylanases, lipases, phospholipases, esterases, cutinases, pectinases, keratinases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, beta-glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase and amylase, or mixtures thereof. A typical combination may be a mixture of conventionally used enzymes such as proteases, lipases, cutinases and/or cellulases with amylases. Enzymes may be used at levels taught in the art, 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 may be used at very low levels, for example 0.001% or less; or they may be used at higher levels (e.g. 0.1% or higher) in heavy duty laundry detergent formulations. Depending on some consumer preferences for "non-biological" detergents, the product may be enzyme-containing or enzyme-free, or both.

Dye transfer inhibiting agents. The product may further comprise 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 inhibiting agents, such as polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidone and polyvinylimidazole, or mixtures thereof.

A chelating agent. The product may contain less than 5% or 0.01% to 3% by weight of the product of a chelating agent, such as citrate; nitrogen-containing, P-free aminocarboxylates such as EDDS, EDTA and DTPA; amino phosphonates such as diethylenetriamine pentamethylenephosphonic acid and ethylenediamine tetramethylene phosphonic acid; nitrogen-free phosphonates, for example, HEDP; and nitrogen-or oxygen-containing, P-free carboxylate chelating agents, such as certain general classes of macrocyclic N-ligands, such as those known for use in bleach catalyst systems.

A whitening agent. The product may also include a whitening agent (also referred to as an "optical whitener") and may include any compound that exhibits fluorescence, including compounds that absorb ultraviolet light and re-emit as "blue" visible light. Non-limiting examples of whitening agents that may be used include derivatives of stilbene or 4,4' -diaminostilbene,Biphenyl, five-membered heterocyclic ring such as triazole, pyrazoline, oxazole, imidazole, etc., or six-membered heterocyclic ring (coumarins, naphthalimide, s-triazine, etc.). Cationic, anionic, nonionic, amphoteric and zwitterionic brighteners can be used. Suitable whitening agents include those sold under the trademark Ciba Specialty Chemicals Corporation (High Point, NC)Those sold.

A bleaching system. Bleaching systems suitable for use herein contain one or more bleaching agents. Non-limiting examples of suitable bleaching agents include catalytic metal complexes; activating a peroxygen source; a bleach activator; a bleach booster; a photo-bleaching agent; a bleaching enzyme; a free radical initiator; h₂O₂(ii) a A hypohalite bleach; a peroxygen source comprising perborate and/or percarbonate salts, and combinations thereof. Suitable bleach activators include perhydrolyzable esters and perhydrolyzable imides, such as tetraacetylethylenediamine, octanoylcaprolactam, benzoyloxybenzenesulfonate, nonanoyloxybenzenesulfonate, benzoylvalerolactam, dodecanoyloxybenzenesulfonate. Other bleaching agents include metal complexes of transition metals with ligands having defined stability constants.

A stabilizer. The product may contain one or more of 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 oil, or variants thereof, and combinations thereof. In some aspects, the crystalline, hydroxyl-containing stabilizer can be a water-insoluble waxy substance, including a fatty acid, fatty ester, or fatty soap. In other aspects, the crystalline, hydroxyl-containing stabilizer can be a derivative of castor oil, such as a hydrogenated castor oil derivative, e.g., castor wax. Stabilizers containing hydroxyl groups 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 gum, and other known types of thickeners and rheological additives. Exemplary stabilizers within this class include gum-type polymers (e.g., xanthan gum), polyvinyl alcohol and derivatives thereof, cellulose and derivatives thereof, including cellulose ethers and esters and tamarind gum (e.g., including xyloglucan polymers), guar gum, locust bean gum (including galactomannan polymers in some aspects), and other industrial gums and polymers.

A deposition aid. In some examples, the fabric and home care products can include from 0.01% to 10%, from 0.05% to 5%, or from 0.15% to 3%, by weight of the product, of the deposition aid. 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 23meq/g, 0.01 to 12meq/g, or 0.1 to 7meq/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 pH of the intended use of the product. Such pH is typically in the range of 2 to 11, more typically in the range of 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 charge may be located on the backbone of the polymer and/or on the side chains of the polymer.

In some examples, the deposition aid may include a cationic acrylic-based polymer. In another aspect, the deposition aid can include a cationic polyacrylamide. In another aspect, the deposition aid can include a polymer consisting of polyacrylamide and polymethacrylamidopropyltrimethylammonium cations. In another aspect, the deposition aid may be comprised of poly (acrylamide-N-dimethylaminoethylacrylate) and quaternized derivatives thereof.

In some examples, the deposition aid may be selected from a cationic polysaccharide or an amphoteric polysaccharide. In some examples, the deposition aid may be selected from cationic and amphoteric cellulose ethers, cationic or amphoteric galactomannans, cationic guar, cationic or amphoteric starches, and combinations thereof.

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 the condensation products of diethylenetriamine with adipic acid, followed by reaction with epichlorohydrin.

The weight average molecular weight of the polymer can be from 500 daltons to 5,000,000 daltons, e.g., from 1,000 daltons to 2,000,000 daltons and from 2,500 daltons to 1,500,000 daltons, as determined by size exclusion chromatography relative to polyethylene oxide standards detected using RI. In some examples, the cationic polymer can have a MW of 500 daltons to 37,500 daltons.

Silicone (Silicone). Suitable silicones include Si-O moieties and may be selected from the group consisting of (a) non-functionalized siloxane polymers, (b) functionalized siloxane polymers, and combinations thereof. The molecular weight of the organosilicone is typically expressed by reference to the viscosity of the material. In one aspect, the organosilicone can have a viscosity of 10 to 2,000,000 centistokes at 25 ℃. In another aspect, suitable organosilicones can have a viscosity of 10 to 800,000 centistokes at 25 ℃.

Suitable organosilicones may be linear, branched or crosslinked. In some examples, the organosilicone may be a cyclic silicone. The cyclic silicone may be of the formula [ (CH)₃)₂SiO]_nWherein n is an integer, which may be 3 to 7 or 5 to 6.

In some examples, the organosilicone may comprise a functionalized siloxane polymer. The functionalized silicone polymer may include one or more functional moieties selected from amino, amido, alkoxy, hydroxyl, polyether, carboxyl, hydride, mercapto, sulfate phosphate, and/or quaternary ammonium moieties. These moieties may be directly attached to the siloxane backbone through a divalent alkylene group (i.e., "pendant"), or may be part of the backbone. Suitable functionalized silicone polymers include materials selected from the group consisting of: amino silicones, amido silicones, silicone polyethers, silicone-urethane polymers, quaternary ABn silicones, amino ABn silicones, and combinations thereof.

In some examples, the functionalized siloxane polymer may include a silicone polyether, also referred to as "dimethicone copolyol. Generally, the silicone polyether comprises a polydimethylsiloxane backbone with one or more polyoxyalkylene chains. The polyoxyalkylene moiety can be incorporated into the polymer as a side chain or as a terminal block. In some examples, the functionalized siloxane polymer may include an aminosilicone.

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

A fabric softening active. Non-limiting examples of fabric softening actives are N, N-bis (stearoyl-oxy-ethyl) N, N-dimethylammonium chloride, N-bis (tallowoyl-oxy-ethyl) N, N-dimethylammonium chloride, N-bis (stearoyl-oxy-ethyl) N- (2-hydroxyethyl) N-methylammonium sulfate; dialkylene dimethyl ammonium salts such as dicamba dimethyl ammonium chloride (dicamba dimethyl lammonium chloride), di (hard) tallow dimethyl ammonium chloride bis rape dimethyl ammonium methyl sulfate; 1-methyl-1-stearoylaminoethyl-2-stearoylimidazolidine methylsulfate; 1-tallowoylamidoethyl-2-tallowoylimidazoline; n, N "-dialkyldiethylenetriamine; a reaction product of N- (2-hydroxyethyl) -1, 2-ethylenediamine or N- (2-hydroxyisopropyl) -1, 2-ethylenediamine and glycolic acid esterified with fatty acids, wherein the fatty acids are (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 of the above. It is to be understood that combinations of the softener actives disclosed above are suitable for use herein.

A fabric toner. The product may also include fabric hueing agents (sometimes referred to as shading agents, bluing agents, or brighteners). Typically, the hueing agent provides a blue or violet hue to the fabric. Toners may be used alone or in combination to create a particular shade of toning and/or to effect shade changes for different types of fabrics. This may be provided, for example, by mixing red and green-blue dyes to produce a blue or violet hue. The hueing agent may be selected from any known chemical class of dyes including, but not limited to, acridines, anthraquinones (including polycyclic quinones), azines, azos (e.g., monoazo, disazo, trisazo, tetrazo, polyazo), including premetallized azos, benzodifurans and benzodifuranones, carotenoids, coumarins, cyanines, diaza-hemicyanines, diphenylmethane, formazan, hemicyanines, indigoids, methane, naphthalimides, naphthoquinones, nitro and nitrosos, 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 falling within the Color Index (CI) classification of acidic, direct, basic, reactive or hydrolytically reactive, solvent or disperse dyes, for example, as blue, violet, red, green or black, and alone or in combination provide the desired hue.

Suitable polymeric dyes include polymeric dyes selected from the group of polymers (dye-polymer conjugates) comprising covalently bound (sometimes referred to as conjugated) chromogens, for example polymers having chromogens copolymerized into the polymer backbone and mixtures thereof. Polymeric dyes include those described in US 7,686,892B 2.

Suitable dye clay conjugates include dye clay conjugates selected from the group consisting of: comprising at least one cationic/basic dye and a smectite clay, and mixtures thereof.

The toner may be incorporated into the product as part of a reaction mixture that is the result of the organic synthesis of the dye molecules, with optional purification steps. Such reaction mixtures generally comprise the dye molecules themselves, and may additionally comprise unreacted starting materials and/or by-products of organic synthetic routes.

A pigment. Suitable pigments include pigments selected from the group consisting of: flavanthrone, indanthrone chloride containing 1-4 chlorine atoms, pyranthrone, dichloropyranthrone, monobromo-dichloropyranthrone, dibromo-dichloropyranthrone, tetrabromo-pyranthroneAnthrone, perylene-3, 4,9, 10-tetracarboxylic acid diimides in which the imide groups may be unsubstituted or substituted by C₁-C₃-alkyl or phenyl or heterocyclic groups, and wherein the phenyl and heterocyclic groups may additionally carry substituents which do not impart water solubility, anthrapyrimidine carboxylic acid amides, anthrone violet, isoanthrone violet, dioxazine pigments, copper phthalocyanines which may contain up to 2 chlorine atoms per molecule, polychlorinated or polybromochlorocopper phthalocyanines which contain up to 14 bromine atoms per molecule, and mixtures thereof.

A structuring agent. Useful structurants that can be added to fully suspend the benefit agent or microcapsules include polysaccharides such as gellan gum, waxy corn or dent corn starch, octenyl succinated starch, derivatized starches such as hydroxyethylated or hydroxypropylated starches, 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 formate, magnesium formate, aluminum chloride, potassium permanganate, hectorite clay, bentonite clay, and mixtures thereof; polysaccharides in combination with inorganic salts; quaternized polymeric materials such as polyetheramines, alkyltrimethylammonium chlorides, diester ditallow ammonium chlorides; imidazole; nonionic polymers with pKa less than 6.0, such as polyethyleneimine, polyethyleneimine ethoxylate; a polyurethane. Such materials are available from the following companies: CP Kelco corp, san diego, CA; degussa AG or dusseldov, germany; BASF AG, ludwigshafen, germany; rhodia corp., klenburl, NJ; baker Hughes corp., houston, TX; hercules corp., wilmington, DE; agrium inc, calgary, alberta, canada; ISP, NJ.

An anti-caking agent. Useful anticaking agents include divalent salts, such as magnesium salts, e.g., 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, e.g., aluminum sulfate, aluminum phosphate, aluminum chloride hydrate, and polymers having the ability to suspend anionic particles, e.g., suspension polymers, such as polyethyleneimine, alkoxylated polyethyleneimine, polyquaternium-6, and polyquaternium-7.

All parts, percentages and proportions referred to herein and in the claims are by weight unless otherwise indicated.

The values and dimensions disclosed herein are not to be understood as being strictly limited to the exact numerical values recited. Rather, unless otherwise specified, each such value is intended to mean 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%".

The term "comprising" is meant to be non-limiting.

The terms "capsule" and "microcapsule" are used interchangeably herein.

The term "curing" as used in polymer chemistry and process engineering refers to the process of toughening or hardening a polymer by crosslinking of the polymer chains, which is caused by heat, chemical additives or light radiation.

As used herein, a "core-shell microcapsule" or more generally a "microcapsule" or "capsule" is a substantially spherical structure 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; limiting the loss of volatile core material; and release the core material under the 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" refers to the retention of an active material in a core until a particular triggering condition occurs. Such triggers include, for example, friction, swelling, pH change, enzymes, temperature change, ionic strength change, or combinations thereof.

The 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, based on the description herein, utilize the present invention to its fullest extent. All publications cited herein are incorporated by reference in their entirety.

Example 1: microcapsule 1 prepared from moderately denatured brown rice protein

Microcapsules 1 were prepared according to the following procedure. First by mixing 28.6 grams (g) of a model fragrance (a model fragrance) and 7.15g of caprylic/capric triglyceride (nuclear solvent, under the trade name ofOil M-5(oil M-5) commercially available, Stepan, Chicago, IL) and aliphatic polyisocyanate (0.7g), a polyisocyanate based on Hexamethylene Diisocyanate (HDI), were usedN100A commercially available, Bayer, levkusen, germany) to prepare the oil phase. In a separate beaker, the rice was prepared by mixing an aqueous solution (46g) containing 10% denatured brown rice protein solution, 10% sodium polystyrene sulfonate (capsule forming aid, under the trade name of "capsule forming aid")II commercially available, Akzo Nobel Surface Chemistry, Oxinine, NY, in aqueous solution (5.8g), 1% carboxymethylcellulose (capsule forming aid, to name a few)CRT 50000A commercially available, Dow Chemical Company, Midland, MI) in aqueous solution (10g) and 20% DABCO crystals (a catalyst, 1, 4-diazabicyclo [2.2.2]]Octane, Evonik, elson, germany) was added to the aqueous solution (0.14g) to obtain an aqueous solution. The oil phase was then emulsified into the water phase to form an oil-in-water emulsion with shear (ULTRA TURRAX, T25 Basic, IKA WERKE) at 7200rpm for 5 minutes. The formulation of microcapsule 1 is shown in table 1 below.

Table 1.

After stirring the oil-in-water emulsion at 25 ℃ for 0.5 h, 2g of 25% aqueous glutaraldehyde solution (Sigma-Aldrich, St. Louis, Mo.) and 5g of 30% aqueous tannic acid solution (Sigma-Aldrich, St. Louis, Mo.) were added with constant stirring. The mixture was cured at room temperature for 1 hour. The pH was then adjusted to 8. After warming to 55 ℃, the resulting capsule slurry was stirred for 1 hour, then for 3 hours at 80 ℃. The encapsulation efficiency was 99.9%.

Efficiency of encapsulation

The packaging efficiency (EE) was calculated as: EE ═ 1- (free oil/total oil) ] x 100%. The analysis of free and total oils was performed according to the method described on page 21 of WO 2017/161364.

Evaluation of sensory Properties

The microcapsule compositions of the present invention were used in fabric conditioner bases and their fragrance intensity was evaluated on the LMS scale from 0 to 30, where 1 score indicates weak odor, 5 score indicates moderate odor, and 15 score indicates strong odor. Each microcapsule was incorporated into a model non-odorous 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.

Post-rub headspace Gas Chromatography (GC)

The microcapsules of the invention were also evaluated on Tenax tubes using headspace GC, where fragrance intensity was measured in ppb units. The washed and dried towels were placed in a plastic bag, sealed and rubbed. The headspace was collected by a nozzle.

Examples 2 to 6

Microcapsule 2 was prepared according to the procedure described in example 1, except that the brown rice protein was slightly denatured by treating the protein dispersion at 80 ℃ for 1 hour without any pH adjustment.

Microcapsule 3 was prepared according to the procedure described in example 1, except that the brown rice protein was not denatured.

Microcapsules 4 were prepared following the procedure described in example 1, except that no glutaraldehyde was added to the slurry mixture for crosslinking.

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

Microcapsules 6 were prepared following the procedure described in example 1, except that the trimethylolpropane adduct of 1% xylylene diisocyanate (as Takenate) was used^TMD-110N commercially available, Mitsui Chemicals Inc., Japan) instead ofN100A。

Example 7

Microcapsules 7 were prepared according to the following procedure. Preparation of a whey protein concentrate (under the trade name Hydrovon) containing 3 wt% whey protein^TM282 commercially available from Glanbia Nutritionals, Chicago, IL), 1.3 wt% guanidine carbonate in water, 0.5% polystyrene sulfonate (R)II, from Akzo Nobel, Eugenine, NJ) and 1% OSA modified starch (under the trade name Purity)Ultra is commercially available from Ingredion, brickworth, NJ). The dispersion is added to a trimethylolpropane adduct containing 1% xylylene diisocyanate (as Takenate)^TMD-110N is commercially available as an oil solution from Mitsui Chemicals Inc., Japan), 32% model fragrance, and caprylic/capric triglyceride. The mixture was homogenized at 7400rpm for 3 minutes, at which time 0.5% tannic acid (SigmaAldrich) was added, mixed for an additional 15 minutes and cured at 55 ℃ for 4 hours.

Examples 8 to 11: denatured hydrolyzed whey protein concentrate microcapsules

A microcapsule 8 was prepared following 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 curing.

Microcapsules 9 were prepared as in example 7, except that whey protein isolate (hydro von) was used^TM195, Glanbia Nutritionals) instead of whey protein concentrate.

Microcapsules 10 were prepared as in example 8, except that no guanidine salt was added.

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

Examples 12 to 20: protein microcapsules

Microcapsules 12-21 were prepared following the same procedure as in example 7, except that a different protein was used in each example.

Microcapsules 12, pea protein (Naturals S85XF, from Roquette),

microcapsules 13, rice protein: (5312 from Kerry,

microcapsule 14, avenin: (From Tate and Lyle),

microcapsules 15, potato protein (Meelunie b.v., the netherlands),

microcapsule 16: wheat protein (A)500, from Scoular),

microcapsule 17: egg proteins (P110, from Henningsen Food),

the microcapsule 18: barley/rice protein (Beretein)^TM，Zea10 LLC)，

Microcapsule 19: brown rice protein (Naked Nutrition), and

microcapsule 20: pumpkin seed protein (Acetar Bio-Tech Inc.)

Table 2 below summarizes each example and the headspace GC readings after kneading. In each embodiment, the microcapsules are provided as microcapsulesThe composition is dispersed in an aqueous phase. Using 3% protein, 1.3% guanidine carbonate as chaotropic agent, 1% trimethylolpropane adduct of xylylene diisocyanate (Takenate) by weight of the microcapsule composition^TMD-110N) as multifunctional electrophile, 0.5% tannin as multifunctional nucleophile, 0.5% polystyrene sulfonate ((S)II) OSA-modified starch (Purity) as emulsifier 1%Ultra) as a co-emulsifier, 32% model perfume, and caprylic/capric triglyceride.

Table 2.

Examples 21 to 24: whey protein capsule

Microcapsule compositions 21-24 were prepared following the same procedure as described in example 7, except that different proteins or chaotropic agents were used. 3% denatured protein, 1.3% chaotropic agent, 1% trimethylolpropane adduct of xylylene diisocyanate (Takenate) was used by weight of the microcapsule composition^TMD-110N) as polyfunctional electrophile, 0.5% tannic acid as polyfunctional nucleophile, 0.5% polystyrene sulfonate ((S)II) OSA-modified starch (Purity) as emulsifier 1%Ultra) as a co-emulsifier, 32% model perfume, and caprylic/capric triglyceride. Comparative composition 1C used 1% trimethylolpropane adduct of xylylenediisocyanate (Takenate)^TMD-110N), 0.5% glutaraldehyde as the polyfunctional nucleophile, 0.5% polystyrene sulfonate (SII), 1% OSA modified starch (Purity)Ultra) as co-emulsifier, 32% model perfume, and caprylic/capric triglyceride were prepared in a similar manner. Table 3 below shows the% free oil and headspace GC readings after kneading for each microcapsule composition.

The microcapsule composition 21 is cured at 55 ℃ or 25 ℃. In the headspace GC analysis, GC readings after kneading were similar.

TABLE 3

Examples 25 to 40: capsule compositions prepared from various multifunctional nucleophiles

The same procedure as described in example 7 was followed using denatured protein (whey protein concentrate, potato or pea protein), 1.3% guanidine carbonate, trimethylolpropane adduct of xylylenediisocyanate (polyisocyanate, Takenate)^TMD-110N), multifunctional nucleophile, 0.5% sulfopolystyrene (S: (A)II), 1% OSA modified starch (Purity)Ultra), 32% model perfume, and caprylic/capric triglyceride to prepare microcapsule compositions 25-40. See table 4 below for composition,% free oil and post-rub flavor intensity from sensory evaluation.

Table 4.

¹BPEI, branched polyethylenimine available from BASFAre commercially available.

²The components of TEC, triethyl citrate,IFF, Youning biqi, N.J..

³DBI, dibutyl itaconate (Sigma Aldrich, st louis, missouri).

⁴Headspace GC readings.

Examples 41 to 43

The same procedure as described in example 7 was followed using 3% denatured whey protein concentrate, guanidine carbonate in various concentrations, 0.5% (example 41) or 1% (examples 42 to 44) trimethylolpropane adduct of xylylene diisocyanate (Takenate)^TMD-110N), 0.5% tannic acid, 0.5% polystyrene sulfonate ((D-110N)II) 1% OSA-modified starch (Purity) as emulsifierUltra) as co-emulsifier, 32% model perfume, and caprylic/capric triglyceride. Comparative composition 2C was prepared in the same manner as in example 42, except that guanidine carbonate was not used. See table 5 below for composition,% free oil and post-rub flavor intensity from sensory evaluation.

The pH of the oil-in-water of example 41 was 7 without adjustment. It is adjusted to pH <7 (e.g. 3) with citric acid or to pH >7 (e.g. 9) with sodium hydroxide. The fragrance intensity was about 4.7 with no significant change with pH adjustment.

TABLE 5

¹Trimethylolpropane adduct of xylylenediisocyanate (Takenate)^TM D-110N)。

Examples 44 and 45: hair conditioner

In example 44, hair conditioner 1 was obtained by adding microcapsule composition 25 to a hair conditioner base at a level of 0.25% neat oil equivalent. The conditioner base contained 4% fatty alcohol, 0.7% behenyltrimethylammonium chloride, 1% terminal aminosilicone, 2.5% silicone, and 0.5% preservative in water.

In example 45, conditioner 2 was obtained by adding microcapsule composition 22 to a conditioner base at 0.25% neat oil equivalent, along with 2% chitosan (commercially available from Glentham Life Sciences, keslem, UK) as a deposition aid.

Hair swatches were rinsed with both conditioners and evaluated after combing on a fragrance intensity scale of 0 to 10 (score 5 indicates strong odor).

The post-combing scent intensities of the hair swatches treated with conditioners 1 and 2 were 5.6 and 4.3, respectively.

Examples 46 to 48: hair washing agent

In example 46, shampoo 1 was obtained by adding microcapsule composition 22 to the shampoo base at a level of 0.25% neat 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.

In example 47, shampoo 2 was obtained by adding the microcapsule composition 25 to the conditioner base at 0.25% neat oil equivalent.

In example 48, shampoo 3 was obtained by adding the microcapsule composition 22 to a conditioner base at 0.25% neat oil equivalent, together with 2% chitosan as a deposition aid.

The hair swatches were washed with three shampoos and evaluated after combing on a fragrance intensity scale from 0 to 10 (score 5 indicates strong odor).

The post-combing fragrance intensity for the hair swatches treated with shampoos 1-3 were 7, 5.2, and 6.8, respectively.

Chitosan coating

To improve deposition of encapsulated perfume, any of the microcapsules of the present invention may be coated with chitosan as follows. A 3% aqueous solution of chitosan (extracted from fungi) was prepared by dissolving chitosan in water with 1% acetic acid. The microcapsule composition was mixed with a dilute sulfuric acid solution until the pH reached 2. The chitosan solution was added to the acidified microcapsule composition such that the chitosan was present at a level of 2%. The resulting microcapsule composition had a pH of 2 and was heated to a temperature of 60 ℃ and held at that temperature for 4 hours to obtain a microcapsule composition having a chitosan coating on the microcapsules.

The chitosan-coated microcapsule composition may be further mixed with 0.25 wt% of a copolymer of acrylamide and acrylamidopropyl trimethyl ammonium chloride ((ACM-APTAC, as a deposition aid) or a copolymer of acrylamide and methacrylamidopropyl trimethyl ammonium chloride (ACM-MAPTAC, as a deposition aid) to obtain a microcapsule composition with a deposition aid.

The chitosan-coated microcapsule compositions and the microcapsule compositions with deposition aids showed higher fragrance intensity in hair conditioner evaluation compared to microcapsule compositions without chitosan, ACM-APTAC or ACM-MAPTAC.

Biodegradability

Biodegradability tests were performed according to OECD 310 protocol. An aliquot of the microcapsule slurry was placed into a Biological Oxygen Demand (BOD) bottle in water containing a microbial inoculum collected from a treatment plant owned by Escatawpa, Mississippi. The bottles were checked at regular intervals for carbon dioxide evolution for 60 days. Intermittent points may also be used because asymptotic values may be reached much earlier than 60 days. Percent degradation was analyzed relative to the positive control starch.

Consumer product embodiments

The microcapsule composition of the present invention can be added to various consumer products. Non-limiting examples are shown in table 6 below.

TABLE 6

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

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

Other embodiments

All features disclosed in this specification may be combined in any combination. Each feature disclosed in this specification may be replaced by alternative features serving the same, equivalent or similar purpose.

For the purpose of encapsulating the active material, one skilled in the art can design and prepare capsule compositions by varying the concentration of wall forming material or catalyst using different encapsulating polymers, coatings and capsule forming aids to achieve the desired release profile in the consumer product. Furthermore, the ratio between the wall forming material, the capsule forming aid, the adjuvant, the core modifier, the active material and the catalyst can also be determined by known assays by a person skilled in the art.

From the above description, one skilled in the art can easily ascertain the essential characteristics of the present invention, and without departing from the spirit and scope thereof, can make various changes and modifications of the invention to adapt it to various usages and conditions. Accordingly, other embodiments are within the scope of the following claims.