WO2016185171A1 - Capsules - Google Patents
Capsules Download PDFInfo
- Publication number
- WO2016185171A1 WO2016185171A1 PCT/GB2016/051330 GB2016051330W WO2016185171A1 WO 2016185171 A1 WO2016185171 A1 WO 2016185171A1 GB 2016051330 W GB2016051330 W GB 2016051330W WO 2016185171 A1 WO2016185171 A1 WO 2016185171A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- copolymer
- capsule
- derivative
- acetylglucosamine
- component
- Prior art date
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/06—Making microcapsules or microballoons by phase separation
- B01J13/10—Complex coacervation, i.e. interaction of oppositely charged particles
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/44—Oils, fats or waxes according to two or more groups of A61K47/02-A61K47/42; Natural or modified natural oils, fats or waxes, e.g. castor oil, polyethoxylated castor oil, montan wax, lignite, shellac, rosin, beeswax or lanolin
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K9/00—Medicinal preparations characterised by special physical form
- A61K9/48—Preparations in capsules, e.g. of gelatin, of chocolate
- A61K9/50—Microcapsules having a gas, liquid or semi-solid filling; Solid microparticles or pellets surrounded by a distinct coating layer, e.g. coated microspheres, coated drug crystals
- A61K9/5005—Wall or coating material
- A61K9/5015—Organic compounds, e.g. fats, sugars
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K9/00—Medicinal preparations characterised by special physical form
- A61K9/48—Preparations in capsules, e.g. of gelatin, of chocolate
- A61K9/50—Microcapsules having a gas, liquid or semi-solid filling; Solid microparticles or pellets surrounded by a distinct coating layer, e.g. coated microspheres, coated drug crystals
- A61K9/5005—Wall or coating material
- A61K9/5021—Organic macromolecular compounds
- A61K9/5036—Polysaccharides, e.g. gums, alginate; Cyclodextrin
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K9/00—Medicinal preparations characterised by special physical form
- A61K9/48—Preparations in capsules, e.g. of gelatin, of chocolate
- A61K9/50—Microcapsules having a gas, liquid or semi-solid filling; Solid microparticles or pellets surrounded by a distinct coating layer, e.g. coated microspheres, coated drug crystals
- A61K9/5089—Processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
- C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
- C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2003—Alcohols; Phenols
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/38—Products with no well-defined composition, e.g. natural products
- C11D3/386—Preparations containing enzymes, e.g. protease or amylase
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N1/00—Microorganisms, e.g. protozoa; Compositions thereof; Processes of propagating, maintaining or preserving microorganisms or compositions thereof; Processes of preparing or isolating a composition containing a microorganism; Culture media therefor
- C12N1/14—Fungi; Culture media therefor
- C12N1/16—Yeasts; Culture media therefor
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P13/00—Preparation of nitrogen-containing organic compounds
- C12P13/04—Alpha- or beta- amino acids
- C12P13/14—Glutamic acid; Glutamine
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P19/00—Preparation of compounds containing saccharide radicals
- C12P19/26—Preparation of nitrogen-containing carbohydrates
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P39/00—Processes involving microorganisms of different genera in the same process, simultaneously
Definitions
- This invention relates to capsules and particularly, although not exclusively, relates to a process for producing capsules which comprise an encapsulated material.
- Encapsulation is used to stabilize, isolate or protect materials from the external environment, enhancing the longevity of the encapsulated material, until such time as it is released. For example, oils sensitive to oxidation may be protected, or a volatile fragrance may be rendered inactive until released by some external force. Encapsulation allows formulations to be compounded with ingredients that would otherwise be unusable, due to incompatibility or reactivity.
- Physical methods consist of spray drying, spray chilling, fluid bed coating, extrusion and diffusion of materials into exhausted yeast or pollen particles.
- the chemical methods include simple and complex coacervation, interfacial polymerization, molecular inclusion and liposomes.
- Complex coacervation has proved to be a versatile technology, providing the ability to produce both very small non-visual capsules ( ⁇ 5 micrometres) up to large visual capsules in the region of 2 millimetres, with a wide array of capsule contents, such as vitamins, polyunsaturated fatty acids (PUFAs), essential oils, flavours, fragrances, cosmetic or health ingredients and pharmaceutical compounds.
- PUFAs polyunsaturated fatty acids
- the complex coacervation process is based on the electrostatic attraction of oppositely charged water soluble polymers, (simple coacervation refers to the use of only one polymer) which, in a controlled manner, can be made to form a wall or shell around very small emulsified droplets of hydrophobic materials such as oils. Finished capsules can be harvested and then applied to various substrates or dispersed into formulations where the core material can be stored until release is required.
- gelatine denatured collagen
- gum arabic derived from the sap of Acacia trees
- Gelatine is an amphoteric biopolymer, whose electrostatic charge is dependent on the pH of the environment.
- Anionic gum arabic obtained from the sap of the acacia tree (Acacia Senegal)
- Adacacia Senegal is a commonly used counter-ion component, although alternative chemistries can be used, such as sodium carboxymethyl cellulose.
- Both polymers are dissolved in water, in alkali conditions, at 50°C.
- the pH is lowered below the isoelectric point of the gelatine, with a weak acid, such as acetic acid, the charge on the gelatine becomes cationic and electrostatically interacts with the anionic polymer, forming the 'coacervate', a polymer rich, viscous phase.
- a weak acid such as acetic acid
- the coacervate solubility decreases and, the viscosity of the coacervate increases and is deposited at the interface of the water and oil droplets, forming a continuous wall or shell.
- the encapsulated oil droplets are then chemically stabilised with a crosslinking agent, such as formaldehyde, glutaraldehyde, or enzymatic treatments, thus isolating, protecting and stabilising the oils until the microcapsules are broken, releasing the contents.
- a crosslinking agent such as formaldehyde, glutaraldehyde, or enzymatic treatments
- coacervate capsules have been increasingly used in consumer goods, such as small, non-visual capsules used in anti-perspirant deodorants, fabric conditioners, hosiery and also large visual coloured microcapsules, in shower gels, toothpaste, handwash, etc.
- gelatine/gum Arabic-based capsules have limitations in areas in which they may be used. For example, in situations where protease enzymes may come into contact with the capsules, such capsules cannot be used since the protease enzyme could prematurely break down the capsule.
- gelatin/gum Arabic capsules relies on dissolution of capsule wall materials at elevated temperature which can require substantial energy usage.
- the quality of a gelatine/gum Arabic-based system is only apparent after hours of controlled cooling. Consequently, if the quality of a batch is found to be poor, much time is expended producing an unusable batch. Additionally, it can be difficult to produce a narrow particle size distribution in the aforementioned gelating/gum-arabic-based system.
- a capsule comprising an encapsulated material and a capsule wall encapsulating the encapsulated material, wherein the capsule wall includes a N-acetylglucosamine/glucosamine copolymer or a derivative of such a copolymer, wherein the N-acetylglucosamine/glucosamine copolymer or a derivative of such a copolymer is derived from a raw material which has a non-animal origin.
- a material from which N-acetylglucosamine/glucosamine copolymer or a derivative of such a copolymer may suitably be a chitin.
- a reference herein to a material which is derived (or cognate expressions) from chitin (or from any other material) does not exclude the possibility that a source material (e.g. chitin) may be subjected to one or more treatments to yield the material which is derived.
- Chitin may be derived from a range of sources.
- chitin may be derived from crustaceans which in the context of the present specification is an animal source.
- non-animal origin excludes chitin derived from crustaceans. It suitably therefore excludes an N-acetylglucosamine/glucosamine copolymer or a derivative of such a copolymer which is derived from crustaceans.
- Said chitin may be derived from a micro-organism. It may be derived from a fungus, for example, a yeast. It may be derived from a biomass. Said biomass may comprise zygomycetes, basidiomycetes, ascomycetes and deuteromycetes. In one preferred embodiment, said chitin may be derived from mycelium, for example of Aspergillus niger.
- Said capsule wall preferably includes no animal-derived component. It preferably only includes components acceptable to vegetarians, especially acceptable to vegans.
- the entirety of said capsule includes no animal-derived component. It preferably only includes components acceptable to vegetarians, especially acceptable to vegans.
- the ratio of the weight of encapsulated material divided by the weight of the capsule wall may be at least 3, preferably at least 5, more preferably at least 7, especially at least 8. The ratio may be less than 25 or less than 20.
- Capsule and encapsulation processes described herein can be used to isolate, stabilise and protect sensitive ingredients or to control the release of active ingredients to a specific moment or point in a process, and may have utility in the following areas: Personal care formulations, such as skin creams, emulsions, bodywashes, handwash, soaps, bodyscrubs, facial wipes, facial lotions, skin gels, shower gels, spritz formulations, lip treatments, antiperspirant deodorants, aftershave treatments, shaving preparations, fragrance delivery systems, including sprays, wipes, roll on, sticks, liquid & bar soaps, shower moisturisers, body/baby oil - other baby products including talc and nappy-rash creams.
- Oral care preparations such as traditional toothpastes, toothpaste gels, mouthwash, dental floss, denture adhesive creams or pastes, denture treatment creams or tablets, plaque disclosure treatments, breath freshening strips, whitening strips, delivery of antimicrobials, whitening actives, flavours.
- Cosmetic applications such as, mascara, lipstick, eye shadow, nail varnish, other nail beneficiating treatments, synthetic nail applications, makeup removal treatments, including cotton wool pads and wipes.
- Foundation powders and sticks tinted moisturisers, concealers, cream & powder blushers/highlighters, liquid & pencil eye-liners, temporary tattoos/decorations
- Haircare preparations such as, hair gels, hair mousses, styling aerosol sprays, anti- frizz treatments, hot oil treatments, pomades, powders, pastes, thermal damage repair treatments, hair removal creams or strips.
- Split end repair treatments such as, hair gels, hair mousses, styling aerosol sprays, anti- frizz treatments, hot oil treatments, pomades, powders, pastes, thermal damage repair treatments, hair removal creams or strips.
- compositions such as transdermal patches, nasal sprays, mouthwashes, ointments, creams, gels, oral tablets and capsules, powdered formulations, eye drops, ear drops, suppositories, pessaries, smoking cessation aides, effervescent tablets, liquid delivery systems, such as gels, sachets, powders.
- Buccal delivery formulations Impregnated bandages or pain relief formulation gels. Insect repellent formulations, sticks, liquids, sprays, wipes, wristbands and other impregnated fabrics.
- Agricultural formulation such as herbicides, pesticides, fungicides, nematodicides, rodenticides, insect repellents, insecticides, insect growth hormones, emulsifiable concentrates water dispersible granules, wettable powders or suspensions, seed treatments, such as water proofers and stickers, fertilisers plant food, nutrient delivery systems.
- Medicated pet collars e.g. fleas, ticks
- Medical and surgical gloves Pet malodour treatments.
- Fruit surface treatments such as herbicides, pesticides, fungicides, nematodicides, rodenticides, insect repellents, insecticides, insect growth hormones, emulsifiable concentrates water dispersible granules, wettable powders or suspensions, seed treatments, such as water proofers and stickers, fertilisers plant food, nutrient delivery systems.
- Homecare products such as hard surface cleaners, furniture polish sprays, gels or wipes, floor cleaners (ready to use or concentrates), dust reduction spray or wipe formulations, plug in air fresheners, air freshener gels, air freshening candles, air or carpet freshening powders, air freshener sprays, antimicrobial wipes, dishwasher tablets or concentrated liquids, laundry detergent powders, sachets or liquids, fabric softener liquids of sachets, dye transfer inhibition liquids or sheets, antistatic or fabric beneficiating products, ironing water, ironing treatment sprays, hand dish liquids or gels, auto dish tablets or liquids, including rinse aides, bathroom cleaners, bleaches, limescale reduction formulations, stainless steel cleaners, mould or fungi reduction treatments, toilet cleaner concentrated liquids and gels, toilet block formulation, flush aides, biocides, kitchen/hob/oven cleaner/degreaser. Chrome polish, integrated floor cleaning/wipe systems. Malodour removal/reduction. Shoe and leather polish
- Beverage formulations such as carbonated soft drinks, still soft drinks, ready to drink fruit based drinks, squash concentrates, alcoholic beverages (spirits, wines, beers, ready to drink mixes) , milkshake concentrates and ready to drink milkshakes (ambient and chilled), fruit juices, smoothies, hot beverages and infusions, such as tea, coffee, hot chocolate, flavoured waters (still or carbonated), mineral water (still or carbonated), energy drinks, dietary beverages (ready to drink or concentrates) powdered or gel versions of the above, sports recovery drinks,
- Food preparations such as baked pastry goods, cakes, breads, confectionary, chocolates, ice cream, desserts, ready-made meals, condiments, such as ketchup, mustard, salad dressings, soups, stews, broths.
- condiments such as ketchup, mustard, salad dressings, soups, stews, broths.
- Emulsions such as mayonnaise.
- Dairy products such as hard and soft cheeses, butter or spreads, yoghurts, creme fraiche, milk (skimmed, semi skimmed, unskimmed, UHT or pasteurised), buttermilk, whey protein based products, double or single cream, powdered whiteners for hot beverages.
- Non-dairy variants such as soy or almond milk.
- Coating and adhesives including solvent, water or powder based paints, both decorative and speciality (can coatings, automotive). Self-healing paint or coatings applications. Controlled release of biocides. Radiation cured coatings (automotive refinish systems, electronics, including nail varnish and artificial nail systems.) Adhesives systems, including water based or solvent based, both 1 pack or 2 pack systems. Paint strippers and diluents.
- Metallurgy metal quenching processing aides, acid pickling, electroplating, metal cleaners, degreasers other surface treatments.
- Oil extraction, production and refining Cementing process chemicals. Gas hydrate inhibition, shale swell prevention additives, delivery of oil field chemicals to the oil wells, fracking. Drill head lubricants, catalysts.
- Printing and inks including font solutions, flexographic printing, ink jet printing, paper making process chemicals, such as sizing agents. Paper coatings used to improve printing performance post manufacture.
- said capsule wall includes:
- component (b) a component (A) or a residue of component (A) after reaction or interaction with material referred to in (a); and, optionally, (c) a cross-linking moiety which may be a residue of a component (B).
- Component (A) may be as described in the second aspect. It is preferably a water- soluble polymer and/or a polysaccharide. Component (B) may be as referred to in the second aspect.
- the ratio of the wt% of components referred to in paragraphs (a) and (b) may be at least 3 and, preferably, is at least 5; and may be less than 10 or less than 8.
- a method of making a capsule comprising an encapsulated material and a capsule wall encapsulating the encapsulated material, the method comprising:
- Said capsule may include any feature of the capsule of the first aspect.
- Said N-acetylglucosamine/glucosamine copolymer or a derivative of such a copolymer is suitably derived from a raw material which is of non-animal origin as described in the first aspect.
- Said N-acetylglucosamine/glucosamine copolymer or a derivative of such a copolymer is preferably derived from a chitin.
- Said chitin may be derived from a micro-organism. It may be derived from a fungus, for example a yeast. It may be derived from a biomass. Said biomass may comprise zygomycetes, basidiomycetes, ascomycetes and deuteromycetes. In one preferred embodiment, said chitin may be derived from mycelium, for example of Aspergillus niger.
- Said N-acetylglucosamine/glucosamine copolymer or a derivative of such a copolymer is preferably prepared as described in WO03/068824, the content of which is hereby incorporated herein by reference.
- the average molecular weight of said N-acetylglucosamine/glucosamine copolymer or a derivative of such a copolymer may be measured by Ubbelohde capillary visosimetry as described in WO03/068824.
- Said N-acetylglucosamine/glucosamine copolymer or a derivative of such a copolymer selected in step (i) may have an average molecular weight of at least 10 kDa, suitably at least 20kDa, preferably at least 40kDa, especially at least 60kDa.
- the average molecular weight may be less than 300kDa, suitably less than 150kDa, especially less than 100kDa.
- Said N-acetylglucosamine/glucosamine copolymer or a derivative of such a copolymer may have a degree of acetylation of at least 0.1 mol%, suitably of at least 5 mol%, preferably at least 10 mol%.
- the degree of acetylation may be in the range 5 to 30 mol%.
- the degree of acetylation may be assessed by method KZ PT-CQ-101 , of Kitozyme
- Said N-acetylglucosamine/glucosamine copolymer or a derivative of such a copolymer may have a viscosity (1 wt% in acetic acid solution (mPa.s)), (measured by method KZ PT- CQ-102 of Kitozyme) of 1 to 40 mPa.s, for example 5-40 mPa.s or 5-25 mPa.s.
- Said N-acetylglucosamine/glucosamine copolymer or a derivative of such a copolymer selected in step (i) suitably includes a moiety of structure
- R H or COCHs
- the method may include selecting a component (A) and subjecting the component (A) to conditions which cause it to be incorporated into said capsule wall.
- Said component (A) and said N-acetylglucosamine/glucosamine copolymer or a derivative of such a copolymer preferably define a coacervate phase which is arranged to encapsulate the material to be encapsulated in the method.
- the method may include subjecting the N-acetylglucosamine/glucosamine copolymer or a derivative of such a copolymer and the component (A) to conditions such that they interact and/or react to define the capsule wall.
- Said component (A) may be polar. Said component (A) may be anionic. Said component (A) may include carboxyl moieties. Said component (A) may be a polymer. Said component (A) may be an organic polymer. Said component (A) may be a cellulose or cellulose derivative, a polysaccharide, for example an anionic polysaccharide, a polyacrylate, an acrylic acid or methacrylic acid polymer, a polyphosphate, albumen or an albumen derivative, an alginate, a vinylacetate polymer, a vinylalcohol polymer, a gum for example carrageenan gum, xanthan gum or gum Arabic, an agar, a starch or a pectin.
- a polysaccharide for example an anionic polysaccharide, a polyacrylate, an acrylic acid or methacrylic acid polymer, a polyphosphate, albumen or an albumen derivative, an alginate, a vinylacetate polymer
- Said component (A) is preferably a polymer. It is preferably a saccharide. It preferably includes a polysaccharide moiety. It is preferably a gum. It is preferably a naturally-occurring gum or a derivative thereof. It is preferably polar. It may be anionic. It preferably includes carboxyl moieties.
- Said component (A) may be a hydrophilic polymer.
- Said component (A) is preferably water soluble.
- Said material to be encapsulated is preferably hydrophobic. It is preferably more hydrophobic than the N-acetylglucosamine/glucosamine copolymer or a derivative of such a copolymer selected in step (i) of the method. It is preferably more hydrophobic than component (A) when provided.
- Said material to be encapsulated may be an oil (e.g. mineral oil, silicone oil, a vegetable-derived oil, an essential oil, a fragrance oil), a butter (e.g. shea or coconut butter) or a wax (e.g. beeswax and carnauba wax).
- the method of the second aspect preferably comprises providing said N- acetylglucosamine/glucosamine copolymer or a derivative of such a copolymer in an aqueous solution (A).
- Said component (A) is suitably also provided in solution in said aqueous solution (A).
- aqueous solution (A) suitably comprises said N-acetylglucosamine/glucosamine copolymer or a derivative of such a copolymer and said component (A).
- the ratio of the wt% of said component (A) divided by the wt% of said N-acetylglucosamine/glucosamine copolymer or a derivative of such a copolymer may be at least 3, preferably at least 5.
- the total wt% of dissolved solids in said solution (A) may be at least 5 wt%, preferably at least 7 wt%. It may be less than 20 wt%, less than 16 wt% or less than 12 wt%.
- Said solution (A) suitably has a pH as follows (or is adjusted to a pH as follows): greater than 1 and preferably less than 4 or less than 3.
- Aqueous solution (A) suitably is arranged to define a coacervate phase.
- the method preferably comprising producing a formulation (B) which comprises aqueous solution (A) and said material to be encapsulated.
- the method may comprise contacting said material to be encapsulated with solution (A) to form formulation (B) and preferably stirring the combination.
- the method preferably therefore includes emulsifying or dispersing said material to be encapsulated in aqueous solution (A).
- Formulation (B) is suitably subjected to conditions whereby complex coacervation of the N- acetylglucosamine/glucosamine copolymer or a derivative of such a copolymer and component (A) occur.
- Such conditions suitably comprise increasing the pH of formulation (B).
- a base is suitably contacted with formulation (B) to increase the pH, for example to a pH which is at least 0.5, for example at least 0.7 pH units higher than the starting pH.
- the pH may be greater than 2 or greater than 2.5 after contact with said base. It may be less than 4 or less than 3.
- the capsule wall is suitably formed by the N- acetylglucosamine/glucosamine copolymer or a derivative of such a copolymer and said component (A).
- the temperature of formulation (B) does not increase to greater than 30°C or greater than 40°C or greater than 50°C; and/or formulation (B) is not actively heated (i.e. formulation (B) is solely subjected to ambient conditions rather than any additional heat source).
- the combination is suitably treated with a component (B) which is suitably arranged to increase the strength and/or integrity of the capsule wall and/or effect cross-linking (or other reaction) between components in the wall.
- Component (B) may be arranged to react with hydroxy moieties in said capsule wall to effect cross-linking.
- Component (B) may be an aldehyde, for example having at least two aldehyde moieties. It may, for example, be glutaraldehyde.
- component (B) may be selected from glutaraldehyde, formaldehyde, genepin, oleuropein, epichlorohydrin, tannic acid, gallic acid, sodium tripolyphosphate and transglutaminase.
- the method preferably comprises recovering said capsule.
- the method comprises making a multiplicity of capsules and recovering said multiplicity of capsules.
- the method may comprise contacting said capsule or capsules with a preservative for preserving the capsules.
- the method described is advantageous over prior methods in terms of the time taken to form capsules and its energy requirements. Furthermore, the capsules made have excellent physical and/or mechanical properties.
- the invention extends, in a third aspect, to a capsule made in the method of the second aspect.
- the capsule may be as described in the first aspect.
- capsule as described in any preceding aspect; (ii) a protease enzyme or an alcohol.
- Protease enzymes may be used in cleaning formulations to break down proteins.
- Alcohols may be included in a range of formulations, for example hand sanitisers.
- the capsules described herein may be advantageously used in formulations which contain protease enzymes or alcohols due to the relative stability of the capsule wall of the capsules in the presence of such enzymes or alcohols.
- Figure 1 is a graph comparing average break strengths of capsules made using different sources of chitosan
- Figure 2 is a graph comparing compression before breakage of capsules made using different sources of chitosan
- Figure 3 is a graph comparing probe distance travelled before failure of capsules made using different sources of chitosan; and Figure 4 is a graph comparing compressibility of capsules made using different sources of chitosan;
- Copolymer (I) - biomass derived N-acetylglucosamine/glucosamine copolymer (commonly referred to as chitosan) having a molecular weight of 80kDa obtained from Kitozyme.
- Copolymer (II) - biomass derived N-acetylglucosanine/glucosamine copolymer having a molecular weight of 10-20 kDa obtained by from Kitozyme.
- HCMF Marine Chitosan
- Chitosan or deacetylated chitin, is a linear copolymer comprised of randomly repeating glucosamine and N-acetylglucosamine units connected by ⁇ (1 ,4) type linkages.
- the chemical structure is as shown below:
- R H or COCHg
- N-acetylglucosamine/glucosamine copolymer is a positively charged polyelectrolyte and will undergo complex coacervation with negatively charged polyelectrolytes such as Gum Arabic.
- N-acetylglucosamine/glucosamine copolymer is not soluble above pH 5 (depending on degree of deacetylation) and therefore the controlled deposition of a coacervate cannot be achieved by adjustment of pH from neutral to acidic to allow precipitation to occur.
- a matrix encapsulation technique can be employed to create beads of N-acetylglucosamine/glucosamine copolymer encasing an active material.
- Material to be encapsulated is mixed into a solution of N-acetylglucosamine/glucosamine copolymer. Then, via a dropping mechanism, an alkali solution is dripped into the mixture which causes N- acetylglucosamine/glucosamine copolymer precipitation.
- the resultant beads which form entrap the active material in a spherical matrix, which can be recovered and maturated.
- Microcapsules formed via complex coacervation will remain mechanically fragile or will maintain the potential to be re-solubilised by warm water or pH changes unless cross-linked.
- This crosslinking is achieved by application of a cross linking agent, which is typically a solution of glutaraldehyde or formaldehyde, although genepin, oleuropein, epichlorhydrin, sodium tripolyphosphate and transglutaminase have also been used.
- Examples 1 and 2 describe the preparation of microcapsules using bio- mass derived N-acetylglucosamine/glucosamine (i.e. chitosan) and, subsequently, results of mechanical tests are provided.
- Example 1 Preparation of microcapsules made using high molecular weight Copolymer (I)
- the internal oil phase component was: High oleic sunflower oil (80 wt%)
- the external water phase components comprised the following:
- the external water phase components were combined (130g) and mixed with an overhead stirrer (at 320rpm), using a 4 blade star propeller in a beaker (400ml), and adjusted to pH 1 .7 with hydrochloric acid (25%, 2.3g).
- the internal oil phase components (100ml) were mixed on a stirrer plate until homogenous.
- the internal oil phase was then added to the external water phase and the stirrer speed was increased to 1400rpm for 120 seconds, yielding oil droplets with a modal average particle size of 50 microns.
- the stirrer speed was then reduced to 450rpm.
- 1 litre deionised water (480ml) was adjusted to pH 1 .7 with hydrochloric acid (25%).
- the emulsion comprising oil droplets was added to this beaker and stirring continued at 500rpm.
- Coacervation formation was as follows: A dropping funnel (50ml) was charged with
- Glutaraldehyde solution (4g, 50%) was then added to effect cross-linking. The solution was left to stir overnight.
- the capsule suspension was transferred to another 2 litres beaker and diluted with deionised water. When the capsules had settled to the top, the suspension was filtered over 60 micron mesh fabric and washed with 4 litres of deionised water. The dry capsule slurry was then transferred to a beaker (400ml) and weighed, yielding 125.68g of approximately 85% solids.
- Preservative solution (87.97g) was added, comprised of deionised water (98.5%), carboxy methylcellulose (1 %) and potassium sorbate (0.5%), adjusted to pH 4.8 with citric acid solution (10%).
- Example 2 Preparation of microcapsules using lower molecular weight Copolymer (II)
- the internal oil phase component used was:
- the external water phase component comprised the following:
- the external water phase components were combined (130g) and mixed with an overhead stirrer (at 320rpm), using a 4 blade star propeller in a beaker (400ml), and adjusted to pH 2.21 with hydrochloric acid (25%, 1 .4g).
- the oil phase (100ml) was then added to the external water phase and the stirrer speed was increased to 1200rpm for 180 seconds, yielding an emulsion comprising oil droplets with a modal average particle size of 60 microns.
- the stirrer speed was then reduced to 400rpm.
- deionised water (428ml) was adjusted to pH 1 .7 with hydrochloric acid (25%).
- the emulsion comprising oil droplets was added to this beaker and stirring continued at 500rpm.
- a dropping funnel (50ml) was charged with 50ml_ of triethanolamine solution (5%wt in deionised water). The pH was monitored as the funnel was set to release approximately 0.33ml/min. The emulsion was regularly checked under the microscope for wall formation and quality.
- Glutaraldehyde solution (3g, 50%) was then added to effect cross-linking. The solution was left to stir overnight.
- One capsule was isolated and centred underneath a probe (set at 5mm height from plate) of a Stable Microsystem Texture Analyzer. The analyser was used to assess the degree of force required to break a single microcapsule.
- test parameters on Stable Micro Systems TA.XT plus Texture Analyser were as follows:
- Trigger Force 0.05g
- Probe Perspex cylinder After a test, the probe and surrounding area were wiped down with a small amount of ethanol and a test repeated.
- capsules of Example 1 were found to have significantly higher break strength compared to capsules of Example 2.
- the internal phase of the capsules consisted of the following:
- the Lutein and Green 6 colourants were included to make particle size determination easier.
- the external phase of the capsules consisted of the following:
- Example 3 For both Examples 3 and 4, the deionised water was lowered to pH 1 .95 (21 .5°C) and the chitosan was added. When it had fully dissolved, the pH and viscosity were measured. The Gum Arabic was then added and stirred until dissolved, and hydrochloric acid (25% wt.) was used to lower the pH of the systems to 1 .9, and the viscosity was again measured. Results are provided in the table below.
- Example 3 Example 4
- Example 3 The Example 3 formulation was clear, whereas the Example 4 formulation was a golden colour.
- the HCMF was faster to dissolve and had a higher viscosity than the Copolymer (I), though the Gum Arabic then took longer to dissolve in HCMF.
- approximately 5% more HCI (25% wt.) was required to achieve the appropriate pH.
- TEA triethanolamine
- the first visible, lasting coacervate was for HCMF at pH 2.55, and Copolymer (I) at pH 2.56, though neither batch had yet formed walls.
- the Copolymer (I) batch had a finer, less visible coacervate at this point; the HCMF batch had more visible, larger coacervate.
- Copolymer (I) batch The coacervate remained recognisable as discrete droplets until a higher pH than HCMF, around pH 2.8.
- Copolymer (I) batch was still producing coacervate locally upon addition of TEA solution.
- the walls were smoother and more consistent and optically clearer, and did not incorporate smaller oil droplets into the walls as the HCMF did.
- HCMF stopped producing locally visible coacervate at pH 2.75.
- the walls appeared thicker than the Copolymer (I) capsules and less optically clear.
- the coacervate was more amorphous.
- Each batch was split, with some half preserved in 0.5% xanthan, 0.5% rokonsal solution, and a quarter each in 0.5% rokonsal and either 2.5% CMC or 0.4% Gellan.
- the capsules were stable in Xanthan and Gellan. The capsules were assessed and results obtained as described further below.
- capsules described in Examples 5 to 9 were further assessed for break strength, compression before breakage, total distance travelled by the probe used to apply the force to the capsules and compressibility (%). Results are presented in Figures 1 to 4. It is found that, in general, capsules based on Copolymer I have higher break strength and are generally more flexible or compressible compared to comparable capsules derived from marine chitosan.
- the following materials may be used:
- Sodium carboxymethylcellulose or other cellulose derivatives sodium polyacrylate, polyacrylic or methacrylic acid, sodium tripolyphosphate, albumen, alginates such as sodium alginate, alginic acid, polyphosphates, polyvinyl acetate, polyvinyl alcohol, carrageenan, casein, calcium caesinate, agar-agar, starch, pectins, Irish moss and xanthan gum.
- the capsules prepared as described have been proven to offer reasonable stability (ie capsule walls remain intact and the capsules contents remain within the capsule) in commonly used personal care products, such as moisturising creams, shower gel, hand wash, shampoo and hydro-alcoholic formulations; in homecare applications, such as hand dish liquid, biological laundry detergent; in beverage formulations including dairy based beverages, like milkshakes and soft drinks, both still and carbonated.
- the capsules retain a relevant encapsulated material when associated with commercially available protease containing, biological liquid laundry products. Other prior art capsules were found to prematurely degrade, releasing the capsule content. Thus, the capsules can be advantageously used in protease enzyme-containing environments.
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Health & Medical Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Bioinformatics & Cheminformatics (AREA)
- Zoology (AREA)
- Medicinal Chemistry (AREA)
- Biotechnology (AREA)
- Genetics & Genomics (AREA)
- Biochemistry (AREA)
- Microbiology (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Animal Behavior & Ethology (AREA)
- Epidemiology (AREA)
- Pharmacology & Pharmacy (AREA)
- General Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Mycology (AREA)
- Molecular Biology (AREA)
- Emergency Medicine (AREA)
- Virology (AREA)
- Biomedical Technology (AREA)
- Tropical Medicine & Parasitology (AREA)
- Botany (AREA)
- Materials Engineering (AREA)
- Polymers & Plastics (AREA)
- Manufacturing Of Micro-Capsules (AREA)
- Cosmetics (AREA)
- General Preparation And Processing Of Foods (AREA)
- Medicinal Preparation (AREA)
Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP16724096.9A EP3297755A1 (en) | 2015-05-20 | 2016-05-10 | Capsules |
BR112017024939A BR112017024939A2 (en) | 2015-05-20 | 2016-05-10 | capsules |
US15/574,671 US20180133678A1 (en) | 2015-05-20 | 2016-05-10 | Capsules |
JP2017560821A JP2018516749A (en) | 2015-05-20 | 2016-05-10 | capsule |
CN201680028959.3A CN107847895A (en) | 2015-05-20 | 2016-05-10 | Capsule |
CA2986316A CA2986316A1 (en) | 2015-05-20 | 2016-05-10 | Capsules |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB1508658.0 | 2015-05-20 | ||
GBGB1508658.0A GB201508658D0 (en) | 2015-05-20 | 2015-05-20 | Capsules |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2016185171A1 true WO2016185171A1 (en) | 2016-11-24 |
Family
ID=53506072
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/GB2016/051330 WO2016185171A1 (en) | 2015-05-20 | 2016-05-10 | Capsules |
Country Status (8)
Country | Link |
---|---|
US (1) | US20180133678A1 (en) |
EP (1) | EP3297755A1 (en) |
JP (1) | JP2018516749A (en) |
CN (1) | CN107847895A (en) |
BR (1) | BR112017024939A2 (en) |
CA (1) | CA2986316A1 (en) |
GB (2) | GB201508658D0 (en) |
WO (1) | WO2016185171A1 (en) |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2020131956A1 (en) | 2018-12-18 | 2020-06-25 | International Flavors & Fragrances Inc. | Hydroxyethyl cellulose microcapsules |
US10695272B2 (en) | 2015-12-30 | 2020-06-30 | International Flavors & Fragrances Inc. | Compositions containing microcapsules coated with deposition proteins |
JP2020528267A (en) * | 2017-07-27 | 2020-09-24 | フイルメニツヒ ソシエテ アノニムFirmenich Sa | Gum arabic / chitosan coacervate |
GB202110132D0 (en) | 2021-07-14 | 2021-08-25 | Cpl Aromas Ltd | Microcapsules and methods for preparing microcapsules |
WO2023102033A1 (en) | 2021-12-03 | 2023-06-08 | International Flavors & Fragrances Inc. | Aqueous fabric conditioner compositions with high performance fragrances |
WO2023168069A1 (en) | 2022-03-04 | 2023-09-07 | International Flavors & Fragrances Inc. | Fragrance compositions for sleep improvement |
WO2023172542A1 (en) | 2022-03-07 | 2023-09-14 | International Flavors & Fragrances Inc. | Fragrance-containing granules |
EP4309499A1 (en) | 2022-07-22 | 2024-01-24 | Givaudan SA | Composition comprising biodegradable microcapsules |
WO2024035547A1 (en) | 2022-08-09 | 2024-02-15 | International Flavors & Fragrances Inc. | Fragrance-containing granules |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110937844A (en) * | 2019-12-02 | 2020-03-31 | 浙江工业大学 | Beer waste yeast microcapsule and application thereof in preparation of self-repairing cement-based material |
KR102596259B1 (en) * | 2021-02-24 | 2023-10-31 | 한영대학교 산학협력단 | Capsule type sanitizer |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2712507A (en) | 1953-06-30 | 1955-07-05 | Ncr Co | Pressure sensitive record material |
WO2003068824A1 (en) | 2002-02-12 | 2003-08-21 | Kitozyme S.A. | Cell wall derivatives from biomass and preparation thereof |
JP2005023281A (en) * | 2003-07-04 | 2005-01-27 | Toppan Printing Co Ltd | Polysaccharide complex |
WO2005034852A2 (en) * | 2003-08-26 | 2005-04-21 | Gel-Del Technologies, Inc. | Protein biomaterials and biocoacervates and methods of making and using thereof |
JP2006299026A (en) * | 2005-04-19 | 2006-11-02 | Toppan Printing Co Ltd | Composite molded body and method for immobilizing active substance using the composite molded body |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6418440A (en) * | 1987-07-10 | 1989-01-23 | Dainippon Pharmaceutical Co | Micro-capsule |
JPH01184440A (en) * | 1988-01-18 | 1989-07-24 | Mitsubishi Heavy Ind Ltd | Testing method for creep or creep rupture of welding-heat affected zone |
IL100096A (en) * | 1991-11-20 | 1996-03-31 | Univ Ramot | Method for entrapment of active materials in chitosan |
NZ596403A (en) * | 2006-06-05 | 2013-02-22 | Ocean Nutrition Canada Ltd | Microcapsules with improved shells with wax in the outer shell |
JP5387554B2 (en) * | 2010-12-21 | 2014-01-15 | 凸版印刷株式会社 | Method for producing composite molded body |
US20140322341A1 (en) * | 2011-08-03 | 2014-10-30 | Diane RUBIN | Novel hemostatic patch and uses thereof |
-
2015
- 2015-05-20 GB GBGB1508658.0A patent/GB201508658D0/en not_active Ceased
-
2016
- 2016-05-10 GB GB1608157.2A patent/GB2542224A/en not_active Withdrawn
- 2016-05-10 WO PCT/GB2016/051330 patent/WO2016185171A1/en active Application Filing
- 2016-05-10 US US15/574,671 patent/US20180133678A1/en not_active Abandoned
- 2016-05-10 BR BR112017024939A patent/BR112017024939A2/en not_active Application Discontinuation
- 2016-05-10 JP JP2017560821A patent/JP2018516749A/en active Pending
- 2016-05-10 CA CA2986316A patent/CA2986316A1/en not_active Abandoned
- 2016-05-10 CN CN201680028959.3A patent/CN107847895A/en not_active Withdrawn
- 2016-05-10 EP EP16724096.9A patent/EP3297755A1/en not_active Withdrawn
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2712507A (en) | 1953-06-30 | 1955-07-05 | Ncr Co | Pressure sensitive record material |
WO2003068824A1 (en) | 2002-02-12 | 2003-08-21 | Kitozyme S.A. | Cell wall derivatives from biomass and preparation thereof |
JP2005023281A (en) * | 2003-07-04 | 2005-01-27 | Toppan Printing Co Ltd | Polysaccharide complex |
WO2005034852A2 (en) * | 2003-08-26 | 2005-04-21 | Gel-Del Technologies, Inc. | Protein biomaterials and biocoacervates and methods of making and using thereof |
JP2006299026A (en) * | 2005-04-19 | 2006-11-02 | Toppan Printing Co Ltd | Composite molded body and method for immobilizing active substance using the composite molded body |
Non-Patent Citations (2)
Title |
---|
DATABASE WPI Week 200514, Derwent World Patents Index; AN 2005-126609, XP002759862 * |
DATABASE WPI Week 200702, Derwent World Patents Index; AN 2007-011989, XP002759861 * |
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US11602494B2 (en) | 2015-12-30 | 2023-03-14 | International Flavors & Fragrances Inc. | Compositions containing microcapsules coated with deposition proteins |
US10695272B2 (en) | 2015-12-30 | 2020-06-30 | International Flavors & Fragrances Inc. | Compositions containing microcapsules coated with deposition proteins |
US11129778B2 (en) | 2015-12-30 | 2021-09-28 | International Flavors & Fragrances Inc. | Compositions containing microcapsules coated with deposition proteins |
JP2020528267A (en) * | 2017-07-27 | 2020-09-24 | フイルメニツヒ ソシエテ アノニムFirmenich Sa | Gum arabic / chitosan coacervate |
WO2020131956A1 (en) | 2018-12-18 | 2020-06-25 | International Flavors & Fragrances Inc. | Hydroxyethyl cellulose microcapsules |
GB202110132D0 (en) | 2021-07-14 | 2021-08-25 | Cpl Aromas Ltd | Microcapsules and methods for preparing microcapsules |
WO2023285609A2 (en) | 2021-07-14 | 2023-01-19 | Cpl Aromas Limited | Microcapsules and methods for preparing microcapsules |
WO2023102033A1 (en) | 2021-12-03 | 2023-06-08 | International Flavors & Fragrances Inc. | Aqueous fabric conditioner compositions with high performance fragrances |
WO2023168069A1 (en) | 2022-03-04 | 2023-09-07 | International Flavors & Fragrances Inc. | Fragrance compositions for sleep improvement |
WO2023172542A1 (en) | 2022-03-07 | 2023-09-14 | International Flavors & Fragrances Inc. | Fragrance-containing granules |
EP4309499A1 (en) | 2022-07-22 | 2024-01-24 | Givaudan SA | Composition comprising biodegradable microcapsules |
WO2024017931A1 (en) | 2022-07-22 | 2024-01-25 | Givaudan Sa | Composition comprising biodegradable microcapsules |
WO2024035547A1 (en) | 2022-08-09 | 2024-02-15 | International Flavors & Fragrances Inc. | Fragrance-containing granules |
Also Published As
Publication number | Publication date |
---|---|
JP2018516749A (en) | 2018-06-28 |
BR112017024939A2 (en) | 2018-07-31 |
GB2542224A (en) | 2017-03-15 |
EP3297755A1 (en) | 2018-03-28 |
CA2986316A1 (en) | 2016-11-24 |
CN107847895A (en) | 2018-03-27 |
GB201508658D0 (en) | 2015-07-01 |
US20180133678A1 (en) | 2018-05-17 |
GB201608157D0 (en) | 2016-06-22 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US20180133678A1 (en) | Capsules | |
US11491089B2 (en) | Reloadable microcapsules | |
US11602494B2 (en) | Compositions containing microcapsules coated with deposition proteins | |
EP3897955B1 (en) | Hydroxyethyl cellulose microcapsules | |
CN108367264B (en) | Process for preparing polyurea microcapsules with improved deposition | |
CN113453656A (en) | Microcapsules prepared from proteins | |
JP7416620B2 (en) | Method for manufacturing microcapsules | |
WO2019173062A1 (en) | Reduced permeability microcapsules | |
CN111225718A (en) | Hydrogel beads | |
WO2018006089A1 (en) | Stable microcapsule compositions | |
EP3356449A1 (en) | Hybrid capsules | |
WO2016054351A1 (en) | Capsules containing polyvinyl alcohol | |
EP3416610A1 (en) | Polyurea capsule compositions | |
CN107072960A (en) | Method for preparing multiple capsules | |
US20220008886A1 (en) | Biodegradable microcapsules | |
US20230064054A1 (en) | Controlled Release Polymer Encapsulated Fragrances | |
WO2024088798A1 (en) | Microcapsules | |
CN118055751A (en) | Perfume-encapsulating microcapsules comprising a shell obtained from a polyisocyanate, an alkyl silicate and a polyethyleneimine |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 16724096 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2017560821 Country of ref document: JP Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 15574671 Country of ref document: US |
|
ENP | Entry into the national phase |
Ref document number: 2986316 Country of ref document: CA |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2016724096 Country of ref document: EP |
|
REG | Reference to national code |
Ref country code: BR Ref legal event code: B01A Ref document number: 112017024939 Country of ref document: BR |
|
ENP | Entry into the national phase |
Ref document number: 112017024939 Country of ref document: BR Kind code of ref document: A2 Effective date: 20171121 |