WO2014064255A2 - Capsules - Google Patents
Capsules Download PDFInfo
- Publication number
- WO2014064255A2 WO2014064255A2 PCT/EP2013/072403 EP2013072403W WO2014064255A2 WO 2014064255 A2 WO2014064255 A2 WO 2014064255A2 EP 2013072403 W EP2013072403 W EP 2013072403W WO 2014064255 A2 WO2014064255 A2 WO 2014064255A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- poly
- acid
- core
- shell
- alt
- Prior art date
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- 239000002775 capsule Substances 0.000 title claims abstract description 63
- 239000011258 core-shell material Substances 0.000 claims abstract description 31
- 239000002253 acid Substances 0.000 claims abstract description 30
- 239000003205 fragrance Substances 0.000 claims abstract description 25
- -1 poly(itaconic acid) Polymers 0.000 claims description 53
- 239000000463 material Substances 0.000 claims description 30
- 229920000642 polymer Polymers 0.000 claims description 25
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 17
- 230000009286 beneficial effect Effects 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 11
- 239000002002 slurry Substances 0.000 claims description 10
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 9
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 9
- 239000011976 maleic acid Substances 0.000 claims description 8
- 229920002845 Poly(methacrylic acid) Polymers 0.000 claims description 7
- 239000000178 monomer Substances 0.000 claims description 7
- 229920002125 Sokalan® Polymers 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 6
- 239000006071 cream Substances 0.000 claims description 6
- 230000003019 stabilising effect Effects 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 238000005538 encapsulation Methods 0.000 claims description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- 239000012736 aqueous medium Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229920001446 poly(acrylic acid-co-maleic acid) Polymers 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- 150000007513 acids Chemical class 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 3
- 239000002609 medium Substances 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 2
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 2
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 229920002732 Polyanhydride Polymers 0.000 claims description 2
- 229920000147 Styrene maleic anhydride Polymers 0.000 claims description 2
- 150000008065 acid anhydrides Chemical class 0.000 claims description 2
- 230000001166 anti-perspirative effect Effects 0.000 claims description 2
- 239000003213 antiperspirant Substances 0.000 claims description 2
- 229920006187 aquazol Polymers 0.000 claims description 2
- 239000012861 aquazol Substances 0.000 claims description 2
- 239000002781 deodorant agent Substances 0.000 claims description 2
- 125000001033 ether group Chemical group 0.000 claims description 2
- 229920005648 ethylene methacrylic acid copolymer Polymers 0.000 claims description 2
- 150000004676 glycans Chemical class 0.000 claims description 2
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 2
- 239000001863 hydroxypropyl cellulose Substances 0.000 claims description 2
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 claims description 2
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 claims description 2
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 claims description 2
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 claims description 2
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 claims description 2
- 229920000609 methyl cellulose Polymers 0.000 claims description 2
- 239000001923 methylcellulose Substances 0.000 claims description 2
- 235000010981 methylcellulose Nutrition 0.000 claims description 2
- 229920002939 poly(N,N-dimethylacrylamides) Polymers 0.000 claims description 2
- 229920003213 poly(N-isopropyl acrylamide) Polymers 0.000 claims description 2
- 229920002432 poly(vinyl methyl ether) polymer Polymers 0.000 claims description 2
- 229920002401 polyacrylamide Polymers 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- 229920001282 polysaccharide Polymers 0.000 claims description 2
- 239000005017 polysaccharide Substances 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 239000002453 shampoo Substances 0.000 claims description 2
- 239000000344 soap Substances 0.000 claims description 2
- 229920001059 synthetic polymer Polymers 0.000 claims description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims 1
- 229920002502 poly(methyl methacrylate-co-methacrylic acid) Polymers 0.000 claims 1
- 239000003381 stabilizer Substances 0.000 claims 1
- 239000012071 phase Substances 0.000 description 27
- 239000011162 core material Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 14
- 238000000151 deposition Methods 0.000 description 6
- 239000003094 microcapsule Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 235000015243 ice cream Nutrition 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 229920002396 Polyurea Polymers 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229920003180 amino resin Polymers 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000007958 cherry flavor Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005192 partition Methods 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000004971 Cross linker Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 238000012695 Interfacial polymerization Methods 0.000 description 1
- 229920001744 Polyaldehyde Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 235000009499 Vanilla fragrans Nutrition 0.000 description 1
- 244000263375 Vanilla tahitensis Species 0.000 description 1
- 235000012036 Vanilla tahitensis Nutrition 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920002589 poly(vinylethylene) polymer Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 238000011417 postcuring Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 235000019613 sensory perceptions of taste Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000001542 size-exclusion chromatography Methods 0.000 description 1
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Inorganic materials [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000035923 taste sensation Effects 0.000 description 1
- 239000004634 thermosetting polymer Substances 0.000 description 1
- 239000008371 vanilla flavor Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Classifications
-
- 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
- C11D3/50—Perfumes
- C11D3/502—Protected perfumes
- C11D3/505—Protected perfumes encapsulated or adsorbed on a carrier, e.g. zeolite or clay
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/0241—Containing particulates characterized by their shape and/or structure
- A61K8/0245—Specific shapes or structures not provided for by any of the groups of A61K8/0241
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/04—Dispersions; Emulsions
- A61K8/06—Emulsions
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/11—Encapsulated compositions
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- A61K8/8147—Homopolymers or copolymers of acids; Metal or ammonium salts thereof, e.g. crotonic acid, (meth)acrylic acid; Compositions of derivatives of such polymers
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- A61K8/817—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions or derivatives of such polymers, e.g. vinylimidazol, vinylcaprolactame, allylamines (Polyquaternium 6)
- A61K8/8176—Homopolymers of N-vinyl-pyrrolidones. Compositions of derivatives of such polymers
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q11/00—Preparations for care of the teeth, of the oral cavity or of dentures; Dentifrices, e.g. toothpastes; Mouth rinses
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q13/00—Formulations or additives for perfume preparations
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q15/00—Anti-perspirants or body deodorants
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
- A61Q19/10—Washing or bathing preparations
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
- A61Q5/02—Preparations for cleaning the hair
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
- A61Q5/06—Preparations for styling the hair, e.g. by temporary shaping or colouring
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
- A61Q5/12—Preparations containing hair conditioners
-
- 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
- B01J13/20—After-treatment of capsule walls, e.g. hardening
- B01J13/22—Coating
-
- 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
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/56—Compounds, absorbed onto or entrapped into a solid carrier, e.g. encapsulated perfumes, inclusion compounds, sustained release forms
Definitions
- the present invention is concerned with encapsulation of beneficial agents, in particular fragrances.
- Core-shell capsules are known in the art. They generally consist of a polymeric shell that is formed around a core containing a beneficial agent, such as a fragrance, and indeed any other ingredients that should be encapsulated.
- a beneficial agent such as a fragrance
- Core-shell capsules are typically formed by forming droplets of core-forming material dispersed in an aqueous continuous phase. Monomers that should react to form a polymeric shell around the core droplets are contained in the droplets and/or the continuous phase. They can be made to react to form polymeric coatings around the droplets, which are subsequently consolidated (hardened) by crosslinking reactions. In this way, it is possible to form core-shell capsules comprising shells formed of aminoplast and resins, in particular thermoset resins, polyureas, polyurethanes, polyamides, gelatin, polyacrylics and the like. Core-shell capsules are very versatile.
- the polymeric shell may have a barrier function, protecting the core contents from the environment external of the capsule, but it may also act as a means of modulating the release of fragrance at a desired rate of release.
- the nature and composition of the shell can influence capsule properties such as hardness, brittleness and porosity, and as such, affect the manner in which the beneficial agent can be released therefrom.
- a disadvantage of forming shells by in-situ polymerisation reactions is that the formed capsules can contain significant levels of unreacted monomers. Residues of monomers, for example, can be particularly undesirable in contact with skin, for instance in Personal Care applications. For this reason it is conventional to carry out numerous post- treatments on capsules to remove these residues after high conversion
- Post-treatment techniques may take the form of post-reacting with another molecule or post curing, volatilization, stream stripping, molecular trapping or extraction using a suitable solvent or ion-exchange resins. Unfortunately, these techniques are not particularly suitable when the capsules contain volatile benefit agents such as fragrances.
- Applicant has found that it is possible to form shells of pre-formed polymeric material based on polycarboxylic acids, around oil droplets comprising a beneficial agent, e.g. a fragrance.
- a beneficial agent e.g. a fragrance.
- capsules can be formed that contain extremely low levels of monomeric material heretofore unachievable using conventional in-situ polymerisation techniques.
- the invention provides in a first aspect core-shell capsules comprising a fragrance- containing core and a shell formed around said core, wherein the shell is formed of polycarboxylic acid having a molecular weight of ⁇ to 10 ooo ooo Daltons, more particularly 50 000 to 2 000 000 Daltons.
- the capsules of the present invention are distinct from conventional polyacrylic capsules in that the shell is formed of pre-formed polymeric material as opposed to the conventional approach whereby monomers are reacted in situ to form the shell. In the latter case, the shell consists of a polymeric mass with no defined or measurable molecular weight.
- preformed polymers By employing preformed polymers to form the shell, one can exert great control over the shell's mechanical properties by selecting the desired molecular weight of the component polymers. Furthermore, the use of pre-formed polymeric materials substantially avoids the problem of residual monomeric contaminants being found in the capsules.
- core-shell capsules comprising a fragrance- containing core and a shell formed around said core, wherein the shell is formed of polycarboxylic acid and wherein any carboxylic acid monomer is present in an amount of 100 ppm or less, more particularly 10 ppm or less, still more particularly 1 ppm or less.
- Residual carboxylic acid can be measured by techniques known in the art, for example by GC analysis.
- a GC column may contain polydimethylsiloxane and the carrier gas may be helium.
- Monomeric residues can be extracted with a suitable solvent such as methanol or the like.
- the polycarboxylic acid employed as a shell-forming material may be selected from the group consisting of polymethacrylic acid, polyacrylic acid, styrene-maleic acid copolymer, poly(itaconic acid), poly(monomethyl itaconate), poly(methyl
- the shell comprises one or more additional polymeric materials that is different from the polycarboxylic acid disclosed herein above.
- the shell consists of multiple layers of polycarboxylic acid, more particularly at least 2 layers, still more particularly 5 to 10 layers or more.
- the shell consists of multiple layers of
- polycarboxylic acid polymer material wherein each layer of polycarboxylic acid is interposed with a layer of said additional polymeric material.
- the additional polymeric material forming said interposed layer or layers is selected for its property of being able to interact with contiguous polycarboxylic acid layers by forming either physical or chemical bonds therewith.
- the polymeric material forming said interposed layer or layers is able to interact with the adjacent polycarboxylic acid layer by forming hydrogen bonds.
- the one or more additional polymeric materials referred to above may be selected from polyvinylpyrrolidone, polyvinyl alcohol, polymers, containing lactame groups like PVP or poly(N-vinyl caprolactame), polymers containing ether groups either in the backbone (Polyethylene oxide, poly propylene glycol) or as pendants (poly(vinyl methyl ether), acrylic type polymers such as polyacrylamide, poly(N- isopropylacrylamide) and poly(N,n-dimethylacrylamide), polymeric alcolohols such as PVA, poly(2-hydroxyethylacrylate) and poly(2-hydroxyethyl vinyl ether), other synthetic polymers such as poly(2-ethyl-2-oxazoline) and poly(N- acetyliminoethylene) and water soluble non ionic polysaccharides such as
- Typical combinations include poly(methacrylic acid)/poly(vinyl pyrrolidone), poly(vinyl acetate)/ ethylene-maleic anhydride copolymer and poly(vinyl
- the shell is from 5 to 150 nm thickness.
- the core-shell capsules are somewhat sensitive to high pH conditions. Indeed, at pH levels at 6.5 or above, the shells will begin to dissociate back into the polymeric material from which they were formed.
- the invention provides in another of its aspects a method of stabilising said core-shell particles by storing them in a suitable medium at a pH of less than about 5, more particularly at a pH of about 2 to 4
- aqueous slurry comprising core-shell capsules as herein described, wherein said slurry has a pH of less than about 5, more particularly 2 to 4.
- the slurry may contain 5 to 50 % by weight of core-shell capsules, more particularly 10 to 40%, still more particularly 20 to 30 % by weight.
- the slurry may contain a stabilizing polymer. It is common to employ stabilising polymers in slurries containing capsules and the skilled person would understand the common types of stabilising polymers that can be employed.
- a particular stabilising polymer is Keltrol.
- the stabilising polymer can be employed in amounts of about 0.05 to 5 % by weight, more particularly 0.1 to 0.3%.
- the remaining mass of the slurry typically is comprised of water.
- Core shell capsules of the present invention are particularly suitable for use in laundry applications including softeners, personal care and hair care applications including shampoo, conditioners, combing creams, leave on conditioners, styling cream, soaps, body creams; deodorants and anti- perspirants; household applications, fine fragrance and oral care.
- the invention provides in another of its aspects a method of encapsulation of a beneficial agent, in particular a fragrance, comprising the steps of
- polycarboxylic acid and at least one additional polymeric material being different from the polycarboxylic acid wherein the polycarboxylic acid has a molecular weight of ⁇ to 10 ooo ooo Daltons.
- a method of encapsulation of a beneficial agent, in particular a fragrance comprising the steps of
- core- shell capsules around liquid droplets containing a beneficial agent without the need of any kind of template or sacrificial core.
- Forming capsule shells around liquid droplets is more challenging than forming shells around solid cores because the former is a more mobile phase and ingredients can partition between the droplets and the external phase during the process of shell formation.
- Fragrances are particularly challenging to encapsulate in this way because their overall character depends on them consisting of complex, multi-component mixtures, which components have different physical properties and partition at different rates and to different extents.
- Core-shell capsules formed according to the present invention are useful for encapsulating, among other useful beneficial agents, fragrance ingredients.
- the capsules can be formed with minimum loss of core material and maintenance of the hedonic character of the fragrance core created by the perfumer.
- each succeeding layer need not be selected from the same materials as the initial two layers. The only requirement is that each succeeding layer is capable of interacting either physically or chemically with the layer adjacent it. This allows considerable versatility in how a capsule may be prepared in order to achieve a particular desired result.
- the polymeric materials may be applied to droplets of a dispersed phase by introducing polymeric material to be deposited into the external phase surrounding the droplets under conditions permitting deposition of the polymeric material on the droplets.
- the polymeric material can be introduced into the external phase in an amount of about 0.2 to 10 % w/w in the external phase, more
- the amount of polymeric material introduced will depend upon its molecular weight (the higher the molecular weight, generally the lower amounts that will be employed in the external phase).
- the core-shell capsules may be formed in this manner using techniques including spray-coating or microfluidics. Once the shell is formed, optionally, it may be crosslinked. This can be achieved by any convenient means.
- polymers having amino or hydroxyl groups may be crosslinked by the addition of materials such as polyaldehyde, polyfunctional isocyanates or epoxides or any other suitable crosslinker.
- the shell thus formed can be used as a templating agent around which chemistry may be carried out to form aminoplast, polyurea, polyurethane, polyacrylic, inorganic microcapsules or hybrid capsules.
- This washed phase is added to i(wt)% aqueous PVP (poly (vinyl pyrrolidone) of 40,ooog/mol molecular weight) solution at ⁇ under gently stirring.
- This phase is allowed to settle for 24I1 and it is then washed with water at pH 3 as described in the previous step. The settling, lower layer removal and washing steps are repeated.
- the final fragrance-containing capsules have an average diameter of ⁇ and a wall thickness of about I4nm.
- the polymers used in this example are poly(acrylic acid) [PAA]of 50,000 g/mol molecular weight and poly( vinyl pyrrolidone) of 40,ooog/mol molecular weight.
- This washed phase is added to i(wt)% aqueous PVP (poly (vinyl pyrrolidone) of 40,ooog/mol molecular weight) solution at pH3 under gently stirring.
- This phase is allowed to settle for 24I1 and it is then washed with water at pH 3 as described in the previous step. The settling, lower layer removal and washing steps are repeated.
- the final fragrance-containing capsules have an average diameter of 3 ⁇ and a wall thickness of about i8nm
- Example 3
- flavour-shifting ice cream comprising 10-layer PMAA/PVP microcapsules of Example 1.
- An ice cream is prepared by mixing the microcapsules containing a cherry flavour into an ice cream formulation at pH 5 containing a vanilla flavour.
- the initial taste sensation is vanilla, quickly followed by cherry flavour after dissolution of capsules at higher pH in the mouth.
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- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Veterinary Medicine (AREA)
- Public Health (AREA)
- General Health & Medical Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- Chemical & Material Sciences (AREA)
- Birds (AREA)
- Epidemiology (AREA)
- Organic Chemistry (AREA)
- Dermatology (AREA)
- Dispersion Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Wood Science & Technology (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Physics & Mathematics (AREA)
- Geometry (AREA)
- Manufacturing Of Micro-Capsules (AREA)
- Cosmetics (AREA)
- Fats And Perfumes (AREA)
- Detergent Compositions (AREA)
- Confectionery (AREA)
- General Preparation And Processing Of Foods (AREA)
- Seasonings (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
Description
Claims
Priority Applications (11)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201380055683.4A CN104870084B (en) | 2012-10-25 | 2013-10-25 | Capsule |
US14/432,101 US20150284665A1 (en) | 2012-10-25 | 2013-10-25 | Capsules |
MX2015004129A MX2015004129A (en) | 2012-10-25 | 2013-10-25 | Capsules. |
JP2015538466A JP6400015B2 (en) | 2012-10-25 | 2013-10-25 | capsule |
EP13795183.6A EP2911780B1 (en) | 2012-10-25 | 2013-10-25 | Capsules |
KR1020157010547A KR102048716B1 (en) | 2012-10-25 | 2013-10-25 | Capsules |
AU2013336579A AU2013336579B2 (en) | 2012-10-25 | 2013-10-25 | Capsules |
CA2886340A CA2886340A1 (en) | 2012-10-25 | 2013-10-25 | Capsules comprising a fragrance-containing core and a composite polymer shell |
BR112015008323A BR112015008323A2 (en) | 2012-10-25 | 2013-10-25 | capsules |
ZA2015/02685A ZA201502685B (en) | 2012-10-25 | 2015-04-21 | Capsules |
US16/149,759 US20190031981A1 (en) | 2012-10-25 | 2018-10-02 | Capsules |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP12290370.1 | 2012-10-25 | ||
EP12290370 | 2012-10-25 |
Related Child Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US14/432,101 A-371-Of-International US20150284665A1 (en) | 2012-10-25 | 2013-10-25 | Capsules |
US16/149,759 Division US20190031981A1 (en) | 2012-10-25 | 2018-10-02 | Capsules |
Publications (2)
Publication Number | Publication Date |
---|---|
WO2014064255A2 true WO2014064255A2 (en) | 2014-05-01 |
WO2014064255A3 WO2014064255A3 (en) | 2014-08-28 |
Family
ID=47221254
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2013/072403 WO2014064255A2 (en) | 2012-10-25 | 2013-10-25 | Capsules |
Country Status (13)
Country | Link |
---|---|
US (2) | US20150284665A1 (en) |
EP (1) | EP2911780B1 (en) |
JP (1) | JP6400015B2 (en) |
KR (1) | KR102048716B1 (en) |
CN (1) | CN104870084B (en) |
AR (1) | AR093134A1 (en) |
AU (1) | AU2013336579B2 (en) |
BR (1) | BR112015008323A2 (en) |
CA (1) | CA2886340A1 (en) |
MX (1) | MX2015004129A (en) |
TW (1) | TWI646978B (en) |
WO (1) | WO2014064255A2 (en) |
ZA (1) | ZA201502685B (en) |
Cited By (9)
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WO2016087598A1 (en) * | 2014-12-04 | 2016-06-09 | Basf Se | Microcapsules |
EP3061500A1 (en) * | 2015-02-25 | 2016-08-31 | Symrise AG | Stable dispersions |
WO2017029302A1 (en) * | 2015-08-18 | 2017-02-23 | Basf Se | Agrochemical microcapsules with a shell of polyvinylalcohol and polyoxazoline |
WO2017040024A1 (en) * | 2015-09-03 | 2017-03-09 | The University Of Massachusetts | Stabilized polymeric nanocapsules, dispersions comprising the nanocapsules, and methods for the treatment of bacterial biofilms |
EP3375492A1 (en) * | 2017-03-17 | 2018-09-19 | Centre National De La Recherche Scientifique | Polymer membrane and methods of manufacturing thereof |
EP3394233B1 (en) | 2015-12-22 | 2019-07-31 | Unilever N.V. | Microcapsule |
US10398632B2 (en) | 2014-11-07 | 2019-09-03 | Givaudan S.A. | Capsule composition |
WO2023111164A1 (en) | 2021-12-15 | 2023-06-22 | Givaudan Sa | Improvements in or relating to organic compounds |
WO2023186333A1 (en) | 2022-03-30 | 2023-10-05 | Symrise Ag | Paper roll as fragrance control release system |
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CN107011539B (en) * | 2017-04-07 | 2018-12-07 | 张剑星 | A kind of method of quadripolymer surface modified nano calcium carbonate |
JP2021512176A (en) * | 2018-02-06 | 2021-05-13 | スリーエム イノベイティブ プロパティズ カンパニー | Microcapsules with a porous or hollow core and a pH sensitive shell and their use |
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EP1393706A1 (en) * | 2002-08-14 | 2004-03-03 | Quest International B.V. | Fragranced compositions comprising encapsulated material |
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WO2005032512A2 (en) * | 2003-10-02 | 2005-04-14 | Trustees Of Stevens Institute Of Technology | Capsules of multilayered neutral polymer films associated by hydrogen bonding |
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- 2013-10-24 AR ARP130103880A patent/AR093134A1/en unknown
- 2013-10-25 WO PCT/EP2013/072403 patent/WO2014064255A2/en active Application Filing
- 2013-10-25 MX MX2015004129A patent/MX2015004129A/en unknown
- 2013-10-25 BR BR112015008323A patent/BR112015008323A2/en not_active Application Discontinuation
- 2013-10-25 CN CN201380055683.4A patent/CN104870084B/en not_active Expired - Fee Related
- 2013-10-25 JP JP2015538466A patent/JP6400015B2/en not_active Expired - Fee Related
- 2013-10-25 EP EP13795183.6A patent/EP2911780B1/en active Active
- 2013-10-25 CA CA2886340A patent/CA2886340A1/en not_active Abandoned
- 2013-10-25 KR KR1020157010547A patent/KR102048716B1/en active IP Right Grant
- 2013-10-25 AU AU2013336579A patent/AU2013336579B2/en not_active Ceased
- 2013-10-25 US US14/432,101 patent/US20150284665A1/en not_active Abandoned
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WO2017029302A1 (en) * | 2015-08-18 | 2017-02-23 | Basf Se | Agrochemical microcapsules with a shell of polyvinylalcohol and polyoxazoline |
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WO2018167297A1 (en) * | 2017-03-17 | 2018-09-20 | Centre National De La Recherche Scientifique | Polymer membrane and methods of manufacturing thereof |
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Also Published As
Publication number | Publication date |
---|---|
JP2016508959A (en) | 2016-03-24 |
AU2013336579B2 (en) | 2017-10-12 |
BR112015008323A2 (en) | 2017-07-04 |
US20190031981A1 (en) | 2019-01-31 |
TWI646978B (en) | 2019-01-11 |
KR102048716B1 (en) | 2019-11-27 |
TW201429494A (en) | 2014-08-01 |
CN104870084A (en) | 2015-08-26 |
JP6400015B2 (en) | 2018-10-03 |
EP2911780B1 (en) | 2021-03-10 |
AU2013336579A1 (en) | 2015-04-16 |
ZA201502685B (en) | 2016-01-27 |
US20150284665A1 (en) | 2015-10-08 |
KR20150087197A (en) | 2015-07-29 |
AR093134A1 (en) | 2015-05-20 |
EP2911780A2 (en) | 2015-09-02 |
MX2015004129A (en) | 2016-02-05 |
CA2886340A1 (en) | 2014-05-01 |
CN104870084B (en) | 2018-07-10 |
WO2014064255A3 (en) | 2014-08-28 |
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