WO2013068255A1 - Stable formaldehyde-free microcapsules - Google Patents
Stable formaldehyde-free microcapsules Download PDFInfo
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- WO2013068255A1 WO2013068255A1 PCT/EP2012/071340 EP2012071340W WO2013068255A1 WO 2013068255 A1 WO2013068255 A1 WO 2013068255A1 EP 2012071340 W EP2012071340 W EP 2012071340W WO 2013068255 A1 WO2013068255 A1 WO 2013068255A1
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- microcapsules
- oxiran
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- 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
- A61K8/062—Oil-in-water emulsions
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- 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
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
- A61K8/41—Amines
- A61K8/416—Quaternary ammonium compounds
-
- 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
- A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L9/00—Disinfection, sterilisation or deodorisation of air
- A61L9/01—Deodorant compositions
- A61L9/012—Deodorant compositions characterised by being in a special form, e.g. gels, emulsions
-
- 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
- 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
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- 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
- B01J13/14—Polymerisation; cross-linking
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B9/00—Essential oils; Perfumes
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- 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
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- 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
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/001—Softening compositions
-
- 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
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61J—CONTAINERS SPECIALLY ADAPTED FOR MEDICAL OR PHARMACEUTICAL PURPOSES; DEVICES OR METHODS SPECIALLY ADAPTED FOR BRINGING PHARMACEUTICAL PRODUCTS INTO PARTICULAR PHYSICAL OR ADMINISTERING FORMS; DEVICES FOR ADMINISTERING FOOD OR MEDICINES ORALLY; BABY COMFORTERS; DEVICES FOR RECEIVING SPITTLE
- A61J2200/00—General characteristics or adaptations
- A61J2200/30—Compliance analysis for taking medication
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- 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
- A61K2800/20—Chemical, physico-chemical or functional or structural properties of the composition as a whole
- A61K2800/30—Characterized by the absence of a particular group of ingredients
-
- 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
- A61K2800/41—Particular ingredients further characterized by their size
- A61K2800/412—Microsized, i.e. having sizes between 0.1 and 100 microns
Definitions
- the present invention relates to the field of perfumery. More particularly, it concerns water-dispersible core-shell microcapsules essentially free of formaldehyde.
- the present invention comprises also the invention's core-shell microcapsules as part of a perfuming composition or of a perfuming consumer product.
- Microcapsules are a widely known type of products, generally used as carrier of a liquid phase.
- a specific type of said microcapsules is the so-called aminoplast microcapsules comprising an external wall obtained by reacting a polyamine (in general melamine, i.e. 2,4,6-triamino-l,3,5-triazine) and an aldehyde (almost always in fact formaldehyde).
- a polyamine in general melamine, i.e. 2,4,6-triamino-l,3,5-triazine
- aldehyde almost always in fact formaldehyde
- capsules which are essentially formaldehyde based, contain always residual amounts of free formaldehyde due to unreacted precursors or a slow decomposition of the thermoset oligomers.
- Capsules which are formaldehyde-free are nowadays desired due to regulatory concerns, therefore there is a need by the industry for formaldehyde free core-shell microcapsules possessing performance similar to the formaldehyde based ones, which have the best performance in stability and product delivery.
- a first object of the present invention is a process for obtaining the above microcapsules.
- a process for the preparation of a core-shell microcapsule said process comprising the steps of:
- an aldehyde component in the form of a mixture of glyoxal, a C 4 _6 2,2-dialkoxy- ethanal and optionally a glyoxalate, said mixture having a molar ratio glyoxal/C 4 _6 2,2-dialkoxy-ethanal comprised between about 1/1 and 10/1; and
- n stands for 2 or 3 and A represents a C 2 -C 6 group optionally comprising from 2 to 6 nitrogen and/or oxygen atoms;
- step 4) cooling said dispersion; and 5) optionally adding to the dispersion of step 4) at least one cationic polymer and/or urea or ethylene urea; and
- the capsule has a size in the micron range (e.g. a mean diameter comprised between about 1 and 600 ⁇ ) and comprises an external solid oligomers-based shell or wall and an internal continuous oil phase enclosed by the external shell.
- a size in the micron range e.g. a mean diameter comprised between about 1 and 600 ⁇
- bodies like coacervates or extrudates i.e. porous solid phases containing droplets of a liquid
- the size of said microcapsules, and consequently of the droplet size in step 1) is comprised between about 5 and 200 ⁇ .
- dispersion in the present invention it is meant a system in which particles are dispersed in a continuous phase of a different composition and specifically includes a suspension or an emulsion.
- the dispersion comprises between about 10% and 50% of oil, percentage being expressed on a w/w basis relative to the total weight of the dispersion. In still another aspect of the invention, the dispersion comprises between about 20% and 45% of oil.
- oil we mean here an organic phase that is a liquid at about 20°C and which will be in the core of the core-shell capsules.
- said oil can be selected amongst a perfume, insecticide, malodor counteracting substance, fungicide, insect repellent, and the mixtures thereof.
- said oil is a perfume.
- Said perfume can be in the form of a pure perfuming ingredient or of a perfuming composition.
- perfuming composition it is meant here the normal meaning of the art, i.e. a composition comprising several perfuming ingredients and optionally at least one suitable solvent and/or at least one perfumery adjuvant.
- perfuming ingredient or “perfuming co-ingredient” it is meant here a compound which is used in a perfuming preparation or a composition to impart a hedonic effect.
- a co-ingredient to be considered as being a perfuming one, must be recognized by a person skilled in the art as being able to impart or modify in a positive or pleasant way the odor of a composition, and not just as having an odor.
- perfuming co-ingredients present in the base do not warrant a more detailed description here, which in any case would not be exhaustive, the skilled person being able to select them on the basis of his general knowledge and according to intended use or application and the desired organoleptic effect.
- these perfuming co-ingredients belong to chemical classes as varied as alcohols, lactones, aldehydes, ketones, esters, ethers, acetates, nitriles, terpenoids, nitrogenous or sulphurous heterocyclic compounds and essential oils, and said perfuming co-ingredients can be of natural or synthetic origin. Many of these co-ingredients are in any case listed in reference texts such as the book by S.
- suitable solvent we mean here a material which is practically neutral from a perfumery point of view, i.e. that does not significantly alter the organoleptic properties of perfuming ingredients and is generally not miscible with water, i.e. possesses a solubility in water below 10%, or even below 5%.
- solvent is in general a solvent commonly used in perfumery, such as for example dipropyleneglycol, diethyl phthalate, isopropyl myristate, benzyl benzoate, 2-(2-ethoxyethoxy)-l-ethanol or ethyl citrate, limonene or other terpenes, isoparaffins such as those known under the trademark Isopar ® (origin: Exxon Chemical) or glycol ethers and glycol ether esters such as those known under the trademark Dowanol ® (origin: Dow Chemical Company).
- Isopar ® oil
- glycol ethers and glycol ether esters such as those known under the trademark Dowanol ® (origin: Dow Chemical Company).
- perfumery adjuvant we mean here an ingredient capable of imparting additional added benefit such as a color, a particular light resistance, chemical stability, etc.
- additional added benefit such as a color, a particular light resistance, chemical stability, etc.
- the water medium comprises, or is essentially, water, as a diluent of the dispersion, and optionally may comprise at least a polyol and/or at least a stabilizer.
- the dispersion comprises between about 0% and 5% of at least a stabilizer, percentage being expressed on a w/w basis relative to the total weight of the dispersion.
- the dispersion comprises between about 0% and 2% of at least a stabilizer.
- the dispersion comprises between about 0% and 1% of at least a stabilizer.
- the aldehyde component comprises also a glyoxalate
- the diamino compound is lH-l,2,4-triazole-3,5- diamine
- the amount of said stabilizer in the dispersion could be 0% (no addition of stabilizer).
- stabilizer or the similar, it is meant the normal meaning understood by a person skilled in the art, i.e. a compound that is capable, or is added to, stabilize the system, e.g. to prevent aggregation or agglomeration of the microcapsules, for example in the application or during their preparation.
- the use of said stabilizer is standard knowledge of the person skilled in the art.
- said stabilizer can be a ionic or non-ionic surfactant or a colloidal stabilizer.
- the exact nature of such stabilizers is well known by a person skilled in the art.
- ionic polymers such as co-polymers of acrylamide and acrylic acid (such as Alcapsol ® 144 from Ciba), e.g. acid/acrylamide copolymers produced from monomer mixture of acrylic acid and acrylamide wherein the acrylic acid content is in the range of from 30 to 70%, acid anionic surfactant (such as sodium dodecyl sulfate), acrylic co-polymers bearing a sulfonate group (such as sodium poly(styrene sulfonate), and co-polymers of vinyl ethers and maleic anhydride.
- acid anionic surfactant such as sodium dodecyl sulfate
- acrylic co-polymers bearing a sulfonate group such as sodium poly(styrene sulfonate
- co-polymers of vinyl ethers and maleic anhydride such as co-polymers of acrylamide and acrylic acid (such as Alcapsol ® 144 from Ciba), e.g
- said stabilizer is a ionic surfactant.
- the dispersion comprises also between about 0% and 10% of at least a polyol, percentage being expressed on a w/w basis relative to the total weight of the dispersion, or even comprised between about 0% and 2% of at least a polyol.
- the diamino compound when the diamino compound is urea, said amount can be comprised between about 0.1% and 2% of at least a polyol.
- the diamino compound when the diamino compound is lH-l,2,4-triazole-3,5-diamine, said amount can be comprised between about 0% and 1.5% or 0.5% of at least a polyol.
- polyol or the similar, it is meant the normal meaning understood by a person skilled in the art, i.e. a compound comprising one or more alcohol functional groups and is generally used to help the reticulation/curing/deposition of the microcapsule's shell.
- the use of said polyol is standard knowledge of the person skilled in the art.
- Said polyol may be selected from aromatic, aliphatic and polymeric polyols.
- aromatic polyols such as 3,5-dihydroxy toluene, resorcinol, xylenol, bisphenol, polyhydroxy naphthalene, polyphenol obtained by the degradation of cellulose
- aliphatic polyols such as humic acids, 2,2,-dimethyl-l,3-propane diol, l,l,l-tris-(hydroxymethyl)-propane, pentaerythritol, sorbitol or sugar derivatives and the similar
- polymeric polyols such as celluloses or carboxymethyl cellulose derivatives such as alkaline salts of carboxymethyl cellulose (e.g. and in particular a sodium salt like Ambergum ® 1221 (from HERCULES AQUALON) or BlanoseTM 12M8P (from Ashland Inc.).
- said polyol is an aliphatic polymeric polyol such as a carboxymethyl ether cellulose derivative (such as, and in particular, Ambergum 1221 or BlanoseTM 12M8P).
- a carboxymethyl ether cellulose derivative such as, and in particular, Ambergum 1221 or BlanoseTM 12M8P.
- the dispersion comprises between about 1% and 20% of oligomeric composition, percentage being expressed on a w/w basis relative to the total weight of the dispersion.
- the dispersion comprises between about 1% and 8% of oligomeric composition.
- the amount of oligomeric composition present in the dispersion can also be defined as being comprised between 4% and 15% of oligomeric composition on a w/w basis relative to the total weight of oil added in the dispersion.
- oligomeric composition may be in particular as described herein below.
- glycoxal is understood to mean both the free di-aldehyde form (i.e. OHC-CHO) and the hydrated form (e.g. (HO) 2 HC-CHO).
- glycoxalate is understood to mean the glyoxalic acid or an alkaline salt of glyoxalic acid (such as OHC-COONa or OHC-COOK) or mixture thereof.
- alHC-COOH free aldehyde form
- hydrated form e.g. (HO) 2 HC-COOH or (HO) 2 HC-COONa
- an oligomeric composition or the similar, it is meant the normal meaning understood by a person skilled in the art, i.e. a mixture of oligomers, as reaction product, and other optional components.
- said optional embodiment can be, as non- limiting example, water and/or unreacted reagent of the process (e.g. the acid catalyst).
- oligomer it is meant a compound which is not itself a macropolymer, as is a resin, but rather a small size molecule comprising between about 4 to 100, or even preferably 30, units derived from the monomeric constituents.
- the invention's oligomers possess a molecular weight (MW) comprised between about 200 g/mol and 2500 g/mol.
- said MW is comprised between about 220 g/mol and 1200 g/mol.
- polyamine component it is used a mixture of melamine and at least one C 1-4 compound comprising two NH 2 functional groups.
- said compound is a C 1-2 compound comprising two NH 2 functional groups.
- C 1-4 compound comprising two NH 2 functional groups or the similar, it is meant a C 1-4 hydrocarbon compound comprising two NH 2 functional groups, and additionally said compound may optionally comprise from one to three nitrogen and/or oxygen atoms.
- said compound is a C 1-2 compound comprising two NH 2 functional groups and a carbonyl or a 1 ,2,4-triazole functional group.
- Non-limiting examples of said C 1-4 compound comprising two NH 2 functional groups can be urea, lH-l,2,4-triazole-3,5-diamine and mixtures thereof.
- any one of the above embodiments of the present invention it can be used mixtures with a molar ratio melamine/diamino compound comprised between about 4/1 and 1/4, or even comprised between about 3.5/1 and 1/3.5, or alternatively between about 2/1 and 1/3, or alternatively between about 1.3/1 and 1/3.
- the diamino compound is lH-l,2,4-triazole-3,5-diamine
- molar ratio melamine/lH-l,2,4-triazole-3,5-diamine comprised between about 1.5/1 and 1/1.5.
- C 4 _6 2,2-dialkoxyethanal it is meant a 2,2-dialkoxyethanal having in total from 4 to 6 carbon atoms.
- said C 4 _ 6 2,2-dialkoxyethanal can be 2,2-dimethoxy- ethanal, 2,2-diethoxy-ethanal and mixtures thereof.
- said aldehyde component has a molar ratio glyoxal/2,2-dialkoxy-ethanal comprised between about 1.1/1 and 7/1, or even comprised between about 1.4/1 and 6.5/1.
- glyoxal/2,2- dialkoxy-ethanal may advantageously be comprised between about 1.5/1 and 6.1/1.
- said glyoxal/2,2-dialkoxy-ethanal may advantageously be comprised between about 1.4/1 and 2.2/1.
- the aldehyde component may also include (as optional constituent) a glyoxalate.
- a glyoxalate when present, said glyoxalate is present in amounts such that molar ratio glyoxal/glyoxalate is comprised between about 4/1 and 1/1, or even comprised between about 3.5/1 and 2/1.
- said glyoxalate is present and within amounts such as stated in the ratio mentioned above, in particular when the diamino compound is lH-l,2,4-triazole-3,5-diamine.
- the said polyamine component and the aldehyde component are admixed in a ratio such that the molar ratio of total amine functional group/total free aldehyde functional group (also referred as (NH 2 )tot/(CHO) t ot) is comprised between about 4/1 and 1/2, or even comprised between about 1.9/1 and 1/1.9, or alternatively between about 1.7/1 and 1/1.7.
- a melamine accounts for 3 amine functional groups and the diamino compound, e.g. urea, for 2.
- glyoxal accounts for 2 free aldehyde functional groups and the C 4 _ 6 2,2-dialkoxy-ethanal or the glyoxalate accounts for 1 free aldehyde functional group.
- said protic acid is a catalyst or initiator of the oligomerisation, and therefore said protic acid may react also with the other components and becoming, at least partially, part of the oligomers formed.
- said protic acid catalyst is selected amongst mineral acids, Ci_6 mono or dicarboxylic acids and mixtures thereof.
- Non-limiting examples of such acids are phosphoric, nitric, sulfuric or hydrochloric acids, or acetic, formic, oxalic or glyoxilic acids. More specifically, said acid catalyst is selected amongst formic, acetic, glyoxylic and nitric acids and mixtures thereof.
- the oligomeric composition is obtained by reacting the various components in water and the oligomeric composition is obtained by a single step process wherein all reagents are mixed together or by a multistep process wherein the reagents are reacted together subsequently.
- the oligomer is obtained by a process where all the various components are reacted together in water, and the pH of the final reaction medium is preferably comprised between 6 and 9.5.
- the oligomer is obtained by a two-step process.
- a first step the polyamine component is reacted with the aldehyde component in an aqueous medium, at a basic pH.
- a second step there is added to the reaction medium the acid catalyst, so as to work at an acidic pH.
- the pH of said first step can be comprised between about 7 and 10, or even between about 8.5 and 10.
- the temperature of reaction of the first step can be comprised between about 20°C and 80°C, or even between about 40°C and 80°C.
- said first step can be carried out for about 0.1 hour to about 4 hours (reaction time).
- the reaction time of said first step depends on the temperature of the reaction, and its pH and can be comprised, for example, between about 1 hour to about 4 hours, for a temperature comprised between about 40°C and about 80°C and a pH between about 8 and about 10.
- said reaction time can be comprised, for example, between about 0.5 hour to about 2 hours, for a temperature comprised between about 50°C and about 80°C and a pH between about 7 and about 9.5.
- the H of said first step can be typically set up by adding to the reaction medium an adequate amount of potassium or sodium hydroxide.
- the said acid catalyst is added to the reaction mixture of the first step in an amount sufficient to acidify the latter.
- the pH of said second step can be comprised between about 4.0 and 6, or even between about 4.5 and 5.5.
- the temperature of reaction of the first step can be comprised between about 40°C and 100°C, or even between about 50°C and 90°C.
- said second step can be carried out for about 0.5 hour to about 4 hours (reaction time).
- the reaction time of said first step depends on the temperature of the reaction, and its pH and can be comprised, for example, between about 1 hour to about 2.5 hours, for a temperature comprised between about 50°C and about 80°C and a pH between about 4.5 and about 5.5.
- said reaction time can be comprised, for example, between about 0.5 hour to about 4 hours, for a temperature comprised between about 50°C and about 80°C and a pH between about 4.5 and about 5.5.
- the result of such process is an aqueous solution comprising the invention's oligomeric composition.
- the aqueous solution comprises between about 30% and 70% of oligomeric composition (solid content), percentage being expressed on a w/w basis relative to the total weight of the solution.
- Said aqueous solution can be used directly for the process of preparation of the microcapsules, as described further below, or can be dried to provide the oligomeric composition.
- the dispersion of step 2) comprises also at least a cross-linker which can be a di- or tri-isocyanates (herein after also referred to as a polyisocyanate) and/or an oxirane based compound (herein after also referred to as a polyoxiran).
- a cross-linker which can be a di- or tri-isocyanates (herein after also referred to as a polyisocyanate) and/or an oxirane based compound (herein after also referred to as a polyoxiran).
- the dispersion comprises between about 0.5% and 15% of at least a cross-linker, percentage being expressed on a w/w basis relative to the total weight of the dispersion, or even comprised between about 1% and 12% of at least a cross-linker.
- aromatic or aliphatic di- or tri-isocyanates it is meant here a hydrocarbon compound, which can be totally aliphatic or comprising also an aromatic group, and which also possesses two or three isocyanate groups.
- biuret, triuret it is meant here a self-addition product of such aromatic or aliphatic di- or tri-isocyanates and which comprise the tri-radical HN- CO-N-CO-NH (biuret functional group) or the tetra-radical HN-CO-N-CO-N-CO-NH (triuret functional group).
- Said biurets or triurets are generally products of reaction of water with a di or tri-isocyanate.
- trimmer it is meant here an isocyanurate derivative of said di- or tri-isocyanates (i.e. a compound comprising the moiety 1,3,5- triazinane-2,4,6-trione).
- trimethylol propane-adduct it is meant here an isocyanate which is a reaction product between the di- or tri-isocyanate and trimethylol propane.
- di- or thi-isocyanates hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, toluene diisocyanate, a trimethylol propane-adduct of toluene diisocyanate (commercially available from Bayer under the tradename Desmodur ® L75), a trimethylol propane-adduct of xylylene diisocyanate (commercially available from Mitsui Chemicals under the tradename Takenate ® D-110N), a trimer of hexamethylene diisocyanate, a trimer of isophorone diisocyanate, a trimethylol propane- adduct of hexamethylene diisocyanate (available from Mitsui Chemicals) or a biuret of hexamethylene diisocyanate (commercially available from Bayer under the tradename Desmod
- oxiran-2-ylmethyl derivatives l,3,5-tris(oxiran-2-ylmethyl)-l,3,5- triazinane-2,4,6-trione, 4-(oxiran-2-ylmethoxy)-N,N-bis(oxiran-2-ylmethyl)aniline, 1,3- bis(oxiran-2-ylmethoxy)benzene (also known as resorcinol diglycidylether), 1,2- bis(oxiran-2-ylmethoxy)ethane (also known as ethyleneglycol diglycidylether) and 2,2'- (2-ethyl-2-((oxiran-2-ylmethoxy)methyl)propane-l,3-diyl)bis(oxy)bis(methylene) dioxirane (also known as trimethylolpropane triglycidylether).
- the cross linker is a di- or tri-isocyanate.
- the dispersion may comprise also a Ci-4 compound comprising two N3 ⁇ 4 functional groups (diamino compound) as defined above. It is believed that said compound helps the hardening of the microcapsule shell. The addition of said compound can be attractive in particular when there is used an oligomer wherein the NH2tot CHO tot ratio is close to the minimum of the range specified above.
- the dispersion of step 2) does comprise said C 1-4 compound comprising two N3 ⁇ 4 functional groups.
- Said C 1-4 compound comprising two N3 ⁇ 4 functional groups (diamino compound) can be urea, lH-l,2,4-triazole-3,5-diamine and mixtures thereof.
- step 2) there is added an amount of diamino compound comprised between about 5% and 100%, or even between about 10% and 80%, or alternatively between about 15% and 75%, percentage being expressed on a w/w basis relative to the total weight of the resin. It is clearly understood by a person skilled in the art that only part of said added diamino compound will be incorporated into the microcapsule shell.
- Typical manners to form the dispersions of step 2) are known by a person skilled in the art, and are also described herein below or in the Examples below.
- the dispersion can be obtained by stirring the components up to 24000 rpm to disperse oil in water (with mechanical stirrer, ultra Turrax or microwave).
- the pH of said dispersion can be set between 4 and 9.5, prior to step 3), for example by adding an appropriate amount of a base such as sodium hydroxide.
- step 3) the dispersion is heated at a temperature comprised between 35°C and 100°C.
- the temperature of said emulsion of dispersion is comprised between 50°C and 90°C.
- Said thermal treatment may be carried on for between about 0.5 hour and 6 hours. More specifically, the time of heating depends on the temperature and the pH of said emulsion or dispersion, and for example can be comprised between about 1 hour to about 5 hours, for a temperature comprised between about 60°C and about 80°C and a pH between about 4.5 and about 9.5.
- Step 4) of the invention's process is meant to stop the process of hardening of the shell of the thus obtained core-shell microcapsule, and can be performed by any known method.
- the dispersion can be cooled at temperatures comprised between about 10° and 30 °C, in general to room temperature.
- Said step 4) may optionally include a neutralization of the thus obtained dispersion at a pH comprised between pH between 6.5 and 7.5, for example by adding an appropriate amount of a base such as sodium hydroxide.
- a base such as sodium hydroxide.
- step 5 one may also add to the invention's dispersion some cationic polymers.
- Preferred cationic polymers will have cationic charge densities of at least 0.5 meq/g, more preferably at least about 1.5 meq/g, but also preferably less than about 7 meq/g, more preferably less than about 6.2 meq/g.
- the cationic charge density of the cationic polymers may be determined by the Kjeldahl method as described in the US Pharmacopoeia under chemical tests for Nitrogen determination.
- the preferred cationic polymers are chosen from those that contain units comprising primary, secondary, tertiary and/or quaternary amine groups that can either form part of the main polymer chain or can be borne by a side substituent directly connected thereto.
- the weight average (Mw) molecular weight of the cationic polymer is preferably between 10,000 and 2M Dalton, more preferably between 50,000 and 1.5M Dalton.
- Salcare ® SC60 cationic copolymer of acrylamidopropyltrimonium chloride and acrylamide, origin: BASF
- Luviquat® such as the PQ UN, FC 550 or Supreme
- PQ UN polyquaternium- 11 to 68 or quaternized copolymers of vinylpyrrolidone origin: BASF
- Jaguar® C13S or C17, origin Rhodia
- step 5 there is added an amount of cationic polymers comprised between about 0% and 60%, or even between about 5% and 40%, percentage being expressed on a w/w basis relative to the total weight of the resin. It is clearly understood by a person skilled in the art that only part of said added cationic polymers will be incorporated into/deposited on the microcapsule shell.
- step 5 one may also add to the invention's dispersion an amount of urea or ethylene urea which can be useful to scavenge possible free glyoxal in the slurry.
- step 5 there is added an amount of urea or ethylene urea comprised between about 0% and 10%, or even between about 1% and 5%, percentage being expressed on a w/w basis relative to the total weight of the dispersion. It is clearly understood by a person skilled in the art that only part of said added cationic polymers will be incorporated into/deposited on the microcapsule shell.
- the result of such process is an aqueous dispersion (or slurry) comprising the invention's core-shell microcapsules.
- the aqueous slurry comprises between 10% and 60% of capsules, percentage being expressed on a w/w basis relative to the total weight of the slurry.
- the aqueous slurry comprises between 20% and 55% of capsules.
- Said aqueous slurry can be used directly as perfuming ingredient, in particular for applications which are aqueous based, e.g. a softener or a liquid soap. Therefore another object of the present invention is an aqueous slurry comprising the invention's microcapsules, for example a slurry as obtained directly for the process of preparation of the microcapsules. Said slurry may further comprise some formulation aids, such as stabilizer or viscosity control agents, or even biocides or bactericides.
- the slurry obtained by the process described above can be submitted to a drying, like spay drying, to provide the microcapsules as such, i.e. in a powdery form. It is understood that any standard method known by a person skilled in the art to perform such drying is also applicable.
- composition of matter as obtained, or obtainable, by the above-described process. It is understood by a person skilled in the art that said composition of matter comprises the core-shell microcapsules in the dry form or as a water-suspension.
- the amount of the core of oil accounts typically between 40% and 98% of the total weight of the microcapsules (i.e. the weight of the dispersion minus the weight of water).
- said core of oil accounts between 70% and 95%, or even between 80% and 90%, of the total weight of the microcapsules.
- the amount of the shell accounts typically between 2% and 60% of the total weight of the capsules.
- said oligomers-based shell accounts between 5% and 30%, or even between 10% and 20%, of the total weight of the microcapsules.
- said core-shell microcapsules are those obtained by using in the invention's process an oil-in-water dispersion wherein the oil is a perfume oil and comprising
- step 2 of the invention's process i.e. a process providing microcapsules capsules comprising glyoxalate and not comprising a stabilizer.
- the invention concerns the use of an invention's microcapsule as perfuming ingredient.
- it concerns a method to confer, enhance, improve or modify the odor properties of a perfuming composition or of a perfumed article, which method comprises adding to said composition or article an effective amount of at least an invention's microcapsule.
- use of an invention's microcapsule it has to be understood here also the use of any composition containing an invention's microcapsule and which can be advantageously employed in perfumery industry.
- compositions which in fact can be advantageously employed as perfuming ingredients, are also an object of the present invention.
- Another object of the present invention is a perfuming composition
- a perfuming composition comprising:
- perfumery carrier we mean here a liquid material which is practically neutral from a perfumery point of view, i.e. which does not significantly alter the organoleptic properties of perfuming ingredients.
- perfumery carrier one may cite, as non-limiting examples, an emulsifying system, i.e. a solvent and a surfactant system, or a solvent commonly used in perfumery.
- a solvent and a surfactant system i.e. a solvent and a surfactant system
- a detailed description of the nature and type of solvents commonly used in perfumery cannot be exhaustive.
- solvents such as dipropyleneglycol, diethyl phthalate, isopropyl myristate, benzyl benzoate, 2-(2- ethoxyethoxy)-l-ethanol or ethyl citrate, which are the most commonly used.
- compositions which comprise both a perfumery carrier and a perfumery base can be also ethanol, water/ethanol mixtures, limonene or other terpenes, isoparaffins such as those known under the trademark Isopar (origin: Exxon Chemical) or glycol ethers and glycol ether esters such as those known under the trademark Dowanol ® (origin: Dow Chemical Company).
- Isopar oil/ethanol mixtures
- glycol ethers and glycol ether esters such as those known under the trademark Dowanol ® (origin: Dow Chemical Company).
- perfumery base we mean here a composition comprising at least one perfuming co-ingredient, as defined above.
- perfumery adjuvant is as defined above.
- An invention's composition consisting of at least one invention's microcapsule and at least one perfumery carrier represents a particular embodiment of the invention as well as a perfuming composition comprising at least one invention's microcapsule, at least one perfumery carrier, at least one perfumery base, and optionally at least one perfumery adjuvant.
- the invention's core-shell microapsules can also be advantageously used in all the fields of modern perfumery, i.e. fine or functional perfumery, to positively impart or modify the odor of a consumer product into which said invention's microcapsules are added. Consequently, a perfuming consumer product which comprises: i) as perfuming ingredient, at least one invention's microcapsule, as defined above; and ii) a perfumery consumer base;
- the invention's compound can be added as such or as part of an invention's perfuming composition.
- perfuming consumer product it is meant a consumer product which is expected to deliver at least a perfuming effect, in other words it is a perfumed consumer product.
- perfumery consumer base we mean here the functional formulation, as well as optionally additional benefit agents, corresponding to a consumer product which is compatible with perfuming ingredients and is expected to deliver a pleasant odor to the surface to which it is applied (e.g. skin, hair, textile, or home surface).
- a perfuming consumer product according to the invention comprises the functional formulation, as well as optionally additional benefit agents, corresponding to the desired consumer product, e.g. a detergent or an air freshener, and an olfactive effective amount of at least one invention' s microcapsule.
- Non-limiting examples of suitable perfumery consumer base can be a perfume, such as a fine perfume, a cologne or an after-shave lotion; a fabric care product, such as a liquid or solid detergent, a fabric softener, a fabric refresher, an ironing water, a paper, or a bleach; a body-care product, such as a hair care product (e.g. a shampoo, a coloring preparation or a hair spray), a cosmetic preparation (e.g. a vanishing cream or a deodorant or antiperspirant), or a skin-care product (e.g.
- a hair care product e.g. a shampoo, a coloring preparation or a hair spray
- a cosmetic preparation e.g. a vanishing cream or a deodorant or antiperspirant
- a skin-care product e.g.
- a perfumed soap, shower or bath mousse, oil or gel, or a hygiene product a perfumed soap, shower or bath mousse, oil or gel, or a hygiene product
- an air care product such as an air freshener or a "ready to use” powdered air freshener
- a home care product such as a wipe, a dish detergent or hard- surface detergent.
- the fine or functional perfumery base is in the form of a fabric, home, or hair care product, such as a fabric softener, a detergent or a shampoo.
- microcapsules according to the invention can be incorporated into the various aforementioned articles or compositions vary within a wide range of values. These values are dependent on the nature of the article to be perfumed and on the desired organoleptic effect as well as the nature of the co-ingredients in a given base when the microcapsules according to the invention are mixed with perfuming co-ingredients, solvents or additives commonly used in the art.
- concentrations are in the order of 0.1 % to 50 % by weight, or even more, of the microcapsules of the invention based on the weight of the composition into which they are incorporated. Concentrations lower than these, such as in the order of 0.01% to 5% by weight, can be used when these microcapsules are incorporated into perfumed articles, percentage being relative to the weight of the article. Examples
- TGA Solid content of resins was measured with a thermogravimetric analyser (Mettler- Toledo TGA/SDTA851 6 ) equipped with a microbalance (accuracy: 1 ⁇ g) and an accurate oven having an internal volume of 35 ml, under a constant nitrogen flow of 20ml/min. Resin (10 mg) was introduced in aluminium pan of 40 ⁇ . The measurement started from 25°C to 100°C at 5°C/min, staid at 100°C for 1 h, and finally to 200°C at 10°C/min. The solid content was determined by doing the ratio between weight of sample (plateau) and the initial weight in the crucible.
- Capsule performance was assessed at 50°C ( Figures la-6a), and 280°C ( Figures 6b-10b) or 300°C ( Figures 9a- 10b) with a similar thermogravimetric analyser. Perfume evaporation was measured as a function of time. Microcapsules dispersion (10 mg) was introduced in alumina pan of 70 ⁇ . The measurement at 50°C started from 25°C to 50°C at 5°C/min, and then staid at 50°C for 4 h. The measurement at 280°C started from 25°C to 280°C at 5°C/min, and then staid at 280°C for 1 h and 5 min. The measurement at 300°C started from 25°C to 300°C at 5°C/min, and then staid at 300°C for 1 h. A slower evaporation of the perfume oil with a long-lasting profile was related to a more stable capsule.
- TOF-MS The analysis of the resin compositions was carried out by liquid chromatography, with a TOF-MS detector (TOF High Resolution > 10000, Agilent 1200 HPLC system Agilent G1969A MS TOF system composed of a Multimode source APCI + ESI) composed of a binary solvent manager (or pump G1312b), and an Auto sampler (gl329a).
- This TOF detector can analyze product having molecular weight up to 3000 g/mol.
- Analyses were carried out in formic acid aqueous solution at 0.1 wt at RT without columns.
- Method Standard Water premix: Acid formic 0.1% (Biosolve n° 23244125 ULC/MSD lot 550361).
- HPLC 0.5 ml/min
- injection volume 1 ⁇ with welplate sampler (without column), temperature of thermostat: 60°C (+/- 0.1 °C).
- One blank run was performed between each sample.
- MSP Multi mode Electro spray (ESI) + APCI Pos LCMSD TOF High Resolution 3 ppm acq.
- Source Mode Positive, Charging Voltage 2000 V, V cap 2500 V, Corona 4 ⁇ , drying gas N 2 , 5 1/min at 325 °C, nebuliser 30 psig at 200°C.
- Fragmentor 140 to 320 V.
- Microcapsule 1 microcapsules prepared in the presence of Desmodur ® N100 as polyisocyanate and Ambergum ® 1221 as polyol
- Microcapsule 2 microcapsules prepared in the presence of Desmodur N100 as polyisocyanate and BlanoseTM 12M8P as polyol
- Oligomeric composition n°l (26.9 wt in water) 28.5 6.8 Polyol (BlanoseTM 12M8P, 2 wt in water) 45 0.8
- Desmodur ® N100 (a polyisocyanate) 5.6 5.0
- Microcapsule 3 microcapsules prepared in the presence of hexamethylene diisocyanate
- Microcapsule 4 microcapsules prepared in the presence of Takenate D- 110N
- Microcapsule 5 microcapsules prepared in the presence of isophorone diisocyanate
- Oligomeric composition n°l (26.9 wt in water) 28.5 6.6
- Microcapsule 6 microcapsules prepared in the presence of Desmodur N100
- Microcapsule 7 microcapsules prepared in the presence of isophorone diisocyanate
- Microcapsule 8 microcapsules prepared in the presence of hexamethylene diisocyanate
- Microcapsule 9 microcapsules prepared in the presence of Takenate D- 110N
- Microcapsule 10 microcapsules prepared in the presence of Takenate polyisocyanate and Ambergum ® 1221 as polyol
- Oligomeric composition n°2 (19.6 wt in water) 33.97 4.4
- Microcapsule 11 microcapsules prepared in the presence of of Takenate D-110N as polyisocyanate, Ambergum ® 1221 as polyol, and Guanidine carbonate as a diamino compound
- Microcapsule 12 microcapsules prepared in the presence of Takenate ® D-110N as polyisocyanate and Ambergum ® 1221 as polyol
- Microcapsule 13 microcapsules prepared in the presence of Takenate ® D-110N as polyisocyanate and Ambergum ® 1221 as polyol
- Microcapsule 15 microcapsules prepared in the presence of ethyleneglycol diglycidylether (a polyoxiran)
- Microcapsule 17 microcapsules prepared in the presence of resorcinol diglycidylether
- Microcapsule 18 microcapsules prepared in the presence of resorcinol diglycidylether at
- Oligomeric composition n°l (26.9 wt in water) 28.5 6.6
- Polyol (Ambergum ® 1221, 2 wt% in water) 45 0.8
- Resorcinol diglycidylether (a polyoxiran) 9.0 7.8
- Microcapsule 19 microcapsules prepared in the presence of trimethylolpropane triglycidylether
- Microcapsule 20 microcapsules prepared in the presence of trimethylolpropane triglycidylether at 80°C for 4 h
- Trimethylolpropane triglycidylether (a polyoxiran) 1.97 2.7
- Comparative Microcapsule 1 preparation with oligomeric composition n°l
- Comparative Microcapsule 2 preparation with oligomeric composition n°l and BlanoseTM 12M8P (a "polyol", 2% w/w in water, 45.00 g), used instead of Ambergum ® 1221
- Oligomeric composition n°l (26.9 wt in water) 28.5 7.2
- Oligomeric composition according to prior art WO 2009/100553
- Aqueous solutions of cationic copolymers were added to anionic capsules at the end of the synthesis. Copolymers are listed below.
- microcapsule 12 In the presence of microcapsule 12:
- Oil leakage (%) 100 x — --i-— — (1)
- Microcapsules were diluted in a fabric softener (composition: Stepantex ® VK90 (Stepan) 16.5%, calcium chloride 0.2%, water 83.3%) to obtain a concentration of perfume at 0.8% w/w. Dispersions were stored at room temperature for 24 hours. An aliquot of softener (1 ml) was diluted in water (4 ml) and then extracted with isooctane (5 mL) containing 1,4-dibromobenzene as internal standard (150 mg/L). Organic solutions were then analyzed by GC to measure the leakage of perfume. The results on oil-leakage of the microcapsules (%) are obtained from equation 1. The corresponding values are reported in the following table:
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Abstract
Description
Claims
Priority Applications (10)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP12777929.6A EP2827978B1 (en) | 2011-11-10 | 2012-10-29 | Stable formaldehyde-free microcapsules |
CN201280055103.7A CN103945929B (en) | 2011-11-10 | 2012-10-29 | Stable formaldehydeless microcapsules |
ES12777929.6T ES2683315T3 (en) | 2011-11-10 | 2012-10-29 | Formaldehyde-free stable microcapsules |
JP2014540392A JP6080859B2 (en) | 2011-11-10 | 2012-10-29 | Microcapsules without stable formaldehyde |
MX2014005477A MX355652B (en) | 2011-11-10 | 2012-10-29 | Stable formaldehyde-free microcapsules. |
US14/357,433 US9358189B2 (en) | 2011-11-10 | 2012-10-29 | Stable formaldehyde-free microcapsules |
BR112014011165-0A BR112014011165B1 (en) | 2011-11-10 | 2012-10-29 | FORMALDEHYD FREE STABLE MICROCapsules |
IN2849CHN2014 IN2014CN02849A (en) | 2011-11-10 | 2012-10-29 | |
ZA2014/03349A ZA201403349B (en) | 2011-11-10 | 2014-05-09 | Stable formaldehyde-free microcapsules |
US15/148,068 US10058491B2 (en) | 2011-11-10 | 2016-05-06 | Stable formaldehyde-free microcapsules |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
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EP11188600.8 | 2011-11-10 | ||
EP11188600 | 2011-11-10 | ||
EP12156387.8 | 2012-02-21 | ||
EP12156387 | 2012-02-21 |
Related Child Applications (2)
Application Number | Title | Priority Date | Filing Date |
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US14/357,433 A-371-Of-International US9358189B2 (en) | 2011-11-10 | 2012-10-29 | Stable formaldehyde-free microcapsules |
US15/148,068 Division US10058491B2 (en) | 2011-11-10 | 2016-05-06 | Stable formaldehyde-free microcapsules |
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WO2013068255A1 true WO2013068255A1 (en) | 2013-05-16 |
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Application Number | Title | Priority Date | Filing Date |
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PCT/EP2012/071340 WO2013068255A1 (en) | 2011-11-10 | 2012-10-29 | Stable formaldehyde-free microcapsules |
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US (2) | US9358189B2 (en) |
EP (1) | EP2827978B1 (en) |
JP (1) | JP6080859B2 (en) |
CN (1) | CN103945929B (en) |
BR (1) | BR112014011165B1 (en) |
ES (1) | ES2683315T3 (en) |
IN (1) | IN2014CN02849A (en) |
MX (1) | MX355652B (en) |
WO (1) | WO2013068255A1 (en) |
ZA (1) | ZA201403349B (en) |
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Also Published As
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ES2683315T3 (en) | 2018-09-26 |
MX355652B (en) | 2018-04-26 |
ZA201403349B (en) | 2017-05-31 |
JP2014534066A (en) | 2014-12-18 |
CN103945929A (en) | 2014-07-23 |
US9358189B2 (en) | 2016-06-07 |
BR112014011165A2 (en) | 2017-05-09 |
EP2827978B1 (en) | 2018-05-16 |
IN2014CN02849A (en) | 2015-07-03 |
CN103945929B (en) | 2016-03-16 |
EP2827978A1 (en) | 2015-01-28 |
US10058491B2 (en) | 2018-08-28 |
BR112014011165B1 (en) | 2019-09-17 |
MX2014005477A (en) | 2014-08-21 |
JP6080859B2 (en) | 2017-02-15 |
US20160243008A1 (en) | 2016-08-25 |
US20140322283A1 (en) | 2014-10-30 |
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