EP3774015A1 - Microparticules sphériques - Google Patents

Microparticules sphériques

Info

Publication number
EP3774015A1
EP3774015A1 EP19715911.4A EP19715911A EP3774015A1 EP 3774015 A1 EP3774015 A1 EP 3774015A1 EP 19715911 A EP19715911 A EP 19715911A EP 3774015 A1 EP3774015 A1 EP 3774015A1
Authority
EP
European Patent Office
Prior art keywords
acid
microparticles
aliphatic
composition
spherical microparticles
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP19715911.4A
Other languages
German (de)
English (en)
Inventor
Bernd Dieter OSCHMANN
Wolfgang Krause
Patrick LEIBACH
Kerstin MUELHEIMS
Ralf Pelzer
Ewelina BURAKOWSKA-MEISE
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP3774015A1 publication Critical patent/EP3774015A1/fr
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0066—Use of inorganic compounding ingredients
    • 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
    • A61K8/025—Explicitly spheroidal or spherical shape
    • 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
    • A61K8/84—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
    • A61K8/85—Polyesters
    • 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
    • A61K9/14—Particulate form, e.g. powders, Processes for size reducing of pure drugs or the resulting products, Pure drug nanoparticles
    • A61K9/16—Agglomerates; Granulates; Microbeadlets ; Microspheres; Pellets; Solid products obtained by spray drying, spray freeze drying, spray congealing,(multiple) emulsion solvent evaporation or extraction
    • A61K9/1605—Excipients; Inactive ingredients
    • A61K9/1629—Organic macromolecular compounds
    • A61K9/1641—Organic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polyethylene glycol, poloxamers
    • A61K9/1647—Polyesters, e.g. poly(lactide-co-glycolide)
    • 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
    • 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
    • B01J13/04—Making microcapsules or microballoons by physical processes, e.g. drying, spraying
    • 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
    • B01J13/203—Exchange of core-forming material by diffusion through the capsule wall
    • 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
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3715—Polyesters or polycarbonates
    • 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
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3719—Polyamides or polyimides
    • 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
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/10—General cosmetic use
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2467/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones

Definitions

  • microparticles based on biopolymers are known in the medical field for the controlled release of active substances.
  • Acta Biomaterialia 10 (2914) 5090-5098 porous microspheres are described with a framework of a copolymer (PLGA) of lactic acid and hydroxyacetic acid (glycolic acid) having an average particle diameter of 84 pm.
  • PLGA copolymer of lactic acid and hydroxyacetic acid
  • EP 467 528 teaches polymeric carrier particles with particle sizes up to 250 ⁇ m and pores on their surface, the maximum pore size being 0.4 ⁇ m.
  • the material of the carrier particles is produced by polymerization of styrene and a polyester of maleic anhydride / phthalic anhydride / propylene glycol.
  • the polyester serves as crosslinker in this radical polymerization.
  • the radical polymerization is carried out as a bulk polymerization by the polyester is polymerized directly in styrene.
  • the microporous polymers of the prior art are usually loaded with drugs or proteins and they are controlled in the form of drugs deliver. Longer bearings are no requirement. Furthermore, such substances are hydrophilic.
  • microparticles should show good long-term stability, ie have good storage stability.
  • the microparticles themselves must be stable to the aroma chemical, which is generally hydrophobic.
  • the spherical microparticles obtainable by this process their use as carriers for aroma chemicals, a process for their filling with at least one aroma chemical and the filled spherical microparticles obtained therefrom were found.
  • compositions of spherical microparticles of a wall material and at least one cavity containing a gas and / or a liquid were found, which have pores on their surface, wherein the spherical microparticles have an average particle diameter of 10 - 600 pm, wherein the spherical microparticles have an average particle diameter of 10 to 600 .mu.m and wherein at least 80% of those microparticles whose particle diameter does not deviate more than 20% from the average particle diameter of the microparticles of the composition have on average at least 10 pores whose diameter in Range of 1/5000 to 1/5 of the average particle diameter and further, the diameter of these pores is at least 20 nm, wherein the wall material consists of a composition containing at least one aliphatic-aromatic polyester and at least one additional polymer, wherein the additional e polymer is selected from the group consisting of polyhydroxy fatty acids, poly (p-dioxanones), polyanhydrides, polyester amides, polys
  • An object of the present invention therefore relates to a composition of spherical microparticles of a wall material and at least one cavity containing a gas and / or a liquid which have pores on its surface, the spherical microparticles having an average particle diameter of 10 - 600 pm and wherein at least 80% of those microparticles whose particle diameters differ by not more than 20% from the average particle diameter of the microparticles of the composition have on average at least 10 pores whose diameter is in the range from 1/5000 to 1/5 of the mean Particle diameter and furthermore the diameter of these pores is at least 20 nm in each case,
  • the wall material consists of a composition comprising at least one aliphatic-aromatic polyester and at least one additional polymer, wherein the additional polymer is selected from the group consisting of polyhydroxy fatty acids, poly (p-dioxanones), polyanhydrides, polyester amides, polysaccharides and proteins.
  • the microparticles can be designed to be biodegradable.
  • composition of spherical microparticles of a wall material and at least one cavity containing a gas and / or a liquid having pores on its surface wherein the spherical microparticles have an average particle diameter of 10 - 600 pm and wherein at least 80% of those microparticles whose particle diameters differ by not more than 20% from the mean particle diameter of the microparticles of the composition have on average at least 10 pores each, whose diameter ranges from 1/5000 to 1/5 of the average particle diameter each having a diameter of at least 20 nm
  • the wall material consisting of a composition comprising at least one aliphatic-aromatic polyester and at least one additional polymer, wherein the additional polymer is selected from the group consisting of polyhydroxy fatty acids, Poly (p-dioxanones), polyanhydrides, polyes steramides, polysaccharides and proteins.
  • PBAzeT polybutylene-azelaate-co-butylene terephthalate
  • PBBrasT polybutylene-brassylate-co-butylene terephthalate
  • PBAT polybutylene adipate terephthalate
  • PBSeT Polybutylene sebacate terephthalate
  • PBST polybutylene succinate terephthalate
  • composition of spherical microparticles according to one of embodiments 1 to 3 characterized in that the composition forming the wall material contains at least one polymer with a glass transition temperature or a melting point in the range of 45 to 140 ° C.
  • Composition of spherical microparticles according to one of embodiments 1 to 4 characterized in that the wall material has a solubility at 25 ° C of at least 50 g / l in dichloromethane.
  • Composition of spherical microparticles according to one of embodiments 1 to 5 characterized in that the wall material consists of a composition
  • composition of spherical microparticles characterized in that the at least one polyhydroxy fatty acid is selected from the group consisting of poly-3-hydroxypropionates (P3HP); Poly-2-hydroxybutyrates (P2HB); Copolymers of at least 2 hydroxybutyric acids selected from the group consisting of 2-hydroxybutyric acid, 3-hydroxybutyric acid and 4-hydroxybutyric acid; Copolymers of 3-hydroxybutyric acid and 4-hydroxybutyric acid; Poly-3-hydroxyvalerate (P3HV); Poly-4-hydroxyvalerate (P4HV); Poly-5-hydroxyvalerates (P5HV); Poly-3-hydroxymethyl valerates (P3MHV); Copolymers of at least 2 hydroxyvaleric acids selected from the group consisting of 3-hydroxyvaleric acid, 4-hydroxyvaleric acid, 5-hydroxyvaleric acid and 3-hydroxymethylvaleric acid; Poly-3-hydroxyhexanoates (P3HHx); Poly-4-hydroxyhexano
  • composition of spherical microparticles according to one of embodiments 1 to 8 characterized in that the polyhydroxy fatty acid is at least one polycaprolactone.
  • Composition of spherical microparticles according to one of embodiments 1 to 9 characterized in that the wall material consists of a composition containing at least one further polymer which is different from the aliphatic-aromatic polyester and from the additional polymer.
  • Composition of spherical microparticles according to embodiment 10 characterized in that the further polymer is selected from the group consisting of polyacrylate, polyamide, polycarbonate, polystyrene, aliphatic-aliphatic polyester, aromatic-aromatic polyester, polyolefin, polyurea and polyurethane.
  • an emulsion is prepared from water or an aqueous solution of a pore-forming agent as a discontinuous phase and a continuous phase comprising a solution of at least one aliphatic aromatic polyester and at least one additional polymer selected from the group consisting of polyhydroxy fatty acids, poly (p-dioxanones), polyanhydrides, polyester amides, polysaccharides and proteins in a non-water-miscible solvent,
  • roxyoctadecanoic acid [P (4HB-co-3HOD)], copolyesters of 3-hydroxybutyric acid with 3-hydroxyoctadecanoic acid [P (3HB-co-3HOD)]; Copolyesters of hydroxyvaleric acid, in particular in particular from 3-hydroxyvaleric acid or 4-hydroxyvaleric acid having at least one monomer selected from the group consisting of 3-hydroxypropionic acid, hydroxyhexanoic acids, hydroxyoctanoic acids and hydroxyoctadecanoic acids; Copolyesters of 3-hydroxyhexanoic acid with at least one monomer selected from the group consisting of 3-hydroxypropionic acid, hydroxyoctanoic acid, preferably 3-hydroxyoctanoic acid and hydroxyoctadecanoic acids; and polycaprolactones. learn to prepare a composition of spherical microparticles according to a
  • Embodiment 14 to 16 characterized in that the polyhydroxy fatty acid is at least one polycaprolactone.
  • composition of spherical microparticles according to any one of embodiments 1 to 13 as a carrier for filling with at least one Aromachemikalie.
  • a process for the preparation of an aroma chemical preparation which comprises impregnating the optionally dried composition of spherical microparticles according to one of embodiments 1 to 13 with at least one aroma chemical.
  • Method according to embodiment 26 characterized in that the microparticles are sprayed or dripped with an aroma chemical or a solution of at least one aroma chemical.
  • a process for the preparation of an aroma chemical preparation which comprises suspending the optionally dried composition of spherical microparticles according to one of embodiments 1 to 13 in a liquid aroma chemical or in a solution of at least one aroma chemical and subsequently at a temperature in the range of 35 to 200 ° C, preferably in the range of 40 to 140 ° C, in particular in the range of 45 to 80 ° C over a period of 1 minute to 10 hours.
  • Aromachemical preparation obtainable by a process according to embodiments 25 to 28.
  • a composition comprising a composition of spherical microparticles according to embodiments 1 to 13 or an aroma chemical preparation according to embodiment 29 in a proportion by weight of 0.01 to 99.9% by weight, based on the total weight of the composition.
  • a process for the preparation of spherical microparticles characterized in that a) an emulsion is prepared from water or preferably an aqueous solution of a pore-forming agent as a discontinuous phase and a continuous phase comprising a solution of at least one aliphatic-aromatic polyester and at least one additional polymer selected from the group consisting of polyhydroxy fatty acids, poly (p-dioxanones), polyanhydrides, polyester amides, polysaccharides and proteins in a non-water-miscible solvent, b) the w / o emulsion obtained from a) in water Presence of at least one dispersant emulsified to a w / o / w emulsion with droplets of mean size of 10 - 600 pm and the non-water-miscible solvent removed at a temperature in the range of 20 to 80 ° C,
  • a method according to embodiment 33 characterized in that the aliphatic-aromatic polyester esterified ester of an aliphatic dihydroxy compound with a composition of aromatic dicarboxylic acid and aliphatic dicarboxylic acid.
  • the aliphatic-aromatic polyester is selected from polybutylene azalate-co-butylene terephthalate (PBAzeT), polybutylene-brassylate-co-butylene terephthalate (PBBrasT), polybutylene adipate terephthalate (PBAT), Polybutylene sebacate terephthalate (PBSeT) and polybutylene succinate terephthalate (PBST).
  • PBAzeT polybutylene azalate-co-butylene terephthalate
  • PBBrasT polybutylene-brassylate-co-butylene terephthalate
  • PBAT polybutylene adipate terephthalate
  • PBSeT Polybutylene sebacate terephthalate
  • PBST polybutylene succinate terephthalate
  • the continuous phase prepared under a) contains as additional polymer at least one polyhydroxyfatty acid selected from the group consisting of poly-3-hydroxyp ropionaten (P3HP); Poly-2-hydroxybutyrates (P2HB); Copolymers of at least 2 hydroxybutyric acids selected from the group consisting of 2-hydroxybutyric acid, 3-hydroxybutyric acid and 4-hydroxybutyric acid; Copolymers of 3-hydroxybutyric acid and 4-hydroxybutyric acid; Poly-3-hydroxyvalerate (P3HV); Poly-4-hydroxyvalerate (P4HV); Poly-5-hydroxyvalerates (P5HV); Poly-3-hydroxymethyl valerates (P3MHV); Copolymers of at least 2 hydroxyvaleric acids selected from the group consisting of 3-hydroxyvaleric acid, 4-hydroxyvaleric acid, 5-hydroxyvaleric acid and
  • roxyoctadecanoic acid [P (4HB-co-3HOD)], copolyesters of 3-hydroxybutyric acid with 3-hydroxyoctadecanoic acid [P (3HB-co-3HOD)]; Copolyesters of hydroxyvaleric acid, in particular of 3-hydroxyvaleric acid or 4-hydroxyvaleric acid with at least one monomer selected from the group consisting of 3-hydroxypropionic acid, hydroxyhexanoic acids, hydroxyoctanoic acids and hydroxyoctadecanoic acids; Copolyesters of 3-hydroxyhexanoic acid with at least one monomer selected from the group consisting of 3-hydroxypropionic acid, hydroxyoctanoic acid, preferably 3-hydroxyacanoic acid and hydroxyoctadecanoic acids; and polycaprolactones.
  • the method according to any one of embodiments 33 to 39 characterized in that the continuous phase prepared under a) contains at least one polycaprolactone as additional polymer.
  • Method according to one of the embodiments 33 to 40 characterized in that the continuous phase produced under a) consists essentially of the solution of an aliphatic-aromatic polyester and at least one additional polymer selected from the group consisting of polyhydroxy fatty acids, poly (p-dioxanones ), Polyanhydrides, polyester amides, polysaccharides and proteins in a non-water-miscible solvent.
  • Method according to one of the embodiments 33 to 41 characterized in that the ratio of aliphatic-aromatic polyester to additional polymer is 3/7 to 7/3.
  • Method according to one of the embodiments 33 to 42 characterized in that the continuous phase produced under a) contains at least one further polymer, wherein the further polymer is different from the aliphatic-aromatic polyester and from the additional polymer.
  • a method according to the embodiments 43 characterized in that the further polymer is selected from the group consisting of polyacrylate, polyamide, polycarbonate, polystyrene, aliphatic-aliphatic polyester, aromatic-aromatic polyester, polyolefin, polyurea and polyurethane.
  • the further polymer is an aliphatic-aliphatic polyester selected from the group consisting of polybutylene succinate adipate, polybutylene succinate, polybutylene sebacate and polybutylene sebacate sebacate.
  • Method according to embodiment 43 characterized in that the further polymer is selected from the group consisting of polyhydroxyacetic acid, PLA copolymers (polylactide and polylactic acid copolymers), PLGA copolymers and polylactic acid.
  • Method according to one of the embodiments 43 to 46 characterized in that the ratio of aliphatic-aromatic polyester to the sum of additional polymer and further polymer is 3/7 to 7/3.
  • Method according to one of the embodiments 33 to 47 characterized in that the non-water-miscible solvent is selected from dichloromethane, chloroform, ethyl acetate, n-hexane, cyclohexane, methyl t-butyl ether, pentanes, diisopropyl ether and benzene, or mixtures thereof Solvent. 49.
  • Spherical microparticles obtainable by a method of Embodiments 33 to 29.
  • Method according to embodiment 52 characterized in that the microparticles are impregnated by a method in which the aroma chemical is in finely divided form, preferably in the form of droplets.
  • Method according to embodiment 52 to 53 characterized in that the micro particles are sprayed or dripped with an aroma chemical or a solution of at least one aroma chemical.
  • a process according to embodiments 55 characterized in that subsequently f) the microparticles obtained according to e) at a temperature in the range 35 to 200 ° C, preferably 40 to 140 ° C, in particular in the range of 45 to 80 ° C via a Lasts from 1 minute to 10 hours.
  • Aromaemikalienzurung obtainable according to one of the embodiments 52 to 56th
  • composition comprising a composition of spherical microparticles according to one of embodiments 1 to 13 or an aroma chemical preparation according to embodiment 57 in a proportion by weight of 0.01 to 99.9 wt .-% based on the total weight of the composition.
  • biodegradable is understood to mean that the substance in question, here the unfilled microparticles, in the test of the OECD Guideline 301 B of 1992 (measurement of CO2 evolution in composting in a mineral sludge and comparison with the theoretical maximum possible evolution of CO2) after 28 days and 25 ° C undergoes a biodegradation of at least 5%, in particular at least 10%, and especially at least 20%.
  • spherical microparticles refers to a spherically shaped polymer microparticle (English: polymer microsphere). In one embodiment, these may be microcapsules, ie particles in which an outer polymer layer encloses a liquid or gaseous core at room temperature.
  • Fillable spherical microparticles have openings on their surface, so that an exchange of the material is possible inside.
  • microcapsules are holes in the outer polymer layer, often referred to as microcapsule shell or microcapsule wall.
  • porous spherical microparticles having a polymer matrix form In these cases, it is an interconnected porous network that has openings on the surface of the microparticle.
  • microparticles whose morphology has both.
  • the microparticles are formed by removing the solvent in a w / o / w emulsion.
  • an emulsion of water droplets or droplets of the aqueous pore-forming agent solution is formed in the polyester solution.
  • This w / o emulsion is in turn emulsified in water and the non-water-miscible solvent is removed.
  • the solvent of the polyester it becomes insoluble and deposits on the surface of the water droplets or of the aqueous pore-forming droplets.
  • the pores are advantageously produced by the pore-forming agent.
  • Pore formers are, for example, compounds which release gas under the process conditions of step b).
  • Pore formers are, for example, gas-releasing agents preferably selected from ammonium carbonate, sodium carbonate, ammonium bicarbonate, ammonium sulfate, ammonium oxalate, sodium bicarbonate, ammonium carbamate and sodium carbamate.
  • gas-releasing agents preferably selected from ammonium carbonate, sodium carbonate, ammonium bicarbonate, ammonium sulfate, ammonium oxalate, sodium bicarbonate, ammonium carbamate and sodium carbamate.
  • water-soluble low molecular weight compounds which build up an osmotic pressure are suitable as pore formers. When the non-water-soluble solvent is removed, a concentration gradient builds up due to the concentration difference between the inner aqueous droplet with the pore former and the outer aqueous dispersed phase, which causes migration from the water towards the inner droplets and thus leads to the formation of pores.
  • Such pore-forming agents are preferably selected from sugars such as monosaccharides, disaccharides, oligosaccharides and polysaccharides, urea, inorganic alkali salts such as sodium chloride and inorganic alkaline earth salts such as magnesium sulfate and calcium chloride. Particularly preferred are glucose and sucrose and urea.
  • polymers which are soluble in both phases such as polyethylene glycol (PEG) and polyvinylpyrrolidone (PVP), are suitable as pore formers. Because these polymers are soluble in both phases, they migrate from the aqueous phase to the oil phase due to diffusion.
  • PEG polyethylene glycol
  • PVP polyvinylpyrrolidone
  • composition of spherical microparticles is also used.
  • the microparticles according to the invention have an average particle diameter of D [4,3] of 10 to 600 ⁇ m (volume-weighted average, determined by means of light scattering).
  • the average particle diameter D [4.3] is 10 to ⁇ 100, preferably up to 30 pm.
  • the average particle diameter D [4.3] is 100-500 ⁇ m.
  • the microparticles according to the invention have on their surface at least 10 pores, preferably at least 20 pores whose diameter lies in the range from 1/5000 to 1/5 of the average particle diameter D [4,3] and furthermore the diameter of these pores is at least minimized. at least 20 nm.
  • the microparticles preferably each have on average at least 10 pores, preferably at least 20 pores whose diameter is in the range from 1/500 to 1/5 of the mean particle diameter D [4,3] and in each case the diameter of these pores is at least at least 20 nm.
  • the microparticles of the mean particle diameter 100-500 ⁇ m, which are preferred according to one embodiment, preferably have pores with an average diameter D [4,3] in the range from 1/500 to 1/100 of the average particle diameter.
  • those microparticles of the composition of spherical microparticles are considered whose particle diameter does not deviate more than 20% from the mean particle diameter D [4,3]. Of these, at least 80% fulfill the required number of pores on the particle surface.
  • an aliphatic-aromatic polyester is used. These include the esters based on aromatic dicarboxylic acids and aliphatic dihydroxy compounds.
  • the aromatic dicarboxylic acids can also be used in a mixture with aliphatic dicarboxylic acids.
  • Aliphatic-aromatic polyesters are preferably polyesters Base of aliphatic and aromatic dicarboxylic acids with aliphatic dihydroxy compound, so-called partly aromatic polyesters. These polymers can be present individually or in their mixtures.
  • the aliphatic-aromatic polyesters used according to the invention preferably have their glass transition temperature (determined by means of dynamic differential thermal analysis (DSC) DIN EN ISO 1 1357) or their melting point in the range from 45 to 140 ° C.
  • DSC dynamic differential thermal analysis
  • aliphatic-aromatic polyester is also understood to mean polyester derivatives of these aliphatic-aromatic polyesters, such as polyether esters, polyester amides or polyetheresteramides and polyester urethanes (see EP Note No. 10171237.0).
  • Suitable aliphatic-aromatic polyesters include linear non-chain extended polyesters (WO 92/09654). Preferred are chain-extended and / or branched aliphatic-aromatic polyesters. The latter are known from WO 96/15173 to 15176, 21689 to 21692, 25446, 25448 or WO 98/12242, to which reference is expressly made. Mixtures of different aliphatic-aromatic polyesters are also possible. Interesting recent developments are based on renewable raw materials (see WO-A 2006/097353, WO-A 2006/097354 and WO 2010/034710).
  • Particularly preferred aliphatic-aromatic polyesters include polyesters containing as essential components
  • C) optionally a component selected from c1) a compound having at least three groups capable of ester formation, c2) a di- or polyisocyanate, c3) a di- or polyepoxide.
  • aliphatic dicarboxylic acids and their ester-forming derivatives (a1) are generally those having 2 to 18 carbon atoms, preferably 4 to 10 carbon atoms, into consideration. They can be both linear and branched. In principle, however, it is also possible to use dicarboxylic acids having a larger number of carbon atoms, for example up to 30 carbon atoms.
  • oxalic acid malonic acid, succinic acid, 2-methylsuccinic acid, glutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, a-ketoglutaric acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, brassylic acid, fumaric acid, 2,2-dimethylglutaric acid, sube - Rinkla (suberic acid), diglycolic acid, oxaloacetic acid, glutamic acid, aspartic acid, itaconic acid and maleic acid.
  • the dicarboxylic acids or their ester-forming derivatives may be used singly or as a mixture of two or more thereof.
  • Succinic acid, adipic acid, azelaic acid, sebacic acid, brassylic acid or their respective ester-forming derivatives or mixtures thereof are preferably used. Particular preference is given to using succinic acid, adipic acid or sebacic acid or their respective ester-forming derivatives or mixtures thereof. Succinic acid, azelaic acid, sebacic acid and brassylic acid also have the advantage that they are accessible from renewable raw materials.
  • polybutylene azalate-co-butylene terephthalate PBAzeT
  • polybutylene-brassylate-co-butylene terephthalate PBBrasT
  • PBAT polybutylene adipate terephthalate
  • PBSeT polybutylene sebacate terephthalate
  • PBST polybutylene succinate terephthalate
  • aromatic dicarboxylic acids or their ester-forming derivatives (a2) may be used singly or as a mixture of two or more thereof. Particular preference is given to using terephthalic acid or its ester-forming derivatives, such as dimethyl terephthalate.
  • the diols (B) are selected from branched or linear alkanediols of 2 to 12 carbon atoms, preferably 4 to 6 carbon atoms, or cycloalkanediols of 5 to 10 carbon atoms.
  • alkanediols examples include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol, 1,5-pentanediol, 2,4-dimethyl-2-ethylhexan-1, 3-diol, 2,2-dimethyl-1,3-propanediol, 2-ethyl-2-butyl-1,3-propanediol, 2-ethyl-2-isobutyl-1,3-propanediol, 2,2, 4-trimethyl-1,6-hexanediol, in particular ethylene glycol, 1,3-propanediol, 1,4-butanediol and 2,2-dimethyl-1,3-propanediol (neopentylglycol);
  • cycloalkanediols examples include cyclopentanediol,
  • the aliphatic-aromatic polyesters may also contain mixtures of different alkanediols in condensed form. Particular preference is given to 1,4-butanediol, in particular in combination with adipic acid or sebacic acid as component a1) and 1, 3-propanediol, especially in combination with sebacic acid as component a1). 1,3-propanediol also has the advantage that it is available as a renewable raw material.
  • the composition of the wall material contains at least one aliphatic-aromatic polyester and at least one additional polymer, wherein the additional polymer is selected from the group consisting of polyhydroxy fatty acids, poly (p-dioxanones), polyanhydrides, polyester amides, polysaccharides and proteins.
  • the additional polymer is at least one polyhydroxy fatty acid, preferably at least one polycaprolactone.
  • the additional polymer is a polymer other than the aliphatic-aromatic polyester.
  • P (3HB) -co-P (3HV) 3-hydroxyvalerates
  • the at least one polyhydroxy fatty acid is selected from the group consisting of
  • Suitable polyhydroxyoctanoates can be selected from the group consisting of poly-3-hydroxyoctanoates (P3HO), poly-4-hydroxyoctanoates (P4HO), poly-6-hydroxy-octanoates (P6HO), and copolymers of at least 2 hydroxyoctanoic acids selected from the group consisting of 3-hydroxyoctanoic acid, 4-hydroxyoctanoic acid and 6-hydroxyoctic acid.
  • Suitable copolyesters of hydroxybutyric acid with at least one monomer selected from the group consisting of 3-hydroxypropionic acid, hydroxyvaleric acids, hydroxyhexanoic acids, hydroxyoctanoic acids and hydroxyoctadecanoic acids can be selected from the group consisting of
  • Polycaprolactones denote polyesters which are obtainable by ring-opening polymerization of epsilon-caprolactone (e-caprolactone).
  • the term polycaprolactone in the sense of the invention means both homopolymers of epsilon-caprolactone and copolymers of epsilon-caprolactone.
  • Suitable copolymers are, for example, copolymers of epsilon-caprolactone with monomers selected from the group consisting of lactic acid, lactide, hydroxyacetic acid and glycolide.
  • Suitable polyanhydrides are described in Kumar et al, Adv. Drug Delivery Reviews 54 (2002), pp. 889-910. Particularly suitable are those described in Kumar et al. Adv. Drug Delivery Reviews 54 (2002), p. 897, the polyanhydrides fully incorporated herein by reference.
  • Polysaccharides which are suitable according to the invention are preferably selected from the group consisting of modified starches, in particular starch ethers and esters, cellulose derivatives, in particular cellulose esters and cellulose ethers, chitin derivatives, chitosan derivatives, As cellulose derivatives, chemically modified celluloses are generally referred to as polymer-analogous reactions. They include both products in which only the hydro-hydrogen atoms of the glucose units of the cellulose are substituted by organic or inorganic groups, as well as those in which a formal exchange of the entire hydroxyl groups has taken place (for example deoxycelluloses ).
  • Suitable cellulose ethers are methylhydroxy (C 1 -C 4) -alkylcellulose.
  • Methylhydroxy- (C 1 -C 4) -alkylcellulose is to be understood as meaning methylhydroxy- (C 1 -C 4) -alkylcellulose of very different degrees of methylation, as well as degrees of alkoxylation.
  • the preferred methylhydroxy (C 1 -C 4) -alkylcelluloses have an average degree of substitution DS of from 1.1 to 2.5 and a molar degree of substitution MS of from 0.03 to 0.9.
  • Suitable cellulose esters are, for example, the esters of cellulose with C 2 -C 4 monocarboxylic acids, such as cellulose acetate (commercially available from Eastman CA-398-3), cellulose butyrates, cellulose acetobutyrates, cellulose propionate and cellulose acetopropionate.
  • Cellulose esters are available in various degrees of polymerization and substitution.
  • At least one of the polymers contained in the continuous phase of a) has a glass transition temperature or a melting point in the range of 45 to 140 ° C. If the polymer has a melting point, that is to say (partly) crystalline, it preferably has a melting point in the range from 45 to 140.degree. If the polymer is amorphous, it preferably has a glass transition temperature in the range of 45 to 140 ° C.
  • the continuous phase prepared under a) consists essentially of the solution of an aliphatic-aromatic polyester and the at least one additional polymer in a non-water-miscible solvent.
  • the continuous phase comprises at least 95% by weight, in particular at least 99% by weight, based on the continuous phase, of the solution of an aliphatic-aromatic polyester and the at least one additional polymer in a non-aqueous phase. water-miscible solvent.
  • the continuous phase prepared under a) contains the aliphatic-aromatic polyester and the at least one additional polymer in a ratio of from 3/7 to 7/3.
  • the continuous phase prepared under a) contains at least one further dissolved polymer.
  • the other polymer is a polymer other than the aliphatic-aromatic polyester and the additional polymer.
  • the continuous phase prepared under a) accordingly contains at least one aliphatic-aromatic polyester, at least one additional polymer selected from the group consisting of polyhydroxy fatty acids, poly (p-dioxanones), polyanhydrides, polyester amides, polysaccharides and Proteins and at least one other polymer.
  • polymers which are different from the aliphatic-aromatic polyesters and the additional polymers include, by way of example, polyacrylate, polyamide, polycarbonate, polystyrene, aliphatic-aliphatic polyester, aromatic-aromatic polyester, polyolefin, polyurea and polyurethane ,
  • At least one polymer selected from the group consisting of polyacrylate, polyamide, polycarbonate, polystyrene, aliphatic-aliphatic polyester, aromatic-aromatic polyester, polyolefin, polyurea and polyurethane is used as further polymer.
  • Suitable polyurethanes are, in particular, those whose diol component consists of polyhydroxy fatty acids, PLA or aliphatic-aromatic polyesters.
  • Aliphatic-aliphatic polyesters are understood as meaning polyesters based on aliphatic dicarboxylic acids and aliphatic dihydroxy compounds and polyesters based on mixtures of aliphatic dicarboxylic acids with aliphatic dicarboxylic acids and aliphatic dihydroxy compounds.
  • Examples of aliphatic carboxylic acids which are suitable for preparing the aliphatic-aliphatic polyesters are the aliphatic dicarboxylic acids mentioned under (a1), in particular those having 2 to 18 carbon atoms, preferably 4 to 10 carbon atoms.
  • Aliphatic-aliphatic polyesters in which the aliphatic dicarboxylic acid is selected from succinic acid, adipic acid, azelaic acid, sebacic acid, brassylic acid and mixtures thereof are preferred. Particularly preferred are succinic acid, adipic acid and sebacic acid and mixtures thereof.
  • succinic acid, adipic acid and sebacic acid and mixtures thereof are also possible to use, instead of the dicarboxylic acids, their respective ester-forming derivatives or mixtures thereof with the aliphatic dicarboxylic acids.
  • aliphatic diols which are suitable for preparing the aliphatic-aliphatic polyesters are the diols mentioned as component (B), for example branched or linear alkanediols having 2 to 12 carbon atoms, preferably 4 to 6 carbon atoms, or cycloalkanediols having 5 to 10 carbon atoms.
  • alkanediols are, in particular, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol, 1,5-pentanediol, 2,4-dimethyl-2-ethylhexane -1, 3-diol, 2,2-dimethyl-1,3-propanediol, 2-ethyl-2-butyl-1,3-propanediol, 2-ethyl-2-isobutyl-1,3-propanediol, 2,2 , 4-trimethyl-1, 6-hexanediol, in particular ethylene glycol, 1, 3-propanediol, 1, 4-butanediol and 2, 2-dimethyl-1, 3-propanediol (neopentyl glycol).
  • cycloalkanediols examples include cyclopentanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol and 2,2,4,4-tetramethyl, 3-cyclobutanediol.
  • the aliphatic-aliphatic polyesters can also contain mixtures of different alkanediols in a single-condenser. Particularly preferred are 1, 4-butanediol, especially in combination with one or two aliphatic dicarboxylic acids, which are selected from succinic acid, adipic acid and sebacic acid as component a1).
  • polyesters examples include polybutylene succinate dipate, polybutylene succinate, polybutylene sebacate, polybutylene succinate sebacate.
  • the preferred aliphatic-aliphatic polyesters frequently have a molecular weight Mn in the range from 1000 to 100 000 g / mol, in particular in the range from 2000 to 75000 g / mol, especially in the range from 5000 to 50 000 g / mol.
  • At least one polymer selected from the group consisting of polyhydroxyacetic acid, PLA copolymers (polylactide and polylactic acid copolymers), PLGA copolymers, and polylactic acid is used as further polymer.
  • Preferred PLGA copolymers are polylactide copolymers.
  • polylactic acid having a molecular weight of 30,000 to 120,000 daltons and a glass transition temperature (T g ) in the range of 50 to 65 ° C.
  • T g glass transition temperature
  • amorphous polylactic acid whose proportion of D-lactic acid is greater than 9%.
  • Preference according to the invention is given to mixtures of an aliphatic-aromatic polyester with the additional polymer, with a weight fraction of the aromatic-aliphatic polyester of from 20 to 99% by weight (based on the total weight of aliphatic-aromatic polyester and additional polymer).
  • the proportion of the aliphatic-aromatic polyester is preferably from 25 to 80% by weight, preferably from 30 to 70% by weight, based on the total weight.
  • melts of an aliphatic-aromatic polyester with an additional polymer are preferred in which the melting point of the aliphatic-aromatic polyester is at least 10 K, preferably at least 20 K, above the melting point of the additional polymer or at least the glass transition temperature of the aliphatic-aromatic polyesters 10 K, preferably at least 20 K, is above the glass transition temperature of the additional polymer. If the additional polymer is an amorphous compound, then the melting point of the aliphatic-aromatic polyesters is at least 10 K, preferably at least 20 K, above the glass transition temperature of the additional polymer.
  • composition of the microparticles is produced by the double emulsion method.
  • the aliphatic-aromatic polyester and the additional polymer and, if appropriate, the further polymer are dissolved in a non-water-miscible solvent.
  • Non-water miscible means that the solvent has a solubility in water at a temperature of 20 ° C and a pressure of 1 bar of ⁇ 90 g / L. Furthermore, the non-water-miscible solvent preferably has a boiling point of at least 30 ° C.
  • solvents are chemically inert with respect to the substances to be dissolved, that is, they serve only the dilution or solution. Radically polymerizable monomers are not solvents in the context of the invention.
  • aprotic-nonpolar and aprotic-polar solvents or solvent mixtures which have a water solubility of ⁇ 90 g / L (at 20 ° C.).
  • Preferred solvents are, for example, dichloromethane, chloroform, ethyl acetate, n-hexane, cyclohexane, methyl t-butyl ether, pentane, diisopropyl ether and benzene or mixtures of two or more of these solvents with one another.
  • Particularly preferred is dichloromethane.
  • solvent mixtures which form an azeotrope whose boiling point falls in the range from 20 to 80 ° C.
  • the azeotrope of hexane and methyl ethyl ketone (MEK) in a weight ratio of 72:28 may be mentioned.
  • the polyester, the additional polymer and, if appropriate, the further polymer are used in the non-water-miscible solvent as a 1 to 50% strength by weight solution.
  • the polymer solution thus prepared is a 2 to 30% strength by weight, in particular a 5 to 20% strength by weight solution, in the non-water-miscible solvent.
  • an emulsion is selected from a solution of at least one aliphatic-aromatic polyester and the at least one additional polymer.
  • an emulsion is selected from a solution of at least one aliphatic-aromatic polyester and the at least one additional polymer and the at least one further polymer.
  • the solution used can be obtained by mixing the individual polymer solutions or by jointly dissolving a polymer mixture.
  • the aliphatic-aromatic polyester or its mixture with the at least one additional polymer (and optionally the at least one further polymer) is the wall material of the later microparticle.
  • the wall material of the microparticles preferably has a solubility at 25 ° C. and 1 bar of at least 50 g / l in dichloromethane.
  • step a water or an aqueous solution of the pore-forming agent is emulsified.
  • the resulting emulsion is also referred to below as w / o emulsion (water-in-oil emulsion).
  • the aqueous solution of the pore-forming agent is preferably a 0.1 to 10% strength by weight aqueous solution of the pore-forming agent, in particular a pore-forming agent selected from ammonium hydrogencarbonate and ammonium carbonate. Particularly preferred is ammonium carbonate, in particular a 0.1 to 1 wt .-% solution of ammonium carbonate in water.
  • the pore-forming agent based on the sum of the wall material forming polymers, used.
  • the polymers forming the wall material consist of at least one aliphatic-aromatic polyester, at least one additional polymer and optionally at least one further polymer. Preference is given to using from 1 to 5 parts by weight, in particular from 1.3 to 3 parts by weight, of the pore-forming agent, based on the sum of the polymers forming the wall material.
  • the emulsification in process step a) takes place with the aid of a disperser (rotor-stator or rotor-rotor).
  • a disperser rotor-stator or rotor-rotor
  • homogenizing or dispersing machines having a high shearing energy are suitable for producing the w / o emulsion.
  • the average droplet size [D4.3] of the emulsion drops is 0.2 to 30 pm.
  • the w / o emulsion prepared in process step a) can be stabilized with at least one dispersant.
  • Dispersants suitable for w / o emulsions are generally known to me and are mentioned, for example, in EP 2794085 and in EP 3 007 815, to the teaching of which reference is expressly made.
  • one or more emulsifiers may be used to prepare the w / o emulsion in step a) and to stabilize it, preferably having an HLB value in the range from 2 to 10, in particular in the Range from 3 to 8.
  • HLB value Hydrophilic-Lipophilic-Balance
  • WC Griffin Classification of surface-active agents by HLB In: J. Soc., Cosmet., Chem., 1, 1949, pp. 31 1-326
  • nonionic emulsifiers having an HLB value according to Griffin in the range of 2 to 10, in particular in the range of 3 to 8.
  • anionic and zwitterionic emulsifiers having an HLB value according to Griffin in the range from 2 to 10, in particular in the range of 3 to 8.
  • such emulsifiers in an amount of 0.1 to 10 wt .-%, in particular 0.5 to 5 wt .-%, based on the total weight of in step a) prepared emulsion.
  • the emulsifier (s) of the solution of the polymer (s) in the non-water-miscible solvent will be added before water or the aqueous solution of the pore builder is emulsified in this solution.
  • Suitable emulsifiers with HLB value according to Griffin in the range from 2 to 10 are:
  • Sorbitan fatty acid esters in particular sorbitan mono-, di- and tri-fatty acid esters and mixtures thereof, such as sorbitan monostearate, sorbitan monooleate, sorbitan monolaurate, sorbitan tristearate, sorbitan sesquioleate, sorbitan dioleate, sorbitan trioleate;
  • Fatty acid esters of glycerol or polyglycerol such as glycerol monostearate, glyceryl distearate, glycerol monooleate, glycerol dioleate, glycerol monostearate monoacetate, glycerol monoacetate monooleate, polyglycerol polyrinoleate (E476), e.g. the commercially available emulsifier PGPR 90
  • Lactyl esters of fatty acid monoesters of glycerol Lactyl esters of fatty acid monoesters of glycerol
  • Ethoxylated and / or propoxylated C 4 -C 16 -alkylphenols having degrees of alkoxylation in the range from 2 to 10, for example nonylphenol ethoxylate having degrees of ethoxylation in the range from 2 to 5 and octylphenol ethoxylate having degrees of ethoxylation in the range from 2 to 5.
  • the emulsification of the w / o emulsion in water to the w / o / w emulsion (water-in-oil-in-water emulsion) in process step b) is carried out by stirring or shearing in the presence of at least one dispersant.
  • an aqueous solution of the dispersant can be added to the aqueous emulsion.
  • the dispersant is preferably initially introduced in the form of an aqueous solution and the w / o emulsion is added.
  • the dispersant listed below affects the size of the emulsion droplet in equilibrium.
  • the concentration of the dispersant in the aqueous dispersant solution is typically in the range of 0.1 to 8.0 wt .-%, in particular in the range of 0.3 to 5.0 wt .-% and especially in the range of 0.5 to 4.0 wt .-%, based on the total weight of the aqueous solution.
  • the weight ratio of the w / o emulsion provided in step a) to water, preferably in the form of the aqueous dispersant solution, is typically in the range from 15:85 to 55:45, in particular in the range from 25:75 to 50:50, and especially in the range of 30:70 to 45:55.
  • the amount of dispersant used is typically at least 0.1% by weight, in particular at least 0.2% by weight, based on the total weight of the w / o / w emulsion, and is in particular in the range of 0 , 1 to 2 wt .-% and especially in the range of 0.2 to 1 wt.% .-%, based on the total weight of w / o / w emulsion.
  • stirrers include, for. B. propeller stirrer, impeller stirrer, disk stirrer, blade stirrer, anchor stirrer, inclined blade stirrer, crossbar stirrer, helical stirrer and screw stirrer. It is possible to add so much shear energy by vigorous stirring that droplet sizes of 10 to ⁇ 100 pm, preferably up to 50 pm, are achieved.
  • the introduced shear energy can be derived directly from the power consumption of the apparatus for generating a shear field, taking into account the heat loss.
  • the shear energy introduced into the w / o / w emulsion is preferably from 250 to 25,000 watts h / m 3 batch size.
  • Particularly preferred is an energy input of 500 to 15 000, in particular 800 to 10,000 watts h / m 3 batch size, calculated on the basis of the motor current.
  • Suitable devices for generating a shear field are comminution machines operating according to the rotor-stator principle, such as sprocket dispersing machines, colloid and corundum disk mills, and high-pressure and ultrasonic homogenizers.
  • the ring gear dispersing machines operating according to the rotor-stator principle are used to generate the shear field.
  • the diameter of the rotors and stators is usually in the range between 2 cm and 40 cm, depending on the machine size and dispersing capacity.
  • the speed of such dispersing machines is generally in the range of 500 to 20,000 rpm, depending on the type.
  • the machines with large rotor diameters tend to turn in the lower speed range, while machines with small rotor diameters are usually operated in the range of high speeds.
  • the distance between the rotating parts and the stationary parts of the dispersing tool is usually 0.1 to 3 mm.
  • the final size of the emulsion droplets of the w / o / w emulsion should be a mean diameter D [4,3] (determined by means of light scattering) of 100 to 600 ⁇ m. As a rule, this final size is already achieved by stirring.
  • the final size of the emulsion droplets of the w / o / w emulsion should have an average diameter of 10 to 100 ⁇ m, preferably 10 to 30 ⁇ m. Usually, this final size is achieved by means of scissors.
  • the w / o / w emulsion is prepared in the presence of at least one dispersant.
  • the w / o / w emulsion can be prepared in the presence of a mixture of different dispersants. Likewise, only one dispersant can be used.
  • Suitable dispersants are, for example, cellulose derivatives such as hydroxyethylcellulose, methylhydroxyethylcellulose, methylcellulose and carboxymethylcellulose, polyvinylpyrrolidone, copolymers of vinylpyrrolidone, gelatin, gum arabic, xanthan, casein, polyethylene glycols and partially hydrolyzed polyvinyl acetates (polyvinyl alcohols) and also methylhydroxypropylcellulose and mixtures of the abovementioned , Preferred dispersants are partially or fully hydrolyzed polyvinyl acetates (polyvinyl alcohols) and methylhydroxy (C 1 -C 4) alkyl cellulose.
  • partially hydrolyzed polyvinyl acetates which are also referred to as partially hydrolyzed polyvinyl alcohols (PVA), preferably those having a degree of hydrolysis of 79% to 99.9%.
  • PVA copolymers as described in WO 2015/165836.
  • Methylhydroxy- (C 1 -C 4) -alkylcellulose is to be understood as meaning methylhydroxy- (C 1 -C 4) -alkylcellulose of very different degrees of methylation, as well as degrees of alkoxylation.
  • the preferred methylhydroxy (C 1 -C 4) -alkylcelluloses have an average degree of substitution DS of 1.1 to 2.5 and a molar degree of substitution MS of 0.03 to 0.9.
  • Suitable methylhydroxy (C 1 -C 4) -alkylcellulose are, for example, methylhydroxyethylcellulose or methylhydroxypropylcellulose.
  • a particularly preferred dispersant is methylhydro- xypropylcellulose.
  • Very particularly preferred dispersants are polyvinyl alcohols, in particular polyvinyl alcohols having a degree of hydrolysis of 79 to 99.9%.
  • a special dispersant for step b) is a carboxy-modified anionic PVA having a carboxyl group content of 1 to 6 mol% and a degree of hydrolysis of 85 to 90 mol%, and especially such a carboxy-modified anionic PVA, the 4 wt. -% Aqueous solution at 20 ° C has a viscosity of 20.0 to 30.0 mPa-s.
  • the dispersant is added in particular to the aqueous phase.
  • concentration of the dispersant in the aqueous phase is typically in the range of 0.1 to 8.0 wt .-%, in particular in the range of 0.3 to 5.0 wt .-% and especially in the range of 0.5 to 4.0 wt .-%, based on the total weight of the aqueous phase.
  • the weight ratio of the w / o emulsion provided in step a) to the aqueous phase containing the dispersant is typically in the range from 15:85 to 55:45, in particular in the range from 25:75 to 50:50, and especially in the range of 30:70 to 45:55.
  • carboxy-modified anionic PVA (having a degree of hydrolysis of 85 to 90 mol% and a viscosity of 20.0 to 30.0 mPa * s and carboxyl group content of 1 to 6 mol%) is prepared as 0.1 to 8 wt .-% aqueous solution, in particular as 0.1 to 5.0 wt .-% aqueous solution and especially as 0.3 to 4.0 wt.% Aqueous solution used.
  • Particularly preferred are aqueous solutions having a PVA content of 0.3 to 4 wt .-%. It is likewise possible to use aqueous solutions having a PVA content of from 0.3 to 2.5% by weight, in particular solutions having a PVA content of from 0.5 to 1.5% by weight.
  • process step b) the emulsification to w / o / w emulsion with a stirrer at a stirring speed of 5000-15 000 rpm over a period of 1-30 minutes.
  • the droplets produced thereby have a mean diameter of 0.2 to 30 pm.
  • the emulsion is prepared at a stirring speed of 100-1000 rpm over a period of 1 to 30 minutes.
  • the resulting mean diameter of the droplets is 100 to 600 pm.
  • the mixture is maintained at a temperature in the range of 20 to 80 ° C.
  • the temperature of the mixture is preferably selected to be below the glass transition temperature of the lowest-softening amorphous polymer or below the melting point of the lowest-melting crystalline polymer of the wall-forming composition. Higher temperatures are possible but may result in partial occlusion of the pores for too long a period of time.
  • the mixture is maintained at a temperature in the range of 20 to 45 ° C, especially from 20 to ⁇ 40 ° C.
  • a vacuum can be additionally applied. For example, it is possible to work in the range from 600 to 800 mbar or below 200 mbar.
  • the mixture is stirred at room temperature for 10 hours with 100 l / h nitrogen flow in a 2 l kettle or 3 h stirring at 45 ° C. jacket temperature with 100 l / hour nitrogen flow at a 2 L boiler.
  • stirring is carried out at 60 ° C. for 6 hours with 100 l / hour nitrogen flow.
  • microparticles formed by separation of the non-water-miscible solvent are separated off in process step c) and preferably dried. Under dried is to be understood that the microparticles contain a residual water content of ⁇ 5 wt .-%, preferably ⁇ 1 wt .-% based on the microparticles.
  • the drying can be carried out, for example, in the air stream and / or by applying a vacuum, if appropriate in each case with heating.
  • convective dryers such as spray dryers, fluidized beds and cyclone dryers, contact dryers such as plate dryers, paddle dryers, contact belt dryers, vacuum drying ovens or radiation stickers such as infrared rotary tube dryers and microwave mixer dryers.
  • the spherical microparticles thus obtained are likewise the subject matter of the present invention. They are characterized by the fact that they are easy to fill, for example by being suspended in a solution.
  • composition according to the invention consists of spherical microparticles, which are constructed from wall material and at least one cavity and have pores on their surface.
  • spherical micro-particles according to the invention having a particle size in the range of 100 to 600 pm, a bulk density (determined according to DIN EN ISO 60: 1999) of 0.1 to 0.5 g / cm 3, preferably 0.15 - 0.4 g / cm 3, in particular from 0.15 to 0.3 g / cm 3 . on.
  • the spherical microparticles according to the invention are used as carrier for filling with an aroma chemical, preferably a fragrance, preferably in a solvent or diluent.
  • an "aroma chemical” is a generic term for compounds that can be used as a "fragrance” and / or as a "flavoring agent.
  • perfume is to be understood as meaning natural or synthetic substances with an inherent odor.
  • flavoring agent is to be understood as natural or synthetic substances with a natural taste.
  • scent or "olfactory perception” is the interpretation of the sensory excitations that are delivered by the chemoreceptors of the nose or other organs of the genitals to the brain of a living being.
  • the smell can therefore be a sensory perception of the nose of fragrances, which takes place when inhaled.
  • the air serves as a smell carrier.
  • a "perfume” is a mixture of fragrances and carriers, in particular an alcohol.
  • a "perfume oil” is a concentrated mixture of several fragrances, which are e.g. in alcoholic solutions for perfuming various products.
  • a "solvent for fragrances” serves for the dilution of the fragrances or the fragrance composition according to the invention to be used according to the invention, without possessing its own odoriferous properties. Some solvents also have fixing properties.
  • the fragrance or a mixture of several fragrances can be admixed with 0.1 to 99% by weight of a diluent or solvent. At least 40% strength by weight solutions, more preferably at least 50% strength by weight solutions, further preferably at least 60% strength by weight solutions, further preferably at least 70% strength by weight solutions are preferred, in particular preference at least 80% strength by weight solutions, more preferably at least 90% strength by weight solutions, preferably in olfactorily acceptable solvents.
  • Preferred olfactorily acceptable solvents are, for example, ethanol, isopropanol, dipropylene glycol (DPG), 1,2-propylene glycol, 1,2-butylene glycol, glycerol, diethylene glycol monoethyl ether, diethyl phthalate (DEP), 1,2-cyclohexanedicarboxylic acid diisononyl ester, isopropyl myristate (IPM). , Triethyl citrate (TEC), benzyl benzoate (BB) and benzyl acetate.
  • DPG dipropylene glycol
  • DPG dipropylene glycol
  • 1,2-propylene glycol 1,2-propylene glycol
  • 1,2-butylene glycol 1,2-butylene glycol
  • glycerol diethylene glycol monoethyl ether
  • DEP diethyl phthalate
  • 1,2-cyclohexanedicarboxylic acid diisononyl ester iso
  • fragrances with which the (E / Z) -cyclopentadecenylcarbaldehydes (I) - (III) e.g. can be combined to form a fragrance composition e.g. in S. Arctander, Perfume and Flavor Chemicals, Vol. I and II, Montclair, N.J., 1969, Adverlag or K. Bauer, D. Garbe and H. Surburg, Common Fragrance and Flavor Materials, 4rd. Ed., Wiley-VCH, Weinheim 2001.
  • S. Arctander, Perfume and Flavor Chemicals Vol. I and II, Montclair, N.J., 1969, Adverlag or K. Bauer, D. Garbe and H. Surburg, Common Fragrance and Flavor Materials, 4rd. Ed., Wiley-VCH, Weinheim 2001.
  • S. Arctander, Perfume and Flavor Chemicals Vol. I and II, Montclair, N.J., 1969, Adverlag or K. Bauer, D
  • ambergris tincture Amyrisöl; Angelica seed oil; Angelica root oil; anise oil; Valerian oil; Basil oil; Tree moss absolute; Bay oil; Mugwort oil; Benzoeresin; Bergamot oil; Beeswax absolute; Bir kenteer oil; Bitter almond oil; Savory oil; Buccorightöl; Cabreuvaöl; cade oil; calamus; camphor oil; Cananga oil; cardamom; Cascarillaöl; cassia; Cassie absolute; Castoreum-Ab Solue; Cedern diligentöl; cedarwood; cistus; citronella; lemon; copaiba balsam; Copaiba balm oil; Coriander oil; costus root; Cuminöl; Cypress oil; Davanaöl; Dill herb oil; Dillsa oil; Eau de Brouts absolute; Oak moss absolute; elemi; Tarragon oil; Eucalyptus citriodora oil; eucalyptus oil
  • fragrances from the group of hydrocarbons such. 3-carene; alpha-pinene; beta-pinene; alpha-terpinene; gamma-terpinene; p-cymene; bisabolene; camphene; caryophyllene; cedrene; farnesene; limonene; longifolene; myrcene; ocimene; valencene; (E, Z) -1, 3,5-undecatriene; styrene; diphenylmethane; the aliphatic alcohols such as e.g.
  • fragrances are suitable as described in PCT / EP2015 / 072544.
  • the present invention further relates to a method for filling and optionally closing the filled microparticles.
  • the filling of the spherical microparticles is carried out by impregnating the spherical microparticles with at least one Aromachemikalie, preferably a fragrance.
  • aroma chemistry preparations The spherical microparticles impregnated with at least one aroma chemical are referred to as aroma chemistry preparations.
  • impregnation encompasses any contacting of the microparticles with at least one aroma chemical, which has the result that the cavity present in the unfilled microparticles is at least partially filled by the aroma chemical (s) or a part of that contained in the microparticles Gas is displaced by the liquid.
  • impregnation comprises contacting the microparticles with the at least one aroma chemical, which has the consequence that the cavity present in the unfilled microparticles is filled to at least 50%, in particular at least 70%, or completely the microparticles contained in the gas is blocked by the liquid.
  • the impregnation can be carried out with a liquid aroma chemical or with a solution of at least one aroma chemical.
  • the microparticles are impregnated by suspending the microparticles in a liquid aroma chemical or in a solution of at least one arochemical.
  • the microparticles are impregnated by a method in which the aroma chemical is in finely divided form, preferably in the form of droplets.
  • a liquid aerobic chemical or a solution of at least one aroma chemical in finely divided form, in particular in the form of droplets can be applied to the unloaded microparticles.
  • the microparticles in solid form, in particular in the form of a powder.
  • the liquid droplets are rapidly absorbed by the unloaded microparticles.
  • the liquid used for impregnation and thus the aroma chemical can be precisely metered, so that a separation of excess liquid avoided, or the associated expense can be reduced.
  • this will be the unloaded microparticles in solid form, in particular in the form of a powder in a mixer for the mixing of solids with liquids submit and the liquid containing the at least one Aromachemikalie, preferably in finely divided form, in particular Form of droplets, eg in the form of discrete droplets or as a spray.
  • the particular liquid containing the at least one aroma chemical will be applied in finely distributed form, in particular in the form of droplets, to the microparticles in motion which are to be loaded.
  • the microparticles it is possible to move the microparticles to be loaded in a suitable manner, in particular to produce a fluidized bed or a fluidized bed of the microparticles to be loaded, and to apply the respective liquid in finely distributed form to the agitated microparticles or fluidized bed or fluidized bed, for example by spraying or dripping.
  • the spraying or dripping can take place in a manner known per se by means of one or more nozzles, for example by means of single or two-substance nozzles or by means of dripping devices.
  • Suitable mixing devices are dynamic mixers, in particular compulsory mixers, or those with a mixer shaft, for example paddle mixers, paddle mixers or plowshare mixers, but also those free-fall mixers, for example drum mixers, and fluidized bed mixers.
  • the duration of the mixing process depends on the type of mixer and the viscosity of the liquid containing the aroma chemical at the loading temperature and thus on the rate of diffusion of the liquid into the microparticles.
  • the time required for loading can be determined by the skilled person in a simple manner. It is usually 1 minute to 5 hours, in particular 2 minutes to 2 hours or 5 minutes to 1 hour.
  • the filling of the spherical microparticles is carried out by suspending the spherical microparticles in a liquid aroma chemical or solution of an aroma gas, preferably a fragrance.
  • a liquid aroma chemical or solution of an aroma gas preferably a fragrance.
  • an aroma gas preferably a fragrance.
  • the suspension e.g. Magnetic stirrer, roller, shaker, various wall-near stirrers (for example, anchor stirrer, spiral stirrer).
  • the duration of the mixing process depends on the solution of the aroma chemical and is usually from 5 minutes to 12 hours.
  • the suspension takes place, for example, over a period of several hours, preferably longer than 1 hour, for example 5 hours, by mixing at room temperature. Prolonged suspension is possible, but at a certain point in time does not lead to any further increase in loading.
  • the filling of the spherical microparticles is carried out by e) suspending the spherical microparticles in a liquid aroma chemical or a solution of at least one aroma chemical and
  • microparticles obtained according to e) at a temperature in the range of 35 to 200 ° C over a period of 1 minute to 10 hours, preferably at a temperature in the range of 40 to 140 ° C, preferably from 45 to 80 ° C, over a period of 1 hour to 10 hours, stops and
  • the suspension obtained according to e) is usually kept at a temperature in the range of 35 to 200 ° C for 1 minute to 10 hours.
  • the suspension is preferably kept at a temperature in the range from 40 to 140.degree. C., in particular from 45 to 80.degree. C., for 1 hour to 10 hours.
  • the majority of the pores, preferably all pores of the microparticles can be closed. By choosing the temperature and time, the extent of occlusion of the pores can be controlled.
  • spherical microparticles consisting of a polymer material of 30 to 70 wt.% PBAT and 30 to 70 wt.% Polycaprolactone are selected. These microparticles are at least 1 hour with at least one liquid Aro mischmetal or a solution of at least one Aromachemikalie mixed, and then heated to a temperature in the range of 55 to 70 ° C and stirred for at least 3 hours.
  • microparticles consisting of a polymer material of 55% by weight of PBAT and 45% by weight of polycaprolactone. These microparticles are heated after filling at a temperature of 60 ° C and stirred for 5 hours. Thereafter, the suspension is cooled to room temperature and the filled microparticles are separated off.
  • spherical microparticles consisting of a polymer material of 30 to 70% by weight of PBSeT and 30 to 70% by weight of polycaprolactone are selected. These microparticles are mixed for at least 1 hour with at least one liquid aerobic chemical or a solution of at least one Aromachemikalie, and then heated to a temperature in the range of 55 to 70 ° C and stirred for at least 3 hours.
  • the filling of the filled microparticles is believed to occur by coalescence of the pores by heating the suspension above its melting point, or, if there is no melting point, above its glass transition temperature, depending on the wall-forming polymer of the microparticle. If the wall material is a composition of at least two polymers, the same principle applies, in which case the values of both polymers are considered.
  • the present invention furthermore relates to a process for the preparation of an aroma gas preparation in which the spherical microparticles obtainable by the process are suspended in an aroma chemical or in a solution of at least one aroma chemical and subsequently at a temperature in the range from 35 to 200 ° C., preferably from 40 to 140 ° C, in particular from 45 to 80 ° C, over a period of 1 minute to 10 hours.
  • spherical microparticles consisting of a polymer material of 55 wt .-% PBAT and 45 wt .-% polycaprolactone and spherical microparticles consisting of a polymer material of 55 wt .-% PBSeT and 45 wt .-% polycaprolactone.
  • the present application relates to the spherical microparticles obtained therefrom and to the use of the filled microparticles obtained by filling and optionally closing in agents selected from perfumes, detergents and cleaners, cosmetics, personal care products, hygiene articles, foods, dietary supplements, fragrance dispensers and fragrances.
  • spherical microparticles or of the aroma chemical preparation by using them in an agent selected from perfumes, detergents and cleaners, cosmetics, personal care products, hygiene articles, foods, food supplements, fragrance dispensers, fragrances.
  • the spherical microparticles filled according to the invention are suitable for the controlled release of aroma chemicals.
  • the filled and optionally closed microparticles are separated from the solution of the aroma chemical added in excess.
  • suitable methods are e.g. Filtration, centrifugation, decantation, vacuum distillation and spray drying.
  • the spherical microparticles filled according to the invention with at least one aroma chemical or the solution of at least one aroma chemical, preferably a fragrance or a solution of a fragrance, can be incorporated into a number of products or applied to such products.
  • Such agents preferably contain the spherical microparticles or an aroma chemicals preparation in a proportion by weight of from 0.01 to 99.9% by weight, based on the total weight of the composition.
  • Spherical microparticles of the invention and the aroma chemical preparations can be used in the preparation of perfumed articles.
  • the olfactory properties as well as the material properties and the toxicological safety of the microparticles according to the invention emphasize their particular suitability for the stated purposes.
  • the microparticles in conjunction with top notes of compositions, for example in perfume compositions, the Dihdrorosan, rose oxides or other more volatile fragrances such.
  • the fragrance or aroma compositions are accordingly dosed at the required time in the required amount.
  • a cooling effect is also purposefully applied, e.g. in chewing gum, confectionery, cosmetic products, technical applications such as textiles, superabsorbers.
  • Another advantage is the high material compatibility of the microparticles with self-reactive or more unstable components such as aldehydes, esters, pyranes / ethers, which can show secondary reactions on the surfaces.
  • the positive properties contribute to the flavoring agent preparations according to the invention being used with particular preference in perfumery products, personal care products, hygiene articles, textile detergents and in cleaners for solid surfaces.
  • the perfumed article is e.g. selected from perfumery, personal care products, hygiene articles, laundry detergents and solid surface cleaners.
  • Preferred perfumed articles according to the invention are furthermore selected from:
  • Perfumery products selected from perfume extracts, eau de perfume, eau de toilette, eau de colognes, eau de solide, extract perfume, air freshener in liquid, gel or solid support form, aerosol sprays, fragrance cleaners and oils;
  • Personal care products selected from shaving waters, pre-shave products, splash colognes, solid and liquid soaps, shower gels, shampoos, shaving soaps, shaving creams, bath oils, cosmetic emulsions of oil-in-water, water-in-water Oil and water-in-oil-in-water type such as skin creams and lotions, face creams and lotions, sunscreen creams and lotions, after-sun creams and lotions, hand creams and lotions, Foot creams and lotions, depilatory creams and lotions, after-shave creams and lotions, tanning lotions and lotions, hair care products such as hair sprays, hair gels, firming hair lotions, hair conditioners, hair shampoo, permanent and semi-permanent hair colorants, hair styling products such as cold whiskers and hair straighteners, hair lotions, hair creams and lotions, deodorants and antiperspirants such as underarm sprays, roll-ons, deodorants, deodorants, decorative cosmetics products such as eyeshadows, nail polishes
  • Solid surface cleaners selected from perfumed acidic, alkaline and neutral detergents, e.g. Floor cleaners, window glass cleaners, dishwashing detergents, bath and sanitary cleaners, scouring cream, solid and liquid toilet cleaners, powder and foam carpet cleaners, waxes and polishes such as furniture polishes, floor waxes, shoe polishes, disinfectants, surface disinfectants and sanitary cleaners, brake cleaners, pipe cleaners, Descaler, grill and oven cleaner, algae and moss remover, mildew remover, facade cleaner;
  • Laundry detergents selected from among liquid detergents, powdered detergents, laundry pretreatment agents such as bleaches, soaking and stain removers, laundry softeners, laundry soap, washing tablets.
  • the aroma chemical preparations according to the invention are suitable for use in surfactant-containing perfumed articles.
  • fragrances and / or fragrance compositions with a rose top note and pronounced naturalness are frequently sought for, in particular, for the perfuming of surfactant-containing formulations, for example detergents (in particular dishwashing detergents and all-purpose cleaners).
  • the aroma chemical formulations of the present invention may be used rosy as an agent for providing (a) hair or (b) textile fibers having the odor note.
  • aroma chemical preparations to be used according to the invention are therefore particularly suitable for use in surfactant-containing perfumed articles.
  • the perfumed article is one of the following:
  • an acidic, alkaline or neutral detergent specially selected from the group consisting of all-purpose cleaners, floor cleaners, window glass cleaners, dishwashing detergents, bath and sanitary cleaners, scouring cream, solid and liquid toilet cleaners, powder and foam carpet cleaners, liquid detergents, powdered detergents, laundry pre-treatment agents such as bleaches, soaking and stain removers, laundry softeners, laundry soaps, washing tablets, disinfectants, surface disinfectants,
  • an air freshener in a liquid, gelatinous or solid support form or as an aerosol spray in a liquid, gelatinous or solid support form or as an aerosol spray
  • a wax or a polish selected in particular from the group consisting of furniture polishes, floor waxes and shoe creams, or
  • a body care agent selected in particular from the group consisting of shower gels and shampoos shaving soaps, shaving foams, bath oils, cosmetic emulsions of Oil-in-water, water-in-oil and water-in-oil-in-water types such as skin creams and lotions, face creams and lotions, sunscreen creams and lotions, after-sun cremes and lotions, hand creams and lotions, foot creams and lotions, depilatory creams and lotions, after-shave creams and lotions, tanning creams and lotions, hair care products such as hair sprays, hair gels, firm hair lotions, hair conditioners, permanent and semipermanent hair dyes, hair styling agents such as cold waving and hair straightening agents, hair lotions, hair creams and lotions, deodorants and antiperspirants such as underarm sprays, rollons, deodorants, deodorants, decorative cosmetics.
  • shower gels and shampoos shaving soaps, shaving foams, bath oils cosmetic emulsions of Oil-
  • fragrances or fragrance compositions according to the invention are generally known and are described, for example, in PCT / EP2015 / 072544, to the teaching of which reference is expressly made.
  • the particle diameter of the w / o / w emulsion or of the particle suspension is determined using a Malvern Mastersizer 2000 from Malvern Instruments, England, sample dispersing unit Hydro 2000S according to a standard measuring method which has been documented in the literature.
  • the value D [4,3] stands for the volume-weighted average.
  • microparticles are determined as powders with a Malvern Mastersizer 2000 from Malvern Instruments, England, including Scirocco 2000 powder feed unit, according to a standard measuring method documented in the literature.
  • the value D [4,3] stands for the volume-weighted average.
  • Pore diameters were determined by scanning electron microscopy (Phenom Pro X). For this purpose, various close-up shots were taken and, in retrospect, these were automatically measured using the ProSuite (FibreMetric) software from Phenom. The pores of a selected area of a particle were detected by the difference in contrast and their areas were automatically measured. Assuming that the faces are circular, the diameter is calculated for each face. (Sample size 100 pores).
  • the image shows only half of the surface area of the particle. If the image of a microparticle shows at least 5 pores whose diameter is at least 20 nm and whose diameter is in the range of 1/5000 to 1/5 of the mean particle diameter, then the total surface area contains at least 10 pores.
  • the average particle diameter D [4,3] of the microparticles was already determined on the microparticle dispersion by means of light scattering. Calculated this results in the upper and lower limits of the particle diameter of the microparticles, which are taken into account for the determination of the pores ( ⁇ 20%).
  • microparticle dispersion was dried.
  • microparticles were selected whose particle diameter is in the range ⁇ 20% of the mean particle diameter of the microparticles. Their particle diameter was measured using Phenom's ProSuite (FibreMetric) software.
  • the individual values of the pore diameters were checked to see if their diameter satisfies the condition that it is in the range of 1/5000 to 1/5 of the mean particle diameter and is at least 20 nm.
  • the bulk density was determined according to DIN EN ISO 60: 1999.
  • the resulting w / o emulsion was converted into 419 g of a 0.8 wt .-% polyvinyl alcohol solution (with a degree of hydrolysis of 88 mol% and a viscosity of 25 mPa * s and Carboxyl phenomenonan- part of 3 mol%) and also emulsified under shear and energy input (one minute at 300 rpm with an anchor stirrer).
  • the w / o / w emulsion thus produced was then further stirred with an anchor stirrer at 150 rpm while being slowly heated to 40 ° C. and kept at this temperature for 4 hours at a nitrogen flow rate of 100 l / hour. Thereafter, the microparticle suspension was cooled to room temperature and filtered.
  • the average particle diameter after filtration was 257 ⁇ m.
  • Water content ⁇ 0.5%
  • Example 2 The procedure was analogous to Example 1 except that the polymer mixtures of aliphatic-aromatic polyester and a copolyester of 3-hydroxybutyrate and 3-hydroxyhexanoate [P (3HB-co-3HHx)] mentioned in Table 1 for the preparation of the fillable spherical microparticles were used.
  • Pore-forming agent solution 0.0225 g of ammonium bicarbonate were dissolved in 4.4775 g of water (pore former).
  • the w / o emulsion thus obtained was converted into 86 g of a 1% strength by weight polyvinyl alcohol solution (having a degree of hydrolysis of 88 mol% and a viscosity of 25 mPa * s and carboxyl group content of 3 mol%) and also under shear and energy input (one minute at 8,000 rpm with a rotor stator) emulsified.
  • the w / o / w emulsion thus produced was then further stirred with an anchor stirrer at 400 rpm and held at room temperature for 10 hours at a nitrogen flow rate of 100 liters / hour.
  • 3HHx 3-hydroxyhexanoate
  • 3HB 3-hydroxybutyrate
  • P (3HB-co-3HHx) copolyester of 3-hydroxybutyric acid and 3-hydroxyhexanoic acid
  • Example 5 Procedure for the preparation of fillable spherical microparticles
  • Pore-forming agent solution 0.54 g of ammonium carbonate were dissolved in 53.46 g of water (pore former).
  • Solution of the aliphatic-aromatic polyester and the additional polymer 15.12 g of PBSeT and 6.48 g of polycaprolactone were stirred into 270.0 g of dichloromethane and dissolved at 25 ° C with stirring.
  • 54.0 g of pore-forming agent solution in the solution of the aliphatic-aromatic polyester and the additional polymer were emulsified for 1 minute at 5,000 rpm with a rotor stator.
  • the resulting w / o emulsion was converted into 419 g of a 0.8 wt .-% polyvinyl alcohol solution (with a degree of hydrolysis of 88 mol% and a viscosity of 25 mPa * s and Carboxyl phenomenonan- part of 3 mol%) and also emulsified under shear and energy input (one minute at 300 rpm with an anchor stirrer).
  • the w / o / w emulsion thus produced was then further stirred with an anchor stirrer at 150 rpm while being slowly heated to 40 ° C. and kept at this temperature for 4 hours at a nitrogen flow rate of 100 l / hour. Thereafter, the microparticle suspension was cooled to room temperature and filtered.
  • the average particle diameter after filtration was 289 ⁇ m; Water content: ⁇ 0.5%
  • Example 5 The procedure was analogous to Example 5 with the difference that the polymer blends mentioned in Table 2 (from aliphatic-aromatic polyester and a polycaprolactone) were used for the preparation of fillable spherical microparticles.
  • Example 7 Procedure for the preparation of fillable spherical microparticles
  • the matrix-forming polymer used was a polymer blend of 70% by weight of PBSeT and 30% by weight of polycaprolactone. The procedure was as follows:
  • Pore-forming agent solution 0.54 kg of ammonium carbonate were dissolved in 53.5 kg of water (pore former).
  • Solution of aliphatic-aromatic polyester 15.1 kg of PBSeT (as in Example 1) and 6.5 kg of polycaprolactone (as in Example 5) were stirred into 270.0 kg of dichloromethane and dissolved at 25 ° C. with stirring.
  • the pore-forming agent solution in the solution of the aliphatic-aromatic polyester was emulsified for 15 minutes at 170 rpm using a double-stage cross-bar stirrer.
  • the w / o emulsion thus obtained was converted into 423 kg of a 0.8% by weight aqueous polyvinyl alcohol solution and likewise emulsified with shear and energy input (one minute at 120 rpm with a round anchor stirrer).
  • the w / o / w emulsion thus produced was then further stirred with an impeller stirrer at 120 rpm, the pressure being reduced to 800 mbar and the jacket temperature slowly heated to 40 ° C. and kept at this temperature for 4 hours. Thereafter, the microparticle suspension was cooled to room temperature, filtered and dried at 37 ° C.
  • the average particle diameter D [4,3] determined from the aqueous suspension was 1 10 pm.
  • PBSeT polybutylene sebacate terephthalate as in Example 1
  • Polycaprolactone commercially available from Perstorp under the tradename Capa TM 6506. Polycaprolactone having an approximate Mw of 50,000 and a melting point of 58-60 ° C.
  • Table 3 Detailed characterization of spherical microparticles using different polymer blends.
  • Rose Oxid 90 (chemical name: tetrahydro-4-methyl-2- (2-methyl-prop-1-enyl) pyran)) with a purity (sum of isomers, CGC) equal to 98.0% (area), cis Isomer 90.0-95.0% (CGC, area) / trans-isomer 5-10% (CGC, area) is commercially available from BASF SE.
  • Example 8c Solution A used was a 10% strength by weight solution of dihydrorosan in 1,2-propylene glycol.
  • Dihydrorosan (chemical name tetrahydro-2-isobutyl-4-methyl-2H-pyrane) with a purity (sum of isomers, GC)> 98.0% (area), with a cis-isomer content of 65-85% (area) che) and trans isomer of 15-35% (area), commercially available from BASF SE.

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Abstract

La présente invention concerne une composition de microparticules sphériques constituées par un matériau de paroi et par au moins un espace creux, qui contient un gaz et/ou un liquide, lesdites microparticules présentant des pores sur leur surface. Les microparticules sphériques présentent un diamètre moyen de particule de 10-600 µm. Au moins 80 % des microparticules, dont le diamètre de particule ne s'écarte pas de plus de 20 % du diamètre moyen de particule des microparticules de la composition, présentent respectivement en moyenne au moins 10 pores, dont le diamètre se situe dans la plage de 1/5000 à 1/5 du diamètre moyen de particule et le diamètre de ces pores est en outre d'au moins 20 nm. Le matériau de paroi est constitué par une composition contenant au moins un polyester aliphatique-aromatique et au moins un polymère supplémentaire choisi dans le groupe composé d'acides gras polyhydroxy, de poly(p-dioxanones), de polyanhydrides, de polyesteramides, de polysaccharides et de protéines. L'invention concerne également un procédé pour leur préparation ainsi que leur utilisation.
EP19715911.4A 2018-04-06 2019-04-04 Microparticules sphériques Pending EP3774015A1 (fr)

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KR102452905B1 (ko) * 2021-10-06 2022-10-12 주식회사 어스피셔스 천연 스피큘과 폴리디옥사논을 함유한 피부개선 화장조성물 제조방법 및 그 화장조성물
CN114634634B (zh) * 2022-03-22 2024-08-09 陈凌卉 一种生物功能复合多孔聚酯微球及其制备方法
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WO2019193094A1 (fr) 2019-10-10
MX2020010544A (es) 2020-11-06
JP2021520294A (ja) 2021-08-19
US20210024715A1 (en) 2021-01-28
BR112020019798A2 (pt) 2021-01-05

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