EP4087676A1 - Capsules de puu submicroniques et leur fabrication - Google Patents

Capsules de puu submicroniques et leur fabrication

Info

Publication number
EP4087676A1
EP4087676A1 EP21701426.5A EP21701426A EP4087676A1 EP 4087676 A1 EP4087676 A1 EP 4087676A1 EP 21701426 A EP21701426 A EP 21701426A EP 4087676 A1 EP4087676 A1 EP 4087676A1
Authority
EP
European Patent Office
Prior art keywords
group
active ingredient
microcapsules
textile product
puu
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
EP21701426.5A
Other languages
German (de)
English (en)
Inventor
Nicolas LUISIER
Giuseppino Fortunato
Claudio TONCELLI
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.)
Eidgenoessische Materialprufungs und Forschungsanstalt EMPA
Original Assignee
Eidgenoessische Materialprufungs und Forschungsanstalt EMPA
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 Eidgenoessische Materialprufungs und Forschungsanstalt EMPA filed Critical Eidgenoessische Materialprufungs und Forschungsanstalt EMPA
Publication of EP4087676A1 publication Critical patent/EP4087676A1/fr
Pending legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/06—Making microcapsules or microballoons by phase separation
    • B01J13/14—Polymerisation; cross-linking
    • B01J13/16—Interfacial polymerisation
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/26—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests in coated particulate form
    • A01N25/28—Microcapsules or nanocapsules
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23P—SHAPING OR WORKING OF FOODSTUFFS, NOT FULLY COVERED BY A SINGLE OTHER SUBCLASS
    • A23P10/00—Shaping or working of foodstuffs characterised by the products
    • A23P10/30—Encapsulation of particles, e.g. foodstuff additives
    • 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
    • A61K8/0208—Tissues; Wipes; Patches
    • 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
    • A61K8/87—Polyurethanes
    • 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
    • A61K8/90—Block copolymers
    • 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
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/005—Compositions containing perfumes; Compositions containing deodorants
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
    • D06M15/03—Polysaccharides or derivatives thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
    • D06M23/12—Processes in which the treating agent is incorporated in microcapsules
    • 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
    • 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
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00—Medicinal preparations characterised by special physical form
    • A61K9/48—Preparations in capsules, e.g. of gelatin, of chocolate
    • A61K9/50—Microcapsules having a gas, liquid or semi-solid filling; Solid microparticles or pellets surrounded by a distinct coating layer, e.g. coated microspheres, coated drug crystals
    • A61K9/5005—Wall or coating material
    • A61K9/5021—Organic macromolecular compounds
    • A61K9/5031—Organic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polyethylene glycol, poly(lactide-co-glycolide)

Definitions

  • the present invention relates to microcapsules comprising a Poly-(Urethane-Urea) wall encapsulating an active ingredient , to compositions comprising such microcapsules and to textiles functionalized with such microcapsules.
  • the inventive microcapsules are obtainable by a process combining ultrasonication, interfacial polymerisation and curing steps.
  • fragrances due to their volatility.
  • delivery systems such as microcapsules containing a fragrance, are developed to protect and later release the core payload.
  • a key requirement from the industry regarding these systems is to survive suspension in challenging conditions without physically dissociating or degrading. This is referred to as performance in terms of stability for the delivery system.
  • functionalized textiles have to comply with a number of requirements, such as: compatibility with the skin, compatibility with existing impregnation processes, cost considerations , stability and release performance.
  • microcapsules for textile uses.
  • the microcapsules are suited to encapsulate neroline and contain Polyurethane walls where the Polyol-component is a cyclodextrine and the isocyanate-component is MDI.
  • the microcapsules are large, 1 ' 500 - 40'000 nm with average size of 15,000 nm and show a broad size distribution of approx. 4 ' 000 nm.
  • the impregnation yield is 74% only and the 50% are of the impregnated material is lost after 6 washing cycles (Azizi, fig.8).
  • Figure 1 Size distribution by number and by volume of microcapsules from example 1 as determined by dynamic light scattering .
  • X-axis represents the diameter in nm and Y- axis represents the number in % (A) and volume in % (B), respectively .
  • X-axis represents the diameter in nm and Y-axis represents the number in % (C).
  • Figure 2 Scanning electron micrograph of microcapsules from example 1. Magnification is 10'000x.
  • Figure 3 Scanning electron micrograph of impregnated textile from example 2. Magnification is 2'000x.
  • FIG.4 Optical microscopy of impregnated textile (I), for comparison (Silva et al, Fig. 9, cited above): microcapsules before (a) and after (b) 1 washing cycle. It is apparent that most of the known microcapsules according to Silva et al (I) are lost after one washing cycle. (II) This invention: microcapsules of example 2 on polyester fibers before (a) and after (b) 1 washing cycle. It is apparent that the inventive microcapsules show a significant improved adherence to the textile.
  • Fig. 5 Optical microscopy of capsule composition, Magnification is 400x for both
  • inventive capsules are significantly smaller with unimodal size distribution.
  • Fig . 6 Example of PUU structure, outlining the difference between a polyurethane (PU) and a polyurethane-urea (PUU).
  • PU polyurethane
  • POU polyurethane-urea
  • the invention in more general terms, in a first aspect, relates to a capsule composition
  • a capsule composition comprising a plurality of poly (urethane-urea) microcapsules ( "PUU-microcapsules”), wherein the PUU microcapsules contain an encapsulated active ingredient and a poly (urethane-urea) wall (“PUU- wall”); and wherein the PUU-microcapsules have a sub-micron size and a unimodal size distribution.
  • POU-microcapsules poly (urethane-urea) microcapsules
  • the inventive compositions show improved properties when compared to known capsule compositions.
  • the inventive capsule compositions show an improved release profile for active ingredients, particularly long lasting properties.
  • they are simple in application on fabrics / textiles, complying with international environmental standards (such as Oekotex).
  • the capsules are safe when used, no adverse effects on the skin are observed.
  • the capsules are compatible with a wide range of active ingredients, no limitation towards specific functional groups, such as -OH incompatibility, was observed.
  • the combination of submicron-sized particles with the PUU wall provides for particularly suitable compositions to reliably encapsulate a broad range of active ingredients and to impregnate a broad range of fabrics.
  • Morphology of Capsules An important aspect of this invention is the morphology of microcapsules, which may be characterized by one or more of the parameters size, size distribution, shell thickness.
  • the inventive capsules are of sub-micron size.
  • the term "sub-micron” includes the range of 20 nm - 1500 nm, more preferably 50 nm - 1000 nm, most preferably 300 nm - 900 nm.
  • the term sub-micron further includes the ranges 20 - 950 nm, such as 20 - 600 nm.
  • the inventive capsules show a unimodal size distribution, typically with a FWHM of 100-800 nm, preferably of 300-500 nm. Size and size distribution may be determined by dynamic light scattering and are indicated in % by number, unless specifically indicated otherwise. Until now, it was not possible to obtain capsules having such sub-micron and having a unimodal size distribution. Such capsules are now obtainable according to the manufacturing method described herein (c.f. 2 nd aspect of the invention). Without being bound to theory, it is believed such size and size distribution contributes to the beneficial properties of the inventive capsules.
  • the shell thickness is 8-50 nm, preferably 8 - 16 nm, such as approximately 10 nm.
  • the capsule compositions show good physical / mechanical properties and safely encapsulate the active ingredients. This is an important feature to allow coating of fabrics / textiles. Nevertheless, the capsule compositions allow a slow release of the active ingredient. This is an important feature to perform its task as a vehicle for delivering / releasing the active ingredient.
  • the combination of both contradicting features, mechanical stability and suitable release profile is achieved with the present capsule composition .
  • a broad range of active ingredients may be encapsulated by the inventive microcapsules.
  • the PUU-wall, hydrophobic active ingredients are preferred.
  • an active ingredient is considered hydrophobic, if it forms a two-phases dispersion when mixed with water.
  • Suitable active ingredient may be selected from the group consisting of fragrances (or perfumes), malodour counteracting agents, repellents, fungicides, bactericides, pharmaceutically active ingredients, cosmetics, and food additives.
  • Suitable active ingredient may further be selected from agrochemicals.
  • Such active ingredients are known per se and commercially available.
  • the term active ingredient includes a single active ingredient (e.g. a repellent), a mixture or combination of active ingredients (e.g. a fragrance composition), in each case optionally diluted with a solvent.
  • the active ingredient may be dissolved in a solvent of current use in the perfume industry.
  • suitable solvents include diethyl phthalate, isopropyl myristate, Abalyn® (rosin resins, available from Eastman), benzyl benzoate, ethyl citrate, limonene or other terpenes, or isoparaffins.
  • the solvent is very hydrophobic and highly sterically hindered, like for example Abalyn®.
  • the active ingredient comprises less than 30%, preferably less than 10% of solvent.
  • the solvent is not an alcohol.
  • the active ingredient is essentially free of, or free of, solvent.
  • repellents include birch, DEET (N,N-diethyl-m- toluamide) , essential oil of the lemon eucalyptus (Corymbia citriodora) and its active compound p-menthane-3,8- diol(PMD), icaridin (hydroxyethyl isobutyl piperidine carboxylate) , Nepelactone, Citronella oil, Neem oil, Bog Myrtle (Myrica Gale), Dimethyl carbate, Tricyclodecenyl allyl ether, 1R3535 (3-[N-Butyl-N-acetyl]-aminopropionic acid, ethyl ester, Ethylhexanediol, Dimethyl phthalate, Metofluthrin, Indalone, SS220, anthranilate-based insect repellents , and mixtures
  • fragrance may be chosen by the skilled person in view of the intended application .
  • Fragrances may belong to chemical classes as varied as alcohols , aldehydes, ketones, esters, ethers, acetates, nitriles, terpenoids, nitrogenous or sulphurous heterocyclic compounds and essential oils. Fragrances may be of natural or synthetic origimn A specific example of a fragrance is limonene.
  • compositions may be chosen by the skilled person in view of the intended application .
  • Pharmaceutically active ingredients may belong to chemical classes as varied as antibacterial compounds, antiviral compounds, analgetics ("painkillers"), insecticides (e.g. Permethrin).
  • Agrochemicals may be chosen by the skilled person in view of the intended application.
  • Agrochemicals may belong to chemical classes as varied as fungicides , fertilizers.
  • Food additives may be chosen by the skilled person in view of the intended application.
  • Food additives may belong to chemical classes as varied as vitamins, preservatives.
  • the inventive microcapsules comprise a PUU wall, surrounding the active ingredient.
  • the PUU wall contains, typically consists of, a urethane-urea-polymer ( "PUU").
  • the polymer may or may not be cross-linked.
  • the PUU is a crosslinked PUU.
  • Such polymers are known per se and described in the prior art cited above. It is apparent that PUU distinguishes from Polyurethanes ( "PU” or "PUR", the reaction product of diisocyanates and diols) and from Polyureas (the reaction product of diisocyanates and diamines).
  • PUU contain both, the urethane moiety (i.e. reaction of polyol and diisocyanate) and urea moiety (i.e. reaction of diamine with diisocyanate), cf. fig. 6.
  • such urethane-urea-polymers are characterized by its starting materials: one or more diisocyanates, one or more polyols, one or more curing agents with amino- groups and optionally one or more crosslinkers.
  • these starting materials are commercial items and / or available according to known methods.
  • the diisocyanate component includes aromatic diisocyanates and aliphatic diisocyanates and combinations thereof.
  • aromatic diisocyanate includes any diisocyanate comprising an aromatic moiety.
  • diisocyanate comprises a phenyl, a toluyl, a xylyl, a naphthyl or a diphenyl moiety, more preferably a toluyl or a xylyl moiety.
  • the aromatic diisocanate is selected from the group consisting of a polyisocyanurate of toluene diisocyanate (commercially available from Bayer under the tradename Desmodur® RC), 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 polyisocyanurate of toluene diisocyanate commercially available from Bayer under the tradename Desmodur® RC
  • 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 Take
  • the aromatic diisocyanate is selected from the group consisting of Methylene diphenyl miisocyanate (MDI), Toluene diisocyanate (TDI), Lupranat® 102 (from BASF) and Lupranat® 105 (from BASF).
  • MDI Methylene diphenyl miisocyanate
  • TDI Toluene diisocyanate
  • Lupranat® 102 from BASF
  • Lupranat® 105 from BASF
  • aliphatic polyisocyanate is defined as a polyisocyanate which does not comprise any aromatic moiety.
  • the aliphatic diisocyanate is selected from the group consisting of Isophorone diisocyanate (IPDI) 4,4'-Methylenebis(cyclohexyl isocyanate) and Hexamethylene diisocyanate.
  • the polyol component includes polyethylene glycols and cyclic diols.
  • the polyethylene glycol is selected from the group consisting of PEG'S 200 - > 5000, preferably PEG'S 200 -> 1000, such as PEG 400.
  • the cyclic diol is isosorbide.
  • the curing agent includes polyamines, preferably diamines.
  • the diamine is selected from the group consisting of hydrazine and ethylenediamine, preferably hydrazine or its hydrate.
  • the crosslinking component includes tri- and / or tetra-functional compounds with reactive hydroxy or amino groups. It is preferred to include crosslinking components. Suitable crosslinkers may be selected from the group consisting of triols, tetraols and polyamines. In one embodiment, the crosslinker is selected from the group consisting of Trimethylol propane, Pentaerythritol, Tris (aminoethyl) amine, and Branched polyethyleneimine.
  • PUU formation is typically induced by a catalyst.
  • the PUU wall may contain a catalyst.
  • Suitable catalysts are known in the field and include organic catalysts such as DABCO, DBU, Dimethylethanolamine and metalorganic catalysts, such as Dibutyltindilaurate and Bismuthneodecanoate.
  • the ratio of the starting materials may be determined by routine experiments to allow full polymerization.
  • Capsule Characteristics Suitably, the inventive microcapsules comply with one or more of the following characteristics . These are obtained when following the manufacturing described below.
  • the microcapsules have a fill factor (number of capsules containing active ingredients / total number of capsules) above 80%, preferably above 90%. Obtaining such a high fill factor is an advantageous property of the inventive microcapsules, observed when following the method described herein.
  • the microcapsules have a high resistance to abrasion. Obtaining such high resistance is an advantageous property of the inventive microcapsules, observed when following the method described herein.
  • the microcapsules have a low residual -NCO monomer content, such as a residual -NCO monomer content ⁇ 0.1 %, preferably below the detection limit. Obtaining suchw low concentration is an advantageous property of the inventive microcapsules, observed when following the method described herein and particularly relevant for the application on textiles as described below.
  • the residual monomer content may be determined by GC-MS or FT-IR.
  • the microcapsules present a linear release profile, such as the smell detected by the end-user is constant over time.
  • Capsule Composition It is apparent from the above that not one single microcapsule is obtained, but a plurality of such microcapsules.
  • the capsule composition is present in the form of a slurry, said slurry preferably comprising the inventive microcapsules dispersed in an aqueous dispersing medium.
  • aqueous dispersing medium may contain, in addition to water, non-reacted starting materials, catalyst, surfactants, stabilizing agents, pH modifying agents.
  • Suitable surfactants may be selected by the skilled person and include commercial products such as Tween 20, Tween 80, Span 20, Span 80, Lutensol, SDS, Triton X-100, and CTAB.
  • Suitable stabilizing agents may be selected by the skilled person and include commercially available stabilizers, such as from the class of poloxamers, of polyvinyl alcohols, of polyacrylic acids, carrageenanes.
  • the capsule composition is present in the form of a dried powder. It was found that the dried microcapsules are stable and may be re-dispersed without detrimentally influencing its properties . This is an important advantage of the inventive microcapsules.
  • the invention in a second aspect, relates to a process for manufacturing a capsule composition as described herein, comprising the step of preparing an oil-in-water emulsion with droplet size of less than 1500 nm with the aid of ultrasonication, the oil phase containing active ingredient and diisocyanate (Step (b) below), causing formation of microcapsules by interfacial polymerisation with polyol, catalyst and optionally crosslinker (step (c) below) and curing the thus obtained microcapsules with a curing agent (step (d) below) to obtain the inventive PUU microcapsules in the form of a slurry.
  • This process allows for manufacturing new capsule compositions with improved properties as described herein. Specifically, it solves the problem of providing highly stable capsules having at the same time a beneficial release profile for the active ingredient .
  • the present solution to this problem, the process described herein is not described or even suggested in any prior art document.
  • the invention provides for a process for preparing a capsule composition as described herein, said process comprising the steps of (a) preparing the following starting materials: (i ⁇ an oil phase comprising a hydrophobic active ingredient, a diisocyanate monomer and optionally a diluent ( "oil phase”); (ii) a 1 st aqueous phase, not miscible with said organic phase, comprising water and a stabilizer; (iii) a 2 nd aqueous phase comprising water, a polyol, optionally a crosslinker and a catalyst;
  • a 3 rd aqueous phase comprising water and a curing agent
  • the invention provides for a process for preparing a capsule composition as described herein comprising as additional steps: (e) separating the capsule composition from the aqueous dispersing medium; (f) optionally purifying the capsule composition followed by either (g) or (h); (g) re-suspending the capsule composition in a 5 th aqueous phase, preferably water, to obtain a slurry; or (h) drying the capsule composition to obtain a dried powder.
  • process steps (a) to (h) shall be explained in further detail below:
  • all starting materials are present in the form of a solution .
  • the components of the starting materials are discussed above, first aspect of the invention .
  • the 1 st aqueous phase typically contains water and an emulsion stabilizer.
  • Suitable stabilizers are known in the field and non-reactive towards the remaining components.
  • stabilizers are polyvinyl alcohol, cellulose derivatives such as hydroxyethyl cellulose, polyethylene oxide, copolymers of polyethylene oxide and polyethylene or polypropylene oxide, copolymers of acrylamide and acrylic acid or cationic polymers such as for example a cationic copolymer of vinylpyrrolidone and of a quaternized vinylimidazole such as those sold under the trade name Luviquat® (commercially available from BASF).
  • the colloidal stabilizer is polyvinyl alcohol or a cationic polymer, which is a copolymer of vinylpyrrolidone and of a quaternized vinylimidazole, or a mixture thereof.
  • Particularly preferred stabilizers are Polyvinylalcohols.
  • emulsification is performed in two consecutive emulsification steps (bl) and (b2).
  • step (bl) an emulsion is prepared with droplet size of more than 1500 nm. This may be achieved by high shear mixing with more than 10000 rpm.
  • droplet size is reduced to less than 1500 nm. This is achieved by ultrasonic treatment with known instruments, e.g. available from Bronson Ultrasonics Corp.
  • Suitable instruments typically have 400 W power, and are operated at 50 % amplitude or more in "pulsed" mode. In embodiments of the invention, instruments are operated at 80 % amplitude. Suitable treatment times are more than 1 minute, such as more than 5 minutes, e.g. 12 minutes.
  • the PU wall of the capsules is the result of the interfacial polymerisation between the polyisocyanate obtained in step (b) and the polyol added in step (c).
  • Said capsules have an encapsulated active ingredient and a particle size of 20 - 1500 nm (preferably 50 - 1000 nm or 20 - 950 nm) and unimodal size distribution as defined above.
  • polymerisation takes place at temperatures at 40 - 100°C for 0.5-5 hrs. Catalyst concentration is determined by routine experiments.
  • the curing step ensures conversion of non-reacted isocyanate groups to urea groups, thereby forming the poly (urea-urethane ) polymer wall of the capsules.
  • curing takes place at 40 - 100oC for 0.5-10 hrs.
  • the invention also relates to a capsule composition obtainable by or obtained by a process as described herein. Accordingly, the invention provides for PUU- submicron-sized capsules containing hydrophobic active ingredients made via interfacial condensation (particularly of isocynanate and polyol), crosslinking (particularly with triols, tetrad s or triamines), curing (particularly with polyamine).
  • the invention relates to the use of capsule compositions as described herein in textile applications.
  • textile applications shall include clothing (such as garments, sportswear and accessories), interior devices for home and transportation (such as curtains, carpets, and seat covers), food packaging and medical textiles (such as wound dressings, cosmetics, wellness textiles , wipes).
  • inventive capsule compositions comprise an active ingredient, having beneficial effects on textiles. For example, no adverse effects on the skin are observed and compatibility with oeko-tex standard 100 is achieved. Also, a stable release profile for the active ingredient is observed.
  • Coated fabrics The capsule compositions are suited to impregnate all types of fabrics, including woven fabrics, non-woven fabrics, and knitted fabrics. Impregnation process may be achieved using standard methods, such as padding (using a foulard; or slope padding), coating (including roll-to-roll coating, reverse coating, gravure coating), spraying or immersion. Fixation of the inventive microcapsules may be ensured via gluing (as in example 2) or alternatively by covalent bonding or ionic bonding. The fixation of choice depends on the capsule and fabric type, as well as the equipment used. The skilled person is in a position to select appropriate impregnation methods.
  • Impregnation process may take place in the presence of a binder, for example a self-crossiinking binder, such as a resin of acrylic, polyurethane, silicone-type or starch.
  • a binder for example a self-crossiinking binder, such as a resin of acrylic, polyurethane, silicone-type or starch.
  • Such binders assist to glue the microcapsules onto the fabric, keeping them in place and thus preventing their loss during washing and wear.
  • the inventive capsule compositions may be directly used in such impregnation process. There is no need for a pre-treatment, such as de-agglomeration by ultrasonication.
  • the invention thus provides for a woven or non-woven or knitted fabric impregnated with a capsule composition as described herein. The impregnation does not modify the fabric ' s touch sensation or colour; no adverse effects to the skin are observed.
  • Textiles The invention further provides for a textile product comprising the coated fabric described herein.
  • the term textile product is used in its broad sense and includes clothing (including sportswear and accessories), interior devices for home and transportation (such as curtains , carpets, and seat covers), food packaging and medical textiles (such as wound dressings, cosmetics, wellness textiles, wipes).
  • inventive textiles no toxicological issues are observed.
  • the textiles are compatible with oeko-tex standard 100.
  • Textiles functionalized with the inventive capsule composition continuously emit fragrances (or other active ingredients ) over extended period of time, such as more than > 6 months. Further, textiles functionalized with the inventive capsule composition resist standard laundry operation in domestic conditions, such as 40°C standard washing program with detergent. As a consequence, the inventive compositions find use in a wide field of applications, including the following:
  • a textile product selected from the group of shirts, tights, socks, gloves, face mask, cosmetic pads, diapers, combined with an active ingredient selected from the group of vitamins.
  • a textile product selected from the group of tarpaulin, architectural membranes, tents, geo textiles, socks, combined with an active ingredient is selected from the group of fungicides.
  • a textile product selected from the group of shirts, tights, socks, gloves, face mask, cosmetic pads, diapers combined with an active ingredient selected from the group of antioxidants.
  • An organic phase was first formed by mixing a 1:1 mixture of glyceryl trioctanoate and limonene (12 mL) and isophorone diisocyanate (4 mL).
  • a first aqueous phase was prepared from deionized (DI) water (100 mL) and PVA (Mowiol 4-88, 1.68 g).
  • a miniemulsion was prepared by mixing these two solutions, emulsifying with a high-shear homogeneizer at 12'000 rpm for 3 minutes and ultrasonication (80% amplitude, pulsed, 12 min).
  • a second aqueous phase made from DI water (40 mL), PEG400 (8.2 mL), trimethylol propane (270 mg) and dibutyltin dilaurate (0.4 mL) was prepared separately.
  • the miniemulsion was transferred to a 250 mL two-necks round bottom flask equipped with an overhead mechanical stirrer and the second aqueous phase was then added to it.
  • the reaction was heated to 55 °C under constant mechanical agitation (150 rpm) for 2h.
  • a third solution of hydrazine hydrate (1.2 mL) in DI water (8 mL) was added dropwise and the mixture was let to react two more hours.
  • the reaction was then cooled down to r.t, and the capsules were recovered by ultracentrifugation at 35'000 xg. Washing was performed by re-suspending the capsules in 1 % aqueous Pluronic F68 solution and the centrifugation step was repeated two times . Finally, the capsules were re-suspended in DI water for storage.
  • Liquor solutions for foulard coating were prepared by mixing the binder polymer solution (30 mb, 150 g/L, Arristan CPU (a modified polyurethane, self-crosslinking upon drying) or Ecoperl HC (a modified polysiloxane, self- crosslinking upon drying) and the capsules of example 1 (12 g, 60 g/L) in DI water (170 mL). Textiles pieces of polyester (30 x 20 cm) were then coated in a laboratory foulard machine wherein the samples are first immersed in the coating liquor described above, and then the excess suspension is squeezed out by two rubber rollers. The coating process is performed at room temperature, the rollers speed is 2 m/min, the wet pick up controlled > 80% in weight and the samples are dried at air.
  • Arristan CPU a modified polyurethane, self-crosslinking upon drying
  • Ecoperl HC a modified polysiloxane, self- crosslinking upon drying
  • An organic phase was first formed by mixing limonene (12 mL) and methylene diphenyl diisocyanate (3.86 mL).
  • a first aqueous phase was prepared from deionized (DI) water (100 mL) and PVA (Mowiol 4-88, 1.68 g).
  • a miniemulsion was prepared by mixing these two solutions, emulsifying with a high-shear homogeneizer at 12'000 rpm for 3 min and ultrasonication (80% amplitude, pulsed, 12 min).
  • DI water 40 mL
  • PEG400 8.2 ml
  • trimethylol propane 270 mg
  • DABCO 280 mg
  • the miniemulsion was transferred to a 250 ml two-necks round bottom flask equipped with an overhead mechanical stirrer and the second aqueous phase was then added.
  • the reaction was heated to 55°C under constant mechanical agitation (150 rpm) for 2h.
  • a third solution of hydrazine hydrate (1.2 ml) in DI water (8 mL) was added dropwise and the mixture was let to react two more hours.
  • the reaction was then cooled down to room temperature, and the capsules were recovered by ultracentrifugation at 35'000 xg. Washing was performed by re-suspending the capsules in 1 % aqueous Pluronic F68 solution and the centrifugation step was repeated two times. Finally, the capsules were re-suspended in DI water for storage.
  • An organic phase was first formed by mixing a complex perfume composition "Atlantic Santal” (12 ml) and toluene diisocyanate (2.73 ml).
  • a first aqueous phase was prepared from deionized (DI) water (100 ml) and PVA (Mowiol 4-88, 1.68 g).
  • a miniemulsion was prepared by mixing these two solutions, emulsifying with a high-shear homogeneizer at 15'000 rpm for 3 min and ultrasonication (70% amplitude, pulsed, 15 min).
  • a second aqueous phase made from DI water (40 mL), PEG800 (4.1 mL), tris(aminoethyl) amine (294 mg) and dibutyltin dilaurate (0.4 mL) was prepared separately.
  • the miniemulsion was transferred to a 250 mL two-necks round bottom flask equipped with an overhead mechanical stirrer and the second aqueous phase was then added to it. The reaction was heated to 55 °C under constant mechanical agitation (150 rpm) for 2h. Then, a third solution of ethylene diamine (1.4 mL) in DI water (8 mL) was added dropwise and the mixture was let to react two more hours.
  • the reaction was then cooled down to room temperature, and the capsules were recovered by ultracentrifugation at 35'000 xg. Washing was performed by resuspending the capsules in 1 % aqueous Pluronic F68 solution and the centrifugation step was repeated two times . Finally, the capsules were resuspended in DI water for storage.
  • An organic phase was first formed by mixing limonene (12 mL) and methylene diphenyl diisocyanate (3.86 mL).
  • a first aqueous phase was prepared from deionized (DI) water (100 ml) and PVA (Mowiol 4-88, 1.68 g).
  • a miniemulsion was prepared by mixing these two solutions, emulsifying with a high-shear homogeneizer at 12'000 rpm for 3 min and ultrasonication (80% amplitude, pulsed, 12 min).
  • DI water 40 mL
  • PEG600 12.2 mL
  • branched polyethyleneimine 300 mg
  • DABCO 280 mg
  • the miniemulsion was transferred to a 250 mL two-necks round bottom flask equipped with an overhead mechanical stirrer and the second aqueous phase was then added to it.
  • the reaction was heated to 60 °C under constant mechanical agitation (150 rpm) for 2h.
  • a third solution of hydrazine hydrate (1.2 mL) in DI water (8 mL) was added dropwise and the mixture was let to react two more hours.
  • the reaction was then cooled down to room temperature, and the capsules were recovered by ultracentrifugation at 35'000 xg. Washing was performed by resuspending the capsules in 1 % aqueous Pluronic F68 solution and the centrifugation step was repeated two times. Finally, the capsules were re-suspended in DI water for storage.
  • An organic phase was first formed by mixing a complex perfume composition “Atlantic Santal” (12 mL) and 4,4'- Methylenebis (cyclohexyl isocyanate, MBCI) (6 mL).
  • a first aqueous phase was prepared from deionized (DI) water (100 mL) and PVA (Moxiol 4-88, 1.68 g).
  • a miniemulsion was prepared by mixing these two solutions, emulsifying with a high-shear homogenizer at 15'000 rpm for 3 min and ultrasonication (70% amplitude, pulsed, 15 min) .
  • a second aqueous phase made from DI water (40 mL), PEG400 (9.2 g), tris(aminoethyl)amine (430 mg) and DABCO (224 mg) was prepared separately.
  • the miniemulsion was transferred to a 250 mL two-necks round bottom flask equipped with an overhead mechanical stirrer and the second aqueous phase was then added to it.
  • the reaction was heated to 55 °C under constant mechanical agitation (150 rpm) for 2h.
  • a graph of the PSD is provided as fig. 1C.

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Abstract

La présente invention concerne des microcapsules comprenant une paroi de poly-(uréthane-urée) encapsulant un ingrédient actif, des compositions comprenant de telles microcapsules et des textiles fonctionnalisés avec de telles microcapsules. Les microcapsules selon l'invention peuvent être obtenues par un procédé combinant des étapes d'ultrasonication, de polymérisation interfaciale et de durcissement.
EP21701426.5A 2020-01-16 2021-01-15 Capsules de puu submicroniques et leur fabrication Pending EP4087676A1 (fr)

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EP20152249.7A EP3851186A1 (fr) 2020-01-16 2020-01-16 Capsules puu submicroniques et leur procédé de fabrication
PCT/EP2021/050862 WO2021144454A1 (fr) 2020-01-16 2021-01-15 Capsules de puu submicroniques et leur fabrication

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EP2461689A1 (fr) * 2009-08-07 2012-06-13 GAT Microencapsulation AG Microcapsules contenant les lactones macrolides abamectine, milbémectine, avermectines, milbémycines, émamectines, ivermectines et mectines en général
EP3083029B1 (fr) * 2013-12-19 2017-09-27 Firmenich SA Micro-capsules hybrides
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