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EP4426477A1 - Procédé d'encapsulation - Google Patents

Procédé d'encapsulation

Info

Publication number
EP4426477A1
EP4426477A1 EP22812544.9A EP22812544A EP4426477A1 EP 4426477 A1 EP4426477 A1 EP 4426477A1 EP 22812544 A EP22812544 A EP 22812544A EP 4426477 A1 EP4426477 A1 EP 4426477A1
Authority
EP
European Patent Office
Prior art keywords
compound
capsules
water
process according
aqueous
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
EP22812544.9A
Other languages
German (de)
English (en)
Inventor
Guillaume Wojciech JAUNKY
Marc Eberhardt
Rainer KNIESBURGES
Nina KOSTINA
Martin Möller
Jürgen OMEIS
Volker THYSSEN-WALLNER
Sebastian Weis
Xiaomin Zhu
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.)
BYK Chemie GmbH
Original Assignee
BYK Chemie GmbH
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 BYK Chemie GmbH filed Critical BYK Chemie GmbH
Publication of EP4426477A1 publication Critical patent/EP4426477A1/fr
Pending legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/06—Making microcapsules or microballoons by phase separation
    • B01J13/14—Polymerisation; cross-linking
    • B01J13/16—Interfacial polymerisation
    • 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
    • A61K8/89—Polysiloxanes
    • A61K8/891—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
    • A61K8/893—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone modified by an alkoxy or aryloxy group, e.g. behenoxy dimethicone or stearoxy dimethicone
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/56—Compounds, absorbed onto or entrapped into a solid carrier, e.g. encapsulated perfumes, inclusion compounds, sustained release forms

Definitions

  • the invention relates to a process of encapsulating a compound, to the capsules obtainable by the process, to the use of the capsules for controlled release, and to a composition comprising the capsules and an organic polymer.
  • WO 2011/131644 relates to a capsule with a core/shell structure, comprising a core which comprises at least one sparingly-soluble or water-insoluble organic active ingredient.
  • This document is concerned with capsules having improved stability and reduced skin irritation potential.
  • the shell of the capsules comprises nanoparticles of a metal oxide or semimetal oxide, and these nanoparticles are joined together by at least one further metal oxide formed by hydrolysis and subsequent polycondensation of a sol-gel precursor.
  • WO 2017/016636 relates to a method for the encapsulation of substances in silica-based capsules.
  • the method uses a polyalkoxysiloxane (PAOS), preferentially a polyalkylalkoxysiloxane (R-PAOS), which acts as a silica source and as an emulsifier.
  • PAOS polyalkoxysiloxane
  • R-PAOS polyalkylalkoxysiloxane
  • Alkenes, alkynes, esters, ethers, ketones, aldehydes, aromatic compounds, and polymers are mentioned as hydrophobic organic liquids which can ben encapsulated by the method.
  • a drawback of the known processes is that the control of the particle size of the capsules becomes increasingly difficult with increasing viscosity of the ingredient to be encapsulated.
  • the formation of small capsules having a high viscous encapsulated material is not possible with the known processes.
  • Capsules having a large particle size can detract from the properties of compositions or materials wherein the capsules are incorporated. In particular, large capsules impair the optical properties of compositions and materials wherein the capsules are incorporated.
  • capsules having a particle diameter exceeding the layer thickness of the coating prevent the formation of an even coating surface. It is therefore desirable to prepare capsules have a small particle size.
  • the invention provides a process of encapsulating a compound having a solubility in water of at most 10 g/l at 20°C, comprising the steps of a) Providing a silicon alkoxide based prepolymer modified with a polyalkylene oxide compound, b) Dissolving the compound having a solubility in water of at most 10 g/l at 20°C in a silicon alkoxide having an average of at least two alkoxide groups per molecule to form a non-aqueous solution of the compound, c) Combining an aqueous liquid with the modified prepolymer provided in step a) and the non-aqueous solution prepared in step b) to form an aqueous dispersion, and d) Stirring the aqueous dispersion formed in step c) to form an aqueous dispersion of capsules.
  • the process of the invention is suitable for encapsulation of materials of various viscosity, and the size of the capsules is independent of the viscosity of the encapsulated material.
  • the process does not rely on the use of external surfactants.
  • the process relates to encapsulating a compound having a solubility in water of at most 10 g/l at 20°C.
  • the compound to be encapsulated suitably has a solubility in water at 20 °C of less than 8 g/l, preferably less than 5 g/l, and most preferably less than 2 g/l.
  • the compounds to be encapsulated may be monomers, oligomers, or polymers. Suitable compounds to be encapsulated generally comprise carbon and hydrogen. In preferred embodiments, the compounds also comprise silicon, such as silicones or modified silicones.
  • the compound to be encapsulated may be a liquid or a solid.
  • the compound to be encapsulated is generally soluble in in a silicon alkoxide having an average of at least two alkoxide groups per molecule.
  • the compound to be encapsulated has a solubility in the silicon alkoxide having an average of at least two alkoxide groups per molecule of at least 50 g/l, preferably at least 100 g/l at a temperature of 20 °C. It is also possible to encapsulate a mixture of two or more compounds, provided that the individual compounds meet the above-mentioned solubility parameters.
  • Examples of compounds to be encapsulated include waxes, e.g. alkanes, esters of alkyl alcohols and alkyl carboxylic acids; alkenes; alkynes; esters; ethers; ketones; aldehydes; aromatic compounds; polymers, e.g. polydialkylsiloxanes or modified versions thereof; vitamins; biocides, oils; perfume oils.
  • the compounds to be encapsulated are oligomers or polymers suitable as additives in the polymer and paint industry, such as silicone- based surface additives, dispersing agents, or rheology control agents.
  • the compounds to be encapsulated further include a wax, in a particular a wax which is solid at a temperature below 30 °C, and which is a liquid at a temperature above 50 °C.
  • a wax in a particular a wax which is solid at a temperature below 30 °C, and which is a liquid at a temperature above 50 °C.
  • Such waxes help to immobilize other encapsulated compounds at ambient temperature in a solid matrix.
  • the encapsulated material When heated to a temperature above the melting point of the wax, the encapsulated material liquifies and release of the encapsulated material is accelerated. This may be useful to trigger the release of encapsulated compounds by heat, for example when the capsules of the invention are included in heat-curable coating compositions.
  • the compounds to be encapsulated further include a disintegrant.
  • Disintegrants are compounds and materials which expand or release gases on an elevation in temperature to a defined temperature range and thus build up the pressure required within the capsule to disintegrate the shell of the capsule. In order to build up a high pressure, it can be advantageous to use compounds which have a very low boiling point, or which participate in a chemical reaction or decomposition with release of gases in a defined temperature range. Such compounds are known to those skilled in the art. It can be advantageous to select the disintegrant so that the expansion, the chemical reaction, or decomposition thereof with release of gases takes place in the previously defined temperature range. As disintegrants, compounds are suitable which release nitrogen (N 2 ) or carbon dioxide (CO 2 ).
  • Suitable disintegrants include are sodium hydrogencarbonate, sodium carbonate, potassium carbonate, potassium hydrogencarbonate, azodicarbonamides, hydrazides, such as, for example, p-toluenesulphonyl hydrazide, carbazides, such as, for example, 4,4-oxy-bis(benzosulphohydrazide), and 2,2- toluylenesulphonyl semicarbazide, tetrazoles, such as, for example, 5-phenyltetrazole and/or citric acid derivatives.
  • hydrazides such as, for example, p-toluenesulphonyl hydrazide
  • carbazides such as, for example, 4,4-oxy-bis(benzosulphohydrazide)
  • 2,2- toluylenesulphonyl semicarbazide tetrazoles, such as, for example, 5-phenyltetrazole and/or citric acid derivatives.
  • the process is also suitable for encapsulating liquid compounds having a higher viscosity while maintaining control over the capsule size.
  • the compound to be encapsulated has a viscosity of at least 25 mPas at a temperature of 20 °C, measured at a shear rate of 300 s’ 1 , preferably at least 50 mPas, and most preferably at least 100 mPas, at least 200 mPas, or at least 300 mPas.
  • a viscosity of the compound to be encapsulated typically has a of at most 100000 mPas at a temperature of 20 °C, measured at a shear rate of 300 s' 1 .
  • the viscosity is suitably determined according to ASTM D4283 - 98(2015).
  • the mentioned viscosities relate to the individual components of the mixture.
  • a silicon alkoxide based prepolymer is provided which is modified with a polyalkylene oxide compound.
  • the silicon alkoxide based prepolymer is modified with a polyalkylene oxide compound by reaction with a polyalkylene oxide compound comprising at least one hydroxyl group, preferably with a polyalkylene oxide compound having one hydroxyl group.
  • the silicon alkoxide based prepolymer is a partially condensed product of tetraalkoxysilanes, or mixtures of tetraalkoxysilanes with alkyltrialkoxysilane and/or dialkyldialkyoxysilane.
  • suitable tetraalkoxysilanes are tetramethoxysilane, tetraethoxysilane, tetrapropxysilane, and tetrabutoxysilane. If so desired, tetraalkoxysillanes having more than one type of alkoxy group can be used, as well as mixtures of different types of tetraalkoxysilanes.
  • Suitable silicon alkoxide prepolymers are available commercially, for example polyethoxysilane with a silica content of 40 % by weight (trade designation Dynasylan® SILBOND® 40 from Evonik), polyethoxysilane with a silica content of 50 % by weight (trade designation Dynasylan® SILBOND® 50 from Evonik), and polymethoxysilane with a silica content of 51 % by weight (trade designation SiSiB® PC5411 from Power Chemical Corporation).
  • Suitable silicon alkoxide prepolymers can also be prepared by know methods, for example as described in the article by Moller et al. in Macromolecules, 2006, 39, pp. 1701-1708.
  • Suitable silicon alkoxide prepolymers generally have a number average molecular weight in the range of 500 to 20000.
  • the number average molecular weight can be determined by gel permeation chromatography in chloroform with evaporative light scattering detector calibrated using polystyrene standards).
  • Modification of the silicon alkoxide based prepolymer with a polyalkylene oxide compound can be carried out by a condensation reaction of the silicon alkoxide based prepolymer with a compound having at least one hydroxyl group. In this reaction a part of the alkoxide groups of the silicon alkoxide based prepolymer is replaced with a polyalkylene oxide group.
  • the reaction can be catalyzed by suitable catalysts, for example tetraalkoxytitanates.
  • modification of the silicon alkoxide based prepolymer can be carried out by a condensation reaction of the silicon alkoxide based prepolymer with a polyalkylene oxide compound which has at least one alkoxysilane group or at least one silanol group, and a terminal hydrocarbyl group, preferably a lower alkyl group having 1 to 4 carbon atoms.
  • a suitable modification compounds is methoxy(polyethyleneoxy)propyltrimethoxy- silane.
  • the advantage of using a using polyalkylene oxide compound which has at least one alkoxysilane group or at least one silanol group is that the polyalkylene oxide is linked to the silicon alkoxide based prepolymer via a non-hydrolyzable bond.
  • Suitable polyalkylene oxide groups are polyethylene oxide groups, polypropylene oxide groups, and polybutylene oxide groups, as well as mixtures thereof.
  • Preferred compounds are polyethylene oxide compounds having one hydroxyl group and a terminal lower alkyl group having 1 to 4 carbon atoms.
  • the polyalkylene oxide compound having at least one hydroxyl group generally have 4 to 30, preferably 5 to 20 alkylene oxide repeating units.
  • the polyalkylene oxide compound in the preparation process of the silicon alkoxide based prepolymer. This can be accomplished by including a polyalkylene oxide compound having at least one hydroxyl group or at least one alkyoxysilane group or at least one silanol group in the reaction mixture for forming the silicon alkoxide based prepolymer. It is also possible to use silicon alkoxides having one or two polyalkylene oxide groups linked to the silicon atom via a Si-O group.
  • the silicon alkoxide based prepolymer modified with a polyalkylene oxide compound generally contains polyalkylene oxide in an amount of 5 to 50 % by weight, preferably 20 to 30 % by weight, calculated on the weight of the modified silicon alkoxide based polymer.
  • step b) of the process of the invention the compound having a solubility in water of at most 10 g/l at 20°C is dissolved in a silicon alkoxide having an average of at least two alkoxide groups per molecule to form a non-aqueous solution of the compound.
  • the compound having a solubility in water of at most 10 g/l at 20°C is dissolved in the silicon alkoxide by suitable mixing processes, for example by stirring at ambient temperature, for example in a temperature range of 15 to 30 °C at atmospheric pressure. If so desired, the process of dissolving can be carried out at a higher or lower temperature.
  • the amount of the compound having a solubility in water of at most 10 g/l at 20°C is in the range of 5 to 80 % by weight, preferably 10 to 70 % by weight, calculated on the weight of the solution.
  • the solution prepared in step b) has a low viscosity, for example a viscosity in the range of 0.5 to 200.0 mPas, preferably 0.5 to 100 mPas, and most preferably 0.5 to 50 mPas, measured at a temperature of 20 °C and a shear rate of 300 s’ 1 .
  • the use of the solution prepared in step b) reduces the interfacial tension between the aqueous phase of step c) and the encapsulant. It is believed that this facilitates the formation of small capsules. It is furthermore believed that a relatively low viscosity of the solution prepared in step b) facilitates the formation of small capsules.
  • the silicon alkoxide has at least two alkoxide groups. In typical embodiments, the silicon alkoxide has three or four alkoxide groups.
  • the non-alkoxide groups linked to the silicon atom are typically alkyl groups, having 1 to 10 carbon atoms. Optionally, the alkyl groups may be substituted by functional groups, such as epoxide groups or amine groups.
  • the alkoxide groups are independently selected from C1 to C4 alkoxide groups.
  • Suitable silicon alkoxides are tetraalkoxysilanes, or mixtures of tetraalkoxysilanes with alkyltrialkoxysilane and/or dialkyldialkyoxysilane.
  • suitable tetraalkoxysilanes are tetramethoxysilane, tetraethoxysilane, tetrapropxysilane, and tetrabutoxysilane. If so desired, tetraalkoxysillanes having more than one type of alkoxy group can be used, as well as mixtures of different types of tetraalkoxysilanes.
  • step c) of the process of the invention an aqueous liquid is combined with the modified prepolymer provided in step a) and the non-aqueous solution prepared in step b) to form an aqueous dispersion.
  • the aqueous liquid comprises water in an amount of 90 % by weight or more.
  • a pH buffer may be present in the aqueous liquid to maintain a desired pH range.
  • the aqueous liquid consists essentially of water, more preferably de-ionized water.
  • the aqueous liquid is combined with the modified prepolymer provided in step a) and the nonaqueous solution prepared in step b).
  • the modified prepolymer provided in step a) and the non-aqueous solution prepared in step b) are added as separate feed streams to the aqueous liquid. They may be added sequentially in any suitable order, or simultaneously. If so desired, it is also possible to mix the modified prepolymer provided in step a) and the nonaqueous solution prepared in step b) prior to addition to the aqueous liquid.
  • the modified prepolymer provided in step a) is added to the aqueous liquid prior to addition of the non-aqueous solution prepared in step b).
  • the aqueous liquid is generally subjected to shear force, for example by stirring, to form an aqueous dispersion. It is particularly preferred add modified prepolymer provided in step a) to the aqueous liquid and to form an emulsion, prior to adding the non-aqueous solution prepared in step b).
  • the modified prepolymer provided in step a) is added to the aqueous liquid in an amount of 0.10 to 15.00 % by weight, preferably 0.50 to 10.00 % by weight, calculated on the weight of the aqueous liquid.
  • the amount of the non-aqueous solution prepared in step b) is added to the aqueous liquid in an amount of 0.05 to 15.00 % by weight, calculated on the weight of the aqueous liquid.
  • step d) of the process of the invention the aqueous dispersion formed in step c) is stirred to form an aqueous dispersion of capsules.
  • step d) of the process the alkoxysilane groups undergo a hydrolysis and condensation reaction to form Si-O-Si bonds.
  • step d) is carried out in a temperature range of 20 to 90 °C, preferably 20 to 80 °C, for a period of 0.5 to 36.0 hours, preferably 2.0 to 24 hours.
  • the pH value of the aqueous phase in step d) suitably is in the range of 7.0 to 13.0, preferably 8.0 to 11 .0.
  • the pH value can be adjusted to the desired level by the addition of acid or base, as is known to the person skilled in the art. If so desired, a buffer may be added to the aqueous phase to maintain the pH value at a desired level.
  • the capsules obtained by the process of the invention generally have an essentially spherical shape.
  • the capsules preferably have a d50 number average particle size in the range of 50 to 600 nm, preferably 60 to 500 nm, determined by dynamic light scattering.
  • the particle size is suitably determined according to ASTM E3247 - 20.
  • the silicon alkoxide based prepolymer modified with a polyalkylene oxide compound has selfemulsifying properties in water, presumably due to the presence of polyalkylene oxide groups. Therefore, it is generally not required to include additional surfactants to the aqueous phase in steps c) and d) of the process of the invention. Accordingly, it is preferred that surfactants are absent or substantially absent in step d) of the process.
  • step d) means that surfactants are either entirely absent in step d) of the process, or that surfactants are present in such a low amount that the properties of the capsules are not materially changed, compared to capsules that are prepared wherein in step d) surfactants are entirely absent.
  • surfactants are present in step d) in an amount of 0.0 to 0.3 % by weight, preferably 0.0 to 0.1 % by weight, calculated on the weight of the capsules.
  • Surfactants are compounds that lower the surface tension (or interfacial tension) between two liquids, between a gas and a liquid, or between a liquid and a solid.
  • Surfactants generally have a molecular weight below 500 g/mol. It is to be understood that for the surfactants to be absent the silicon alkoxide based prepolymer modified with a polyalkylene oxide is not considered to be a surfactant.
  • the capsules are obtained as an aqueous dispersion of capsules.
  • the capsules can be separated from the aqueous phase by known separation processes, such as centrifugation, filtration, or evaporation of water, such as spray drying, pervaporation through membranes or freeze drying.
  • one or more additives for specific purposes may be included in the aqueous dispersion of capsules.
  • suitable additives include biocides, rheology control agents, and dispersion stabilizers.
  • the capsules comprise 30 to 90 % by weight, preferably 40 to 80 % by weight, of the compound having a solubility in water of at most x g/l at 20°C, calculated on the weight of the capsules.
  • the invention further relates to the capsules obtainable by the process of the invention.
  • the invention also relates to the use of the capsules obtainable by the process of the invention for controlled release of a compound having a solubility in water of at most 10 g/l at 20°C.
  • Controlled release means that the compound is released from the capsule over a longer period of time, for example during days, weeks, or months.
  • the invention relates to a method of controlled release of a compound having a solubility in water of at most 10 g/l at 20°C, comprising providing the compound in the form of the capsules obtainable by the process of the invention.
  • the invention further relates to a composition comprising the capsules obtainable by the process of the invention in an amount of 0.1 to 20.0 % by weight, calculated on the weight of the composition, and at least one other functional ingredient.
  • functional ingredients are organic polymers, detergents, and skin moisturizers.
  • the composition may, for example, be formulated as a coating composition, a molding composition, a home care composition, or a personal care composition.
  • Said composition preferably contains the capsules of the invention in an amount of from 0.2 to 15.0 % by weight, preferably of from 0.3 to 12.0 % by weight, more preferably of from 0.5 to 10.0 % by weight, based in each case on the total weight of the composition.
  • compositions in particular of coating compositions, moulding compositions, home care compositions, and personal care compositions are not impaired by the amount of the inventive capsules present therein.
  • the presence or use of these capsules does not have a negative effect e.g. in respect of corrosion protection, gloss preservation, weather resistance and/or mechanical strength of the coatings obtained from these compositions.
  • the composition is liquid at ambient temperature, for example at a temperature of 20°C.
  • the organic polymer present in the composition is liquid.
  • the composition may be liquid at ambient temperature without the need of a liquid volatile diluent.
  • it may be required or desirable to render the composition liquid or to achieve a desired viscosity by including a volatile diluent.
  • the volatile diluent may be water or an organic solvent, or mixtures thereof.
  • the composition may be an aqueous composition or a non-aqueous composition.
  • the inventive compositions comprise at least one organic polymer. All customary organic polymers known to the skilled person are suitable as polymer component of the composition of the invention.
  • the organic polymer used in accordance with the invention may have crosslinkable functional groups. Any customary crosslinkable functional group known to the skilled person is contemplated here. More particularly the crosslinkable functional groups are selected from the group consisting of hydroxyl groups, amino groups, carboxylic acid groups, and unsaturated carbon double bonds, isocyanates, polyisocyanates, and epoxides such as ethylene oxides.
  • the organic polymer is preferably selected from the group consisting of epoxide resins, polyesters, wherein the polyesters may be unsaturated, vinyl ester-based resins, poly(meth)acrylates, polyurethanes, polyureas, polyamides, polystyrenes, polyethers, polycarbonates, polyisocyanates, and melamine formaldehyde resins. These polymers may be homopolymers or copolymers.
  • composition of the invention can be provided as a one-component system or as a two- component system.
  • the composition of the invention preferably comprises the organic polymer in an amount of 3 to 90 % by weight, preferably in an amount of 5 to 80 % by weight, more preferably in an amount of 10 to 75 % by weight, based on the total weight of the composition.
  • the composition of the invention may comprise one or more customarily employed additives as component.
  • additives are preferably selected from the group consisting of emulsifiers, flow control assistants, solubilizers, defoaming agents, stabilizing agents, preferably heat stabilizers, process stabilizers, and UV and/or light stabilizers, catalysts, waxes, flexibilizers, flame retardants, reactive diluents, adhesion promoters, organic and/or inorganic nanoparticles having a particle size ⁇ 100 nm, process aids, plasticizers, fillers, glass fibers, reinforcing agents, additional wetting agents and dispersants, light stabilizers, ageing inhibitors and mixtures of the aforesaid additives.
  • Said additive content of the composition of the invention may vary very widely depending on intended use.
  • the content, based on the total weight of the composition of the invention, is preferably 0.01 to 10.00 % by weight, more preferably 0.01 to 8.00 % by weight, very preferably 0.01 to 6.00 % by weight, especially preferably 0.01 to 4.00 % by weight, and particularly 0.01 to 2.00 % by weight, calculated on the total weight of the composition.
  • the inventive compositions may be used in pigmented or unpigmented form and may also comprise fillers such as calcium carbonate, aluminum hydroxide, reinforcing fibers such as glass fibers, carbon fibers and aramid fibers.
  • compositions of the invention may be applied to a large number of substrates, such as wood, paper, glass, ceramic, plaster, concrete and metal, for example.
  • substrates such as wood, paper, glass, ceramic, plaster, concrete and metal
  • the coatings may also be applied to primers, primer-surfacers or basecoats. Curing of the compositions depends on the particular type of crosslinking and may take place within a wide temperature range from, for example, -10° C to 250° C.
  • compositions are moulding compounds, they preferably comprise at least one polymer selected from the group consisting of alkyd resins, polyester resins, epoxy resins, polyurethane resins, unsaturated polyester resins, vinyl ester resins, polyethylene, polypropylene, polyamides, polyethylene terephthlate, PVC, polystyrene, polyacrylonitrile, polybutadiene, polyvinyl chloride or mixtures of these polymers or any copolymers thereof.
  • polymer selected from the group consisting of alkyd resins, polyester resins, epoxy resins, polyurethane resins, unsaturated polyester resins, vinyl ester resins, polyethylene, polypropylene, polyamides, polyethylene terephthlate, PVC, polystyrene, polyacrylonitrile, polybutadiene, polyvinyl chloride or mixtures of these polymers or any copolymers thereof.
  • PEOS is synthesized according to a protocol (Macromolecules, 2006, 39 (5), pp 1701-1708).
  • the mixture is heated to 135 °C under intensive stirring.
  • the ethanol produced is continuously distilled off. When no further ethanol passes, the reaction is stopped, and the product is dried for 1 h under high vacuum. A yellow oil is obtained.
  • Ti(OEt)4 is typically used as a catalyst in the transesterification. Since Ti(OEt)4 is also used in the production of PEOS, no addition of catalyst is necessary here.
  • 0.7 g of PEOS-PEG-10 compound was added to 80 g of distilled water at 25 °C and shaken to obtain a homogenous opaque mixture.
  • 0.7 g of PDMS 2000 polydimethylsiloxane having a viscosity of 2000 mPas at 25 °C
  • TEOS tetraethoxysilane
  • the pH was adjusted to 9 with aqueous ammonia.
  • the resulting capsules were centrifuged for 25 min at 11 .000 rpm.
  • the d50 number average particle size (dynamic light scattering, Zetasizer) of the resulting particles was 240 nm.
  • a reaction vessel was charged with 10 L distilled water at ambient conditions.
  • the stirrer was set to 1100 rpm and 150 g PEOS-PEG-10 was added.
  • the stirrer and the rotor were started, and instantly 500 g of a hydroxy-functional polydimethylsiloxane having a viscosity of 80 mPas at 20 °C and 250 g TEOS, which were previously mixed, was added.
  • the speed of the stirrer was kept at 1100 rpm, and the speed of the rotor at 5000 rpm. After 6.5 minutes the rotor was stopped, and the resulting white dispersion was transferred to a reaction vessel.
  • the pH was adjusted to 9 with ammonia and the whole mixture was stirred at 60 °C for 24 hours.
  • a milky white dispersion of capsules in water was obtained.
  • the d50 number average particle size (dynamic light scattering, Zetasizer) of the resulting particles was 350 nm.
  • PEOS-PEG-10 compound was added to 200 g of distilled water at 25 °C and shaken to obtain a homogenous opaque mixture.
  • 2.0 g of an aralkyl-modified polymethylalkylsiloxane having a viscosity of 700 mPas at 20 °C and 2.0 g of TEOS were thoroughly mixed and then added to the water.
  • the mixture was emulsified with an Ultra-Turrax® T25 at 18.000 rpm for 10 min.
  • the dispersion was then transferred to a round-flask and stirred vigorously on a magnetic stirrer at 70 °C for 24 h. After 30 min of the 24h, the pH was adjusted to 9 with aqueous ammonia.
  • the resulting capsules were centrifuged for 25 min at 11 .000 rpm.
  • the d50 number average particle size (dynamic light scattering, Zetasizer) of the resulting particles was 450 nm.
  • 1 .0 g of PEOS-PEG-10 compound was added to 80 g of distilled water at 25 °C and shaken to obtain a homogenous opaque mixture.
  • 1 .0 g of a hydroxy-functional polydimethylsiloxane having a viscosity of 288 mPas at 20 °C and 1 .0 g of TEOS were thoroughly mixed and then added to the water.
  • the mixture was emulsified with an Ultra-Turrax® T25 at 18.000 rpm for 10 min.
  • the dispersion was then transferred to a round-flask and stirred vigorously on a magnetic stirrer at 60 °C for 24 h.
  • the pH was adjusted to 9 with aqueous ammonia.
  • the resulting capsules were centrifuged for 25 min at 11 .000 rpm.
  • the d50 number average particle size (dynamic light scattering, Zetasizer) of the resulting particles was 310 nm.
  • 35 g of PEOS-PEG-10 compound was added to 900 g of distilled water at 25 °C and shaken to obtain a homogenous opaque mixture.
  • 30 g of PDMS 2000 (polydimethylsiloxane having a viscosity of 2000 mPas at 25 °C) and 20 g of TEOS were thoroughly mixed and then added to the water.
  • the mixture was emulsified with an IKA Magic Lab at 23.000 rpm for 5 min.
  • the dispersion was then transferred to a round-flask and stirred vigorously on a magnetic stirrer at 60 °C for 24 h.
  • the resulting capsules were centrifuged for 25 min at 11 .000 rpm.
  • the d50 number average particle size (dynamic light scattering, Zetasizer) of the resulting particles was 430 nm.
  • 10 g of PEOS-PEG-10 compound was added to 1000 g of distilled water at 25 °C and shaken to obtain a homogenous opaque mixture.
  • 10 g of PDMS 2000 (polydimethylsiloxane having a viscosity of 2000 mPas at 25 °C) and 10 g of TEOS were thoroughly mixed and then added to the water.
  • the mixture was emulsified with an IKA Magic Lab at 23.000 rpm until it reached 60 °C after 4 min. The dispersion was then transferred to a round-flask.
  • the pH was adjusted to 9 with aqueous ammonia, afterwards the dispersion was stirred vigorously on a magnetic stirrer at 60 °C for 24 h.
  • the resulting capsules were centrifuged for 25 min at 11 .000 rpm.
  • the d50 number average particle size (dynamic light scattering, Zetasizer) of the resulting particles was 370 nm.
  • 10 g of PEOS-PEG-10 compound was added to 1000 g of distilled water at 25 °C and shaken to obtain a homogenous opaque mixture.
  • 10 g of PDMS 100 (polydimethylsiloxane having a viscosity of 100 mPas at 25 °C) and 10 g of TEOS were thoroughly mixed and then added to the water.
  • the mixture was emulsified with an I KA Magic Lab at 23.000 rpm until it reached 60 °C after 4 min. The dispersion was then transferred to a round-flask.
  • the pH was adjusted to 9 with aqueous ammonia, afterwards the dispersion was stirred vigorously on a magnetic stirrer at 60 °C for 24 h.
  • the resulting capsules were centrifuged for 25 min at 11 .000 rpm.
  • the d50 number average particle size (dynamic light scattering, Zetasizer) of the resulting particles was 290 nm.
  • Octyl-PEOS-PEG-10 8% Octyl side chains
  • PDMS 100 polydimethylsiloxane having a viscosity of 100 mPas at 25 °C
  • TEOS a polydimethylsiloxane having a viscosity of 100 mPas at 25 °C
  • TEOS a polydimethylsiloxane having a viscosity of 100 mPas at 25 °C
  • 3 TEOS 3 g
  • the mixture was emulsified with an Ultra- Turrax® T25 at 18.000 rpm for 10 min.
  • the dispersion was then transferred to a round-flask.
  • the d50 number average particle size (dynamic light scattering, Zetasizer) of the resulting particles was 150 nm.
  • 0.2 g of PDMS-PEOS-PEG-10 (5.5% PDMS sidechains, 500 g/mol) compound was added to 200 g of distilled water at 25 °C and shaken to obtain a homogenous opaque mixture.
  • 0.5 g of a polymethylalkylsiloxane having a viscosity of 500 mPas at 20 °C and 0.5 g of TEOS were thoroughly mixed and then added to the water. The mixture was emulsified with an Ultrasonic tip for 10 min in a 1 s on 1s off mode. After 30s of dispersion, 0.25 g of PEOS are added. The dispersion is in total dispersed for 10 min.
  • the dispersion was transferred to a roundflask. After 30 min, the pH was adjusted to 9 with aqueous ammonia, afterwards the dispersion was stirred vigorously on a magnetic stirrer at 60 °C for 24 h. The resulting capsules were centrifuged for 25 min at 11 .000 rpm. The d50 number average particle size (dynamic light scattering, Zetasizer) of the resulting particles was 120 nm.
  • PDMS-PEOS-PEG-10 5.5% PDMS sidechains, 500 g/mol
  • PDMS-PEOS-PEG-10 5.5% PDMS sidechains, 500 g/mol
  • 0.5 g of an aralkyl-modified polymethylalkylsiloxane having a viscosity of 725 mPas at 20 °C and 0.5 g of TEOS were thoroughly mixed and then added to the water.
  • the mixture was emulsified with an Ultrasonic tip for 10 min in a 1 s on 1s off mode. After 30s of dispersion, 0.25 g of PEOS are added. The dispersion is in total dispersed for 10 min.
  • the dispersion was transferred to a round-flask. After 30 min, the pH was adjusted to 9 with aqueous ammonia, afterwards the dispersion was stirred vigorously on a magnetic stirrer at 60 °C for 24 h. The resulting capsules were centrifuged for 25 min at 11 .000 rpm. The d50 number average particle size (dynamic light scattering, Zetasizer) of the resulting particles was 150 nm.
  • 0.2 g of PDMS-PEOS-PEG-10 (5.5% PDMS sidechains, 500 g/mol) compound was added to 200 g of distilled water at 25 °C and shaken to obtain a homogenous opaque mixture.
  • 0.5 g of a polyether-modified polymethylalkylsiloxane having a viscosity of 300 mPas at 20 °C and 0.5 g of TEOS were thoroughly mixed and then added to the water. The mixture was emulsified with an Ultrasonic tip for 10 min in a 1 s on 1s off mode. After 30s of dispersion, 0.25 g of PEOS are added. The dispersion is in total dispersed for 10 min.
  • the dispersion was transferred to a round-flask. After 30 min, the pH was adjusted to 9 with aqueous ammonia, afterwards the dispersion was stirred vigorously on a magnetic stirrer at 60 °C for 24 h. The resulting capsules were centrifuged for 25 min at 11 .000 rpm. The d50 number average particle size (dynamic light scattering, Zetasizer) of the resulting particles was 150 nm.
  • Example 13 0.7 g of PEOS-PEG-10 compound was added to 80 g of distilled water at 25 °C and shaken to obtain a homogenous opaque mixture. 0.46 g of a polydimethylsiloxane having a viscosity of 10000 mPas at 25 °C and 0.93 g of TEOS were thoroughly mixed and then added to the water. The mixture was emulsified with an Ultra-Turrax® T25 at 18.000 rpm for 10 min. The dispersion was then transferred to a round-flask. After 30 min, the pH was adjusted to 9 with aqueous ammonia, afterwards the dispersion was stirred vigorously on a magnetic stirrer at 60 °C for 24 h. The resulting capsules were centrifuged for 25 min at 11.000 rpm. The d50 number average particle size (dynamic light scattering, Zetasizer) of the resulting particles was 300 nm.
  • PEOS-PEG-10 compound was added to 80 g of distilled water at 25 °C and shaken to obtain a homogenous opaque mixture.
  • 0.46 g of a polydimethylsiloxane having a viscosity of 30000 mPas at 25 °C and 0.93 g of TEOS were thoroughly mixed and then added to the water.
  • the mixture was emulsified with an Ultra-Turrax® T25 at 18.000 rpm for 10 min.
  • the dispersion was then transferred to a round-flask. After 30 min, the pH was adjusted to 9 with aqueous ammonia, afterwards the dispersion was stirred vigorously on a magnetic stirrer at 60 °C for 24 h.
  • the resulting capsules were centrifuged for 25 min at 11.000 rpm.
  • the d50 number average particle size (dynamic light scattering, Zetasizer) of the resulting particles was 300nm.
  • Tetraethoxysilane was mixed with 32 g acetic anhydride, 27.2 g Dynasylan 4148 ((EO) propyltrimethoxysilane) and 0.25 g titanium trimethylsiloxide under an argon atmosphere in a 250 mL three-neck round-bottom flask equipped with a mechanical stirrer and a dephlagmator connected with a distillation bridge.
  • the mixture was heated to 135 °C in a silicon oil bath under intensive stirring.
  • the resulting ethyl acetate was continuously distilled off. The supply of heat was continued until the distillation of ethyl acetate stopped. Afterwards, the product was cooled to room temperature and dried in a vacuum for 1 h. A yellowish oily liquid was obtained.
  • the product contains 14% PEG and 86% alkoxy functionality, PEG-14-PEOS.
  • Step b) 0.7 g of PEG-14-PEOS compound was added to 80 g of distilled water at 25 °C and shaken to obtain a homogenous opaque mixture.
  • 0.7 g of PDMS 2000 polydimethylsiloxane having a viscosity of 2000 mPas at 25 °C
  • 0.7 g of TEOS were thoroughly mixed and then added to the water.
  • the mixture was emulsified with an Ultra-Turrax® T25 at 18.000 rpm for 10 min.
  • the dispersion was then transferred to a round-flask and stirred vigorously on a magnetic stirrer at 60 °C for 24 h.
  • the pH was adjusted to 9 with aqueous ammonia.
  • the resulting capsules were centrifuged for 25 min at 11 .000 rpm.
  • the d50 number average particle size (dynamic light scattering, Zetasizer) of the resulting particles was 340 nm.
  • the following coating formulation was prepared.
  • Position 1 was placed in a polyethylene cup and stirred using a Dispermat® CV ( OOrpm, 3.6m/s with a 7cm diameter, toothed dissolver-disc). Positions 2 - 7 were added in the stated order. Position 8 and 9 were mixed in a separate cup and then added.
  • the resulting liquid coating formulation was stored overnight at room temperature. On the next day, the respective additive listed in the following table was incorporated in the coating formulation using a Dispermat® CV (3 minutes, 1865 rpm, 3.4m/s with a 3.5 cm diameter, toothed dissolver-disc).
  • a spiral blade was used to apply a 120pm coating (wet film thickness) on a glass substrate.
  • the film was dried for 20 minutes at room temperature and after that cured at 140°C for 25 minutes.
  • the coated panels were measured using an Altek 9505AER device. A 1 kg weight was drawn over the coated panels at a speed of 127 mm I min. and the required force was measured. The value obtained was multiplied by a factor of 0.01 to calculate the COF value. A low COF value corresponds accordingly to a low sliding resistance.
  • the contact angle measurements were carried out under controlled conditions (23°C, 65% relative humidity) using a contact angle measuring device from Kruss (model DSA 100 equipped with a camera) and fully deionized water. The contact angles were evaluated with a corresponding analysis software. Three measurements were performed for each sample. The indicated values are mean values.

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Abstract

L'invention concerne un procédé d'encapsulation d'un composé ayant une solubilité dans l'eau d'au plus 10 g/l à 20 °C. Ledit procédé comprend les étapes consistant à : a) fournir un prépolymère à base d'alcoxyde de silicium modifié avec un composé d'oxyde de polyalkylène ; b) dissoudre le composé ayant une solubilité dans l'eau d'au plus 10 g/l à 20 °C dans un alcoxyde de silicium ayant une moyenne d'au moins deux groupes alcoxyde par molécule pour former une solution non aqueuse du composé ; c) combiner un liquide aqueux avec le prépolymère modifié obtenu à l'étape a) et la solution non aqueuse préparée à l'étape b) pour former une dispersion aqueuse ; et d) agiter la dispersion aqueuse formée à l'étape c) pour former une dispersion aqueuse de capsules.
EP22812544.9A 2021-11-05 2022-10-27 Procédé d'encapsulation Pending EP4426477A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP21206736 2021-11-05
PCT/EP2022/080111 WO2023078783A1 (fr) 2021-11-05 2022-10-27 Procédé d'encapsulation

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Publication number Priority date Publication date Assignee Title
AU2007330996C1 (en) * 2006-12-12 2014-07-03 Sol-Gel Technologies Ltd. Formation of nanometric core-shell particles having a metal oxide shell
JP6054289B2 (ja) 2010-04-20 2016-12-27 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ 活性成分を含むカプセル
EP3124112A1 (fr) 2015-07-30 2017-02-01 DWI - Leibniz-Institut für Interaktive Materialien e.V. Procédé pour l'encapsulation de substances dans des capsules à base de silice et produits ainsi obtenus
WO2020077451A1 (fr) * 2018-10-16 2020-04-23 Silicycle Inc. Processus accordable pour préparer des capsules/sphères de silice et leur utilisation
CN113249973A (zh) * 2021-05-06 2021-08-13 天津孚信阳光科技有限公司 一种改性长效光致变色微胶囊及其制备方法

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