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EP3007815A1 - Procédé de production d'une dispersion de microcapsules contenant des microcapsules dotées d'un noyau hydrophile - Google Patents

Procédé de production d'une dispersion de microcapsules contenant des microcapsules dotées d'un noyau hydrophile

Info

Publication number
EP3007815A1
EP3007815A1 EP14726608.4A EP14726608A EP3007815A1 EP 3007815 A1 EP3007815 A1 EP 3007815A1 EP 14726608 A EP14726608 A EP 14726608A EP 3007815 A1 EP3007815 A1 EP 3007815A1
Authority
EP
European Patent Office
Prior art keywords
monomers
weight
ethylenically unsaturated
methacrylic acid
microcapsules
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.)
Withdrawn
Application number
EP14726608.4A
Other languages
German (de)
English (en)
Inventor
Regina Klein
Tina SCHRÖDER-GRIMONPONT
Patrick LEIBACH
Britta Katz
Peter Hahn
Achim PIESCH
Jutta BRUST
Joseph STRACKE
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
Priority to EP14726608.4A priority Critical patent/EP3007815A1/fr
Publication of EP3007815A1 publication Critical patent/EP3007815A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/10—Homopolymers or copolymers of methacrylic acid esters
    • C09D133/12—Homopolymers or copolymers of methyl methacrylate
    • 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
    • A01N25/02—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 containing liquids as carriers, diluents or solvents
    • A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/11—Encapsulated compositions
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • A61K8/8152—Homopolymers or copolymers of esters, e.g. (meth)acrylic acid esters; Compositions of derivatives of such polymers
    • 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
    • B01J13/06—Making microcapsules or microballoons by phase separation
    • B01J13/14—Polymerisation; cross-linking
    • B01J13/18—In situ polymerisation with all reactants being present in the same phase
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
    • C04B20/10—Coating or impregnating
    • C04B20/1018—Coating or impregnating with organic materials
    • C04B20/1029—Macromolecular compounds
    • C04B20/1033—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • C04B38/02—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by adding chemical blowing agents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
    • 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
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38672—Granulated or coated enzymes
    • 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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3942—Inorganic per-compounds
    • 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
    • C11D3/395—Bleaching agents
    • 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
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/0045—Polymers chosen for their physico-chemical characteristics
    • C04B2103/0058—Core-shell polymers

Definitions

  • the present invention relates to a process for producing a microcapsule dispersion comprising microcapsules comprising a hydrophilic capsule core and a capsule wall polymer, characterized in that a water-in-oil emulsion containing a hydrophobic diluent as the continuous phase and the hydrophilic capsular core material, a monomer composition and an amphiphilic Polymer and then the monomers are radically polymerized,
  • Methacrylic acid maleic acid, acrylic acid and / or methacrylic acid esters which carry hydroxyl and / or carboxy groups (monomers II),
  • 0 to 30 wt .-% of one or more other monomers (monomers IV) in each case based on the total weight of the monomers and the amphiphilic polymer is obtainable by free radical polymerization of a monomer composition comprising at least one ethylenically unsaturated hydrophilic monomer and at least one ethylenically unsaturated hydrophobic monomer.
  • the present invention relates to the microcapsules obtainable hereinafter and their use for the sustained release of active ingredients for construction, cosmetic, washing and cleaning or plant protection applications.
  • Microcapsules with a hydrophobic capsule core are known for numerous applications.
  • EP 457 154 teaches microcapsules containing a color former-containing core oil and walls obtained by polymerization of methacrylates in an oil-in-water emulsion.
  • EP 1 029 018 describes microcapsules with capsule wall polymers based on (meth) acrylates and a capsule core of lipophilic waxes as latent heat storage materials.
  • WO 201 1/064312 teaches microcapsules with crop protection active ingredients dissolved in a hydrophobic oil as the capsule core and likewise a (meth) acrylate-based capsule wall.
  • encapsulation processes are also known in which the two phases are reversed. These methods are also referred to as inverse microencapsulation.
  • DE 10120480 describes such an inverse encapsulation. It teaches microcapsules with a capsule core containing water-soluble substances and a capsule wall made of melamine / formaldehyde resins.
  • WO 03/015910 teaches microcapsules with a capsule core containing water-soluble substances and a capsule wall of polyureas.
  • EP-A-0 148 169 describes microcapsules having a water-soluble core and a polyurethane wall which are produced in a vegetable oil.
  • capsule core material besides herbicides, water-soluble dyes are mentioned, inter alia.
  • water-soluble dyes are mentioned, inter alia.
  • Capsule core which can be used, for example, as a pore-forming agent in building materials. It is also desirable in this way to protect acid whose release can be controlled as an accelerator for example, pressboard. The delayed release of water-soluble active substances for crop protection or cosmetic applications is also of interest.
  • the earlier PCT application PCT / EP2012 / 073932 teaches the preparation of microcapsules having a hydrophilic capsule core whose capsule wall is a copolymer of (meth) acrylates and hydrophilic (meth) acrylates having hydroxy and / or carboxy groups.
  • the water-in-oil emulsion is stabilized by means of an emulsifier mixture comprising a linear block copolymer having hydrophobic and hydrophilic structural units.
  • the object of the present invention was to develop a further process for the preparation of microcapsule dispersions containing aqueous solutions or else water in the capsule core.
  • the microcapsules according to the invention comprise a capsule core and a capsule wall.
  • the capsule core consists predominantly, to more than 90 wt .-%, of water or aqueous solutions.
  • the mean particle size D [4,3] of the microcapsules is 0.5 to 100 ⁇ m.
  • the average particle size of the capsules 0.5 to 75 ⁇ , preferably 0.5 to 50 ⁇ . In this case, preferably 90% of the particles have a particle size of less than twice the average particle size.
  • the weight ratio of capsule core to capsule wall is generally from 50:50 to 98: 2.
  • Preferred is a core / wall ratio of 70:30 to 95: 5.
  • a hydrophilic capsule core (capsule core material) is understood as meaning water and aqueous solutions of water-soluble compounds whose content is at least 10% by weight. a water-soluble compound.
  • the aqueous solutions are preferably at least 20% by weight of a water-soluble compound.
  • the water-soluble compounds are, for example, organic acids or their salts, inorganic acids, inorganic bases, inorganic acid salts such as sodium chloride or sodium nitrate, water-soluble dyes, agrochemicals such as dicamba ®, flavoring agents, pharmaceutical actives, fertilizers or cosmetic actives.
  • Water and aqueous solutions of organic acids such as acetic acid, formic acid, propionic acid and methanesulfonic acid, and / or their salts, inorganic acids such as phosphoric acid and hydrochloric acid, and / or salts of inorganic acids and sodium silicate are preferred as the hydrophilic capsular core material.
  • the capsules are impermeable or poorly permeable to the hydrophilic capsule core material. With heavily permeable capsules, controlled release of the hydrophilic capsular core material can be achieved.
  • the water contained in the capsule core is usually from isolated microcapsules, so released from the hydrophobic diluent microcapsules, evaporate over time. If in the context of this application of (meth) acrylates is mentioned, both the corresponding acrylates, ie the derivatives of acrylic acid, as well as the methacrylates, the derivatives of methacrylic acid, to understand.
  • the polymers of the capsule wall generally contain at least 30% by weight, preferably at least 35% by weight, in particular 40% by weight and in a particularly preferred form at least 50% by weight and generally at most 100% by weight. , preferably at most 95 wt .-%, in particular at most 90 wt .-% and in a particularly preferred form at most 85 wt .-% Ci-C24-alkyl esters of acrylic and / or methacrylic acid (monomers I) polymerized, based on the Total weight of the monomers.
  • the polymers of the capsule wall may preferably at least 10 wt .-%, preferably at least 15 wt .-%, preferably at least 20 wt .-% and generally at most up to 70 wt .-%, preferably at most 60 wt .-% of one or a plurality of monomers (II) selected from acrylic acid, methacrylic acid, maleic acid, acrylic acid esters which carry hydroxy and / or carboxy groups, and methacrylic acid esters which carry hydroxyl and / or carboxyl groups, based on the total weight of the monomers, in copolymerized form.
  • monomers (II) selected from acrylic acid, methacrylic acid, maleic acid, acrylic acid esters which carry hydroxy and / or carboxy groups, and methacrylic acid esters which carry hydroxyl and / or carboxyl groups, based on the total weight of the monomers, in copolymerized form.
  • the polymers may preferably at least 5 wt .-%, preferably at least
  • monomers II I ethylenic embedded in unsaturated amounts
  • monomers II I ethylenic embedded in unsaturated amounts
  • up to 30% by weight of other monomers IV which are different from the monomers I, II and III, may be present in the capsule wall in copolymerized form.
  • monomer compositions are used to form the capsule wall comprising, preferably consisting of at least 95 wt .-% of, in particular consisting of 100 wt .-% of
  • Suitable monomers I are C 1 -C 24 -alkyl esters of acrylic and / or methacrylic acid and the glycidyl esters of acrylic and / or methacrylic acid.
  • Preferred monomers I are methyl, ethyl, n-propyl and n-butyl acrylate and the corresponding methacrylates.
  • the methacrylates are preferred.
  • Particular preference is given to C 1 -C 4 -alkyl methacrylates, especially methyl methacrylate.
  • monomer I is methyl methacrylate and / or one or more C 2 -C 24 -alkyl esters of acrylic and / or methacrylic acid.
  • the monomer composition contains 30-80% by weight of methyl methacrylate.
  • Monomers II are selected from acrylic acid, methacrylic acid, maleic acid, acrylic esters which carry hydroxyl and / or carboxy groups and methacrylic acid esters which carry hydroxyl and / or carboxy groups. Preference is given to (meth) acrylic acid esters which carry at least one radical selected from among carboxylic acid and hydroxy radical.
  • the preferred (meth) acrylic acid esters are hydrophilic, that is, they have a water solubility of> 50g / l at 20 ° C and atmospheric pressure.
  • Preferred monomers II are methacrylic acid, hydroxyalkyl acrylates and hydroxyalkyl methacrylates, such as 2-hydroxyethyl acrylate and methacrylate, hexapropyl acrylate and methacrylate, hydroxybutyl acrylate and diethylene glycol monoacrylate.
  • Compounds having two or more ethylenically unsaturated radicals (monomers III) act as crosslinkers. Preference is given to using monomers having vinyl, allyl, acrylic or methacrylic groups.
  • Suitable monomers III having two ethylenically unsaturated radicals are, for example, divinylbenzene and divinylcyclohexane and preferably the diesters of diols with acrylic acid or methacrylic acid, furthermore the diallyl and divinyl ethers of these diols.
  • examples which may be mentioned are ethanedioldiacrylate, ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, diethylene glycol diacrylate, dipropylene glycol diacrylate, methallyl methacrylamide, allyl acrylate and allyl methacrylate.
  • Particularly preferred are propanediol, butanediol, pentanediol and hexanediol diacrylate and the corresponding methacrylates.
  • Preferred monomers II I having more than two, preferably three, four or more nonconjugated ethylenic double bonds are the esters of polyhydric alcohols with acrylic acid and / or methacrylic acid, furthermore the allyl and vinyl ethers of these polyhydric alcohols, trivinylbenzene and trivinylcyclohexane.
  • trimethylol and pentaerythritol may be mentioned as polyhydric alcohols.
  • pentaerythritol tetraacrylate is generally present in technical mixtures mixed with pentaerythritol triacrylate and smaller amounts of oligomerization products.
  • Suitable other monomers IV are monoethylenically unsaturated monomers which are different from the monomers I and I I, such as styrene, ⁇ -methylstyrene, ⁇ -methylstyrene, vinyl acetate, vinyl propionate and vinylpyridine.
  • water-soluble monomers IV such as acrylonitrile, methacrylamide, maleic anhydride, N-vinylpyrrolidone, and acrylamido-2-methylpropanesulfonic acid.
  • N-methylolacrylamide, N-methylolmethacrylamide, dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate may be mentioned in particular.
  • the monomer composition of the monomers I and I I and optionally the monomers I I I and optionally the monomers IV are preferred.
  • monomer compositions comprising, preferably at least 95 wt .-% consisting of, in particular to 100 wt .-% consisting of
  • the monomer composition consists of 55 to
  • the monomer composition of the monomers I and I II and optionally the monomers II and optionally the monomers IV are monomer compositions comprising, preferably at least 95 wt .-% consisting of, in particular to 100 wt .-% consisting of
  • the monomer composition consists of the monomers I, II and III and optionally the monomers IV.
  • monomer compositions comprising, preferably at least 95 wt .-% consisting of, in particular to 100 wt .-% consisting of
  • Monomer mixture of 30 to 50% by weight of monomers I, 15 to 40% by weight of monomers II, 20 to 50% by weight of monomers III and 0 to 30% by weight of monomers IV are preferably used to form the capsule wall polymer.
  • the microcapsules of the invention are obtainable by preparing a water-in-oil
  • the monomers of the monomer composition can be metered in as a mixture. However, it is equally possible to separate them, depending on their hydrophilicity and thus solubility in
  • the monomers II are preferably in mixture with dosed to the hydrophilic capsule core material.
  • the monomers I are preferably metered in admixture with the hydrophobic diluent.
  • the continuous phase of the emulsion contains the amphiphilic polymer in order to prevent the droplets or agglomeration of the particles formed from flowing together.
  • the water or aqueous solution is the discontinuous later disperse phase and the hydrophobic diluent is the continuous phase.
  • the stabilized droplets have a size which corresponds approximately to the size of the later microcapsules.
  • the wall formation takes place by polymerization of the monomers, which is started by addition of a radical starter.
  • hydrophobic diluent is understood below to mean diluents which have a solubility in water of ⁇ 1 g / l, preferably ⁇ 0.5 g / l at 20 ° C. and atmospheric pressure.
  • the hydrophobic diluent is selected from
  • Hydrocarbon oils such as paraffin oil, diisopropylnaphthalene, purcellin oil, perhydrosqualene and solutions of microcrystalline waxes in hydrocarbon oils,
  • Esters of saturated or unsaturated fatty acids such as alkyl myristates, e.g., i-propyl, butyl or cetyl myristate, hexadecyl stearate, ethyl or i-propyl palmitate and cetyl ricinolate.
  • Silicone oils such as dimethylpolysiloxane, methylphenylpolysiloxane and the silicone glycol copolymer,
  • Glycerol esterols are esters of saturated or unsaturated fatty acids with glycerol. Suitable are mono-, di- and triglycerides and their mixtures. Preference is given to fatty acid triglycerides. Examples of fatty acids which may be mentioned are C 6 -C 12 fatty acids, such as hexane, octane, decane and dodecanoic acid. Preferred glycerol ester oils are C 6 -C 12 fatty acid triglycerides, in particular octanoic and decanoic acid triglycerides, and also their mixtures. Such
  • Octanoylglycerid / Decanoylglycerid mixture is, for example Miglyol ® 812 from. Hüls.
  • hydrophobic diluents are low-boiling alkanes or alkane mixtures such as cyclohexane, naphtha, petroleum, Cio-Ci2-isoalkanes as they are commercially available as Isopar TM.
  • Diisopropylnaphthalene which is obtainable, for example, as KMC oil from RKS, is also particularly preferably used.
  • an amphiphilic polymer which is obtainable by radical polymerization is used a monomer composition comprising ethylenically unsaturated hydrophilic monomers and ethylenically unsaturated hydrophobic monomers.
  • the amphiphilic polymer preferably shows a statistical distribution of the monomer units.
  • the amphiphilic polymer preferably attaches to and stabilizes at the interface of the emulsion droplets because of its monomer composition containing both hydrophilic and hydrophobic moieties.
  • Suitable ethylenically unsaturated hydrophobic monomers V include long chain monomers having C 8 -C 20 alkyl radicals. Suitable examples are alkyl esters of C 8 -C 20 -alcohols, preferably C 12 -C 20 -alcohols, in particular C 16 -C 20 -alcohols, with ethylenically unsaturated carboxylic acids, in particular with ethylenically unsaturated C 3 -C 6 -carboxylic acids such as acrylic acid, methacrylic acid, fumaric acid, itaconic acid and aconitic.
  • Particularly preferred are octadecyl acrylate and octadecyl methacrylate.
  • Hydrophilic means in the context of ethylenically unsaturated hydrophilic monomers that they have a water solubility of> 50g / l at 20 ° C and atmospheric pressure.
  • Suitable ethylenically unsaturated hydrophilic monomers VI are ethylenically unsaturated monomers having acid groups and their salts, ethylenically unsaturated quaternary compounds, hydroxy (C 1 -C 4) -alkyl esters of ethylenically unsaturated acids, alkylaminoalkyl (meth) acrylates and alkylaminoalkyl (meth) acrylamides.
  • Acrylic acid, methacrylic acid, 2-acrylamide-2-methylpropanesulfonic acid, itaconic acid, maleic acid, fumaric acid may be mentioned by way of example as ethylenically unsaturated hydrophilic monomers having acid groups or salts of acid groups.
  • Ethylenically unsaturated quaternary compounds which may be mentioned are dimethylaminoethyl acrylate or methacrylates which are quaternized with methyl chloride.
  • Other suitable ethylenically unsaturated hydrophilic monomers are maleic anhydride and acrylamide.
  • amphiphilic polymer may contain in copolymerized form further comonomers (monomers VII) which are different from the monomers of groups V and VI.
  • Such ethylenically unsaturated comonomers can be chosen so as to modify the solubility of the amphiphilic polymer.
  • Suitable other monomers are nonionic monomers which optionally have C 1 -C 4 -alkyl radicals.
  • the other monomers are preferably selected from styrene, C 1 -C 4 -alkylstyrenes such as methylstyrene, vinyl esters of C 3 -C 6 -carboxylic acids such as vinyl acetate, vinyl halides, acrylonitrile, methacrylonitrile, ethylene, butylene, butadiene and other olefins, C 1 -C 4 -alkyl esters and Glycidyl esters of ethylenically unsaturated carboxylic acids.
  • C 1 -C 4 -alkyl esters and glycidyl esters of ethylenically unsaturated C 3 -C 6 -carboxylic acids such as acrylic acid, methacrylic acid, fumaric acid, itaconic acid and aconitic acid, for example methyl acrylate, methyl methacrylate, butyl acrylate or butyl methacrylate and glycidyl methacrylate.
  • the weight ratio of ethylenically unsaturated hydrophobic monomers / ethylenically unsaturated hydrophilic monomers is preferably 95/5 to 20/80, in particular 90/10 to 30/60.
  • the amphiphilic polymers preferably contain at least 20% by weight, particularly preferably at least 30% by weight, in particular 40% by weight and very particularly preferably at least 45% by weight and preferably at most 95% by weight, preferably at most 90 wt .-% of ethylenically unsaturated hydrophobic monomers V copolymerized, based on the total weight of the monomers.
  • the amphiphilic polymers contain in preferred form at least 5 wt .-%, particularly preferably at least 7 wt .-%, and most preferably at least 10 wt .-% and preferably at most 80 wt .-%, preferably at most 60 wt .-% and more preferably at most 50% by weight of ethylenically unsaturated hydrophilic monomers VI copolymerized, based on the total weight of the monomers.
  • amphiphilic polymers contain in preferred form at least 5 wt .-%, particularly preferably at least 7 wt .-%, in particular 10 wt .-% and preferably at most 55
  • Amphiphilic polymers which are obtainable by free-radical polymerization of a monomer composition comprising, preferably consisting of, are preferably used.
  • amphiphilic polymers which are obtainable by free-radical polymerization of a monomer composition comprising, preferably consisting of,
  • amphiphilic polymers which are obtainable by free-radical polymerization of a monomer composition comprising, preferably consisting of, 40 to 90% by weight of one or more alkyl esters of C 16 -20 alcohols with ethylenically unsaturated carboxylic acids,
  • styrene 0 to 40% by weight of one or more monomers selected from styrene, C 1 -C 4 -alkylstyrene, vinyl esters of C 3 -C 6 -carboxylic acids, vinyl halides, acrylonitrile, methacrylonitrile and methyl methacrylate,
  • amphiphilic polymers obtainable by free-radical polymerization of a monomer composition, preferably consisting of
  • amphiphilic polymers which are obtainable by free-radical polymerization of a monomer composition comprising, preferably consisting of,
  • the amphiphilic polymer generally has an average molecular weight M w (determined by gel permeation chromatography) of from 5000 to 500,000, preferably from> 10,000 to 400,000 and more preferably from 30,000 to 200,000.
  • amphiphilic polymers are preferably prepared by initially introducing the total amount of the monomers as a mixture and then carrying out the polymerization. Furthermore, it is possible under polymerization conditions discontinuously in one or more subsets or continuously in constant or changing flow rates to meter the monomers.
  • amphiphilic polymer for stabilizing the hydrophilic droplets before the reaction and the microcapsules after the reaction is influenced on the one hand by the amphiphilic polymer itself, on the other hand by the reaction temperature, the desired microcapsule size and by the wall materials, as well as the core composition. Simple series tests can easily determine the optimum amount required.
  • the amphiphilic polymer for preparing the emulsion in an amount of 0.01 to 15 wt -.%, Preferably 0.05 to 12 wt -.% And in particular 0.1 to 10 wt .-% based on the cap - applied (wall and core).
  • polymerization initiators it is possible to use all compounds which decompose into free radicals under the polymerization conditions, eg. As peroxides, hydroperoxides, persulfates, azo compounds and the so-called redox initiators.
  • mixtures of different polymerization initiators for. B. mixtures of hydrogen peroxide and sodium or potassium peroxodisulfate. Mixtures of hydrogen peroxide and sodium peroxodisulfate can be used in any proportion.
  • Suitable organic peroxides are, for example, acetylacetone peroxide, methyl ethyl ketone peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, tert-amyl perpivalate, tert-butyl perpivalate, tert-butyl perohexanoate, tert-butyl perisobutyrate, tert-butyl per-2-ethylhexanoate, tert Butyl perisononanoate, tert-butyl permaleate, tert-butyl perbenzoate, tert-butyl per-3,5,5-tri-methylhexanoate and tert-Amylperneodekanoat.
  • Suitable polymerization initiators are azo initiators, e.g. 2,2'-azobis (2-amidinopropane) dihydrochloride, 2,2'-azobis (N, N-dimethylene) isobutyramidine dihydrochloride, 2- (carbamoylazo) isobutyronitrile and 4,4'-azobis (4 -cyanovalerianklare).
  • azo initiators e.g. 2,2'-azobis (2-amidinopropane) dihydrochloride, 2,2'-azobis (N, N-dimethylene) isobutyramidine dihydrochloride, 2- (carbamoylazo) isobutyronitrile and 4,4'-azobis (4 -cyanovalerianklare).
  • azo initiators and peroxides as polymerization initiators is preferred.
  • the polymerization initiators mentioned are used in conventional amounts, for. B. in amounts of from 0.1 to 5, preferably 0.1 to 2.5 mol%, based on the monomers to be polymerized.
  • the dispersion of the core material is carried out in a known manner, depending on the size of the capsules to be prepared. For the preparation of large capsules, dispersing is accomplished using effective stirrers, especially anchor and MIG (cross-bar) agitators. Small capsules, especially if the size should be below 20 ⁇ m, require homogenizing or dispersing machines.
  • the capsule size can be determined by the number of revolutions of the dispersing device / homogenizer and / or by the concentration of the amphiphilic polymer or by its molecular weight, ie. H. controlled by the viscosity of the continuous phase within certain limits.
  • the size of the dispersed droplets decreases as the number of turns increases up to a limit of the number of laps.
  • dispersers are used at the start of capsule formation. For continuous flow devices, it is sometimes advantageous to send the emulsion through the shear field several times.
  • the polymerization is carried out at 20 to 100 ° C, preferably at 40 to 95 ° C. Conveniently, the polymerization is carried out at atmospheric pressure, but it is also possible at reduced or slightly elevated pressure z. B. at a polymerization above 100 ° C, work, that is about in the range of 0.5 to 5 bar.
  • microcapsule dispersions containing from 5 to 50% by weight of microcapsules can be prepared by the process according to the invention.
  • the microcapsules are single capsules.
  • suitable conditions in the dispersion capsules can be produced with an average particle size in the range of 0.5 to 100 ⁇ .
  • microcapsules directly as a microcapsule dispersion, as obtained by the above method. Furthermore, it may be advantageous to use the microcapsules as a solid.
  • the obtained microcapsules can be isolated by removing the hydrophobic solvent. This can be done for example by evaporation of the hydrophobic solvent or by suitable spray drying in an inert gas atmosphere.
  • the inventive method allows the production of microcapsules having a hydrophilic capsule core and a capsule wall of a polymer based on (meth) acrylic acid esters.
  • the capsules according to the invention can be used in a wide variety of fields.
  • microcapsules with a water core are suitable as pore formers for concrete.
  • Another application in building materials is the use of encapsulated water-soluble catalysts in binders.
  • Microcapsules with encapsulated inorganic or organic acids can be used advantageously as a drilling aid for example geothermal wells, since they allow release only at the borehole. Thus, they allow the increase of permeability in subterranean, carbonic petroleum and / or natural gas carrying and / or hydrothermal rock formations. Thus, these capsules can be used to dissolve carbonaceous and / or carbonate-containing impurities in the production of crude oil and / or natural gas or the energy obtained by hydrothermal geothermal, by a formulation containing inventive microcapsules with encapsulated inorganic or organic acids by at least a hole in the rock formation presses. Furthermore, encapsulated acids, which indeed allow a delayed or targeted release of the acid, are also suitable as catalysts for the production of pressboard boards.
  • microcapsule dispersion according to the invention with water-soluble bleaches or enzymes as core material makes it possible to use it as a constituent in detergents and cleaners, in particular in liquid formulations.
  • bleaching agents are generally based on organic and / or inorganic peroxygen compounds.
  • the present invention also relates to the use of the microcapsule dispersion in detergents for textiles and in detergents for non-textile surfaces.
  • Such detergents and cleaners may contain, in addition to the microcapsules of the invention, builders, surface-active surfactants, bleaches, bleach activators, water-miscible organic solvents, enzymes, sequestering agents, electrolytes, pH regulators and other auxiliaries, such as optical brighteners, graying inhibitors, foam regulators and dyes and fragrances contain.
  • active substances which are intended to be released in a controlled manner be they medicinally active substances, cosmetic active substances or crop protection active ingredients, can be prepared in such a way that, due to the impermeability of the capsule wall, they are released over a relatively long period of time.
  • the template was filled and heated to 85 ° C. Subsequently, feed 2 was started. After 5 minutes, feed 1 was started and both feeds were added in 2 hours. Then, the temperature was maintained at 85 ° C for 2 hours and then cooled to room temperature. A solution of the polymer in Isopar TM G having a solids content of 19.6% by weight was obtained.
  • amphilic polymer solutions were used, which were prepared in analogy to the amphiphilic polymer solution S1:
  • Amphiphilic polymer solution S2 polymer of 65 weight equivalent stearyl methacrylate
  • Amphiphilic Polymer Solution S3 Polymer of 88 parts by weight of stearyl methacrylate and 12 parts by weight of methacrylic acid in the form of a 31.0% by weight solution in Isopar TM G.
  • Amphiphilic polymer solution S4 Polymer based on 66.7 weight equivalent of stearyl methacrylate and 33.3 weight equivalent of methacrylic acid, in the form of a 22.2 weight percent solution in aliphatic hydrocarbons.
  • Amphiphilic polymer S5 polymer of stearyl methacrylate and methyl methacrylate, in the form of a 25% by weight solution in Isopar TM G.
  • Amphiphilic polymer S6 polymer of 39.5 weight equivalents of methyl methacrylate, 48.1 weight equivalents of stearyl methacrylate, 6.2 weight equivalents of methacrylic acid and 6.2 weight equivalents of acrylic acid, in the form of a 30.8 weight percent -% solution in Isopar G.
  • the molecular weight distribution of the amphiphilic polymer was determined by large-size exclusion chromatography (SEC).
  • SEC large-size exclusion chromatography
  • the elution curve was converted into the actual distribution curve using a polystyrene calibration curve (polystyrene standard (580 g / mol to 7 500 000 g / mol) from Polymer Laboratories GmbH) and calibration by means of hexylbenzene (162 g / mol).
  • the eluent was tetrahydrofuran added with 0.1% by weight trifluoroacetic acid.
  • the injection volume was 100 ⁇ _ with a flow of 1 mL / g.
  • the sample concentration was 2 mg / mL and the column temperature 35 ° C.
  • a set of 3 columns was used by Agilent Technologies:
  • the oil phase was initially charged and feeds 1 and 2 were added. It was emulsified for 40 minutes at 3500 rpm. Subsequently, feed 3 was added and heated to a temperature of 75 ° C. over a period of 10 minutes. The mixture was held at this temperature for one hour and then heated to 85 ° C. in 10 minutes and held at this temperature for a further 2 hours. Thereafter, the mixture was cooled to room temperature over the course of one hour, while feed 4 was added.
  • the wall thickness of the microcapsules was 20% by weight, based on the wall and core.
  • the solids content was
  • Example 2 225 g of water without sodium chloride were encapsulated analogously to Example 2.
  • An oil-based microcapsule dispersion having an average particle size of D [4,3] 78.3 ⁇ m was obtained.
  • the wall thickness of the microcapsules was 10 wt .-% based on wall and core.
  • the solids content was 35% by weight.
  • the oil phase was initially charged, feed 1 was added and the mixture was emulsified for 20 minutes at 3500 rpm. The mixture was then heated to 75 ° C and fed feed 2 in 2 hours and fed feed 3 in 2.5 hours. Thereafter, the temperature was maintained at 75 ° C for a further 60 minutes. An oil-based microcapsule dispersion having a solids content of 35.51% was obtained. Subsequently, the cyclohexane was distilled off and cooled to room temperature.
  • Example 6 was carried out analogously to Example 5 wherein 4.00 g of 1, 4-butanediol diacrylate were replaced by 4.00 g of pentaerythritol triacrylate.
  • Example 7
  • the oil phase was initially charged, feed 1 was added and the mixture was emulsified for 20 minutes at 3500 rpm. The mixture was then heated to 75 ° C and fed feed 2 in 2 hours and fed feed 3 in 2.5 hours. Thereafter, the temperature was maintained at 75 ° C for a further 60 minutes. An oil-based microcapsule dispersion having a solids content of 35.6% was obtained. Subsequently, the cyclohexane was distilled off and cooled to room temperature.
  • Basacid Blue 756 (BASF) (C.I. 42090 Acid Blue 9)
  • Example 4 The procedure was as in Example 4 with the difference that as emulsifier ® Tamol DN (anionic surfactant: sodium salt of condensation product of naphthalenesulfonic acid) verwen- it was.
  • the wall thickness of the microcapsules was 10 wt .-% based on wall and core.
  • the solids content was 35% by weight.
  • PETIA pentaerythritol triacrylate
  • the dye Basacid Blau 756 in the capsule core is only water-soluble and can not be detected in the continuous oil phase.
  • a calibration curve was prepared by preparing aqueous solutions of this dye of different concentration ⁇ (0.00051 g / L to 0.01303 g / L) and their extinction E at 630 nm using a UV / VIS spectrometer (UV1800 from Shimadzu). in 1 cm thick disposable cuvettes (polystyrene, VWR) were measured:

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Abstract

L'invention concerne un procédé de production d'une dispersion de microcapsules contenant des microcapsules qui comprennent un noyau hydrophile et un polymère de paroi. Ledit procédé est caractérisé en ce que l'on produit une émulsion eau dans huile contenant un diluant hydrophobe comme phase continue, le matériau de noyau hydrophile, une composition monomère et un polymère amphiphile, et en ce que le monomère est ensuite soumis à une polymérisation radicalaire. Ladite composition monomère comprend 30 à 100 % en poids d'un ou plusieurs monomères choisis parmi un ester d'alkyle C1 à C24 de l'acide acrylique et/ou méthacrylique (monomères I), 0 à 70 % en poids d'un ou plusieurs monomères choisis parmi l'acide acrylique, l'acide méthacrylique, l'acide maléique, des esters d'acide acrylique et/ou méthacrylique qui portent des groupes hydroxy et/ou carboxy (monomères II), 0 à 50 % en poids d'un ou plusieurs monomères qui comportent deux ou plusieurs radicaux éthyléniquement insaturés, (monomères III) et 0 à 30 % en poids d'un ou plusieurs autres monomères (monomères IV) respectivement par rapport au poids total des monomères; et le polymère amphiphile peut être obtenu par polymérisation radicalaire d'une composition monomère comprenant au moins un monomère hydrophile éthyléniquement insaturé et au moins un monomère hydrophobe éthyléniquement insaturé. L'invention concerne également les microcapsules pouvant être produites de cette façon et leur utilisation pour la libération retardée de substances actives dans des applications de construction, des produits cosmétiques, des produits de lavage et détergents ou pour des utilisations dans la protection phytosanitaire.
EP14726608.4A 2013-06-14 2014-05-27 Procédé de production d'une dispersion de microcapsules contenant des microcapsules dotées d'un noyau hydrophile Withdrawn EP3007815A1 (fr)

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EP13172032 2013-06-14
PCT/EP2014/060945 WO2014198531A1 (fr) 2013-06-14 2014-05-27 Procédé de production d'une dispersion de microcapsules contenant des microcapsules dotées d'un noyau hydrophile
EP14726608.4A EP3007815A1 (fr) 2013-06-14 2014-05-27 Procédé de production d'une dispersion de microcapsules contenant des microcapsules dotées d'un noyau hydrophile

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WO2018065481A1 (fr) 2016-10-07 2018-04-12 Basf Se Microparticules sphériques
WO2019193094A1 (fr) 2018-04-06 2019-10-10 Basf Se Microparticules sphériques
WO2021009040A1 (fr) 2019-07-12 2021-01-21 Basf Se Procédé de production de microparticules chargées d'un actif organique volatil
WO2022090460A1 (fr) 2020-10-30 2022-05-05 Basf Se Procédé de production de microparticules chargées d'un arôme chimique
WO2024038046A1 (fr) 2022-08-18 2024-02-22 Basf Se Procédé de production de microparticules
WO2024056309A1 (fr) 2022-09-15 2024-03-21 Basf Coatings Gmbh Compositions de matériaux de revêtement par électrodéposition comprenant des particules composites contenant un catalyseur contenant du métal
WO2024056308A1 (fr) 2022-09-15 2024-03-21 Basf Coatings Gmbh Compositions de matériau de revêtement par électrodéposition comprenant une suspension de pigment et des particules composites contenant un catalyseur contenant du métal

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JP6250211B1 (ja) * 2017-01-17 2017-12-20 森下仁丹株式会社 水含有カプセル、並びに水含有カプセルの製造方法
CN108395269B (zh) * 2017-02-08 2021-04-20 协兴建筑科技有限公司 水胶囊及其制备方法、轻质混凝土的制备方法及其结构
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EP3592792B1 (fr) 2017-03-09 2020-12-16 Construction Research & Technology GmbH Catalyseur de polyaddition micro-encapsulé
FR3064191B1 (fr) * 2017-03-21 2019-04-26 Calyxia Procede de preparation de capsules comprenant au moins une substance hydrosoluble ou hydrophile et capsules obtenues
USD844450S1 (en) 2017-07-12 2019-04-02 Korex Canada Company Detergent pouch
FR3075219B1 (fr) * 2017-12-14 2019-11-22 S.P.C.M. Sa Composition comprenant un (co)polymere hydrosoluble encapsule dans une enveloppe et son utilisation dans la recuperation assistee du petrole et du gaz
JP7080988B2 (ja) 2018-07-02 2022-06-06 エルジー ハウスホールド アンド ヘルスケア リミテッド マイクロカプセルの製造方法
WO2020009438A1 (fr) * 2018-07-02 2020-01-09 주식회사 엘지생활건강 Procédé de préparation de microcapsules
CN114423518A (zh) * 2019-09-30 2022-04-29 富士胶片株式会社 微胶囊、微胶囊的制造方法
CN115672213B (zh) * 2021-07-23 2025-05-06 中国科学院化学研究所 一种具有亲水/疏水叠层壳结构的微胶囊及其制备方法和应用
CN113801611B (zh) * 2021-10-29 2022-06-10 新元化学(山东)股份有限公司 工业化连续大规模生产无醛水性粘合剂的绿色安全环保工艺
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Cited By (8)

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Publication number Priority date Publication date Assignee Title
WO2018065481A1 (fr) 2016-10-07 2018-04-12 Basf Se Microparticules sphériques
US11491090B2 (en) 2016-10-07 2022-11-08 Basf Se Spherical microparticles with polyester walls
WO2019193094A1 (fr) 2018-04-06 2019-10-10 Basf Se Microparticules sphériques
WO2021009040A1 (fr) 2019-07-12 2021-01-21 Basf Se Procédé de production de microparticules chargées d'un actif organique volatil
WO2022090460A1 (fr) 2020-10-30 2022-05-05 Basf Se Procédé de production de microparticules chargées d'un arôme chimique
WO2024038046A1 (fr) 2022-08-18 2024-02-22 Basf Se Procédé de production de microparticules
WO2024056309A1 (fr) 2022-09-15 2024-03-21 Basf Coatings Gmbh Compositions de matériaux de revêtement par électrodéposition comprenant des particules composites contenant un catalyseur contenant du métal
WO2024056308A1 (fr) 2022-09-15 2024-03-21 Basf Coatings Gmbh Compositions de matériau de revêtement par électrodéposition comprenant une suspension de pigment et des particules composites contenant un catalyseur contenant du métal

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CN105451872A (zh) 2016-03-30
WO2014198531A1 (fr) 2014-12-18
RU2016100814A (ru) 2017-07-19
US20160145459A1 (en) 2016-05-26
KR20160019549A (ko) 2016-02-19

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