EP4351773A1 - Microcapsules dégradables de couleur neutre - Google Patents

Microcapsules dégradables de couleur neutre

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Publication number
EP4351773A1
EP4351773A1 EP22737736.3A EP22737736A EP4351773A1 EP 4351773 A1 EP4351773 A1 EP 4351773A1 EP 22737736 A EP22737736 A EP 22737736A EP 4351773 A1 EP4351773 A1 EP 4351773A1
Authority
EP
European Patent Office
Prior art keywords
weight
layer
barrier layer
hydrogen
stability
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
EP22737736.3A
Other languages
German (de)
English (en)
Inventor
Claudia Meier
Jeanette HILDEBRAND
Michael BIEDENBACH
Christian Kind
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.)
Koehler Innovation and Technology GmbH
Original Assignee
Koehler Innovation and Technology 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 Koehler Innovation and Technology GmbH filed Critical Koehler Innovation and Technology GmbH
Publication of EP4351773A1 publication Critical patent/EP4351773A1/fr
Pending legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/20—After-treatment of capsule walls, e.g. hardening
    • B01J13/206—Hardening; drying
    • 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
    • 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
    • A61K8/8158—Homopolymers or copolymers of amides or imides, e.g. (meth) acrylamide; Compositions of derivatives of such polymers
    • 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
    • A61K8/817—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 a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions or derivatives of such polymers, e.g. vinylimidazol, vinylcaprolactame, allylamines (Polyquaternium 6)
    • A61K8/8182—Copolymers of vinyl-pyrrolidones. Compositions of derivatives of such polymers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00—Medicinal preparations characterised by special physical form
    • A61K9/48—Preparations in capsules, e.g. of gelatin, of chocolate
    • A61K9/50—Microcapsules having a gas, liquid or semi-solid filling; Solid microparticles or pellets surrounded by a distinct coating layer, e.g. coated microspheres, coated drug crystals
    • A61K9/5005—Wall or coating material
    • A61K9/5021—Organic macromolecular compounds
    • A61K9/5026—Organic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polyvinyl pyrrolidone, poly(meth)acrylates
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/20—After-treatment of capsule walls, e.g. hardening
    • B01J13/22—Coating
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0097—Dye preparations of special physical nature; Tablets, films, extrusion, microcapsules, sheets, pads, bags with dyes
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B9/00—Essential oils; Perfumes
    • C11B9/0003—Compounds of unspecified constitution defined by the chemical reaction for their preparation
    • 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
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/378—(Co)polymerised monomers containing sulfur, e.g. sulfonate
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/50—Perfumes
    • C11D3/502—Protected perfumes
    • C11D3/505—Protected perfumes encapsulated or adsorbed on a carrier, e.g. zeolite or clay
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/10—General cosmetic use
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/41—Particular ingredients further characterized by their size
    • A61K2800/412—Microsized, i.e. having sizes between 0.1 and 100 microns
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • 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
    • A61K2800/52—Stabilizers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2425/00—Presence of styrenic polymer
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2433/00—Presence of (meth)acrylic polymer

Definitions

  • the invention relates to improved biodegradable microcapsules with environmentally friendly wall materials for use in areas of application with high demands on the tightness and stability of the microcapsules and their production process.
  • the invention also relates to microcapsule dispersions consisting of these microcapsules and having a specific coloring.
  • Microencapsulation is a versatile technology. It offers solutions for numerous innovations - from the paper industry to household products, microencapsulation increases the functionality of a wide variety of active substances. Encapsulated active ingredients can be used more economically and improve the sustainability and environmental compatibility of many products.
  • microcapsule walls based on the natural product gelatine and therefore completely biodegradable have long been used in carbonless paper.
  • a process for gelatine encapsulation that was developed as early as the 1950s is disclosed in US Pat. No. 2,800,457. Since then, a multitude of variations in terms of materials and procedural steps have been described.
  • biodegradable or enzymatically degradable microcapsule walls are used in order to use enzymatic degradation as a method for releasing the core material.
  • Such microcapsules are described, for example, in WO 2009/126742 A1 or WO 2015/014628 A1.
  • microcapsules are unsuitable for many industrial applications and household products. This is because microcapsules based on natural substances do not meet the requirements for diffusion tightness, chemical resistance and temperature resistance, for example for detergents and cleaning agents, adhesive systems, paints and dispersions, nor for the required core material loading. In these so-called high-demand areas, traditional organic polymers such as melamine-formaldehyde polymers (see, for example, EP 2 689 835 A1, WO 2018/114056 A1, WO 2014/016395 A1, WO 2011/075425 A1 or
  • WO 2011/120772 A1 polyacrylates (see e.g. WO 2014/032920 A1, WO 2010/79466 A2); polyamides; Polyurethane or polyureas (see e.g. WO 2014/036082 A2 or WO 2017/143174 A1) are used.
  • the capsules made from such organic polymers have the required diffusion tightness, stability and chemical resistance. However, these organic polymers are enzymatically or biologically degradable only to a very small extent.
  • WO 2014/044840 A1 describes a method for producing two-layer microcapsules with an inner polyurea layer and an outer layer containing gelatin.
  • the polyurea layer is produced by polyaddition on the inside of the gelatine layer obtained by coacervation.
  • the capsules obtained in this way have the necessary stability and tightness for use in detergents and cleaning agents due to the polyurea layer and, in addition, due to the gelatin they are sticky so that they can be attached to surfaces. Concrete stability and resistance are not mentioned.
  • a disadvantage of poly urea capsules is the unavoidable side reaction of the core materials with the diisocyanates used to produce the urea, which have to be added to the oil-based core.
  • microcapsules based on biopolymers are also described in the prior art, which, by adding a protective layer, achieve improved impermeability or stability with respect to environmental influences or a targeted setting of a delayed release behavior.
  • WO 2010/003762 A1 describes particles with a core-shell-shell structure.
  • the core of each particle is a poorly water-soluble or water-insoluble organic substance.
  • the shell directly encasing the core contains a biodegradable polymer and the outer shell contains at least one metal or semimetal oxide. With this structure, a biodegradable shell is obtained.
  • the microcapsules are nevertheless used in foods, cosmetics or pharmaceuticals, but cannot be used for the high-demand areas according to the invention due to a lack of tightness.
  • microcapsules with a multilayer structure of the shells which are essentially biodegradable and yet have sufficient stability and tightness to be able to be used in high-demand areas such as detergents and cleaning agents.
  • a stability layer makes up the main part of the capsule shell, which consists of naturally occurring and easily biodegradable materials, in particular such as gelatine or alginate or of materials that are ubiquitously present in nature.
  • This stability layer is combined with a barrier layer, which can consist of materials known for microencapsulation, such as melamine-formaldehyde or meth(acrylate). It has been possible to design the barrier layer with a previously unimaginable small wall thickness and still ensure adequate tightness. The proportion of the barrier layer in the overall wall is thus kept very low, so that the microcapsule wall has a biodegradability of at least 40%, measured according to OECD 301 F.
  • the present invention is based, inter alia, on the discovery that microcapsules with a multilayer shell structure consisting of a readily biodegradable stability layer and a thin barrier layer can be improved by using emulsion stabilizers after the inner barrier layer has been produced.
  • Emulsion stabilizers are regularly used to stabilize the core material emulsion.
  • a treatment of the surface of the core material enveloping barrier layer with an emulsion stabilizer, in particular a copolymer containing certain acrylic acid derivatives leads to improved deposition of the stability layer and thus to a greater average layer thickness of the stability layer (see Examples 2 to 4).
  • the invention relates to biodegradable microcapsules comprising a core material and a shell, the shell consisting of at least one barrier layer and a stability layer, the barrier layer surrounding the core material, the stability layer comprising at least one biopolymer, and on the outer surface the barrier layer is arranged, and wherein an emulsion stabilizer is arranged at the transition from the barrier layer to the stability layer.
  • the emulsion stabilizer according to the invention is a polymer or copolymer made from certain acrylic acid derivatives, N-vinylpyrrolidone; and/or styrene.
  • the invention relates to the use of an emulsion stabilizer to increase the amount of a stability layer that can be deposited on the surface of a barrier layer, the barrier layer and the stability layer forming the capsule wall of a microcapsule, the emulsion stabilizer preferably being a polymer or copolymer consisting of a or more monomers selected from:
  • Ri, R 2 and R 3 are selected from hydrogen and a Ci-4-alkyl group, where Ri and R 2 are in particular hydrogen and R 3 is in particular hydrogen or methyl; and F is -OX or -NR5R6, where X is hydrogen, an alkali metal, an ammonium group or a Ci- Ci8 -alkyl optionally substituted by -SO3M or -OH, where M is hydrogen, an alkali metal or ammonium, where which is optionally substituted by -SO3M or -OH Ci-Cis-alkyl is preferably methyl, ethyl, n-butyl, 2-ethylhexyl, 2-sulfoethyl or 3-sulfopropyl, where R5 and R6 independently represent hydrogen or an optionally substituted -SO3M substituted C1-C10 alkyl wherein at least one of R5 and R6 is not hydrogen, and preferably wherein R5 is H and R 6 is 2-methyl-propan-2-y
  • the emulsion stabilizer is preferably an acrylate copolymer containing 2-acrylamido-2-methylpropanesulfonic acid (AMPS).
  • AMPS 2-acrylamido-2-methylpropanesulfonic acid
  • a suitable copolymer is available, for example, under the trade name Dimension PA 140.
  • the barrier layer is made up of one or more components selected from the group consisting of an aldehyde component, an aromatic alcohol, an amine component, an acrylate component and an isocyanate component, and the stability layer comprises at least one biopolymer.
  • Another advantage is that the improved structural absorption of the stability layer by the barrier layer by adding the emulsion stabilizer ensures the structural (covalent) connection of all wall-forming components, so that the individual layers can be inseparably connected and viewed as a monopolymer.
  • the invention relates to a product containing microcapsules according to the first aspect, wherein the product is selected from the group consisting of an adhesive material system; a pharmaceutical product; a coating material, in particular a coated paper; a thermal storage coating, a self-healing coating, or a corrosion coating; and coatings for functional packaging materials containing such microcapsules.
  • the invention relates to the use of microcapsules according to the first aspect for the production of a product according to the third aspect.
  • the invention relates to a method for producing biodegradable microcapsules according to the first aspect, the method having the following steps: a) producing an oil-in-water emulsion by emulsifying a core material in an aqueous phase in the presence of the wall-forming Component(s) of the inner barrier layer with the addition of protective colloids; b) deposition and curing of the wall-forming component(s) of the barrier layer, the wall-forming component(s) of the barrier layer preferably being an aldehyde component, an amine component and an aromatic alcohol, particularly preferably formaldehyde, melamine and resorcinol; c) addition of an emulsion stabilizer and d) addition of the wall-forming component(s) of the stability layer, followed by deposition and curing, the wall-forming component(s) of the stability layer containing at least one biopolymer, preferably a protein and/or a polysaccharide, particularly preferably gelatin and alginate,
  • a further advantage of the microcapsules obtained with the production process described herein is the light coloration of the microcapsule dispersions.
  • the invention thus relates to a microcapsule dispersion containing biodegradable microcapsules according to the first aspect, these having a color locus with an L * value of at least 50 in the L * a * b * color space.
  • FIG. 1 shows a light micrograph of various microcapsule dispersions, each on the left, magnified 50 times and 500 times, taken with an Olympus BX 50 microscope.
  • FIG. 2 shows two microscopic photographs of the microcapsule dispersions Slurry 2 and MK1 with auxiliary lines for determining the thickness of the stability layer of the microcapsules and details of the measured thicknesses.
  • Slurry 2 and Slurry 3 shows a diagram of the course of the biological degradation according to OECD 301 F over 60 days after washing the microcapsule dispersions according to the invention and references.
  • Slurry 2 and Slurry 3 as well as the reference microcapsule dispersion MK1.
  • A) the degradation of Slurry 2 and Slurry 3 is shown as well as the degradation of ethylene glycol and walnut shell flour as positive controls.
  • B) Slurry 2 and Slurry 3 are shown in comparison with the MK1 reference capsule.
  • FIG. 4 shows a diagram of the storage stability of various microcapsule dispersions as described in Example 5.
  • FIG. 5 shows the diagram of the development of the L * a * b * of the microcapsule dispersions Slurry 3 and 3A over a period of 8 days.
  • Barrier layer refers to the layer of a microcapsule wall that is essentially responsible for the tightness of the capsule shell, i. H. Prevents the core material from escaping.
  • Biodegradability refers to the ability of organic chemicals to be broken down biologically, i.e. by living beings or their enzymes. In the ideal case, this chemical metabolism proceeds completely up to mineralization, but it can also stop in the case of transformation products that are stable in degradation.
  • the tests of the OECD test series 301 (A-F) demonstrate rapid and complete biodegradation (ready biodegradability) under aerobic conditions. Different test methods are available for readily or poorly soluble as well as for volatile substances.
  • the manometric respiration test (OECD 301 F) is used within the scope of the application.
  • the basic biological degradability inherent biodegradability
  • OECD 302 C the measurement standard OECD 302 C.
  • Biodegradable or “biodegradable” in the context of the present invention refers to microcapsule walls which have a biodegradability measured according to OECD 301 F of at least 40% within 60 days. From a limit of at least 60% degradation measured within 60 days after OECD 301 F microcapsule walls are also referred to as rapidly biodegradable.
  • a “biopolymer” is a naturally occurring polymer, such as a polymer found in a plant, fungus, bacterium, or animal.
  • the biopolymers also include modified polymers based on naturally occurring polymers.
  • the biopolymer can be obtained from the natural source or it can be artificially produced.
  • Tightness against a substance, gas, liquid, radiation or similar is a property of material structures. According to the invention, the terms “tightness” and “tightness” are used synonymously. Tightness is a relative term and always refers to given framework conditions.
  • Emmulsion stabilizer are additives used to stabilize emulsions.
  • the emulsion stabilizers can be added in small amounts to the aqueous or oily phase (of emulsions), whereby they are enriched in the interface in a phase-oriented manner and, on the one hand, facilitate the breakdown of the inner phase by further reducing the interfacial tension and, on the other hand, increase the breakdown resistance of the emulsion.
  • High-demand areas within the meaning of the invention are areas of application with high demands on the tightness and stability of the microcapsules.
  • (meth)acrylate designates both methacrylates and acrylates.
  • microcapsules is understood according to the invention as meaning particles containing an inner space or core which is filled with a solid, gelled, liquid or gaseous medium and surrounded (encapsulated) by a continuous shell (shell) of film-forming polymers. These particles preferably have small dimensions.
  • microcapsules core-shell capsules or simply “capsules” are used interchangeably.
  • Microencapsulation is a manufacturing process in which small and very small portions of solid, liquid or gaseous substances are surrounded by a shell made of polymer or inorganic wall materials. The microcapsules obtained in this way can have a diameter of a few millimeters to less than 1 ⁇ m.
  • the microcapsule according to the invention has a multi-layer “shell”.
  • the shell encasing the core material of the microcapsule is also regularly referred to as the “wall” or “shell”.
  • microcapsules according to the invention have a shell composed of several components with different functions. These components are gradually reacted and combined covalently as a whole by aldehyde crosslinking. In the context of describing the capsule structure, the components are referred to as individual layers or individual shells. "Multi-layered” and “multi-layered” are therefore used synonymously.
  • Stability layer refers to the layer of a capsule wall that is essentially responsible for the stability of the capsule shell, i. H. usually makes up the main part of the shell.
  • “Wall builders” are the components that make up the microcapsule wall.
  • the invention relates to biodegradable microcapsules comprising a core material and a shell, the shell consisting of at least one barrier layer and a stability layer, the barrier layer surrounding the core material, the stability layer comprising at least one biopolymer, and on the outer surface of the Barrier layer is arranged, and wherein an emulsion stabilizer is arranged at the transition from barrier layer to stability layer.
  • This arrangement can consist of an intermediate layer of emulsion stabilizer, which can be continuous or discontinuous, covering part or all of the inner barrier layer.
  • only individual molecules of the emulsion stabilizer on the surface of Barrier layer be arranged such that they mediate a bond between stability layer and barrier layer.
  • the emulsion stabilizer acts here as a mediator.
  • the microcapsule shells according to the invention have a significantly increased thickness of the stability layer due to the use of the emulsion stabilizer.
  • the proportion of natural components in the capsule is further increased compared to the multilayer microcapsules described above.
  • the surface of the barrier layer is brought into contact with the emulsion stabilizer before the stability layer is formed.
  • the capacity of the surface for the structural connection of the stability layer is increased.
  • the emulsion stabilizer attaches itself to the partially polar surface of the barrier layer, in particular a melamine-resorcinol-formaldehyde layer, and thus provides the biopolymers of the stability layer with both a framework and a sufficiently non-polar surface finish for the separation of the formed coacervate.
  • any emulsion stabilizer can be used as a mediator for the production of the microcapsules according to the invention.
  • the emulsion stabilizer is a polymer or copolymer consisting of one or more monomers selected from:
  • Ri, R 2 and R 3 are selected from hydrogen and a Ci- 4 alkyl group; and F is -OX or -NR5R6, where X is hydrogen, an alkali metal, an ammonium group or a Ci- Ci8 -alkyl optionally substituted by -SO3M or -OH, where M is hydrogen, an alkali metal or ammonium where R5 and R6 independently represent hydrogen or a C1-C10 alkyl optionally substituted by -SO 3 M, where at least one of R 5 and R 6 is not hydrogen,
  • Ci-4-hydroxyalkyl groups can be ethyl, n-propyl, i-propyl and n-butyl.
  • Ri and R 2 are hydrogen and R 3 is hydrogen or methyl.
  • R 3 is an acrylate (hydrogen) or methacrylate (methyl).
  • the C 1 -C 18 alkyl groups optionally substituted by -OH or -SO 3 M for X are preferably selected from methyl, ethyl, C 2-4 -hydroxyalkyl, C 2-4 -sulfoalkyl and C 4 - C18 alkyl groups.
  • the C2-4 hydroxyalkyl groups can be selected from ethyl, n-propyl, i-propyl and n-butyl.
  • Examples of unsubstituted C4-18 alkyl groups are n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, ethylhexyl, octyl, decyl, dodecyl or stearyl groups .
  • the n-butyl and ethylhexyl are particularly suitable.
  • the ethylhexyl is in particular 2-ethylhexyl.
  • 2-Sulfoethyl and 3-Sulfopropyl can be mentioned in particular as C.sub.2-4-Sulfoalkyl groups.
  • R 4 is -NR5R6 where R5 is H and R 6 is 2-methyl-propan-2-yl-1-sulfonic acid.
  • Ri , R 2 and R 3 are in particular hydrogen.
  • R 4 is -OX and X is hydrogen.
  • Ri , R 2 and R 3 are in particular hydrogen (acrylic acid).
  • R 3 is methyl (methacrylate).
  • R 4 is -OX and X is methyl.
  • Ri , R 2 and R 3 are in particular hydrogen (methyl acrylate).
  • R 4 is -OX and X is 2-ethylhexyl.
  • Ri , R 2 and R 3 are in particular hydrogen (ethyl hexacrylate).
  • F is -OX and X is n-butyl.
  • Ri , R 2 and R 3 are in particular hydrogen (n-butyl acrylate).
  • R 4 is -OX and X is 2-sulfoethyl.
  • Ri , R 2 and R 3 are in particular hydrogen (sulfoethyl acrylate).
  • R4 is - OX and X is 3-sulfopropyl.
  • Ri and R 2 are hydrogen and R 3 is methyl (sulfopropyl (meth)acrylate).
  • n is an integer of at least 3.
  • n can be greater than 5, 10, 20, 30, 40, 50, 60, 70, 80, or 100, for example. In one embodiment, n ranges from 5 to 5000. In one embodiment, n ranges from 10 to 1000.
  • the group of these polymers and copolymers represents a useful generalization of the copolymers present in Dimension PA 140.
  • the emulsion stabilizer is preferably an acrylate copolymer which contains at least two different monomers of the formula (I).
  • the copolymer contains AMPS, optionally in combination with (meth)acrylic acid and/or at least one alkyl (meth)acrylate.
  • the copolymer contains AMPS and one or more monomers selected from acrylate, methacrylate, methyl acrylate, ethyl hexacrylate, n-butyl acrylate, N-vinylpyrrolidone and styrene.
  • the copolymer contains AMPS, acrylate, methyl acrylate, and styrene. According to one embodiment, the copolymer contains AMPS, acrylate, methyl acrylate, and ethyl hexacrylate. According to one embodiment, the copolymer contains AMPS, methyl acrylate, N-vinylpyrrolidone and styrene. According to one embodiment, the copolymer contains AMPS, acrylate, methyl acrylate, and ethyl hexacrylate. According to one embodiment, the copolymer contains AMPS, methyl acrylate, N-vinylpyrrolidone and styrene.
  • the copolymer contains AMPS, methyl acrylate and styrene. According to one embodiment, the copolymer contains AMPS, methacrylate and styrene. According to one embodiment, the copolymer contains AMPS, acrylate, methyl acrylate, and n-butyl acrylate.
  • the emulsion stabilizer is a copolymer as defined in EP0562344B1, which is incorporated herein by reference.
  • the emulsion stabilizer is a copolymer containing a) AMPS, sulfoethyl or sulfopropyl (meth)acrylate or vinyl sulfonic acid, in particular in a proportion of 20 to 90%; b) a vinylically unsaturated acid, in particular with a proportion of 0 to 50%; c) methyl or ethyl acrylate or methacrylate, C2-4 hydroxyalkyl acrylate or N-vinylpyrrolidone, in particular in a proportion of 0 to 70% and d) styrene or C4-18 alkyl acrylate or C4-18 alkyl methacrylate, in particular in a proportion from 0.1 to 10%.
  • the emulsion stabilizer is a copolymer containing a) 2-acrylamido-2-methylpropanesulfonic acid, sulfoethyl or sulfopropyl (meth)acrylate or vinylsulfonic acid, in particular with a proportion of 40 to 75% b) acrylic acid or methacrylic acid, in particular with a proportion from 10 to 40% c) methyl or ethyl acrylate or methacrylate, C2-4-hydroxyalkyl acrylate or N-vinylpyrrolidone, in particular with a proportion of 10 to 50% and d) 0.5 to 5% styrene or C4-is -Alkyl acrylate or methacrylate, in particular with a proportion of 0.5 to 5%.
  • the emulsion stabilizer is a copolymer containing a) 40 to 75% of 2-acrylamido-2-methylpropanesulfonic acid, sulfoethyl or sulfopropyl (meth)acrylate or vinylsulfonic acid, in particular with a proportion of 40 to 75% b) acrylic acid or methacrylic acid, 10 to 30% c) methyl or ethyl acrylate or methacrylate or N-vinylpyrrolidone, in particular with a proportion of 10 to 50% and d) styrene or C4-is-alkyl acrylate or methacrylate, in particular with a proportion of 0 .5 to 5%.
  • the emulsion stabilizer does not consist of or include N-vinylpyrrolidone, polyvinylpyrrolidine homopolymer, or polyvinylpyrrolidine copolymer.
  • the proportion of the emulsion stabilizer used in the components used for the microencapsulation can be in the range from 0.1 to 15% by weight.
  • the proportion of the emulsion stabilizer used can be 0.1% by weight, 0.2% by weight, 0.5% by weight, 1% by weight, 2% by weight, 3% by weight, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt% -% can be 13%, 14% or 15% by weight.
  • the emulsion stabilizer is used with a proportion of the components used for the microencapsulation in the range from 0.25% by weight to 5% by weight. In a particularly preferred embodiment, the proportion of the emulsion stabilizer used is in the range from 0.5% by weight to 4% by weight.
  • the proportion of the emulsion stabilizer based on the total weight of the microcapsule wall is in the range from 0.5 to 15.0% by weight.
  • the proportion of the emulsion stabilizer used can be 0.5% by weight, 1.0% by weight, 1.5% by weight, 2.0% by weight, 2.5% by weight, 3% by weight -%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt% , 12% by weight, 13% by weight, 14% by weight or 15% by weight
  • the proportion of the wall-forming components of the microcapsule shell used is in the range from 1% by weight to 11% by weight.
  • the proportion of the emulsion stabilizer used is in the range from 2% by weight to 7% by weight.
  • the barrier layer preferably contains, as a wall former, one or more components selected from the group consisting of an aldehyde component, an aromatic alcohol, an amine component, an acrylate component. Production processes for producing microcapsules with these wall materials are known to those skilled in the art. A polymer selected from a polycondensation product of an aldehyde component with one or more aromatic alcohols and/or amine components can be used to produce the barrier layer.
  • the small wall thickness of the barrier layer can be achieved in particular with a melamine-formaldehyde layer containing aromatic alcohols or m-aminophenol. Consequently, the barrier layer preferably comprises an aldehyde component, an amine component and an aromatic alcohol.
  • amine-aldehyde compounds in the barrier layer in particular melamine-formaldehyde, has the advantage that these compounds form a hydrophilic surface with a high proportion of hydroxyl functionality, which thus ensures basic compatibility with the coacervation partners of the stability layer, such as biodegradable proteins.
  • Polysaccharides, chitosan, lignins and phosphazenes but also inorganic wall materials such as CaC03 and polysiloxanes.
  • polyacrylates in particular from the components styrene, vinyl compounds, methyl methacrylate, and 1, 4-butanediol acrylate, methacrylic acid, by initiation, for example, with t-butyl hydroperoxide in a free-radically induced polymerization
  • polyacrylates can be produced as a microcapsule wall that has a hydrophilic surface form a high proportion of hydroxy functionality, which are therefore just as compatible with the components of the stability layer according to the invention.
  • a wall former of the barrier layer is an aldehyde component.
  • the aldehyde component of the barrier layer is selected from the group consisting of formaldehyde, glutaraldehyde, succinaldehyde, furfural and glyoxal. Microcapsules have already been successfully produced with all of these aldehydes (see WO 2013 037 575 A1), so it can be assumed that capsules with a similar density as with formaldehyde are obtained with them.
  • the proportion of the aldehyde component for wall formation based on the total weight of the barrier layer should be in the range from 5% by weight to 50% by weight.
  • the proportion of the aldehyde component can be 5% by weight, 6% by weight, 7% by weight, 8% by weight, 9% by weight, 10% by weight or 15% by weight 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt% or 50 wt%. Outside these limits, it is considered that a sufficiently stable and dense thin film cannot be obtained.
  • the concentration of the aldehyde component in the barrier layer is preferably in the range from 10% by weight to 30% by weight.
  • the concentration of the aldehyde component in the barrier layer is particularly preferably in the range from 15% by weight to 20% by weight.
  • melamine, melamine derivatives and flarn material or combinations thereof come into consideration as the amine component in the barrier layer.
  • Suitable melamine derivatives are etherified melamine derivatives and methylolated melamine derivatives. Melamine in the methylolated form is preferred.
  • the amine components can be used, for example, in the form of alkylated mono- and polymethylol-flame precondensation products or partially methylolated mono- and polymethylol-1,3,5-triamono-2,4,6-triazine precondensation products such as Dimension SD® (from Solenis).
  • the amine component is melamine.
  • the amine component is a combination of melamine and flamboyant.
  • the aldehyde component and the amine component can be present in a molar ratio ranging from 1:5 to 3:1.
  • the molar ratio can be 1:5, 1:4.5, 1:4, 1:3.5, 1:3, 1:2.5, 1:2, 1:1.8, 1:1.6, 1:1.4, 1:1.35, 1;1.3, 1:1, 2, 1:1, 1.5:1, 2:1, 2.5:1, or 3:1.
  • the molar ratio is preferably in the range from 1:3 to 2:1.
  • the molar ratio of the aldehyde component and the amine component can particularly preferably be in the range from 1:2 to 1:1.
  • the aldehyde component and the amine component are generally used in a ratio of about 1:1.35.
  • This molar ratio allows a complete reaction of the two reactants and leads to a high tightness of the capsules.
  • aldehyde-amine capsule walls with a molar ratio of 1:2 are also known. These capsules have the advantage that the proportion of the highly crosslinking aldehyde, in particular formaldehyde, is very low. However, these capsules are less tight than the capsules with a ratio of 1:1.35. Capsules with a ratio of 2:1 have an increased tightness, but have the disadvantage that the aldehyde component is partly unreacted in the capsule wall and the slurry.
  • the proportion of the amine component(s) (e.g. melamine and/or urea) in the barrier layer is in the range from 20% by weight to 85% by weight, based on the total weight of the barrier layer.
  • the proportion of the amine component can be 20% by weight, 25% by weight, 30% by weight, 35% by weight, 40% by weight, 45% by weight, 50% by weight, 55 wt%, 60 wt%, 65 wt%, 70 wt%, 75 wt%, 80 wt% or 85 wt%.
  • the proportion of the amine component in the barrier layer, based on the total weight of the barrier layer is in the range from 40% by weight to 80% by weight.
  • the proportion of the amine component is particularly preferably in the range from 55 to 70% by weight.
  • the aromatic alcohol it is possible to greatly reduce the wall thickness of the barrier layer made up of the amine component and the aldehyde component in order to nevertheless obtain a layer which has the necessary tightness and is stable enough, at least in combination with the stability layer.
  • the aromatic alcohols give the wall increased tightness, since their highly hydrophobic aromatic structure makes it difficult for low-molecular substances to diffuse through.
  • particularly suitable aromatic alcohols are phloroglucinol, resorcinol or m-aminophenol.
  • the aromatic alcohol is selected from the group consisting of phloroglucinol, resorcinol and aminophenol.
  • the aromatic alcohol is used in a molar ratio to the aldehyde component in the range from (alcohol:aldehyde) 1:1 to 1:20, preferably in the range from 1:2 to 1:10.
  • the proportion of the aromatic alcohol in the barrier layer is in the range from 1.0% by weight to 20% by weight.
  • the proportion of the aromatic alcohol can be 1.5% by weight, 2.0% by weight, 2.5% by weight, 3.0% by weight, 4.0% by weight, 5.0 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt% 13 wt% %, 14%, 15%, 16%, 17%, 18%, 19% or 20% by weight. Due to their aromatic structure, the aromatic alcohols give the capsule wall a color that increases with the proportion of aromatic alcohol. Such coloring is undesirable in a number of applications.
  • the aromatic alcohols are susceptible to oxidation, which leads to a change in color over time. As a result, the undesired coloration of the microcapsules can hardly be compensated for with a dye. For this reason, the aromatic alcohols should not be used above 20.0% by weight. Below 1.0% by weight, no effect on the tightness can be detected.
  • the proportion of the aromatic alcohol in the barrier layer is in the range from 5.0% by weight to 15.0% by weight. Up to a percentage of 15.0% by weight, coloration is tolerable in most applications.
  • the proportion of the aromatic alcohol in the barrier layer is in the range from 6% by weight to 16.0% by weight. In particular, the proportion of the aromatic alcohol in the barrier layer is in the range from 10% by weight to 14.0% by weight.
  • the aldehyde component of the barrier layer can be used together with an aromatic alcohol such as resorcinol, phloroglucinol or m-aminophenol as the wall-forming component(s), i.e. without the amine component(s).
  • an aromatic alcohol such as resorcinol, phloroglucinol or m-aminophenol
  • the barrier layer contains melamine, formaldehyde and resorcinol. In one embodiment, the barrier layer contains the microcapsules melamine, urea, formaldehyde and resorcinol. In a preferred embodiment, the barrier layer contains melamine in the range from 25 to 40% by weight, formaldehyde in the range from 15 to 20% by weight and resorcinol in the range from 10 to 14% by weight and optionally urea in the range from 25 to 35% by weight. The proportions relate to the amounts used to form the wall of the layer and are based on the total weight of the barrier layer without protective colloid.
  • an emulsion stabilizer is preferably used as a protective colloid to encapsulate the core material with the barrier layer composed of an aldehyde component, an amine component and an aromatic alcohol.
  • the emulsion stabilizer used as protective colloid can be a polymer or copolymer as defined above as a mediating agent.
  • the protective colloid is a copolymer AMPS) Dimension® PA 140, from Solenis ) or its salts. In one embodiment, the same copolymer is used as the protective colloid and as the mediator.
  • melamine, melamine derivatives and urea or combinations thereof come into consideration as the amine component in the barrier layer.
  • Suitable melamine derivatives are etherified melamine derivatives and methylolated melamine derivatives. Melamine in the methylolated form is preferred.
  • the amine components can be used, for example, in the form of alkylated mono- and polymethylol-urea precondensation products or partially methylolated mono- and polymethylol-1,3,5-triamono-2,4,6-triazine precondensation products such as Dimension SD® (from Solenis).
  • the amine component is melamine.
  • the amine component is a combination of melamine and urea.
  • the stability layer forms the main component of the microcapsule shell and thus ensures high biodegradability according to OECD 301 F of at least 40% within 60 days.
  • Biopolymers suitable as wall formers for the stability layer are proteins such as gelatin, whey protein, plant storage protein; Polysaccharides such as alginate, gum arabic modified gum, chitin, dextran, dextrin, pectin, cellulose, modified cellulose, hemicellulose, starch or modified starch; phenolic macromolecules such as lignin; polyglucosamines such as chitosan, polyvinyl esters such as polyvinyl alcohols and polyvinyl acetate; Phosphazenes and polyesters such as polylactide or polyhydroxyalkanoate.
  • the biopolymers can be selected appropriately for the respective application in order to form a stable multi-layer shell with the material of the stability layer.
  • the biopolymers can be selected in order to achieve compatibility with the chemical conditions of the area of application.
  • the biopolymers can be combined in any way in order to influence the biodegradability or, for example, the stability and chemical resistance of the microcapsule.
  • the shell of the microcapsules has a biodegradability of 50% according to OECD 301F. In another embodiment, the shell of the microcapsule has a biodegradability of at least 60% (OECD 301F). In another embodiment, the biodegradability is at least 70% (OECD 301 F). The biodegradability is measured over a period of 60 days. In the extended degradation process ("enhanced ready biodegredation"), the biodegradability is measured over a period of 60 days (see Opinion on an Annex XV dossier proposing restrictions on intentionally-added microplastics of June 11, 2020 ECHA/RAC/RES-0-0000006790- 71-01/F).
  • the microcapsules are preferably freed from residues by washing before the biodegradability is determined.
  • replica microcapsules for this test are made with an inert, non-biodegradable core material such as perfluorooctane (PFO) in place of the perfume oil.
  • PFO perfluorooctane
  • the capsule dispersion is prepared by centrifuging three times and redispersing in dist. water washed. For this, the sample is centrifuged (eg for 10 min at 12,000 rpm). After sucking off the clear supernatant, it is filled up with water and the sediment is redispersed by shaking.
  • microcapsule according to the invention shows a similar, preferably better, biodegradability over a period of 28 or 60 days than the walnut shell flour.
  • Residues in the microcapsule dispersions are substances that are used in the manufacture of the microcapsules and have a non-covalent interaction with the shell, such as deposition aids, preservatives, emulsifiers/protective colloids, excess ingredients. These residues have a proven impact on the biodegradability of microcapsule dispersions. For this reason, washing is necessary before determining biodegradability.
  • the capsules were packed using the method described in Gasparini et al. Quantification method described in 2020 based on Py-GC-MS for polymer-encapsulated fragrances (Gasparini G, Semaoui S, Augugliaro J, Beschung A, Berthier D, Seyfried M, Begnaud F. Quantification of Residual Perfume by Py-GC-MS in Fragrance Encapsulate Polymerie Materials Intended for Biodegradation Tests Molecules 2020;25(3):718.).
  • This method incorporates a multi-step purification protocol for polymers from complex samples such as microcapsule dispersions and enables quantification of residual volatile components suspected to be non-covalently bound into the 3D polymer network and therefore amenable to other standard methods (e.g. SPME-GC -MS or TGA) are not quantifiable.
  • other standard methods e.g. SPME-GC -MS or TGA
  • individual layers of the microcapsule according to the invention in particular the barrier layer and the stability layer, can be inseparably connected and regarded as a monopolymer. It can be assumed that adding the emulsion stabilizer not only improves the structural absorption of the stability layer by the barrier layer, but also increases the structural (covalent) connection of all wall-forming components.
  • a high biodegradability value according to the invention is achieved on the one hand by the wall-forming agents used and on the other hand by the structure of the shell according to the invention. Because the use of a certain percentage of biopolymers does not automatically lead to a corresponding biodegradability value. This depends on how the biopolymers are present in the shell.
  • the stability layer contains gelatin as a biopolymer.
  • the stability layer contains alginate as a biopolymer.
  • the stability layer contains gelatin and alginate as biopolymers.
  • both gelatin and alginate are suitable for the production of microcapsules according to the invention with high biodegradability and high stability.
  • an emulsion stabilizer in particular a copolymer containing AMPS, leads to a strong increase in the layer thickness of the stability layer (see Examples 1-4).
  • Other suitable combinations of natural components in the stability layer are gelatin and gum arabic.
  • the stability layer contains one or more curing agents.
  • Curing agents according to the invention are aldehydes such as glutaraldehyde, formaldehyde and glyoxal and tannins, enzymes such as transglutaminase and organic anhydrides such as maleic anhydride, epoxy compounds, polyvalent metal cations, amines, polyphenols, maleimides, sulfides, phenol oxides, hydrazides, isocyanates, isothiocyanates, N-hydroxysulfosuccinimide derivatives, carbodiimide - Derivatives, and polyols.
  • the curing agent is preferably glutaraldehyde because of its very good crosslinking properties.
  • the curing agent glyoxal is preferred because of its good crosslinking properties and, compared to glutaraldehyde, lower toxicological classification. Through the use of hardening agents, a higher tightness of the stability layer is achieved. However, curing agents lead to reduced biodegradability of the natural polymers.
  • the barrier layers do not contain any isocyanates. Some isocyanates such as methylenediphenyl isocyanate (MDI), hexamethylene diisocyanate (HDI), toluene-2,4-diisocyanate (TDI) have a certain toxicity and should be viewed critically from the point of view of occupational safety. Furthermore, side reactions with components of the core material can also occur with isocyanates.
  • the barrier layers according to the invention contain no silane monomers, silane oligomers or silicates.
  • these components can be disadvantageous for the formation of the capsule according to the invention.
  • silicates such as TEOS and TMOS (tetraethyl orthosilicate or methyl orthosilicate) enter into side reactions with its components, for example fragrances, when added to an oil phase and thus have a negative effect on the properties of the oil phase, i.e. the core material, for example (fragrance oil). .
  • TEOS and TMOS are to be classified as critical for reasons of occupational safety due to their high flammability and toxicity and are preferably not used according to the invention.
  • the barrier layers do not contain a silicone-melamine-polyurethane copolymer.
  • Side reactions with the core material, i.e. the oil phase, in particular the fragrances contained therein, can also occur with silicone-melamine-polyurethane copolymers.
  • a silicone-melamine-polyurethane copolymer is to be classified as critical with regard to occupational safety.
  • the proportion of the hardening agent in the stability layer is less than 25% by weight.
  • the proportions of the components of the layers relate to the total weight of the layer, i.e. the total dry weight of the components used for the preparation, without taking into account the components used in the preparation that are not or only slightly incorporated into the layer, such as surfactants and protective colloids. Above this value the biodegradability according to the invention according to OECD 301 F cannot be guaranteed.
  • the proportion of the curing agent in the stability layer can be, for example, 1.0% by weight, 2.0% by weight, 3.0% by weight, 4.0% by weight, 5.0% by weight, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt% %, 15 wt%, 16 wt%, 17 wt%, 18 wt%, 19 wt%, 20 wt%, 21 wt%, 22 wt%, 23% or 24% by weight.
  • the proportion of the curing agent in the stability layer is preferably in the range from 1 to 15% by weight.
  • This proportion leads to effective cross-linking of the gelatine and, in a quantitative reaction, results in as little residual monomer as possible being formed.
  • the range from 4 to 12% by weight is particularly preferred, it ensures the required degree of crosslinking and a stable coating of the barrier layer in order to buffer the otherwise sensitive barrier layer and has only a small amount of residual aldehyde, which can be removed in a downstream alkaline adjustment of the slurry via an aldol reaction is dismantled.
  • the stability layer contains gelatin and glutaraldehyde. According to a further embodiment, the stability layer contains gelatin, alginate and glutaraldehyde. In an additional embodiment, the stability layer contains gelatin and glyoxal. According to another embodiment, the stability layer contains gelatin, alginate and glyoxal.
  • the exact chemical composition of the stability layer is not critical. However, the effect according to the invention is preferably achieved with polar biopolymers.
  • the use of the emulsion stabilizer according to the invention on the surface of the barrier layer significantly increases the average thickness of the stability layer.
  • the mean thickness of the stability layer is at least 1 ⁇ m.
  • the average thickness of the stability layer can be 1 ⁇ m, 1.2 ⁇ m, 1.4 ⁇ m, 1.6 ⁇ m, 1.8 ⁇ m, 2 ⁇ m, 2.2 ⁇ m, 2.4 ⁇ m, 2.6 ⁇ m, 2.8 ⁇ m , 3pm, 3.5pm, 4pm, 4.5pm, 5pm, 5.5pm, 6pm, 6.5pm, 7pm, 7.5pm, 8pm, 8.5pm, 9 pm, 9.5 pm, or 10 pm.
  • the stability layer often has an elliptical shape in cross section, so the thickness of the stability layer varies across the microcapsule surface. Therefore, an average thickness of the microcapsules is calculated. Above this, the deposition varies from microcapsule to microcapsule. This is taken into account by determining the average thickness of a plurality of microcapsules and calculating the average from this. Thus, strictly speaking, the average thickness mentioned here is an average average Thickness.
  • the layer thickness of the stability layer can be determined in two ways. First of all, the light microscopic approach should be mentioned here, i.e. the direct, optical measurement of the observed layer thickness using a microscope and appropriate software. A large number of microcapsules of a dispersion are measured and, due to the variance within the capsules, at least the diameter of each individual microcapsule.
  • a second possibility is the measurement of the particle size distribution by means of laser diffraction.
  • the modal value of a particle size distribution without the layer to be measured can be compared to the modal value of a particle size distribution with the layer to be measured.
  • the increase in this mode reflects the increase in the hydrodynamic diameter of the main fraction of microcapsules measured. Forming the difference from the two measured modal values ultimately results in twice the layer thickness of the layer.
  • the average thickness of the stability layer is at least 2 ⁇ m.
  • stability layers with an average ceiling of 6 ⁇ m or more can be formed.
  • the mean thickness of the stability layer is at least 3 ⁇ m.
  • the microcapsules according to the invention are very tight. According to one embodiment, the microcapsules are tight enough to ensure that no more than 50% by weight of the core material used escapes after storage for a period of 4 weeks at a temperature of 0 to 40.degree. This makes the capsules suitable for use in high-demand areas.
  • the microcapsules according to the invention have a tightness that ensures that at most 80% by weight of the core material used escapes after storage for a period of 12 weeks at a temperature of 0 to 40° C., preferably at most 75% by weight and more preferably at most 70% by weight.
  • the microcapsules according to the invention contain after storage over a period of time of 12 weeks at a temperature of 0 to 40° C., ie at least 20% by weight, preferably at least 25% by weight and in particular at least 30% by weight of the core material used.
  • the microcapsules according to the invention after storage for a period of 4 weeks at a temperature of 0 to 40° C., still contain at least 50% by weight of the core material used.
  • the tightness also depends on the type of core material.
  • the tightness of the microcapsules according to the invention was determined according to the invention for the scented oil Weiroclean from Kitzing, since the chemical properties of this scented oil are representative of microencapsulated scented oils.
  • Weiroclean has the following components (with proportion based on the total weight):
  • the core material is hydrophobic.
  • the core material can be solid or liquid. In particular, it is liquid. It is preferably a liquid hydrophobic core material.
  • the core material is a fragrance. It is particularly preferred to use fragrance oils optimized for microencapsulation for the washing and cleaning agent sector, such as the Weiroclean fragrance formulation (from Kurt Kitzing GmbFI).
  • the tightness of the capsule wall can be influenced by the choice of shell components.
  • the microcapsules have a tightness that allows leakage of at most 45% by weight, at most 40% by weight, at most 35% by weight, at most 30% by weight, at most 25% by weight, at most 20% by weight of the core material used when stored over a period of 4 weeks at a temperature of 0 to 40 °C.
  • the microcapsules still contain at least 55% by weight, preferably at least 60% by weight, more preferably at least 65% by weight, even more when stored for a period of 4 weeks at a temperature of 0 to 40°C preferably at least 70% by weight, even more preferably at least 75% by weight, even more preferably at least 80% by weight of the core material used.
  • the microcapsules are stored in a model formulation that corresponds to the target application.
  • the microcapsules are also storage stable in the product in which they are used.
  • the guide formulations for these products are known to those skilled in the art.
  • the pH around the microcapsules during storage is in the range of 2 to 10.
  • the microcapsule shells according to the invention have at least two layers, ie they can have, for example, two layers, three layers, four layers or five layers.
  • the microcapsules preferably have two or three layers.
  • the microcapsule has a third layer which is arranged on the outside of the stability layer.
  • This third layer can be used to tailor the surface properties of the microcapsule for a specific application. Mention should be made here of the improvement in the adhesion of the microcapsules to a wide variety of surfaces and a reduction in agglomeration.
  • the third layer also binds residual aldehyde quantities, thereby reducing the content of free aldehydes in the capsule dispersion. Furthermore, it can provide additional (mechanical) stability or further increase the tightness.
  • the third layer can contain a component selected from amines, organic salts, inorganic salts, alcohols, ethers, polyphosphazenes and noble metals.
  • Precious metals increase the tightness of the capsules and can give the microcapsule surface additional catalytic properties or the antibacterial effect of a silver layer, for example.
  • Organic salts especially ammonium salts, lead to cationization of the microcapsule surface, which means that it adheres better to e.g. textiles.
  • alcohols When incorporated via free hydroxyl groups, alcohols also lead to the formation of H bridges, which also allow better adhesion to substrates.
  • An additional polyphosphazene layer or a coating with inorganic salts, e.g. silicates leads to an additional increase in impermeability without affecting biodegradability.
  • the third layer contains activated melamine.
  • the melamine catches possible free aldehyde components of the stability and/or barrier layer, increases the tightness and stability of the capsule and can also influence the surface properties of the microcapsules and thus the adhesion and agglomeration behavior.
  • the proportion of the barrier layer in the shell is at most 30% by weight.
  • the proportion of the barrier layer in the shell based on the total weight of the shell can for example 30%, 28%, 25%, 23%, 20% by weight. 18 wt%, 15 wt%. 13%, 10%, 8%, or 5% by weight.
  • the proportion is at most 25% by weight based on the total weight of the shell.
  • the proportion of the barrier layer is particularly preferably not more than 20% by weight.
  • the proportion of the stability layer in the shell, based on the total weight of the shell is at least 40% by weight.
  • the proportion of the stability layer in the shell can be, for example, 40% by weight, 43% by weight, 45% by weight, 48% by weight, 50% by weight. 53 wt%, 55 wt%. 58 wt%, 60 wt%, 63 wt%, 65 wt%, 68 wt%, 70 wt% 75 wt%, 80 wt%, 85 wt% -%, or 90% by weight.
  • the proportion of the stability layer is at least 50% by weight, particularly preferably at least 60% by weight.
  • the proportion of the third layer in the shell, based on the total weight of the shell is at most 35% by weight.
  • the proportion of the third layer in the shell can be, for example, 35% by weight, 33% by weight, 30% by weight, 28% by weight, 25% by weight, 23% by weight. %, 20% by weight. 18 wt%, 15 wt%. 13%, 10%, 8%, or 5% by weight.
  • the proportion of the third layer is preferably at most 30% by weight, particularly preferably at most 25% by weight.
  • the size of the microcapsules according to the invention is in the range customary for microcapsules.
  • the diameter can be in the range from 100 nm to 1 mm. The diameter depends on the exact capsule composition and the method of manufacture.
  • the peak maximum of the particle size distribution is regularly used as a parameter for the size of the capsules.
  • the peak maximum of the particle size distribution is preferably in the range from 1 ⁇ m to 500 ⁇ m.
  • the peak maximum of the particle size distribution can be, for example, at 1 pm, 2 pm, 3 pm, 4 pm, 5 pm, 10 pm, 15 pm, 20 pm, 30 pm, 40 pm, 50 pm, 60 pm, 70 pm, 80 pm , 90 pm, 100 pm, 120 pm, 140 pm, 160 pm, 180 pm 200 pm, 250 pm, 300 pm 350 pm, 400 pm, 450 pm or 500 pm.
  • the microcapsules have a peak maximum of the particle size distribution of 10 ⁇ m to 100 ⁇ m.
  • the peak maximum of the particle size distribution is in the range from 10 ⁇ m to 50 ⁇ m.
  • the use of an emulsion stabilizer to increase the amount of a stability layer that can be deposited on the surface of a barrier layer relates to the barrier layer and the stability layer forming the capsule wall of a microcapsule.
  • the emulsion stabilizer and all other components of the microcapsules can be as defined in the first aspect.
  • the invention relates to a product containing microcapsules according to the first aspect.
  • the product is not a product from the field of detergents and cleaning agents and cosmetic products.
  • the product can be an adhesive system; a pharmaceutical product; a coating material, in particular a coated paper; a thermal storage coating, a self-healing coating, or a corrosion coating; or a coating for functional packaging materials containing microcapsules.
  • the invention relates to the use of microcapsules according to the first aspect to produce a product according to the third aspect.
  • the microcapsules can be used in the preparation of such a product. Consequently, the invention further relates to the use of the microcapsules according to the first aspect for the manufacture of the product, wherein the product is selected from the group consisting of an adhesive material system; a pharmaceutical product; a coating material, in particular a coated paper; a thermal storage coating, for a self-healing coating or a corrosion coating; and coatings for functional packaging materials containing such microcapsules.
  • Processes for producing core/shell microcapsules are known to those skilled in the art.
  • an oil-based core material that is insoluble or sparingly soluble in water is emulsified or dispersed in an aqueous phase containing the wall-forming agents.
  • a wide variety of units are used, from simple stirrers to high-performance dispersers, which distribute the core material into fine oil droplets.
  • the wall formers are separated from the continuous water phase on the oil droplet surface and can then be crosslinked.
  • This mechanism is used in the in situ polymerization of amino and phenoplast microcapsules and in the coacervation of water-soluble hydrocolloids.
  • free-radical polymerization uses oil-soluble acrylate monomers to form the wall.
  • methods are used in which water-soluble and oil-soluble starting materials are reacted at the phase boundary of the emulsion droplets that form the solid shell.
  • Examples of this are the reaction of isocyanates and amines or alcohols to form polyurea or polyurethane walls (interfacial polymerization), but also the hydrolysis of silicate precursors with subsequent condensation to form an inorganic capsule wall (sol-gel process).
  • the invention relates to a method for producing microcapsules comprising a fragrance as the core material and a shell consisting of three layers.
  • the barrier layer serving as a diffusion barrier is provided as a template.
  • suitable protective colloids e.g. Poly-AMPS
  • the wall-forming agent for example a suitable pre-condensate based on aminoplast resin, can form a very thin shell (layer) with the stirring speed now greatly reduced.
  • the thickness of the shell can be further reduced, in particular by adding an aromatic alcohol, for example m-aminophenol.
  • an aromatic alcohol for example m-aminophenol.
  • the use of the emulsion stabilizer according to the invention made it possible to further increase the separation of the biopolymers.
  • the method comprises at least the following steps: a) producing an oil-in-water emulsion by emulsifying a core material in an aqueous phase in the presence of the wall-forming component(s) of the inner barrier layer with the addition of protective colloids; b) deposition and curing of the wall-forming component(s) of the barrier layer, the wall-forming component(s) of the barrier layer preferably being an aldehyde component, an amine component and an aromatic alcohol, particularly preferably formaldehyde, melamine and resorcinol; c) adding an emulsion stabilizer, preferably wherein the emulsion stabilizer is as defined in the first aspect; d) addition of the wall-forming component(s) of the stability layer, followed by deposition and curing, the wall-forming component(s) of the stability layer comprising at least one biopolymer, preferably a protein and/or a polysaccharide, particularly preferably gelatin and alginate, and a curing agent, are preferably
  • a thickener such as Jaguar HP105 (Solvay) can be beneficial.
  • the thickening agent serves in particular to adjust the viscosity.
  • An increase in viscosity for example up to a viscosity of 2500 mPas (measured with Brookfield, RT, S3) can stabilize the microcapsule dispersion and thus improve the stirrability and storage.
  • the addition of the emulsion stabilizer is preferably done slowly over at least two minutes.
  • the microcapsule dispersion is agitated.
  • a paddle stirrer for example, can be used for stirring.
  • the stirring speed is preferably in the range of 150 to 250 rpm. Above 250 rpm there is a risk of air entering the microcapsule dispersion. Mixing may not be sufficient below 150 rpm.
  • the temperature is preferably in the range of 15°C to 35°C.
  • the temperature can be 15°C, 18°C, 20°C, 23°C, 25°C, 28°C, 30°C, 33°C, or 35°C.
  • the temperature is particularly preferably 25.degree.
  • the microcapsule dispersion is stirred until a homogeneous mixture is formed. In one embodiment, the microcapsule dispersion is stirred for at least 5 minutes after addition. In a preferred embodiment, the microcapsule dispersion is stirred for at least 10 minutes after addition.
  • steps a) and b) can be carried out as follows: a) Production of an oil-in-water emulsion by emulsifying a core material in an aqueous phase in the presence of the wall-forming component(s) of the inner barrier layer, optionally with the addition of protective colloids ; b) Deposition and curing of the wall-forming component(s) of the inner barrier layer, the wall-forming component(s) of the inner barrier layer being in particular an aldehyde component, an amine component and an aromatic alcohol.
  • This process can be carried out either sequentially or as a so-called one-pot process.
  • steps a) and b) are carried out in a first method until microcapsules are obtained with only the inner barrier layer as the shell (intermediate microcapsules). A portion or the total amount of these intermediate microcapsules is then subsequently transferred to a further reactor. The further reaction steps are then carried out in this. In the one-pot process, all process steps are carried out in a batch reactor. The implementation without changing the reactor is particularly time-saving.
  • the overall system should be matched to the one-pot process.
  • the right choice of the solids content, the right temperature control, the coordinated addition of formulation components and the sequential addition of the wall-forming agents is possible in this way.
  • the method comprises the preparation of a water phase by dissolving a protective colloid, in particular a polymer based on acrylamidosulfonate and a methylated pre-polymer, in water.
  • a protective colloid in particular a polymer based on acrylamidosulfonate and a methylated pre-polymer
  • the pre-polymer is preferably produced by reacting an aldehyde with either melamine or urea.
  • methanol can be used.
  • the water phase can be thoroughly mixed by stirring and setting a first temperature, the first temperature being in the range from 30.degree. C. to 40.degree.
  • An aromatic alcohol in particular phloroglucinol, resorcinol or aminophenol can then be added to the water phase and dissolved therein.
  • an oil phase can be produced by mixing a fragrance composition or a phase change material (PCM) with aromatic alcohols, in particular phloroglucinol, resorcinol or aminophenol.
  • aromatic alcohols in particular phloroglucinol, resorcinol or aminophenol.
  • reactive monomers or diisocyanate derivatives can also be incorporated into the fragrance composition.
  • the first temperature can then be set.
  • a further step can be the production of a two-phase mixture by adding the oil phase to the water phase and then increasing the speed.
  • the emulsification can then be started by adding formic acid. A regular determination of the particle size is recommended. Once the desired particle size has been reached, the two-phase mixture can be stirred further and a second temperature can be set to harden the capsule walls. The second temperature can be in the range from 55°C to 65°C.
  • a melamine dispersion can then be added to the microcapsule dispersion and a third temperature can be set, the third temperature preferably being in the range from 75.degree. C. to 85.degree.
  • Another suitable step is the addition of an aqueous urea solution to the microcapsule dispersion.
  • the emulsion stabilizer is then added to the microcapsule dispersion before this is added to a solution of gelatine and alginate to produce the stabilization layer.
  • the microcapsule dispersion can then be cooled to a fourth temperature, the fourth temperature being in the range of 20°C to 30°C. It can then be cooled to a fifth temperature, the fifth temperature being in a range from 4°C to 17°C, in particular at 8°C.
  • the pH of the microcapsule dispersion would then be adjusted to a value in the range 4.3 to 5.1 and glutaraldehyde or glyoxal added.
  • the reaction conditions in particular temperature and pH, can be chosen differently depending on the crosslinker.
  • the person skilled in the art can derive the respectively suitable conditions from the reactivity of the crosslinker, for example.
  • the added amount of glutaraldehyde or glyoxal influences the crosslinking density of the stability layer and thus, for example, the tightness and Degradability of the microcapsule shell. Accordingly, the person skilled in the art can vary the amount in a targeted manner in order to adapt the property profile of the microcapsule.
  • a melamine suspension consisting of melamine, formic acid and water can be produced to produce the additional third layer.
  • the melamine suspension is then added to the microcapsule dispersion.
  • the pH of the microcapsule dispersion would be adjusted to a value in the range of 9 to 12, especially 10 to 11.
  • the microcapsule dispersion can be heated to a temperature in the range from 20° C. to 80° C. for curing in step e). As shown in Example 8, this temperature has an impact on the color stability of the microcapsules.
  • the temperature can be at 20°C, 25°C, 30°C, 35°C, 40°C, 45°C, 50°C, 55°C, 60°C, 65°C, 70°C, 75° C, or 80 °C. Below a temperature of 20 °C, no influence on the color fastness is to be expected. A temperature above 80 °C could adversely affect the microcapsule properties. According to one embodiment, the temperature is in the range of 30°C to 60°C. According to a preferred embodiment, the temperature is in the range of 35°C to 50°C.
  • the microcapsule dispersion is maintained at the heating temperature for a period of at least 5 minutes.
  • the time period can be 10 minutes, 15 minutes, 20 minutes, 25 minutes, 30 minutes, 35 minutes, 40 minutes, 45 minutes, 50 minutes, 55 minutes, 60 minutes, 70 minutes, 80 minutes, 90 minutes, 100 minutes, 110 minutes, 120 minutes.
  • the microcapsule dispersion is held at the heating temperature for a period of at least 30 minutes.
  • the microcapsule dispersion is held at the heating temperature for a period of at least 60 minutes.
  • Microcapsules are usually in the form of microcapsule dispersions.
  • the present invention also relates to microcapsule dispersions containing microcapsules according to the first aspect.
  • the microcapsule dispersions according to the invention have only a slight coloration.
  • the L * a * b * color model is standardized in EN ISO 11664-4 "Colorimetry -- Part 4: CIE 1976 L * a * b * color space".
  • the L * a * b * color space (also: CIELAB, CIEL * a * b * , Lab colors) describes all perceptible colors. It uses a three-dimensional color space in which the lightness value L * is perpendicular to the color plane (a * ,b * ).
  • the a-coordinate gives the chromaticity and chroma between green and red
  • the b-coordinate gives the chromaticity and chroma between blue and yellow.
  • the properties of the L * a * b * color model include device independence and perception-relatedness, ie colors are defined as they are perceived by a normal observer under standard lighting conditions, regardless of how they are produced or how they are reproduced.
  • the microcapsule dispersions according to the invention have a color locus with an L * value of at least 50 in the L * a * b * color space.
  • the L * value can be 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71 , 72, 73, 74, 75, 76, 77, 78, 79, or 80.
  • the microcapsule dispersions according to the invention have a color locus with an L * value of at least 50 in the L * a * b * color space.
  • the color point is particularly preferably at least 60.
  • the microcapsule dispersions produced using the production process according to the invention are particularly color-stable.
  • the color locus of the microcapsule dispersion has an L * value of at least 50 in the L * a * b * color space after storage.
  • the L * value after storage can be, for example, 51, 52, 53, 54, 55, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70 , 71, 72, 73, 74, 75, 76, 77, 78, 79, 80.
  • the microcapsule dispersions according to the invention Storage in the L * a * b * color space has a color locus with an L * value of at least 60.
  • the color point is particularly preferably at least 65.
  • the microcapsule dispersion may contain a thickening agent such as Jaguar HP105 (Solvay).
  • the thickening agent serves in particular to adjust the viscosity.
  • An increase in viscosity for example up to a viscosity of 2500 mPas (measured with Brookfield, RT, S3), can stabilize the microcapsule dispersion and thus improve the stirrability and storage.
  • the storage time is at least four weeks, preferably at least six weeks and in particular at least eight weeks.
  • Dimension SD was stirred into deionized water and then Dimension PA140 was added and stirred until a clear solution formed.
  • the solution was warmed to 30-35°C in a water bath.
  • the perfume oil was added at 1100 rpm while stirring with a dissolver disk.
  • the pH of the oil-in-water emulsion was adjusted to 3.3-3.8 with 10% formic acid. Thereafter, the emulsion was stirred further for 30 min at 1100 rpm until a droplet size of 20-30 ⁇ m was reached or correspondingly prolonged until the desired particle size of 20-30 ⁇ m (peak max) was reached.
  • the particle size was determined using a Beckmann-Coulter device (laser diffraction, Fraunhofer method).
  • the speed was reduced in such a way that thorough mixing was ensured. This speed was used for stirring at 30 to 40° C. for a further 30 minutes. The emulsion was then heated to 60° C. and stirred further. The melamine suspension was adjusted to a pH of 4.5 with formic acid (10%) and metered into the reaction mixture. The batch was kept at 60° C. for 60 min and then heated to 80° C. After stirring at 80° C. for 60 min, the urea solution was added.
  • microcapsule dispersion was filtered through a 200 ⁇ m mesh filter.
  • Slurry 2 and Slurry 5 are shown in Table 3.
  • Table 3 List of substances used to produce Slurry 2 and 5
  • reaction mixture 1 Dimension PA140 and Dimension SD with addition of deionized water 1 were weighed into a beaker and premixed with a 4 cm dissolver disk. The beaker was fixed in the water bath and stirred with the dissolver disc at 500 rpm and 30° C. until a clear solution formed. As soon as the Dimension SD / Dimension PA140 solution was clear and had reached 30-40°C, the quantity of perfume oil was added slowly and the speed adjusted (1100 rpm) so that the desired particle size was achieved. Then the pH of this mixture was acidified by the addition of Formic Acid Feed 1. It was emulsified for 20-30 minutes or extended accordingly until the desired particle size of 20-30 ⁇ m (peak max) was reached. The particle size was determined using a Beckmann-Coulter device (laser diffraction, Fraunhofer method). After the particle size had been reached, the speed was reduced in such a way that gentle mixing was ensured.
  • the resorcinol solution was then stirred in and preformed with gentle stirring for 30 - 40 minutes. After the preforming time had elapsed, the emulsion temperature was increased to 50° C. within 15 minutes. Upon reaching this temperature, the mixture was ramped to 60°C over a period of 15 min maintained this temperature for a further 30 min.
  • the melamine suspension addition 1 was then adjusted to a pH of 4.5 with the aid of 20% formic acid and metered into the reaction mixture over a period of 90 minutes. Thereafter, the temperature was held for 30 min. After the 30 minutes had elapsed, the temperature was initially increased to 70° C. within 15 minutes. The temperature was then increased to 80° C. within 15 minutes and maintained for 120 minutes.
  • reaction mixture 1 was cooled to room temperature.
  • sodium sulfate was dissolved in tap water while stirring with a paddle stirrer at 40-50°C.
  • Sodium alginate and pigskin gelatin are slowly sprinkled into the heated water.
  • reaction mixture 1 was added to the prepared gelatin/sodium alginate solution with stirring.
  • the pH was adjusted to 3.9 by slow dropwise addition of formic acid 2, after which the heat source was removed.
  • the batch was then cooled to room temperature. After reaching room temperature, the reaction mixture was cooled with ice.
  • the melamine suspension addition 2 which had been acidified to a pH value of 4.5 using 20% formic acid, was then metered in slowly.
  • the reaction mixture was then heated to 60° C. and held for 60 min when this temperature was reached. After this holding time, the heat source was removed and the microcapsule suspension was gently stirred for 14 hours. After 14 hours had elapsed, the microcapsule suspension was adjusted to a pH of 10.5 by adding sodium hydroxide solution 2.
  • microcapsule MK1 obtained was examined under a light microscope. Typical recordings are shown in Figure 1E.
  • pH value the pH value, the solids content, the viscosity, the particle size, the content of core material in the slurry and the L * value of the color locus are determined. The result is shown in Table 5.
  • the core material was added slowly, adjusting the speed (e.g. 1100 rpm) to achieve the desired particle size.
  • preforming was carried out for 30-40 minutes. After the preforming time had elapsed, the emulsion temperature was increased to 50° C. within 15 minutes. When this temperature was reached, the mixture was increased to 60° C. over a period of 15 minutes and this temperature was maintained for a further 30 minutes. The melafin suspension addition 1 was then adjusted to a pH of 4.5 with the aid of 20% formic acid and metered into the reaction mixture over a period of 90 minutes.
  • the temperature was held for 30 min. After the 30 minutes had elapsed, the temperature was initially increased to 70° C. within 15 minutes. The temperature was then increased to 80° C. within 15 minutes and maintained for 90 minutes. Thereafter, the aqueous urea solution was added, the heat source was switched off and the reaction mixture 1 was cooled to room temperature. After Reaction Mixture 1 reaches room temperature, Dimension PA140 Addition 2 is added.
  • reaction mixture 1 was added to the prepared gelatin/sodium alginate solution with stirring. When a homogeneous mixture was reached, the pH was adjusted to 3.7 by slow dropwise addition of the formic acid addition 2, after which the heat source was removed and the batch was naturally cooled to room temperature.
  • the reaction mixture was cooled with ice. When the temperature had reached 8° C., the ice bath was removed and the pH was increased to 4.7 with addition 1 of sodium hydroxide solution. Then 50% glutaraldehyde was added. Care was taken to ensure that the temperature did not exceed 16-20° C. before the 50% glutaraldehyde was added.
  • the melamine suspension addition 2 which had been acidified to a pH value of 4.5 using 20% formic acid, was then metered in over a period of about 2 minutes.
  • the microcapsule suspension was then gently stirred at room temperature for 14 h. After 14 hours had elapsed, the microcapsule suspension was adjusted to a pH of 10.5 by adding sodium hydroxide solution 2 over a period of about 15 minutes.
  • reaction mixture 1 Dimension PA140 and Dimension SD with addition of water 1 were weighed into a beaker and premixed with a 4 cm dissolver disk. The beaker was fixed in the water bath and stirred with the dissolver disc at 500 rpm and 30° C. until a clear solution formed. Once the Dimension SD / Dimension PA140 solution was clear and had reached 30-40°C, the core material was slowly added, adjusting the speed (eg 1100 rpm) to achieve the desired particle size. Then the pH of this mixture was acidified by the addition of Formic Acid Feed 1. It was emulsified for 20-30 minutes or extended accordingly until the desired particle size of 20-30 ⁇ m (peak max) was reached. The particle size was determined using a Beckmann-Coulter device (laser diffraction, Fraunhofer method). After the particle size had been reached, the speed was reduced in such a way that gentle mixing was ensured.
  • the resorcinol solution was then stirred in and preformed with gentle stirring for 30 - 40 minutes. After the preforming time had elapsed, the emulsion temperature was increased to 50° C. within 15 minutes. When this temperature was reached, the mixture was increased to 60°C over a period of 15 min and this temperature was maintained for a further 30 min.
  • the melamine suspension addition 1 was then adjusted to a pH of 4.5 with the aid of 20% formic acid and metered into the reaction mixture over a period of 90 minutes. Thereafter, the temperature was held for 30 min. After the 30 minutes had elapsed, the temperature was initially increased to 70° C. within 15 minutes. The temperature was then increased to 80° C. within 15 minutes and maintained for 120 minutes.
  • reaction mixture 1 was cooled to room temperature.
  • sodium sulfate was dissolved in tap water while stirring with a paddle stirrer at 40-50°C.
  • Sodium alginate and pigskin gelatin are slowly sprinkled into the heated water.
  • reaction mixture 1 was added to the prepared gelatin/sodium alginate solution with stirring.
  • the pH was adjusted to 3.9 by slow dropwise addition of formic acid 2, after which the heat source was removed.
  • the batch was then cooled to room temperature. After reaching room temperature, the reaction mixture was cooled with ice.
  • microcapsule MK4 obtained was examined by light microscopy. Typical recordings are shown in Figure 1G.
  • pH value the pH value, the solids content, the viscosity, the particle size, the content of core material in the slurry and the L * value of the color locus were determined. The result is shown in Table 9.
  • the core material was added slowly, adjusting the speed (e.g. 1100 rpm) to achieve the desired particle size.
  • preforming was carried out for 30-40 minutes. After the preforming time had elapsed, the emulsion temperature was increased to 50° C. within 15 minutes. When this temperature was reached, the mixture was increased to 60° C. over a period of 15 minutes and this temperature was maintained for a further 30 minutes. The melamine suspension addition 1 was then adjusted to a pH of 4.5 with the aid of 20% formic acid and metered into the reaction mixture over a period of 90 minutes.
  • the temperature was held for 30 min. After the 30 minutes had elapsed, the temperature was initially increased to 70° C. within 15 minutes. The temperature was then increased to 80° C. within 15 minutes and maintained for 90 minutes.
  • reaction mixture 1 was added to the prepared gelatin/sodium alginate solution with stirring. When a homogeneous mixture was reached, the pH was adjusted to 3.7 by slow dropwise addition of the formic acid addition 2, after which the heat source was removed and the batch was naturally cooled to room temperature.
  • the reaction mixture was cooled to a temperature of 8°C with ice and the temperature was kept at 8°C.
  • the pH value is increased to 4.7 by adding sodium hydroxide solution 1.
  • 40% glyoxal was then added at a temperature of 8° C. and then the melamine suspension, acidified to a pH of 4.5 using 20% formic acid, was metered in over a period of about 2 minutes.
  • the ice bath is removed and the reaction mixture is heated to 40° C. and kept at this temperature for 1 hour.
  • microcapsule suspension was stirred gently at room temperature for 14 h.
  • the resulting microcapsules Slurry 3 and Slurry 6 according to the invention were examined under a light microscope. Typical recordings are shown in Figures 1B and 1D.
  • the pH, the solids content, the viscosity, the particle size, the content of core material in the slurry and the L * value of the color locus were determined. The result is shown in Table 10.
  • Example 4 Microscopic determination of the thickness of the stability layer
  • the thickness of the stability layer can be determined in two ways. First of all, the light microscopic approach should be mentioned here, i.e. the direct, optical measurement of the observed layer thickness using a microscope and appropriate software.
  • a second possibility is the measurement of the particle size distribution by means of laser diffraction.
  • the modal value of a particle size distribution of the pure barrier template (cf. example 1) can be compared to the modal value of a particle size distribution for a microcapsule according to the invention.
  • the increase in this reading should reflect the increase in hydrodynamic diameter (due to the application of the stability layer) of the main fraction of measured microcapsules. Forming the difference between the two measured modal values ultimately results in twice the layer thickness of the stability layer.
  • the layer thickness of the stability layer was determined by light microscopy on an Olympus BX50 microscope.
  • the software OLYMPUS Stream Essentials 2.4.2 (Build 20105) was used for the measurement.
  • a highly diluted sample of the capsule slurry according to the invention was prepared with tap water. A drop of this dispersion was placed on a slide and covered with a coverslip.
  • a magnification of 500x was selected on the microscope and the corresponding microcapsules according to the invention in the applied sample dispersion were focused.
  • the diameter of the visible barrier template was then recorded in the above-mentioned software using the "3-point circle” function. Finally, the layer thickness of the stability layer could be measured at three characteristic points using the ruler function.
  • microcapsules according to the invention Due to the elliptical shape of the stability layer, several layer thickness measurements were taken per focused microcapsule to reflect the variance in the layer thickness.
  • the microcapsules according to the invention have a larger layer thickness at two opposite vertices and a smaller layer thickness at the remaining two opposite vertices. To reduce this measurement error when specifying a layer thickness for the stability layer, an average value was prepared for 10 individual microcapsules.
  • Table 11 Results of the layer thickness measurement of the stabilization layer using Slurry 3 as an example
  • the light microscope images of the prepared layer thickness measurement for slurry 3 and a comparison of the microcapsule MK1 are shown in FIG. 2 as an example.
  • the result of the measurement of 10 capsules of Slurry 3 is shown in Table 11.
  • microcapsules To determine the stability of microcapsules, they were stored in a model fabric softener formulation at 40° C. for a period of up to 4 weeks and the concentration of the fragrances diffused from the interior of the capsule into the surrounding formulation was determined using HS-GC/MS. Based on the measured values, the residual proportion of the perfume oil still in the capsule was calculated.
  • microcapsule dispersions Slurry 2, Slurry 3, Slurry 5, Slurry 6 and MK1, MK2 and MK4 were carefully homogenized and stored in the heating cabinet at a concentration of 1% by weight in the model formulation at 40° C., sealed airtight.
  • the non-encapsulated fragrance with an analogous concentration of fragrance in the model formulation serves as a comparison.
  • the samples were removed from the heating cabinet and an aliquot was weighed into a 20 ml headspace vial. The vial was then immediately sealed.
  • the microcapsules Slurry 2, Slurry 3, Slurry 5 and Slurry 6 according to the invention show a stability comparable to the MF reference MK2 after 4 weeks of storage in a model formulation. Furthermore, it is found that the microcapsules according to the invention with an increased layer thickness of the stability layer slurry 2 and 3 have improved stability over a storage period of 4 weeks compared to the reference capsules MK1 and MK4 (cf. FIGS. 4B and 4C).
  • a change in concentration of 16 individual ingredients of the encapsulated fragrance was considered for the calculation of the capsule stability.
  • a reduction in stability results in the encapsulated fragrance escaping, which can then be detected by gas chromatography using headspace SPME. Since all capsule dispersions were adjusted to a defined oil content of 15% by weight, a direct comparison of the capsule samples examined is possible. Individual ingredients (or their individual signals recorded by gas chromatography) which, due to fluctuations caused by measurement technology, indicate higher concentrations than were theoretically possible in comparison with the reference standard, were only taken into account in the evaluation up to the theoretical maximum concentration.
  • the standard test concentration of the samples to be examined is 1000 mg/l O2.
  • the measuring heads and the controller measure the oxygen consumption in a closed system. Due to the consumption of oxygen and the simultaneous binding of the resulting carbon dioxide to caustic soda pellets, a negative pressure is created in the system. The measuring heads register and save this pressure over the set measuring period. The stored values are read into the controller using infrared transmission. They can be transferred to a PC and evaluated using the Achat OC program.
  • OxiTop Control measuring system WTW incl. Controller OxiTop OC
  • microcapsule dispersions Slurry 2 and Slurry 3 were produced according to the descriptions of Examples 2 to 3, with the difference that the completely persistent perfluorooctane (degradation rate ⁇ 1%) was used as the core material instead of the perfume oil. This eliminates any influence of the core material on the test result.
  • the microcapsule slurries were washed after preparation by centrifuging and redispersing in water three times in order to separate off dissolved residues. For this purpose, a sample of 20-30 mL is centrifuged for 10 minutes at 12,000 rpm. After sucking off the clear residue, 20-30 mL water is added and the sediment is redispersed by shaking.
  • ethylene glycol 711.6 mg were dissolved in a 1 l volumetric flask and filled up to the mark. This corresponds to a COD of 1000 mg/l O2.
  • Ethylene glycol is considered to be readily biodegradable and serves as a reference here.
  • Walnut shell flour consists of a mixture of biopolymers, particularly cellulose and lignin, and serves as a solid-based biobased reference. Due to the slow degradation of walnut shell flour, the course of the test can be followed over the entire 60-day period. For this purpose, 117.36 g of walnut shell flour were dispersed homogeneously in 1 l of water with stirring. Aliquots of this mixture were taken with stirring for COD determination. Based The required quantity was calculated from the average COD value of 1290 ⁇ 33 mg/l O2 and transferred to the OxiTop bottles while stirring.
  • Activated sludge was removed from the outlet of the activated sludge tank of a factory or municipal wastewater treatment plant using a 20 l bucket. After 30 minutes of settling, the supernatant water was discarded.
  • the concentrated organic sludge in the bucket was then permanently aerated for 3 days with the help of the aquarium pump and an air stone.
  • the COD value of the samples to be examined was determined using the COD LCK 514 cuvette test.
  • the sample is diluted with water until the COD value of 1000 mg/l O2 is reached.
  • microcapsule dispersions Slurry 2 and Slurry 3 show very good biodegradability in the OECD301F test. After 14 days (slurry 3) or 26 days (slurry 2), the requirements of the OECD/ECHA are met, as there is a degree of degradation of >60%.
  • the course of degradation of the ethylene glycol reference sample indicates a healthy inoculum and also shows the functionality of the instrument over the entire duration of the experiment.
  • the walnut shell flour is characterized by the typical, gradual degradation process, which was expected for a complex mixture of biopolymers. Due to the continuous increase in biol. Degradability over the entire test period of 60 days can also be used to conclude that the inoculum is healthy.
  • Example 7 Determination of the color of the microcapsule dispersions
  • the color of the microcapsule dispersions Slurry 2 and 3 as the color locus in the L * a * b * color space was determined using the following test protocol.
  • the portable spectrophotometer "spectro-color d/8°C" from Dr. Long used in conjunction with glass measuring cells for liquids. Furthermore, the measurement took place in the associated measurement setup, which darkens the sample during the measurement (and thus minimizes the influence of scattered light). Before starting the measurements, a calibration was performed against a black and white standard (LZM268 standard set).
  • the corresponding capsule dispersion is filled undiluted into a round glass cuvette (approx. 5-6 mL).
  • the measuring range is set to a defined layer thickness and any air inclusions in the dispersion are removed using the associated PTFE stamp.
  • the color measurement was carried out as part of a triple determination, with the cuvette being rotated by approx. 30° after each individual measurement. The mean value and standard deviation are then calculated.
  • Table 15 Determination of the color locus of slurry 2 and 3 in the L*a*b* color space after production and after storage
  • Slurry 3A In order to determine the influence of the heat treatment in the last curing step on the color stability, the manufacturing process of Slurry 3 was modified.
  • the reaction mixture was not heated to 40° C. for 1 h before stirring at room temperature for 14 h.
  • the resulting microcapsule dispersion is referred to as Slurry 3A.
  • Slurries 3 and 3A were prepared in parallel and the color locus of samples of both microcapsule dispersions was determined directly thereafter according to the protocol described in Example 7. On the following days 1, 2, 3, 4 and 8, samples were taken from slurries 3 and 3A and the color locus of these samples was again determined. Three samples per microcapsule dispersion and day were measured and the mean value for the three L * a * b * coordinates was calculated.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Dispersion Chemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Veterinary Medicine (AREA)
  • Public Health (AREA)
  • Animal Behavior & Ethology (AREA)
  • Epidemiology (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
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  • Medicinal Chemistry (AREA)
  • Pharmacology & Pharmacy (AREA)
  • Bioinformatics & Cheminformatics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Dermatology (AREA)
  • Manufacturing Of Micro-Capsules (AREA)

Abstract

Selon un premier aspect, l'invention concerne des microcapsules biodégradables comprenant un matériau de cœur et une écorce, l'écorce étant constituée d'au moins une couche barrière et d'une couche de stabilité, la couche barrière entourant le matériau de cœur, la couche de stabilité comprenant au moins un biopolymère et étant située sur la surface externe de la couche barrière, et un stabilisateur d'émulsion étant situé au niveau de la transition entre la couche barrière et la couche de stabilité. L'invention concerne également : l'utilisation d'un stabilisateur d'émulsion pour augmenter la quantité d'une couche de stabilité qui peut être déposée sur la surface d'une couche barrière ; un produit comprenant les microcapsules biodégradables ; et un procédé de fabrication des microcapsules biodégradables.
EP22737736.3A 2021-06-11 2022-06-10 Microcapsules dégradables de couleur neutre Pending EP4351773A1 (fr)

Applications Claiming Priority (2)

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DE102021205957.0A DE102021205957A1 (de) 2021-06-11 2021-06-11 Farbneutrale abbaubare Mikrokapseln
PCT/DE2022/200122 WO2022258118A1 (fr) 2021-06-11 2022-06-10 Microcapsules dégradables de couleur neutre

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EP4351773A1 true EP4351773A1 (fr) 2024-04-17

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CN120349145B (zh) * 2025-06-24 2025-08-26 湖南现代环境科技股份有限公司 一种利用尾矿材料制成的声屏障及其制备方法

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DE4209632A1 (de) 1992-03-25 1993-09-30 Basf Ag Sulfogruppenhaltige Polymere
DE10000621A1 (de) 2000-01-10 2001-07-12 Basf Ag Niedrigviskose, formaldehydreduzierte Dispersionen von Mikrokapseln aus Melamin-Formaldehyd-Harzen
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PL2336285T3 (pl) 2009-12-18 2014-01-31 Procter & Gamble Kompozycja zawierająca mikrokapsułki
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DE102011082496A1 (de) 2011-09-12 2013-03-14 Henkel Ag & Co. Kgaa Mikrokapselhaltiges Mittel
EP2689835B1 (fr) 2012-07-26 2019-05-08 Papierfabrik August Koehler SE Encapsulage d'huile parfumée
CN104755162B (zh) 2012-08-28 2018-01-09 奇华顿股份有限公司 芳香剂的载体体系
US20140066357A1 (en) 2012-08-30 2014-03-06 P. H. Glatfelter Company Heat-stable microencapsulated fragrance oils
EP2897723B1 (fr) 2012-09-24 2019-08-28 Firmenich SA Microcapsules à noyau/enveloppe multicouche
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WO2018114056A1 (fr) 2016-12-22 2018-06-28 Symrise Ag Microcapsules
CN113993499B (zh) 2019-04-12 2024-07-23 国际香料和香精公司 用交联剂的组合制备的可持续性核壳微胶囊
FR3099711B1 (fr) 2019-08-06 2021-07-16 Microcapsules Tech Procédé de fabrication de microcapsules renfermant un actif lipophile, microcapsules préparées par ce procédé et leur utilisation
WO2021110273A1 (fr) 2019-12-05 2021-06-10 Symrise Ag Substances odorantes encapsulées à base d'acides aminés naturels

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US20240293791A1 (en) 2024-09-05
WO2022258118A1 (fr) 2022-12-15

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