WO2023147855A2 - Procédé de fabrication de microcapsules - Google Patents

Procédé de fabrication de microcapsules Download PDF

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Publication number
WO2023147855A2
WO2023147855A2 PCT/EP2022/052501 EP2022052501W WO2023147855A2 WO 2023147855 A2 WO2023147855 A2 WO 2023147855A2 EP 2022052501 W EP2022052501 W EP 2022052501W WO 2023147855 A2 WO2023147855 A2 WO 2023147855A2
Authority
WO
WIPO (PCT)
Prior art keywords
crosslinking
microcapsules
polyisocyanate
protein
oil
Prior art date
Application number
PCT/EP2022/052501
Other languages
German (de)
English (en)
Inventor
Ralf Bertram
Benjamin ROST
Andreas Vogel
Britta RAABE
Christina KOEPKE
Lisette HOFFARTH
Daniela GREGOR
Original Assignee
Symrise Ag
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 Symrise Ag filed Critical Symrise Ag
Priority to PCT/EP2022/052501 priority Critical patent/WO2023147855A2/fr
Priority to PCT/EP2022/057952 priority patent/WO2023147889A1/fr
Priority to PCT/EP2023/052523 priority patent/WO2023148253A1/fr
Publication of WO2023147855A2 publication Critical patent/WO2023147855A2/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/06—Making microcapsules or microballoons by phase separation
    • B01J13/14—Polymerisation; cross-linking
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23P—SHAPING OR WORKING OF FOODSTUFFS, NOT FULLY COVERED BY A SINGLE OTHER SUBCLASS
    • A23P10/00—Shaping or working of foodstuffs characterised by the products
    • A23P10/30—Encapsulation of particles, e.g. foodstuff additives
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23P—SHAPING OR WORKING OF FOODSTUFFS, NOT FULLY COVERED BY A SINGLE OTHER SUBCLASS
    • A23P10/00—Shaping or working of foodstuffs characterised by the products
    • A23P10/30—Encapsulation of particles, e.g. foodstuff additives
    • A23P10/35—Encapsulation of particles, e.g. foodstuff additives with oils, lipids, monoglycerides or diglycerides
    • 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
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/64—Proteins; Peptides; Derivatives or degradation products thereof
    • A61K8/645—Proteins of vegetable origin; Derivatives or degradation products thereof
    • 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
    • A61K9/5052—Proteins, e.g. albumin
    • 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
    • A61K9/5089—Processes
    • 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
    • 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
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents ; Methods for using cleaning compositions
    • C11D11/04—Special methods for preparing compositions containing mixtures of detergents ; Methods for using cleaning compositions by chemical means, e.g. by sulfonating in the presence of other compounding ingredients followed by neutralising
    • 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
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3726—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/382—Vegetable products, e.g. soya meal, wood flour, sawdust
    • 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
    • A61K9/5036—Polysaccharides, e.g. gums, alginate; Cyclodextrin

Definitions

  • the present invention relates to a process for the production of microcapsules, in particular vegetable protein-based microcapsules and dispersions of such microcapsules (microcapsule slurry) which enclose at least one hydrophobic active ingredient, preferably perfume- or aroma-containing vegetable protein-based microcapsules, which have a balanced Have a balance of stability and performance compared to microcapsules of the prior art.
  • the present invention relates to plant protein-based microcapsules which can be obtained using the method according to the invention.
  • the present invention relates to the use of the plant protein-based microcapsules and dispersions according to the invention as a component of household products, textile care products, detergents, fabric softeners, cleaning agents, scent boosters or fragrance enhancers in liquid or solid form, cosmetics, personal care products, perfume compositions, agricultural products, pharmaceuticals products or print coating for paper.
  • the present invention relates to consumer products comprising such microcapsules or microcapsule dispersions according to the invention.
  • Microcapsules are particles consisting of a core and a wall material surrounding the core, where the core can be a solid, liquid or gaseous substance, which is surrounded by a polymeric dense, permeable or semipermeable wall material.
  • the core is also called the inner phase. Names such as outer phase, shell or coating are also used for the wall.
  • the diameter of the microcapsules typically varies in the range from 1 to 1000 ⁇ m.
  • the wall thickness is typically 0.5 to 150 ⁇ m, but can be varied in the range from 5 ⁇ 10′ 9 m to 5 ⁇ 10′ 6 m. Loadings of 25 to 95% by weight are typically possible, but loadings of 1 to 99% by weight are also possible.
  • taste, smell and color masking e.g. bitter or pungent flavors
  • moisture protection e.g. hygroscopic salts or minerals
  • Hydrophobic active ingredients such as, for example, fragrances or flavorings or fragrances or fragrances, can easily be incorporated into numerous and different application formulations by encapsulation.
  • microcapsules can generally be released in various ways and is based in particular on one of the mechanisms described below:
  • the capsules are mechanically destroyed by crushing or shearing. This mechanism is used, for example, in carbonless copy paper. The capsules are destroyed by melting the wall material. According to this mechanism, ingredients such as raising agents or aromas in baking mixes, for example, are only released during the baking process.
  • the capsules are destroyed by dissolving the wall material.
  • This mechanism is used in washing powder, for example, so that encapsulated ingredients such as enzymes are only released during the washing process.
  • the capsules remain intact, the capsule contents are gradually released by diffusion through the capsule wall.
  • This mechanism can be used, for example, to achieve a slow and steady release of active pharmaceutical ingredients in the body.
  • microcapsules are used in various areas, including the printing industry, the food industry (vitamins, aromas, plant extracts, enzymes, microorganisms), agricultural chemistry (fertilizers, pesticides), the animal feed industry (minerals, vitamins, enzymes, Drugs, microorganisms), the pharmaceutical industry, the detergent industry and the cosmetics industry.
  • fragrances or fragrances or fragrance or fragrance mixtures are now perfumed with fragrances or fragrances or fragrance or fragrance mixtures.
  • fragrances or fragrances interact with other components of the formulation or the more volatile components of a perfume evaporate prematurely. As a rule, this means that the scent impression of the perfuming changes over time or even disappears completely.
  • microencapsulation of such fragrance or fragrance mixtures offers the possibility of reducing or completely preventing interactions in the perfumed product or the evaporation of the volatile fragrance components.
  • a large number of capsule wall or coating materials are known for the production of microcapsules.
  • the capsule wall can be made of either natural, semi-synthetic, or synthetic materials.
  • shell materials are gum arabic, agar-agar, agarose, maltodextrins, alginic acid or salts thereof, eg sodium alginate or calcium alginate, fats and fatty acids, cetyl alcohol, collagen, chitosan, lecithin, gelatin, albumin, shellac, polysaccharides such as starch or dextran , polypeptides, protein hydrolysates, sucrose and waxes.
  • Semisynthetic capsule wall materials include chemically modified celluloses, particularly cellulose esters and cellulose ethers, eg cellulose acetate, ethyl cellulose, hydroxypropyl cellulose, hydroxypropylmethyl cellulose and carboxymethyl cellulose, and starch derivatives, particularly starch ethers and starch esters.
  • synthetic shell materials are polymers such as polyacrylates, polyamides, polyvinyl alcohol or polyvinylpyrrolidone.
  • microcapsules with different properties in terms of diameter, size distribution and physical and/or chemical properties are formed.
  • Polyurea microcapsules or polyurea/polyurethane microcapsules formed by polymerisation between a polyisocyanate and a polyamine and/or a diol or polyol are known capsules used in a variety of technical fields including perfumery.
  • Polyurea microcapsules obtained by reacting two polyisocyanates and a polyamine are described, for example, in WO 2011/161229 or WO 2011/160733.
  • the polyurea microcapsules are produced in the presence of polyvinylpyrrolidone (PVP) as a protective colloid.
  • PVP polyvinylpyrrolidone
  • WO 2012/107323 discloses polyurea microcapsules with a polyurea shell which comprises the reaction product of a polyisocyanate with guanazole (3,5-diamino)-1,2,4-triazole) and an amino acid in the presence of anionic stabilizers or surfactants such as anionic polyvinyl alcohol.
  • EP 0 537 467 B describes microcapsules made from polyisocyanates containing polyethylene oxide groups in the presence of stabilizers such as polyvinyl alcohol.
  • stabilizers such as polyvinyl alcohol.
  • microencapsulation can take place in an oil phase which is emulsified in a continuous aqueous phase which is generally stabilized by a surfactant system such as polyvinyl alcohols or carboxylated and sulfonated derivatives thereof.
  • the exemplary delivery systems from the prior art described above have both good stability, namely the ability to retain the active ingredient and thus the ability of the capsules to avoid the loss of the volatile components, and good performance, for example fragrance or fragrance release in the case of fragrance or fragrance capsules.
  • microcapsules of the prior art described above have the disadvantage that the polymeric capsule wall or capsule shell material requires a large proportion of polymer in order to ensure adequate stability and not to suffer excessive losses of active ingredient.
  • microencapsulation introduces plastic into the environment, which as "microplastic” can cause problems there, which may result in environmental damage or health problems.
  • microcapsules that have both good stability and good drug release.
  • the ability to retain the active ingredient and thus the ability of the capsules to avoid the loss of the volatile components depends in particular on the stability of the capsules in the product base.
  • capsules in particular with good stability do not automatically have good biodegradability.
  • the stability of the microcapsules increases as the degree of crosslinking increases, but at the same time the ability of the capsule shell to biodegrade also decreases.
  • the performance for example sensory performance, is lower, since the number of microcapsules which break open and release active substances as a result of pressure, friction, etc. decreases. If they are too unstable, they will be destroyed during storage and will not perform either.
  • vegan microcapsules can be understood and referred to as plant protein-based microcapsules. They are free from any animal components, especially animal protein components. This can also be understood and described in such a way that the plant protein-based microcapsules according to the invention are free from protein components of animal origin.
  • the present invention is to be understood and described in particular in such a way that plant protein-based microcapsules, ie vegan microcapsules, do not contain any animal protein components and also no other components of animal origin.
  • a vegetable protein-based microcapsule according to the present invention thus consists exclusively of proteins or protein components of vegetable origin with regard to the proteins used. Animal proteins or protein components, for example gelatin, are explicitly excluded with regard to the microcapsule according to the invention. This applies in the same way to the microcapsule slurry according to the invention.
  • the present invention is therefore based on the complex task of providing vegan, i.e. plant protein-based, microcapsules which preferably meet one, several or preferably all of the following requirements:
  • a vegetable protein-based microcapsule is produced from a vegetable protein and a crosslinking agent in an aqueous emulsion by interfacial polymerization.
  • the crosslinking makes it possible to form a very stable capsule shell or capsule wall with which a wide range of hydrophobic or lipophilic active ingredients can be encapsulated.
  • an internal non-aqueous phase is provided, comprising at least one aliphatic polyisocyanate as a crosslinking agent and at least one hydrophobic active ingredient.
  • the use of at least one aliphatic polyisocyanate is crucial here in order to obtain a vegetable protein-based microcapsule which, in particular, has excellent stability with significantly improved release behavior of one or more encapsulated or encapsulated active substance or active substances.
  • the invention thus relates to a method for producing a vegetable protein-based microcapsule, which comprises the following steps in this order:
  • an external aqueous phase comprising at least one plant protein, and optionally at least one first polysaccharide and/or at least one further crosslinking agent and/or at least one polyhydroxyphenol and/or at least one protective colloid, and further optionally adjusting the pH of the aqueous phase to a pH below the isoelectric point of the vegetable protein;
  • the present invention relates to a microcapsule or a microcapsule slurry that is produced by the process of the invention.
  • the subject of the present invention is a vegetable protein-based microcapsule, comprising or consisting of (a) a core comprising or consisting of at least one hydrophobic agent;
  • a capsule shell comprising or consisting of a crosslinking matrix or crosslinking units of at least one plant protein and at least one aliphatic polyisocyanate as crosslinking agent and optionally at least one polysaccharide; and optionally at least one/one protective colloid and/or optionally at least one/another crosslinking agent.
  • the present invention relates to the use of the plant protein-based microcapsules according to the invention or of dispersions which comprise the plant protein-based microcapsules according to the invention for the production of household products, textile care products, detergents, fabric softeners, cleaning agents, scent boosters, scent lotions or fragrance enhancers in liquid or solid form, cosmetics, personal care products, perfume compositions, agricultural products, pharmaceutical products or print coating for paper.
  • a combination of plant protein and subsequent crosslinking with an aliphatic polyisocyanate leads to stable plant protein-based microcapsules and thus ensures efficient encapsulation of lipophilic active ingredients with subsequent targeted release of these active ingredients can be.
  • the plant protein-based and thus vegan microcapsules according to the invention thus have excellent sensory properties in addition to excellent stability.
  • biodegradability can be made possible due to their bio-based and biodegradable building blocks.
  • a particular advantage of the process according to the invention is sometimes that the amount of aliphatic polyisocyanate used as a crosslinking agent can be reduced compared to the prior art.
  • FIG. 1 is a diagram showing a comparison of the stability in a fabric softener of some vegetable protein-based microcapsules according to the invention with already known microcapsules made of gelatin in relation to various polyisocyanates used as crosslinking agents.
  • FIG. 2 is a diagram showing the sensory performance of microcapsules according to the invention in a fabric softener in relation to various polyisocyanates used as crosslinking agents.
  • FIG. 3 is a diagram showing the sensory performance of various plant protein-based microcapsules according to the invention.
  • FIG. 4 is a diagram which shows a further comparison of the stabilities of plant protein-based microcapsules according to the invention in a fabric softener.
  • FIG. 5 is a diagram that shows a comparison of the stabilities of plant protein-based microcapsules according to the invention in a fabric softener in relation to the amounts of polyisocyanate used and the influence of hyaluronic acid.
  • FIG. 6 is a diagram showing the sensory evaluation of microcapsules according to the invention in relation to the amounts of polyisocyanate used and the influence of hyaluronic acid.
  • FIG. 7 is a diagram showing a further comparison of the stabilities of plant protein-based microcapsules according to the invention in relation to the amounts of polyisocyanate used and the influence of glycerol and a combination of glycerol and hyaluronic acid.
  • FIG. 8 is a diagram showing a sensory evaluation of microcapsules according to the invention in relation to the amounts of polyisocyanate used and the influence of hyaluronic acid and glycerol.
  • the present invention relates to a method for producing a vegetable protein-based microcapsule, which comprises the following steps in this order:
  • microcapsules are understood to mean microparticles which have at least one or more active substance(s) as the core material inside the capsule and are enclosed by a capsule shell or capsule wall.
  • the active ingredients are preferably hydrophobic or lipophilic active ingredients. Such active substances are not soluble or only sparingly soluble in water, but readily soluble in fats and oils.
  • microcapsule and capsule or “hydrophobic” and “lipophilic” are used synonymously for the purposes of the present invention.
  • the capsule shell or capsule wall is preferably made up of several crosslinking matrices or crosslinking units, which preferably have different compositions and are generated by several process steps or process sequences, in particular crosslinking steps, in the production of the microcapsule according to the invention.
  • the crosslinking matrix comprises at least one plant protein.
  • These capsule wall components are crosslinked with one another by means of a crosslinking agent and optionally a catalyst by interfacial polymerization, optionally via specifically catalyzed mechanisms, so that a three-dimensional network comprising plant protein and aliphatic polyisocyanate as crosslinking agent and optionally at least one polysaccharide is formed.
  • an internal non-aqueous phase which comprises at least one aliphatic polyisocyanate as a crosslinking agent and at least one hydrophobic active ingredient and optionally at least one further crosslinking agent.
  • Polyisocyanates with two isocyanate groups are also referred to as diisocyanates.
  • the at least one polyisocyanate used in step (i) is an aliphatic polyisocyanate.
  • the at least one aliphatic polyisocyanate is linear or branched.
  • the use of at least one aliphatic polyisocyanate is particularly favorable when using plant proteins and thus in the production of plant protein-based microcapsules. It may be possible here that the reduced reactivities of aliphatic polyisocyanates compared to aromatic polyisocyanates have a particularly advantageous effect on the stability of the vegetable protein-based microcapsules.
  • the stabilities achieved by the vegetable protein-based microcapsules are in any case significantly lower when using aromatic polyisocyanates or mixtures with aromatic polyisocyanates than when using aliphatic polyisocyanates.
  • reduced reactivity in relation to the at least one polyisocyanate used as a crosslinking agent is particularly preferred in the production of the vegetable protein-based microcapsules, and therefore in the method according to the invention. Accelerated reactivity of the polyisocyanates used and thus also the production time of the microcapsules per se are therefore not in the foreground in the process according to the invention.
  • At least difunctional, preferably polyfunctional, polyisocyanates are very particularly preferably used in the process according to the invention, i.e. all aliphatic and alicyclic, ie cycloaliphatic, isocyanates are suitable provided they have at least one, preferably two or more, reactive isocyanate groups.
  • Aliphatic, cycloaliphatic or heterocyclic polyisocyanates, their substitution products and mixtures of the aforementioned monomeric or oligomeric compounds are particularly preferred.
  • These include, for example, aliphatic or cycloaliphatic di-, tri- and higher polyisocyanates.
  • R represents aliphatic or alicyclic radicals.
  • the radicals have five or more carbon atoms.
  • At least one of the aliphatic polyisocyanates or the one aliphatic polyisocyanate is a cycloaliphatic polyisocyanate having two or more isocyanate groups.
  • aliphatic polyisocyanate refers to any polyisocyanate molecule that is not aromatic.
  • the molecule comprises at least two isocyanate groups, i.e. at least 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 20, 50, 100, 200 or more isocyanate groups, directly bonded to a corresponding number of different carbon atoms of the same aliphatic molecule, and derivatives of such compounds.
  • the aliphatic polyisocyanate molecule containing at least two isocyanate groups, i.e. at least 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 20, 50, 100, 200 or has more isocyanate groups, may further be linear, branched or cyclic and may have any substitutions including, for example, aliphatic substituents, one or more heteroatoms such as nitrogen, oxygen, phosphorus and/or sulfur, halogens such as fluorine, chlorine, bromine and/or iodine and/or other functional groups such as alkoxy groups.
  • the linear aliphatic polyisocyanate molecule may preferably be selected from C2 to C20 linear alkyl, preferably C3 to C15 linear alkyl, C4 to C12 linear alkyl, C5 to C10 linear alkyl, C6 to C9 linear linear alkyl or C7 to C8 linear alkyl. In any case, the linear aliphatic molecule does not include an aromatic structure.
  • the branched aliphatic polyisocyanate molecule may preferably be selected from C2 to C20 branched alkyl, preferably C3 to C15 branched alkyl, C4 to C12 branched alkyl, C5 to C10 branched alkyl, C6 to C9 branched alkyl, C7 to C8 branched alkyl.
  • a cycloaliphatic polyisocyanate is also to be understood and described as an aliphatic polyisocyanate.
  • the cyclic aliphatic polyisocyanate molecule may comprise at least 1, i.e. 1, 2, 3, 4 or more, non-aromatic ring structures, the ring structure itself preferably consisting of only C atoms.
  • the carbon atoms of the ring structure can carry suitable substituents.
  • the at least 1-ring structures preferably consist, independently of one another, of 3, 4, 5, 6, 7 or 8-membered rings.
  • the cyclic aliphatic molecule preferably comprises 2 to 20 carbon atoms, such as 3 to 15 carbon atoms, 4 to 12 carbon atoms, 5 to 10 carbon atoms, 6 to 9 carbon atoms or 7 to 8 carbon atoms.
  • the linear, branched or cyclic aliphatic polyisocyanate can be present as a monomer or polymer.
  • a monomeric polyisocyanate is a molecule that is not connected to another molecule, particularly not through one or more crosslinking agents.
  • a polymeric polyisocyanate comprises at least two monomers linked together by one or more crosslinking agents. The at least two monomers do not necessarily have to be the same monomers, but can also be different.
  • a polymeric polyisocyanate preferably comprises at least 2 or more monomers, ie at least 2, 3, 4, 5, 10, 20, 30, 40, 50, 100 or more monomers linked together by at least one crosslinking agent.
  • the linear, branched, or cyclic aliphatic polyisocyanate is preferably of limited size/molecular weight, allowing reactivity with the one or more crosslinking agents.
  • suitable molecular weights preferably include about 100 g/mol to 5 ⁇ 10 4 ; g/mol, preferably 120 g/mol to 2 ⁇ 10 4 g/mol, 140 g/mol to 10 4 ; g/mol 160 g/mol to 5 * 10 3 g/mol, 180 g/mol to 2 ⁇ 10 3 g/mol, 200 g/mol to 10 3 g/mol, 220 g/mol to 900 g/mol, 240 g/mol to 800 g/mol, 260 g/mol to 700 g/mol, 280 g/mol to 600 g/mol, 300 g/mol to 500 g/mol, 320 g/mol to 450 g/mol or 340 g/mol to 400 g/mol.
  • any number of different linear, branched and/or cyclic aliphatic polyisocyanates can be used in the context of the invention.
  • at least one or more, i. H. at least 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 different linear aliphatic polyisocyanates are used.
  • at least one or more, i. H. at least 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 different branched aliphatic polyisocyanates are used.
  • at least one or more, i. H. at least 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 different branched cyclic polyisocyanates are used as crosslinking agents.
  • Derivatives of the linear, branched and/or cyclic aliphatic polyisocyanates are preferably used.
  • a derivative as used herein, is understood in its broadest sense as a compound derived from a compound by a chemical reaction.
  • Examples of derivatives include oligomers and/or adducts of the above linear or branched aliphatic polyisocyanates.
  • Preferred oligomers are biurets, isocyanurates, uretdiones, iminooxadiazinediones and preferred adducts are trimethylolpropane adducts. These oligomers/adducts are well known in the art and are disclosed, for example, in US Pat. No. 4,855,490 or US Pat. No. 4,144,268.
  • the aliphatic polyisocyanate is present only in monomeric form and/or dimerized form (as isocyanate) or in oligomeric form.
  • the derivatives of the linear, branched or cyclic polyisocyanates and/or mixtures thereof can also be obtained by reacting the polyisocyanates with polyalcohols (e.g. glycerol), polyamines, polythiols (e.g. dimercaprol).
  • the isocyanate compounds as defined above expressly include the different isomers, if any, alone or in combination.
  • methylenebis(cyclohexyl isocyanate) H12MDI
  • H12MDI methylenebis(cyclohexyl isocyanate)
  • H12MDI includes 4,4'-methylenebis(cyclohexyl isocyanate), 2,4'-methylenebis(cyclohexyl isocyanate), and/or 2,2'-methylenebis(cyclohexyl isocyanate).
  • Exemplary aliphatic polyisocyanates include those that are commercially available, e.g. BAYHYDUR N304 and BAYHYDUR N3Q5, which are aliphatic water-dispersible polyisocyanates based on hexamethylene diisocyanate, DESMODUR N3400, DESMODUR N3600, DESMODUR N3700 and DESMODUR N3900, which are low viscosity, polyfunctional aliphatic polyisocyanates based on hexamethylene diisocyanate, and DESMODUR 3600 and DESMODUR N 100 which are aliphatic polyisocyanates based on hexamethylene diisocyanate, each of which is available from Bayer Corporation, Pittsburgh, PA.
  • BAYHYDUR N304 and BAYHYDUR N3Q5 which are aliphatic water-dispersible polyisocyanates based on hexamethylene diisocyanate
  • DESMODUR N3400 DESMODUR N3600,
  • the linear or branched aliphatic and/or cycloaliphatic polyisocyanates is or are selected from the group consisting of pentamethylene diisocyanate (PDI, such as Stabio D-370N or D-376N from Mitsui Chemicals Inc., Japan), hexamethylene diisocyanate (HDI), ethyl ester lysine triisocyanate, lysine diisocyanate ethyl ester and derivatives thereof, preferably wherein each of the derivatives comprises more than one isocyanate group and optionally further comprises one or more groups selected from the group consisting of biuret , isocyanurate, uretdione, iminooxadiazinedione and trimethylolpropane adduct and/or where the cyclic aliphatic polyisocyanates are or are selected from the group consisting of isophorone diisocyanate (IPDI), 1,3-bis
  • Aliphatic polyisocyanates obtained from renewable raw materials such as PDI (Stabio D-370N or D-376N from Mitsui Chemicals Inc., Japan) are particularly preferred. It has been found that such aliphatic polyisocyanates, which are obtained from renewable raw materials, do not adversely affect the quality/properties of the core-shell capsules.
  • the polyisocyanate used in the production of the vegetable protein-based microcapsules according to the present invention is used as the sole polyisocyanate component, i.e. without the admixture of another, different polyisocyanate component.
  • Examples of the monomeric polyisocyanates which can be used according to the invention and which contain at least two polyisocyanate groups are:
  • the polymerizable compounds having at least two polyisocyanate groups are preferably industrially produced di- and poly- isocyanates are preferred, for example HDI: hexamethylene diisocyanate-(1,6) and/or IPDI: isophorone diisocyanate.
  • diisocyanates such as 1,4-diisocyanatobutane, 1,6-diisocyanatohexane, 1,5-diisocyanato-2,2-dimethylpentane, 2,2,4- and 2,4,4 -Trimethyl-1,6-diisocyanatohexane, 1,10-diisocyanatodecane, 1,3- and 1,4-diisocyanatocyclohexane, 1-polyisocyanato-3,3,5-trimethyl-5-polyisocyanatomethylcyclohexane (isophorone diisocyanate), 4,4 '-diisocyanatodicyclohexylmethane, 2,4- and 2,6-diisocyanatomethylcyclohexane and mixtures thereof.
  • diisocyanates such as 1,4-diisocyanatobutane, 1,6-diisocyanatohexane, 1,5-diiso
  • diisocyanates include, for example, 1-methyl-2,4-diisocyanatocyclohexane, 1,6-diisocyanato-2,2,4-trimethylhexane, 1,6-diisocyanato-2,4,4-trimethylhexane, 1-Isocyanatomethyl-3-isocyanato-1,5,5-trimethylcyclohexane, chlorinated and brominated diisocyanates, phosphorus-containing diisocyanates, tetramethoxybutane-1,4-diisocyanate, butane-1,4-diisocyanate (HDI), Dicyclohexylmethane diisocyanate, cyclohexane-1,4-diisocyanate, ethylene diisocyanate.
  • the internal non-aqueous phase comprises a mixture of two or more different polymerizable polyisocyanates, for example polyisocyanates with different chain lengths, which can form copolymers.
  • aliphatic polyisocyanates can be provided within the scope of the process according to the invention.
  • the different reaction rates of the polyisocyanates are used.
  • Short-chain aliphatic polyisocyanates ie aliphatic polyisocyanates having one to five carbon atoms, preferably three to five carbon atoms, can enable higher reaction rates compared to longer-chain analogs.
  • the different aliphatic polyisocyanates therefore also have different chain lengths.
  • longer-chain polyisocyanates preferably have six, seven, eight, nine, ten, eleven, twelve, thirteen, fourteen, 20, 25 or more carbon atoms, but more preferably have six to twelve carbon atoms and particularly preferably six to eight carbon atoms .
  • Shorter-chain polyisocyanates are to be understood as meaning polyisocyanates having one to five carbon atoms and preferably polyisocyanates having three to five carbon atoms.
  • aliphatic polyisocyanates are to be given particular preference, not least because of their chemical relationship to bio-based systems.
  • both lysine and 1,5-diisocyanato- pentane the same degradation product, 1, 5-diaminopentane, and are therefore particularly suitable for improved biodegradability of microcapsules, taking environmental aspects into account.
  • Primary versions include mixtures of longer-chain and shorter-chain diisocyanates in any mixing ratio.
  • the mixing ratio of longer-chain diisocyanates to shorter-chain diisocyanates is preferably in a range from 4:1 to 1:4 and particularly preferably from 2:1 to 1:2.
  • the polyisocyanates are present in a mixture of monomeric or oligomeric or polymeric form.
  • short-chain aliphatic polyisocyanate (monomer or oligomer or polymer) and short-chain aliphatic polyisocyanate (monomer or oligomer or polymer); short chain aliphatic polyisocyanate (monomer or oligomer or polymer) and long chain aliphatic polyisocyanate (monomer or oligomer or polymer); long chain aliphatic polyisocyanate (monomer or oligomer or polymer) and short chain aliphatic polyisocyanate (monomer or oligomer or polymer); long chain aliphatic polyisocyanate (monomer or oligomer or polymer) and long chain aliphatic polyisocyanate (monomer or oligomer or polymer); long chain aliphatic polyisocyanate (monomer or oligomer or polymer) and long chain aliphatic polyisocyanate (monomer or oligomer or polymer); with the definitions for short-
  • polyisocyanate combinations or polyisocyanate mixtures of two different aliphatic can be particularly stable and better, i. H. create more densely branched crosslinks within the capsule shell.
  • high-performance (fragrance or fragrance release) vegetable protein-based microcapsules can be produced, which are produced from a mixture of two different aliphatic polyisocyanates.
  • Such vegetable protein-based microcapsules are very stable and are characterized by outstanding fragrance storage properties, which in turn is reflected in better performance (fragrance or fragrance release) of the capsules, for example in the field of fragrance or fragrance encapsulation.
  • microcapsule made from an aliphatic-aliphatic polyisocyanate mixture is significantly improved at least in terms of stability compared to a microcapsule made from an aliphatic-aromatic polyisocyanate mixture, as illustrated in the following exemplary embodiments. Accordingly, the use of aliphatic polyisocyanates in the combination described above is fundamentally provided for in the present invention. The In any case, the use of any aromatic polyisocyanates is explicitly excluded in the present case.
  • the proportion of the crosslinking agent(s), preferably the polyisocyanate or polyisocyanates, in the internal non-aqueous phase is in a range from 0.1 to 5% by weight, preferably in a range from 0.2 to 4% by weight based on the total weight of the non-aqueous phase.
  • the crosslinking agent is used in the internal non-aqueous phase in a range of 0.5 to 2% by weight based on the total weight of the non-aqueous phase.
  • the total weight of the non-aqueous phase is made up of all components of the non-aqueous phase.
  • the crosslinking agent is added to the internal non-aqueous phase either as such, e.g. as a solid, or in the form of an aqueous solution.
  • the amount Total polyisocyanate, based on the amount of wall-forming agent is 15 to 70 percent by weight, preferably 20 to 50 percent by weight, particularly preferably 25 to 35 percent by weight, or the total amount of polyisocyanates used as crosslinking agent together is 0.5% to 4%, preferably 1% up to 3%, particularly preferably 1.5% to 2.5%, based on the total amount of hydrophobic active substance used, preferably fragrance or fragrance, in particular in the core of the capsule.
  • Wall formers within the meaning of the invention are all solid components of the internal and the external phase and any optionally added polysaccharides, in particular further crosslinking agents and/or polyhydroxyphenols and/or Catalysts and in the present disclosure all other suitable substances.
  • a non-internal, non-aqueous phase comprising an aliphatic polyisocyanate as a crosslinking agent and a cycloaliphatic polyisocyanate as a crosslinking agent, the aliphatic polyisocyanate and the cycloaliphatic polyisocyanate can be used in a respective molar ratio of 85:15 to 15:85.
  • plant protein-based microcapsules can be produced in this way which have particularly good stability properties combined with very good sensory properties (scent or fragrance release).
  • the total content of polyisocyanates used as crosslinking agents can be reduced, which has a positive impact on the environment.
  • a non-internal non-aqueous phase comprising two different aliphatic polyisocyanates as crosslinking agents, the two aliphatic polyisocyanates in a respective molar ratio of 85 : 15 to 15:85 can be used.
  • an internal non-aqueous phase comprising three crosslinking agents, the three crosslinking agents being different aliphatic or cycloaliphatic polyisocyanates, preferably at least one cycloaliphatic polyisocyanate and at least one aliphatic polyisocyanate being present, the three polyisocyanates each being present in amounts of from 20% to 60% by total weight of the three polyisocyanates are used together.
  • a cycloaliphatic polyisocyanate and two different aliphatic polyisocyanates can also be particularly advantageous for a cycloaliphatic polyisocyanate and two different aliphatic polyisocyanates to be used.
  • the three cycloaliphatic polyisocyanates are each used in equal parts. Furthermore, it can be provided that the cycloaliphatic polyisocyanate and the two different aliphatic polyisocyanates are each used in equal parts.
  • At least one further crosslinking agent can be added to the internal non-aqueous phase to improve the crosslinking of the at least one polysaccharide and/or the at least one plant protein.
  • the further crosslinking agent is different from the (first) crosslinking agent.
  • the at least one further crosslinking agent can be the same as the crosslinking agent. It can also be possible for the crosslinking agent to comprise the at least one further crosslinking agent.
  • step (i) at least one further crosslinking agent and/or in step (ii) and/or in step (vii) a further crosslinking agent is added.
  • the at least one further crosslinking agent can be selected in the case of addition in step (i) or the further crosslinking agent in the case of addition in step (ii) and/or in step (vii) is/are selected from the group which consists of transglutaminase, peroxidase, phytochemicals selected from the Group consisting of polyphenols, polyhydroxyphenols, in particular tannin, gallic acid, ferulic acid, hesperidin, cinnamaldehyde, vanillin, carvacrol and mixtures of two or more of the aforementioned crosslinking agents.
  • the at least one further crosslinking agent can be a polyphenol and/or a polyhydroxyphenol.
  • transglutaminase catalyses cross-linking via isopeptide bonds of two amino acids, glutamine and lysine.
  • the phenolic groups of the secondary plant substances cross-link the peptides via hydrogen bonds.
  • the aldehydes, cinnamaldehyde and vanillin react covalently with the free amino groups of the proteins via the reactive aldehyde groups.
  • Cinnamaldehyde, tannin, ferulic acid and gallic acid are particularly preferred among the aforementioned further crosslinking agents.
  • the further crosslinking agent can be added to the internal non-aqueous phase either as such, for example as a solid, or in the form of a solution.
  • the at least one crosslinking agent is first essentially dissolved together with the at least one or more active substance(s) to be encapsulated, optionally in an inert, nonaqueous solvent or a solvent mixture of inert, nonaqueous solvents .
  • the term “essentially dissolved” means that at least 90% by weight, preferably at least 98% by weight, more preferably 99.9% by weight, of the aforementioned components are dissolved in the solvent or in the solvent mixture to be able to use them in this procedure.
  • the at least one polyisocyanate and the at least one active substance to be encapsulated are preferably completely dissolved in the solvent or in the solvent mixture. If a solvent does not ensure sufficient solubility of the isocyanates, it is possible to overcome this disadvantage by using suitable solubility promoters.
  • Preferred solvents for the internal non-aqueous phase are water-immiscible and non-reactive with the isocyanate component(s) or the active component(s) and have little or no odor at the levels used.
  • solvent in the context of the present invention includes all kinds of oil bodies or oil components, in particular vegetable oils such as Rapeseed oil, sunflower oil, soybean oil, olive oil and the like, modified vegetable oils, eg alkoxylated sunflower or soybean oil, synthetic (tri)glycerides such as technical mixtures of mono-, di- and triglycerides of C6 to C22 fatty acids, fatty acid alkyl esters, eg methyl or ethyl esters of vegetable oils (Agnique® ME 18 RD-F, Agnique® ME 18 SD-F, Agnique® ME 12C-F, Agnique® ME1270), fatty acid alkyl esters based on these C6 to C22 fatty acids, mineral oils and mixtures thereof.
  • vegetable oils such as Rapeseed oil, sunflower oil, soybean oil, olive oil and the like
  • modified vegetable oils eg alkoxylated sunflower or soybean oil
  • synthetic (tri)glycerides such as technical mixtures of mono-, di- and triglycerides of
  • Suitable and preferred lipophilic solvents are: Guerbet alcohols based on fatty alcohols having 6 to 18, preferably 8 to 10 carbon atoms, esters of linear C6 to C22 fatty acids with linear or branched C6 to C22 fatty alcohols or esters of branched C6 - to C13 carboxylic acids with linear or branched C6 to C22 fatty alcohols, such as myristyl myristate, myristyl palmitate, myristyl stearate, myristyl isostearate, myristyl oleate, myristyl behenate, myristyl rucate, cetyl myristate, cetyl palmitate, cetyl stearate, cetylisostearate, cetyl oleate, cetyl behenate, cetylerucate, stearyl myristate, stearyl palmitate , stearyl stearate, stearyl isostearate,
  • esters of linear C6 to C22 fatty acids with branched alcohols especially 2-ethylhexanol, esters of C18 to C38 alkyl hydroxycarboxylic acids with linear or branched C6 to C22 fatty acids, especially dioctylalate, esters of linear or branched fatty acids with polyhydric alcohols (such as propylene glycol, dimer diol or trimer triol) and/or Guerbet alcohols, triglycerides based on C6 to C10 fatty acids, liquid mono/di/triglyceride mixtures of C6 to C18 fatty acids, esters of C6 to C22 fatty alcohols and/or Guerbet alcohols with aromatic carboxylic acids, in particular benzoic acid, esters of C2 to C12 dicarboxylic acids with linear or branched alcohols having 1 to 22 carbon atoms or polyols having 2 to 10 carbon atoms and 2 to 6 hydroxyl groups, vegetable oils,
  • Preferred solvents are in particular esters of linear C6 to C22 fatty acids with branched alcohols, esters of C18 to C38 alkyl hydroxycarboxylic acids with linear or branched C6 to C22 fatty alcohols, linear or branched C6 to C22 fatty alcohols, in particular Dioctyl malate, esters of linear or branched fatty acids with polyhydric alcohols, such as. B.
  • liquid linear and/or branched and/or saturated or unsaturated hydrocarbons or any desired mixtures thereof can be used as solvents in the context of the present invention.
  • solvents can be, for example, alkanes having 4 to 22, preferably 6 to 18, carbon atoms, or any mixtures thereof.
  • alkylaromatic hydrocarbons such as diisopropylnaphthalene or substituted biphenyls, chlorinated diphenyl, paraffins, chlorinated paraffin, natural vegetable oils such as cottonseed oil, peanut oil, palm oil, tricresyl phosphate, silicone oil, dialkyl phthalates, Dialkyl adipates, partially hydrogenated terphenyl, alkylated biphenyl, alkylated naphthalene, diaryl ether, aryl alkyl ether and higher alkylated benzene, benzyl benzoate, isopropyl myristate and any mixtures of these hydrophobic solvents and mixtures of one or more of these hydrophobic solvents with kerosene, paraffins and/or isoparaffins.
  • alkylaromatic hydrocarbons such as diisopropylnaphthalene or substituted biphenyls, chlorinated diphenyl, paraffins, chlorinated
  • Vegetable oils, triglycerides, benzyl benzoate or isopropyl myristate are preferably used as solvents for providing the internal non-aqueous phase.
  • Most preferred are vegetable oils selected from the group consisting of palm oil, soybean oil, canola oil, sunflower oil, palm kernel oil, cottonseed oil, peanut oil, corn oil, coconut oil, olive oil, sesame oil, linseed oil, safflower oil, modified vegetable oils and mixtures thereof.
  • the aforementioned solvents are used in the process of the present invention either individually or as a mixture of two or more solvents.
  • the at least one polyisocyanate is dissolved directly in a solution of at least one active substance, preferably one or more fragrance or flavoring substance / fragrance or flavoring substances or a perfume oil, so that essentially no Solvent as described above is present in the core of the vegetable protein-based microcapsule according to the invention.
  • the avoidance of a solvent in the microcapsule core is advantageous in that it reduces manufacturing costs and takes into account environmental considerations.
  • the fragrances or flavorings are in particular dissolved in solvents which are customarily used in the perfume or flavoring industry.
  • the solvent is preferably not an alcohol since alcohols react with the isocyanates.
  • suitable solvents are diethyl phthaloate, isopropyl myristate, Abalyn® (rosins available from Eastman), benzyl benzoate, ethyl citrate, limonene, or other terpenes or isoparaffins.
  • the solvent is very hydrophobic.
  • the fragrance or flavoring solution contains less than 30% solvent. More preferably, the fragrance or flavor solution comprises less than 20% and even more preferably less than 10% solvent, all such percentages being defined by weight relative to the total weight of the fragrance or flavor solution. Most preferably, the fragrance or aromatic is essentially free of solvents.
  • the at least one hydrophobic active substance is already present in a mixture with a solvent or a solvent mixture, the use of an inert solvent or a solvent mixture is not necessary.
  • the at least one crosslinking agent can be mixed directly with the hydrophobic agent to obtain an internal non-aqueous phase.
  • any material that is suitable for inclusion in microcapsules can be used as the active substance to be encapsulated or as the core material for producing the microcapsules according to the invention in the process according to the invention is.
  • Active ingredients to be encapsulated are preferably hydrophobic, ie water-insoluble or water-immiscible, liquids or solids and also suspensions. These are predominantly non-polar substances. Such hydrophobic substances are almost always lipophilic, which means they dissolve well in fat and oil.
  • the core material is a hydrophobic active ingredient, i.e. a substance that has a specific effect or causes a specific reaction, for example a drug, a crop protection agent, a cosmetic active ingredient, a food ingredient, or the like.
  • the at least one active substance to be encapsulated which is used in the method according to the invention, is a hydrophobic or lipophilic active substance. This ensures that the active ingredient to be encapsulated is in the internal non-aqueous phase during production of the microcapsule according to the invention and does not mix with the external aqueous phase, since otherwise no emulsion can form and the capsule wall material cannot separate on the droplet surface. As a result, during the subsequent emulsification and crosslinking of the capsule wall components, the lipophilic active substance is completely enclosed inside the microcapsule as the core material.
  • the internal non-aqueous phase formed in this way is characterized by its organically hydrophobic, oily character.
  • a further crosslinking agent is added in step (ii).
  • This can be a crosslinking agent selected from the group consisting of transglutaminase, peroxidase, phytochemicals selected from the group consisting of polyphenols, polyhydroxyphenols, in particular tannin, gallic acid, ferulic acid, hesperidin, cinnamaldehyde, vanillin , carvacrol and mixtures of two or more of the aforementioned crosslinking agents.
  • the amount of the further crosslinking agent, which is optionally added in step (ii), is 0.1% to 1.0%, preferably 0.15% to 0.5%, particularly preferably 0.17% % to 0.23% based on the total amount of the external aqueous phase.
  • the at least one lipophilic or hydrophobic active ingredient is in particular a lipophilic or hydrophobic fragrance or flavoring or a lipophilic or hydrophobic perfume oil or flavor (fragrance or flavoring mixture), a cooling agent, a TRPV1 or a TRPV3 modulator, a substance causing a pungent taste or a warmth or heat sensation on the skin or mucous membranes, or a tingling or tingling sensation in the mouth or throat, or active substances with an astringent effect, a pesticide, a biocide Insecticide, a substance from the group of repellents, a food additive, a cosmetic active ingredient, a pharmaceutical active ingredient, a dye, a dye precursor; an agrochemical, a dye, a fluorescent paint, an optical brightener, a solvent, a wax, a silicone oil, a lubricant, a print coating for paper, or a mixture of two or more of the foregoing.
  • hydrophobic or lipophilic active ingredients are in particular hydrophobic fragrances or fragrances or mixtures of two or more fragrances or fragrances (perfume oils) or hydrophobic flavorings or flavoring mixtures of two or more flavorings (flavors) or also biogenic principles into consideration.
  • the microcapsules have a core material in the form of a hydrophobic individual fragrance or individual fragrance, the core material comprising at least one individual fragrance or individual fragrance or mixtures thereof, selected from one or more of the following groups: extracts of natural raw materials and also fractions thereof or components isolated therefrom; individual fragrances from a group of hydrocarbons; aliphatic alcohols; aliphatic aldehydes and acetals; aliphatic ketones and oximes; aliphatic sulfur-containing compounds; aliphatic nitriles; esters of aliphatic carboxylic acids; formates, acetates, propionates, isobutyrates, butyrates, isovalerates, pentanoates, hexanoates, crotonates, tiglinates, and 3-methyl-2-butenoates of acyclic terpene alcohols; acyclic terpene aldehydes and keto
  • fragrances and flavors for the production of the capsules according to the invention are described, for example, in “Fragrances”, in Steffen Arctander, in “Perfume and Flavor Chemicals", self-published, Montclair, N.J. 1969; H. Surburg, J. Panten, in “Common Fragrance and Flavor Materials", 5th edition, Wiley-VCH, Weinheim 2006.
  • the plant protein-based microcapsules according to the invention preferably have a core material in the form of a hydrophobic single fragrance or single flavoring, the core material comprising at least one single fragrance or single flavoring selected from one or more of the following groups : hydrocarbons such as B. 3-carene; a-pinene; beta-pinene; alpha-terpinene; gamma-terpinene; p-cymene; bisabolene; camphene; caryophyllene; cedren; farnese; limonene; longifolia; myrcene; ocimene; valencene; (E,Z)-1,3,5-undecatriene;
  • Aliphatic alcohols such as B. Hexanol; octanol; 3-octanol; 2,6-dimethylheptanol; 2-methylheptanol, 2-methyloctanol; (E)-2-hexenol; (E)- and (Z)-3-hexenol; 1-octen-3-ol; mixture of 3,4,5,6,6-pentamethyl-3,4-hepten-2-ol and 3,5,6,6-tetramethyl-4-methyleneheptan-2-ol; (E,Z)-2,6-nonadienol; 3,7-dimethyl-7-methoxyoctan-2-ol; 9-decenol; 10-undecenol; 4-methyl-3-decen-5-ol;
  • Aliphatic aldehydes and their acetals such as. B. hexanal; heptanal; octanal; nonanal; decanal; undecanal; dodecanal; tridecanal; 2-methyloctanal; 2-methylnonanal; (E)-2-hexenal; (Z)-4-heptenal; 2,6-dimethyl-5-heptenal; 10-undecenal; (E)-4-decenal; 2-dodecenal; 2,6,10-trimethyl-5,9-undecadienal; heptanal diethyl acetal; 1,1-dimethoxy-2,2,5-trimethyl-4-hexene;
  • Aliphatic ketones and their oximes such as.
  • Aliphatic sulfur-containing compounds such as. B. 3-methylthiohexanol; 3-methylthiohexyl acetate; 3-mercaptohexanol; 3-mercaptohexyl acetate; 3-mercaptohexyl butyrate; 3-acetylthiohexyl acetate; 1-menthene-8-thiol;
  • Aliphatic nitriles such as B. 2-nononitrile; 2-tridecenonitrile; 2,12-tridecenonitrile; 3,7-dimethyl-2,6-octadienonitrile; 3,7-dimethyl-6-octenonitrile;
  • Aliphatic carboxylic acids and their esters such as. B. (E)- and (Z)-3-hexenyl formate; ethyl acetoacetate; isoamyl acetate; hexyl acetate; 3,5,5-trimethylhexyl acetate; 3-methyl-2-butenyl acetate; (E)-2-hexenyl acetate; (E)- and (Z)-3-hexenyl acetate; octyl acetate; 3-octyl acetate; 1 -octen-3-yl acetate; ethyl butyrate; butyl butyrate; isoamyl butyrate; hexyl butyrate; (E)- and (Z)-3-hexenyl isobutyrate; hexyl crotonate; ethyl isovalerate; ethyl 2-methylpentanoate; ethyl hexan
  • Acyclic terpene alcohols such as. B. Citronellol; geraniol; nerol; linalool; lavadulol; nerolidol; farnesol; tetrahydrolinalool; tetrahydrogeraniol; 2,6-dimethyl-7-octen-2-ol; 2,6-dimethyloctan-2-ol; 2-methyl-6-methylene-7-octen-2-ol; 2,6-dimethyl-5,7-octadien-2-ol; 2,6-dimethyl-3,5-octadien-2-ol; 3,7-dimethyl-4,6-octadien-3-ol; 3,7-dimethyl-1,5,7-octatrien-3-ol; 2,6-dimethyl-2,5,7-octatrien-1-ol; and their formates, acetates, propionates, isobutyrates, butyrates,
  • Acyclic terpene aldehydes and ketones such as. B. Geranium; neral; citronellal; 7-hydroxy-3,7-dimethyloctanal; 7-methoxy-3,7-dimethyloctanal; 2,6,10-trimethyl-9-undecenal; geranylacetone; as well as the dimethyl and diethyl acetals of geranial, neral, 7-hydroxy-3,7-dimethyloctanal;
  • Cyclic terpene alcohols such as. B. Menthol; isopulegol; a-terpineol; terpinenol- 4; menthan-8-ol; menthan-1 -ol; menthan-7-ol; borneol; isoborneol; linalool oxide; nopole; cedrol; ambrinol; vetiverol; guajol; and their formates, acetates, propionates, isobutyrates, butyrates, isovalerianates, pentanoates, hexanoates, crotonates, tiglinates, 3-methyl-2-butenoates;
  • Cyclic terpene aldehydes and ketones such as. B. menthone; isomenthone; 8-mercaptomenthan-3-one; carvone; camphor; fenchone; a-ionone; beta-ionone; a-n-methyl ionone; beta-n-methyl ionone; a-isomethyl ionone; beta-isomethylionone; a-iron; ß-iron; a-damascenone; beta-damascenone; gamma-damascenone; d-damascenone; 1-(2,4,4-Trimethyl-2-cyclohexen-1-yl)-2-buten-1-one; 1,3,4,6,7,8a-hexahydro-1,1,5,5-tetramethyl-2H-2,4a-methanonaphthalen-8(5H)-one;
  • nootkatone nootkatone; dihydronootkatone; a-sinensal; beta-sinensal; acetylated cedarwood oil (methyl cedryl ketone);
  • Cyclic alcohols such as. B. 4-tert-butylcyclohexanol; 3,3,5-trimethylcyclohexanol; 3-isocamphylcyclohexanol; 2,6,9-trimethyl-(Z2,Z5,E9)-cyclododecatrien-1-ol; 2-isobutyl-4-methyltetrahydro-2H-pyran-4-ol; from the group of cycloaliphatic alcohols such.
  • Cyclic and cycloaliphatic ethers such as. B. cineole; cedryl methyl ether; cyclododecyl methyl ether; (ethoxymethoxy)cyclododecane; a-cedrene epoxide; 3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan; 3a-ethyl-6,6,9a-trimethyl-dodecahydronaph-tho[2,1-b]furan; 1,5,9-trimethyl-13-oxabicyclo[10.1,0]trideca-4,8-diene; rose oxide; 2-(2,4-dimethyl-3-cyclohexen-1-yl)-5-methyl-5-(1-methylpropyl)-1,3-dioxane;
  • Cyclic ketones such as B. 4-tert-butylcyclohexanone; 2,2,5-trimethyl-5-pentylcyclopentanone; 2-heptylcyclopentanone; 2-pentylcyclopentanone; 2-hydroxy-3-methyl-2-cyclopenten-1-one; 3-methyl-cis-2-penten-1-yl-2-cyclopenten-1-one; 3-methyl-2-pentyl-2-cyclopenten-1-one; 3-methyl-4-cyclopentadecenone; 3-methyl-5-cyclopentadecenone; 3-
  • methylcyclopentadecanone 4-(1-ethoxyvinyl)-3,3,5,5-tetramethylcyclohexanone; 4-tert-pentylcyclohexanone; 5-cyclohexadecen-1-one; 6,7-dihydro-1,1,2,3,3-pentamethyl-4(5H)-indanone; 9-cycloheptadecen-1-one; cyclopentadecanone; cyclohexadecanone;
  • Cycloaliphatic aldehydes such as. B. 2,4-dimethyl-3-cyclohexenecarbaldehyde; 2-methyl-4-(2,2,6-trimethyl-cyclohexen-1-yl)-2-butenal; 4-(4-hydroxy-4-methylpentyl)-3-cyclohexenecarbaldehyde; 4-(4-methyl-3-penten-1-yl)-3-cyclohexenecarbaldehyde;
  • Cycloaliphatic ketones such as. B. 1-(3,3-dimethylcyclohexyl)-4-penten-1-one; 1-(5,5-dimethyl-2-cyclohexen-1-yl)-4-penten-1-one; 2,3,8,8-tetramethyl
  • Esters of cycloaliphatic carboxylic acids such as.
  • Aromatic hydrocarbons such as B. styrene and diphenylmethane
  • Araliphatic alcohols such as B. benzyl alcohol; 1-phenylethyl alcohol; 2-phenylethyl alcohol; 3-phenylpropanol; 2-phenylpropanol; 2-phenoxyethanol; 2,2-dimethyl-3-phenylpropanol; 2,2-dimethyl-3-(3-methylphenyl)propanol; 1,1-dimethyl-2-phenylethyl alcohol; 1,1-dimethyl-3-phenylpropanol; 1-ethyl-1-methyl-3-phenylpropanol; 2-methyl-5-phenylpentanol; 3-methyl-5-phenylpentanol; 3-phenyl-2-propen-1-ol; 4-methoxybenzyl alcohol; 1-(4-isopropylphenyl)ethanol;
  • Esters of araliphatic alcohols and aliphatic carboxylic acids such as. B. benzyl acetate; benzyl propionate; benzyl isobutyrate; benzyl isovalerianate; 2-phenylethyl acetate; 2-phenylethyl propionate; 2-phenylethyl isobutyrate; 2-phenylethyl isovalerianate; 1 -phenylethyl acetate; a-trichloromethylbenzyl acetate; a,a-dimethylphenylethyl acetate; ⁇ , ⁇ -dimethylphenylethyl butyrate; cinnamyl acetate; 2-phenoxyethyl isobutyrate; 4-methoxybenzyl acetate;
  • Araliphatic ethers such as. B. 2-phenylethyl methyl ether; 2-phenylethyl isoamyl ether; 2-phenylethyl-1-ethoxyethyl ether;
  • Aromatic and araliphatic aldehydes such as. B. Benzaldehyde; phenylacetaldehyde; 3-phenylpropanal; hydratropaaldehyde; 4-methylbenzaldehyde; 4-methylphenylacetaldehyde; 3-(4-ethylphenyl)-2,2- dimethylpropanal; 2-methyl-3-(4-isopropylphenyl)propanal; 2-methyl-3-(4-tert-butylphenyl)propanal; 3-(4-tert-butylphenyl)propanal; cinnamaldehyde; a-butylcinnamaldehyde; a-amylcinnamaldehyde; ⁇ -hexylcinnamaldehyde; 3-methyl-5-phenylpentanal; 4-methoxybenzaldehyde; 4-hydroxy-3-methoxybenzaldehyde; 4-hydroxy-3-ethoxy
  • Aromatic and araliphatic ketones such as B. acetophenone; 4-methylacetophenone; 4-methoxyacetophenone; 4-tert-butyl-2,6-dimethylacetophenone; 4-phenyl-2-butanone; 4-(4-hydroxyphenyl)-2-butanone; 1-(2-naphthalenyl)ethanone; benzophenone; 1,1,2,3,3,6-hexamethyl-5-indanyl methyl ketone; 6-tert-butyl 1-1 ,1 -dimethyl-4-indanylmethyl ketone; 1 -[2,3-dihydro-1,1,2,6-tetramethyl-3-(1-methylethyl)-1H-5-indenyl]ethanone; 5',6',7',8'-tetrahydro-3',5',5',6',8',8'-hexamethyl-2-acetonaphthone;
  • Aromatic and araliphatic carboxylic acids and their esters such as.
  • Nitrogen-containing aromatic compounds such as. B. 2,4,6-trinitro-1,3-dimethyl-5-tert-butylbenzene; 3,5-dinitro-2,6-dimethyl-4-tert-butylacetophenone;
  • lactones such as B. 1,4-octanolide; 3-methyl-1,4-octanolide; 1,4-nonanolide; 1,4-decanolide; 8-decene-1,4-olide; 1,4-undecanolide; 1,4-dodecanolide; 1,5-decanolide; 1,5-dodecanolide; 1,15-pentadecanolide; cis- and trans-11-pentadecene-1,15-olide; cis and trans 12-pentadecene-1,15-olide; 1,16-hexadecanolide; 9-hexadecene
  • 1,16-hexadecanolide 1,12-dodecanedioate; ethylene 1,13-tridecanedioate; coumarin; 2,3-dihydrocoumarin; octahydrocoumarin; and the stereoisomers, enantiomers, positional isomers, diastereomers, cis/trans isomers or epimers of the substances mentioned above.
  • Aldehydic fragrances or fragrances which also include the corresponding acetals and esters and lactones, can be divided into the following groups, viz
  • fragrances or fragrances with aldehyde, carboxylic acid or ester functionality and mixtures thereof are selected from one or more of the following groups:
  • Aliphatic aldehydes and their acetals such as. B. hexanal; heptanal; octanal; nonanal; decanal; undecanal; dodecanal; tridecanal; 2-methyloctanal; 2-methylnonanal; (f)-2-hexenal; (Z)-4-heptenal; 2,6-dimethyl-5-heptenal; 10-undecenal; (f)-4-decenal; 2-dodecenal; 2,6,10-trimethyl-5,9-undecadienal; heptanal diethyl acetal; 1,1-dimethoxy-2,2,5-trimethyl-4-hexene;
  • Cycloaliphatic aldehydes such as. B. 2,4-dimethyl-3-cyclohexenecarbaldehyde; 2-methyl-4-(2,2,6-trimethyl-cyclohexen-1-yl)-2-butenal; 4-(4-hydroxy-4-methylpentyl)-3-cyclohexenecarbaldehyde; 4-(4-methyl-3-penten-1-yl)-3-cyclohexenecarbaldehyde;
  • Aromatic and araliphatic aldehydes such as. B. Benzaldehyde; phenylacetaldehyde; 3-phenylpropanal; hydratropaaldehyde; 4-methylbenzaldehyde; 4-methylphenylacetaldehyde; 3-(4-ethylphenyl)-2,2-dimethylpropanal; 2-methyl-3-(4-isopropylphenyl)propanal; 2-methyl-3-(4-tert-butylphenyl)propanal; 3-(4-tert-butylphenyl)propanal; cinnamaldehyde; a-butylcinnamaldehyde; a-amylcinnamaldehyde; ⁇ -hexylcinnamaldehyde; 3-methyl-5-phenylpentanal; 4-methoxybenzaldehyde; 4-hydroxy-3-methoxybenzaldehyde; 4-hydroxy-3-eth
  • Aliphatic carboxylic acid esters such as. B. (E)- and (Z)-3-hexenyl formate; ethyl acetoacetate; isoamyl acetate; hexyl acetate; 3,5,5-trimethylhexyl acetate; 3-methyl-2-butenyl acetate; (f)-2-hexenyl acetate; (E)- and (Z)-3-hexenyl acetate; octyl acetate; 3-octyl acetate; 1 -octen-3-yl acetate; ethyl butyrate; butyl butyrate; isoamyl butyrate; hexyl butyrate; (E)- and (Z)-3-hexenyl isobutyrate; hexyl crotonate; ethyl isovalerate; ethyl 2-methylpentanoate; ethyl hexanoate
  • Esters of cyclic alcohols such as. B. 2-tert-butylcyclohexyl acetate; 4-tert-butylcyclohexyl acetate; 2-meri-pentylcyclohexyl acetate; 4th/t-
  • Esters of araliphatic alcohols and aliphatic carboxylic acids such as. B. benzyl acetate; benzyl propionate; benzyl isobutyrate; benzyl isovalerianate; 2-phenylethyl acetate; 2-phenylethyl propionate; 2-phenylethyl isobutyrate; 2-phenylethyl isovalerianate; 1 -phenylethyl acetate; a-trichloromethylbenzyl acetate; ⁇ , ⁇ -dimethylphenylethyl acetate; ⁇ , ⁇ -dimethylphenylethyl butyrate; cinnamyl acetate; 2-phenoxyethyl isobutyrate; 4-methoxybenzyl acetate;
  • Esters of cycloaliphatic carboxylic acids such as.
  • Aromatic and araliphatic carboxylic acid esters such as. B. methyl benzoate; ethyl benzoate; hexyl benzoate; benzyl benzoate; methyl phenyl acetate; ethyl phenyl acetate; geranyl phenyl acetate; phenylethylphenyl acetate; methyl cinnamate; ethyl cinnamate; benzyl cinnamate; phenylethyl cinnamate; cinnamyl cinnamate; allylphenoxy acetate; methyl salicylate; isoamyl salicylate; hexyl salicylate; cyclohexyl salicylate; cis-3-hexenyl salicylate; benzyl salicylate; phenylethyl salicylate; methyl 2,4-dihydroxy-3,6-dimethylbenzoate; ethy
  • aldehydes 2-methylpentanal; aldehyde C12 MNA HM; aldehydes C 4; aldehydes C 5; aldehydes C 6; aldehydes C 7; aldehydes C 8; aldehydes C 9; aldehydes C 10; aldehydes C 11 ISO; aldehydes C 11 MOA PURE; aldehydes C 11 UNDECANAL; aldehydes C 11 UNDEYLENIC; aldehydes C 12; ; aldehydes C 12 MNA; aldehydes C 13; ALDEHYDE MADARINE; AMYL CINNAMIC ALDEHYDE ALPHA; ANISALALDEHYDE-O; ANISYL ALDEHYDE; BENZALDEHYDE NAT.; MOUNTAIN MAL; BORONAL; strengenoal; CAMPHONELIC ALDEHYDE; CITRAL; CITRONELLAL HM; CITRONELLYL
  • PHENYLACETALDEYHDEDIMETHYLACETAL ester: JASMAL; EVER; KHARISMAL; TIRAMISONE®.
  • flavorings can also be encapsulated as core material in the form of an individual flavoring, with the core material comprising at least one individual flavoring substance or mixtures thereof as active ingredient.
  • Typical examples of flavorings or aromas that can be encapsulated according to the invention are selected from the group consisting of: acetophenone; allyl caproate; alpha-ionone; beta-ionone; anisaldehyde; anisyl acetate; anisyl formate; benzaldehyde; benzothiazole; benzyl acetate; benzyl alcohol; benzyl benzoate; beta-ionone; butyl butyrate; butyl caproate; butylidenephthalide; carvone; camphene; caryophyllene; cineole; cinnamyl acetate; citral; citronellol; citronellal; citronellyl acetate; cyclohexyl acetate; cymene; damascone; decalactone; dihydrocoumarin; dimethyl anthranilate; dimethyl anthranilate; dodecalactone; e
  • Hedione® heliotropin; 2-heptanone; 3-heptanone; 4-heptanone; trans-2-heptenal; cis-4-heptenal; trans-2-hexenal; cis-3-hexenol; trans-2-hexenoic acid; trans-3-hexenoic acid; cis -2-hexenyl acetate; cis -3-hexenyl acetate; cis -3-hexenylcaproate; trans -2-hexenylcaproate; cis-3-hexenyl formate; cis -2-hexyl acetate; cis -3-hexyl acetate; trans -2-hexyl acetate; cis -3-hexyl formate; para-hydroxybenzylacetone; isoamyl alcohol; isoamyl isovalerianate; isobutyl butyrate; isobutyraldehyde;
  • a fragrance or fragrance mixture or a perfume oil or a flavor mixture or a flavor is used in the plant protein-based microcapsules according to the invention as the active ingredient to be encapsulated or as the core material.
  • compositions that contain at least one fragrance or fragrance or flavoring.
  • Such compositions in particular fragrance or fragrance mixtures or perfume oils, preferably comprise two, three, four, five, six, seven, eight, nine, ten or more fragrances or fragrances.
  • the fragrance or fragrance mixtures or perfume oils are preferably selected from the group of extracts from natural raw materials such as essential oils, concretes, absolutes, resins, resinoids, balsams, tinctures such as. B.
  • ambergris tincture amyris oil; angelica seed oil; angelica root oil; anise oil; valerian oil; basil oil; tree moss absolute; bay oil; mugwort oil; benzoresine; bergamot oil; beeswax absolute; birch tar oil; bitter almond oil; savory oil; buckwheat oil; cabreuva oil; cade oil; Calmus oil; camphor oil; cananga oil; cardamom oil; cascarilla oil; cassia oil; Cassie-Absolu; castoreum absolute; cedar leaf oil; cedarwood oil; cistus oil; citronellol; lemon oil; copaiva balm; copaiva balm oil; coriander oil; costus root oil; cumin oil; cypress oil; davana oil; dill weed oil; dill seed oil; eau de brouts absolute; oakmoss absolute; elemi oil; tarragon oil; eucalyptus citri
  • fragrances or fragrances or flavorings are used in the process according to the invention, which are selected from the group consisting of: AGRUMEX LC; AGRUNITRILE; ALDEHYDE C11 UNDECYLENIC; ALDEHYDE C12 LAURIN; ALDEHYDE C12 MNA; ALDEHYDE C14 SOG; ALDEHYDE C16 SOG.; ALLYLAMYL GLYCOLATE; ALLYL CAPRONATE; ALLYLCYCLOHEXYLPROPIONATE; ALLYL HEPTYLATE; AMBROCENIDE® 10 TEC; AMBROCENIDE® Crist. 10% IPM; AMBROXIDES; ANETHOL NAT.
  • Exemplary cooling agents (cooling agents) used as hydrophobic active ingredients in the preparation of the microcapsules of the invention include one or more of menthol and menthol derivatives (e.g. L-menthol, D-menthol, racemic menthol, isomenthol, neoisomenthol, neomenthol ), menthyl ether (e.g. (1-menthoxy)-2-propanediol, (1-menthoxy)-2-methyl-1,2-propanediol, 1-menthyl methyl ether), menthyl esters (e.g.
  • menthol and menthol derivatives e.g. L-menthol, D-menthol, racemic menthol, isomenthol, neoisomenthol, neomenthol
  • menthyl ether e.g. (1-menthoxy)-2-propanediol, (1-menthoxy)-2-methyl-1,2-propanediol,
  • menthyl formate menthyl acetate, menthyl isobutyrate, menthyl lactate, L -Menthyl-L-lactate, L-menthyl-D-lactate, menthyl-(2-methoxy)-acetate, menthyl-(2-methoxyethoxy)-acetate, menthylpyroglutamate
  • menthyl carbonates e.g. menthyl propylene glycol carbonate, menthyl ethylene glycol carbonate, menthyl glycerol- carbonate or mixtures thereof
  • the semiesters of menthol with a dicarboxylic acid or its derivatives e.g.
  • L-menthone glycerol ketal 2,3-dimethyl-2-(2-propyl)butanoic acid derivatives (e.g. 2,3-dimethyl-2-(2-propyl)butanoic acid N-methylamide [WS23]) , isopulegol or its esters (l-(-)-isopulegol, 1-(-)-isopulegol acetate), menthane derivatives (e.g. p-menthane-3,8-diol), cubebol or synthetic or natural mixtures containing cubebol, pyrrolidone derivatives of cycloalkyldione derivatives (e.g.
  • cooling agents are menthol (L-menthol, D-menthol, racemic menthol, isomenthol, neoisomenthol, neomenthol), L-menthyl methyl ether, menthyl formate, menthyl acetate), menthone, isopulegol, L-(-)-isopulegol acetate) and cubebol have a cooling taste effect.
  • Suitable coolants are well known in the art and are described, for example, in US 2017/216802 (A1), US 2010/273887 (A1), EP 2 033 688 (A2) and EP 1 958 627 (A2).
  • a TRPV1 or a TRPV3 modulator is used in the plant protein-based microcapsules according to the invention as the active substance to be encapsulated or as the core material.
  • TRPV1 and TRPV3 modulators are known in the art and refer to TRP channels (Transient Receptor Potential channels) of the vanilloid (TRPV) subfamily.
  • TRPV1 - modulators impart a pungent taste and the hot feeling associated with capsaicin and piperine.
  • the TRPV3 protein belongs to the family of nonselective cation channels that function in a variety of processes including temperature sensing and vasoregulation.
  • the TRPV3 channel is directly activated by various natural compounds such as carvacrol, thymol and eugenol. Some other monoterpenoids that either cause a feeling of warmth or are skin sensitizers can also open the channel. Monoterpenoids also induce agonist-specific desensitization of TRPV3 channels in a calcium-independent manner.
  • the plant protein-based microcapsules according to the invention it is used as the active ingredient to be encapsulated or as the core material Active ingredient for use, which is selected from the group consisting of substances that cause a pungent taste or a warmth or heat sensation on the skin or mucous membranes or a tingling or tingling sensation in the mouth or throat or active ingredients with a pungent or biting or astringent effect Effect.
  • the caustic or pungent active ingredients are preferably selected from the group consisting of: paprika powder, chili pepper powder, extracts of paprika, extracts of pepper, extracts of chili pepper, extracts of ginger roots, extracts of grains of compassion (Aframomum melegueta ), extracts of paracress (Jambu oleoresin; Spilanthes acmella or Spilanthes oleracea), extracts of Japanese pepper (Zanthoxylum piperitum), extracts of Kaempferia galanga, extracts of Alpinia galanga, extracts of water pepper (Polygonium hydropiper), capsaicinoids, in particular capsaicin , dihydrocapsaicin or nonivamide; Gingeroids, in particular gingerol [6], gingerol [8], or gingerol [10]; shogaols, in particular shogaol-[6], shogaol-[8], shogaol
  • the active ingredients that can be perceived as stinging or biting are preferably selected from the group consisting of: aromatic isothiocyanates, in particular phenylethyl isothiocyanate, allyl isothiocyanate, cyclopropyl isothiocyanate, butyl isothiocyanate, 3-methylthiopropyl isothiocyanate, 4-hydroxybenzyl isothiocyanate, 4-methoxybenzyl isothiocyanate and mixtures thereof.
  • the active ingredients that cause a tingling sensation are preferably selected from the group consisting of 2E,4E-decadienoic acid-N-isobutylamide (trans-pellitorin), in particular those as described in WO 2004/043906; 2E,4Z-decadienoic acid-N-isobutylamide (cis-pellitorin), especially those like described in WO 2004/000787; 2Z,4Z-decadienoic acid-N-isobutylamide; 2Z,4E-decadienoic acid-N-isobutylamide; 2E,4E-decadienoic acid N-([2S]-2-methylbutyl)amide; 2E,4E-decadienoic acid N-([2S]-2-methylbutyl)amide; 2E,4E-decadienoic acid-N-([2R]-2-methylbutylamide); 2E,4Z-decadienoic acid N-(2-methylbutyl)amide
  • 2E,4E,8Z,11E-tetradecatetraenoic acid N-(2-hydroxy-2-methylpropyl)amide (isobungeanool); 2E,4E,8Z-tetradecatrienoic acid N-(2-hydroxy-2-methylpropyl)amide (dihydrobungeanool) and 2E,4E-tetradecadienoic acid N-(2-hydroxy-2-methylpropyl)amide (tetrahydrobungeanool) and mixtures thereof.
  • Active ingredients with an astringent effect are preferably selected from the group consisting of: catechins, in particular epicatechins, gallocatechins, epigallocatechins and their respective gallic acid esters, in particular epigallocatechin gallate or epicatechin gallate, their oligomers (procyanidins, proanthocyanidins, prodelphinidins, procyanirins, thearubigenins, theogallins) and their C- and O-glycosides; Dihydroflavonoids such as dihydromyricetin, taxifolin and their C and O glycosides, flavonols such as myricetin, quercetin and their C and O glycosides such as quercetrin, rutin, gallic acid esters of carbohydrates such as Tannin, pentagalloyl glucose or their reaction products such as elligatannin, aluminum salts such as alum, and mixtures thereof.
  • catechins in particular epicatechins, gallocate
  • biogenic principles can also be encapsulated as core material, with the core material comprising at least one biogenic principle or mixtures thereof.
  • Biogenic principles are to be understood as meaning active substances with biological activity, for example tocopherol, tocopherol acetate, tocopherol palmitate, ascorbic acid, carnotine, carnosine, caffeine, (deoxy)ribonucleic acid and its fragmentation products, ⁇ -glucans, retinol, bisabolol, allantoin, phytantriol, panthenol , AHA acids, amino acids, ceramides, pseudoceramides, essential oils, plant extracts and vitamin complexes.
  • substances for print coatings for paper are also used as the active ingredient to be encapsulated or as the core material, as described in US Pat becomes.
  • the internal non-aqueous phase may contain, for example, 20 to 80% by weight, preferably 25 to 75% by weight and more preferably 33 to 50% by weight of the hydrophobic active ingredient to be encapsulated, 0.1 to 5% by weight %, preferably 0.15 to 3.5% by weight and even more preferably 0.5 to 2.5% by weight of crosslinking agent and additionally to 100% by weight of a hydrophobic solvent, based on the total weight of the internal non-aqueous phase.
  • an external aqueous phase comprising at least one plant protein and optionally at least one first polysaccharide and/or at least one further crosslinking agent and/or at least one polyhydroxyphenol and/or at least one protective colloid , and further optionally adjusting the pH of the aqueous phase to a pH below the isoelectric point of the vegetable protein.
  • the polyhydroxyphenol optionally added in step (ii) can also be another crosslinking agent.
  • the polyhydroxy phenol itself can also be a crosslinking agent.
  • the polyhydroxyphenol can optionally be added in step (i) as an alternative or in addition.
  • the polyhydroxyphenol is also preferably a tannin.
  • Suitable solvents for preparing the external aqueous phase are water or mixtures of water with at least one water-miscible organic solvent.
  • suitable organic solvents are glycerol, 1,2-propanediol, 1,3-propanediol, ethanediol, diethylene glycol, triethylene glycol and other analogues.
  • the solvent is water.
  • the at least one plant protein or at least one other plant protein is selected from the group consisting of protein isolates, plant proteins in the form of fractions, partial or complete hydrolysates or by physico-chemical processes or fermentative or enzymatic treatment intermediate products produced from the proteins, in particular plant proteins from the group consisting of: cereals, in particular wheat, barley, rye, spelt, gluten, in particular wheat gluten, rapeseed, rice, potatoes, corn, soya, beans, chickpeas, lentils, lupins, peanuts, Alfalfa, fava beans, peas, hemp, pumpkin and sunflower, other proteins from edible plants, chitosan and mixtures thereof.
  • the amino acids can be proteinogenic L-amino acids. These can be selected from the group consisting of L-alanine, L-arginine, L-asparagine, L-aspartic acid, L-cysteine, L-glutamine, L-glutamic acid, L-glycine, L-histidine, L-isoleucine , L-Leucine, L-Lysine, L-Methionine, L-Phenylalanine, L-Proline, L-Serine, L-Threonine, L-Tryptophan, L-Tyrosine and L-Valine.
  • L-alanine L-arginine
  • L-asparagine L-aspartic acid
  • L-cysteine L-glutamine
  • L-glutamic acid L-glycine
  • L-histidine L-histidine
  • L-isoleucine L-Leucine
  • L-Lysine L-Methionine
  • proteins mentioned above also have the advantageous effect that they have an emulsifying effect. Due to their emulsifying effect, they help to stabilize the emulsion. Due to their more or less flexible structure and their differently charged areas within the molecule, proteins are amphiphilic and therefore surface-active.
  • the secondary and/or tertiary structure of the molecule can be changed by modifying the proteins, for example by physical or chemical modification.
  • the emulsifying properties can be influenced by changing the spatial availability of charged areas of the molecule or by exposing amino acid side chains. Due to these advantageous properties, an additional emulsifier or a protective colloid can be dispensed with in the process according to the invention.
  • the proportion of at least one protein, preferably pea protein, pumpkin protein, hemp protein or sunflower protein in the external aqueous phase is in a range from 0.01 to 5.0% by weight, preferably in a range from 0.05 to 3 % by weight, particularly preferably in a range from 0.07 to 1.5% by weight, based on the total weight of the external aqueous phase.
  • the at least one first polysaccharide and/or the at least one further polysaccharide can be selected from the group consisting of indigestible fibers and roughage, in particular insoluble roughage, in particular cellulose, cellulose derivatives such as hydroxyethylcellulose, in particular quaternized hydroxyethyl cellulose, carboxymethyl cellulose (CMC) and microcrystalline cellulose (MCC), hemicelluloses, lichenin, chitin, chitosan, lignin, xanthan, vegetable fibres, in particular grain fibres, potato fibres, apple fibres, citrus fibres, bamboo fibres, extracted sugar beet fibres; Oat fibers and soluble roughage, in particular inulin, in particular native inulin, highly soluble inulin, granulated inulin, high performance inulin, pectins, alginates, agar, carrageenan, gum arabic, konjac gum, gurdian (param
  • Starches in particular starch from wheat, potatoes, corn, rice, tapioca and oats, chemically, mechanically and/or enzymatically modified starch; and starch derivatives, e.g. dextrins or maltodextrins, in particular dextrins and maltodextrins from wheat, potatoes, corn, rice and oats, in particular maltodextrins DE8-10, DE17-20, DE18-20, cyclodextrins, oligosaccharides, in particular oligofructose; and
  • Sugar alcohols in particular sorbitol, mannitol, isomalt, maltitol, maltilol syrup, lactitol, xylitol, erythritol;
  • gellan Glucose, glycosaminoglycans, in particular hyaluronic acid, and mixtures of the aforementioned polysaccharides.
  • gum arabic and maltodextrins are particularly preferred.
  • the proportion of the at least one polysaccharide in the external aqueous phase is in a range from 0.1 to 3.0% by weight, preferably in a range from 0.2 to 1.0% by weight, based on the total weight of the external aqueous phase.
  • the at least one polysaccharide is used in a range of 0.25 to 0.75% by weight based on the total weight of the external aqueous phase.
  • the external aqueous phase is provided with both major components of the capsule shell, i.e. at least one protein and at least one polysaccharide.
  • the emulsion formed in this way has less of a tendency to form aggregates, so that the addition of a protective colloid or an additional emulsifier is not necessary in the process according to the invention.
  • the following combinations of protein and polysaccharide are particularly preferred for constructing the capsule wall or capsule shell: pea protein and maltodextrin; hemp protein and maltodextrin; pumpkin Protein and Maltodextrin, Sunflower Protein and Maltodextrin.
  • the external aqueous phase is provided with only one of the main components of the capsule shell, protein or polysaccharide.
  • the other main component, polysaccharide or protein is optionally added in process step (iv) and/or in step (vi) after the emulsification/dispersion and before or with an addition of the catalyst, which optionally takes place in process step (v).
  • a protective colloid can optionally be added to the external aqueous phase.
  • a protective colloid is a polymer system which, in suspension or dispersion, prevents the emulsified, suspended or dispersed components from clumping together (agglomeration, coagulation, flocculation).
  • protective colloids bind large amounts of water and, depending on the concentration, produce high viscosities in aqueous solutions.
  • the protective colloid attaches itself to the primary particles with its hydrophobic part and turns its polar, i. H. hydrophilic part of the molecule, the aqueous phase too. This accumulation at the interface reduces the interfacial tension and prevents agglomeration of the primary particles. In addition, it stabilizes the emulsion and promotes the formation of comparatively smaller droplets and thus the corresponding microcapsules.
  • the protective colloid also has emulsifying properties in addition to the above properties.
  • emulsifying properties of the protective colloid such as carboxymethyl cellulose, acid-modified starch, polyvinyl alcohol, ammonium derivatives of polyvinyl alcohol, polystyrene sulfonates, polyvinyl pyrollidone, polyvinyl acrylates, in the process according to the invention advantageously even the use of an emulsifier in the downstream emulsifying/dispersing step (iii) can be dispensed with.
  • the protective colloid used in the method of the invention is selected from the group consisting of
  • Diols in particular ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, isomeric butanediol, 1,2-pentanediol, 1,2-hexanediol, 1,2-octanediol, 1,2-decanediol, 1,2-dodecanediol, and
  • Polyols preferably triols, in particular glycerol and its ethoxylation and propoxylation products, trimethylolpropane and its ethoxylation and propoxylation products, polyvinyl alcohol (PVOH) and its derivatives, in particular ammonium- or sulfonate-functionalized polyvinyl alcohols, polyphenols, preferably 1,3,5-trihydroxybenzene,
  • Polysaccharides in particular glucose, starches or chemically, mechanically and/or enzymatically modified starches, cellulose derivatives such as
  • Hydroxyethyl cellulose in particular quaternized hydroxyethyl cellulose, and carboxymethyl cellulose, polyvinylpyrrolidone, maleic acid vinyl copolymers, sodium lignosulfonates, maleic anhydride/styrene copolymers, ethylene/maleic anhydride copolymers, copolymers of ethylene oxide, propylene oxide and acid esters of polyethoxylated sorbitol, sodium dodecyl sulfate, vegetable polymers, in particular gum arabic (Senegal type and Seyal type), Olibanum resin, shellac, lignin, chitosan, saponin and mixtures of the aforementioned compounds.
  • Starches in particular modified starches or vegetable polymers, are naturally occurring substances which are biodegradable. In combination with the polyisocyanates described herein, bio-based and biodegradable capsule shells can thus be provided with the present method. In the process according to the invention, the starch and the vegetable polymers therefore also act as so-called bio-crosslinkers.
  • the starch used in the method according to the invention is selected from the group consisting of corn starch, potato starch, rye starch, wheat starch, barley starch, oat starch, rice starch, pea starch, tapioca starch and mixtures thereof.
  • the chemically modified starches are preferably acid-modified starches, alkali-modified starches, oxidized starches, acetylated starches, succinated starches or ocentylsuccinated starches.
  • the external aqueous phase preferably comprises at least one protective colloid selected from polyvinylpyrrolidones, polyvinyl alcohols, polyols, polyphenols or starches and mixtures thereof. .
  • polyols, polyphenols or starch, in particular modified starch are used as the protective colloid.
  • Particular preference is given to using polyvinyl alcohol or its ammonium derivatives, 1,3,5-trihydroxybenzene, modified starch or carboxymethylcellulose as a protective colloid to produce the microcapsules according to the invention.
  • combinations of two or more different protective colloids can also be used to produce the microcapsule according to the invention.
  • a combination of one of the abovementioned protective colloids with starch is used as a further protective colloid in the external aqueous phase.
  • Such a combination stabilizes the emulsion due to the high number of functional hydroxyl groups and, on the other hand, promotes a reaction between the protective colloid and the polyisocyanate(s), the reaction equilibrium in the reaction of the protective colloids with the polyisocyanate(s) is pushed to the side of the products, ie the polyurethanes.
  • the large number of functional hydroxyl groups in starch also enables the formation of spatially particularly pronounced crosslinks.
  • the above-mentioned protective colloids have different reaction rates with the isocyanate groups of the at least one polyisocyanate.
  • glycerin reacts more quickly with the isocyanate groups than, for example, starch.
  • the crosslinking of the protective colloid with the isocyanate groups of the polyisocyanate can therefore be controlled by the selection of the protective colloid.
  • Glycerol with starch or with modified starch or the combination of glycerol with quaternized hydroxyethyl cellulose or Seyal gum arabic has proven to be a particularly advantageous combination; Such a combination makes use of the previously described properties of both protective colloids: high reaction rate of the glycerol on the one hand and number of polymerizable functional groups of the other protective colloid on the other.
  • the protective colloids used in the method according to the invention have a dual function in that they act as a protective colloid and thus prevent the agglomeration of the emulsified, suspended or dispersed components, stabilize the emulsion subsequently formed, promote the formation of small droplets and ultimately stabilize formed microcapsule dispersion.
  • the external aqueous phase is prepared, preferably with stirring, by successively adding the polysaccharide and/or the protein and optionally the protective colloid or vice versa to the external aqueous phase, or by adding the components simultaneously to the external aqueous phase.
  • the pH of the external aqueous phase is optionally adjusted to a pH below the isoelectric point of the protein, ie to a pH that is lower than the isoelectric point of the protein used.
  • the isoelectric point is understood to be the pH value at which the isoelectric state is reached, i.e. at which the positive and negative charges are balanced in the case of ampholytes or zwitterions (e.g. amino acids and proteins). This value is a constant that is characteristic of each amino acid and depends on the p s value of the functional group.
  • ampholytes or zwitterions e.g. amino acids and proteins.
  • This value is a constant that is characteristic of each amino acid and depends on the p s value of the functional group.
  • peptides and proteins also have an isoelectric point. At the isoelectric point, the amino acids, and thus also proteins, have the lowest water solubility.
  • the pH of the aqueous phase is adjusted to a pH in the range of 2.0 to 7.0, more preferably to a pH in the range of 2.0, depending on the isoelectric point of the protein used to 6.0 and most preferably to a slightly acidic pH in the range of 3.0 to 5.0.
  • the pH value adjustment to a pH value below the isoelectric point, i.e. to a pH value lower than the isoelectric point, of the protein has the advantage that at such a pH value the emulsifying properties and the solubility of the protein at the are largest.
  • the pH of the external aqueous phase is adjusted by adding an organic acid.
  • an organic acid for example formic acid or acetic acid, is added to the external aqueous phase before the emulsification step and a pH value in the above-mentioned ranges is set.
  • the internal non-aqueous phase which comprises at least one crosslinking agent and at least one hydrophobic active ingredient, is emulsified or dispersed in a further process step (iii) in the external aqueous phase to form an oil-in-water emulsion/dispersion .
  • the oil-in-water emulsion is prepared by mixing the internal non-aqueous phase and the external aqueous phase.
  • the weight ratio of internal non-aqueous phase to external aqueous phase is preferably in a range from 70:30 to 60:40, preferably in a range from 30:70 to 60:40.
  • a stabilizer and/or an emulsifier or an emulsifying aid is optionally added to the emulsion or dispersion in the process according to the invention.
  • a stabilizer is preferably added to the external aqueous phase, which stabilizes the emulsion/dispersion in order to prevent the internal non-aqueous (oily) phase and the external aqueous phase from separating.
  • the preferred stabilizers for preparing the polysaccharide and protein-based microcapsules according to the present invention are above all acrylic copolymers that have sulfonate groups. Also suitable are copolymers of acrylamides and acrylic acid, copolymers of alkyl acrylates and N-vinylpyrrolidone such as LUVISKOL® K15, K30 or K90 (BASF); Sodium polycarboxylates, sodium polystyrene sulfonates, vinyl and methyl vinyl ether-maleic anhydride copolymers and ethylene, isobutylene or styrene-maleic anhydride copolymers, microcrystalline cellulose, which is commercially available, for example, under the name VIVAPUR®, diutan gum, xanthan gum or carboxymethyl cellulose.
  • the amount of stabilizers used can be in the range from 0.01 to 10% by weight and preferably in the range from 0.1 to 3% by weight, based in each case on the external aqueous phase.
  • an emulsifier preferably an O/W emulsifier, is used in the method according to the invention, which enables a homogeneous distribution of the oil droplets of the internal non-aqueous phase in the external aqueous phase and stabilizes the emulsion.
  • O/W emulsifier is used in the method according to the invention, which enables a homogeneous distribution of the oil droplets of the internal non-aqueous phase in the external aqueous phase and stabilizes the emulsion.
  • O/W emulsifier preferably an O/W emulsifier
  • an emulsifier is optional, in particular when the protein or the protective colloid has no or only slight, i.e. insufficient, emulsifying properties. If an emulsifying protein and/or protective colloid is used, the use of an emulsifier can advantageously be dispensed with in the method according to the invention.
  • Suitable emulsifiers are nonionic surfactants from at least one of the following groups:
  • Alkyl and/or alkenyl oligoglycosides having 8 to 22 carbon atoms in the alk(en)yl radical and their ethoxylated analogues;
  • Partial esters of polyglycerol (average degree of self-condensation 2 to 8), polyethylene glycol (molecular weight 400 to 5000), trimethylolpropane, pentaerythritol, sugar alcohols (e.g. sorbitol), alkyl glucosides (e.g Methyl glucoside, butyl glucoside, lauryl glucoside) and polyglucosides (e.g. cellulose) with saturated and/or unsaturated, linear or branched fatty acids having 12 to 22 carbon atoms and/or hydroxycarboxylic acids having 3 to 18 carbon atoms and their adducts with 1 to 30 moles of ethylene oxide, preferably Cremophor® ;
  • polysiloxane polyalkyl polyether copolymers or corresponding derivatives block copolymers, e.g., polyethylene glycol-30 dipolyhydroxystearates; polymer emulsifiers, for example Pemulen types (TR-1, TR-2) from Goodrich or Cosmedia® SP from Cognis;
  • polyalkylene glycols and glycerol carbonate polyalkylene glycols and glycerol carbonate.
  • Typical anionic emulsifiers that can be used in the process of the invention for preparing the isocyanate-based microcapsules are aliphatic fatty acids having 12 to 22 carbon atoms, such as palmitic acid, stearic acid or behenic acid, and dicarboxylic acids having 12 to 22 carbon atoms, such as azelaic acid or sebacic acid.
  • zwitterionic surfactants can be used as emulsifiers in the method according to the invention for the production of the polysaccharide- and protein-based microcapsules.
  • Zwitterionic surfactants are surface-active compounds which contain at least one quaternary ammonium group and at least one carboxylate and one sulfonate group in the molecule.
  • Particularly suitable zwitterionic surfactants are the so-called betaines, such as the N-alkyl-N,N-dimethylammonium glycinates, for example coconut alkyldimethylammonium glycinate, N-acylaminopropyl-N,N-dimethylammonium glycinates, for example cocoacylaminopropyldimethyl ammonium glycinate, and 2-alkyl-3-carboxylmethyl-3-hydroxyethylimidazolines each having 8 to 18 carbon atoms in the alkyl or acyl group, and cocoacylaminoethylhydroxyethylcarboxymethylglycinate.
  • the fatty acid amide derivative known under the CTFA name Cocamidopropyl Betaine is particularly preferred.
  • ampholytic surfactants are surface-active compounds which, in addition to a C8/18-alkyl or acyl group, contain at least one free amino group and at least one --COOH or --SOsH group in the molecule and are capable of forming inner salts.
  • ampholytic surfactants are N-alkylglycine, N-alkylpropionic acid, N-alkylaminobutyric acid, N-alkyliminodipropionic acid, N-hydroxyethyl-N-alkylamidopropylglycine, N-alkyl taurine, N-alkylsarcosine, 2-alkylaminopropionic acid and alkylaminoacetic acid, each with about 8 to 18 carbon atoms in the alkyl group.
  • Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate and C12/18-acylsarcosine.
  • cationic surfactants are also suitable as emulsifiers, with those of the esterquat type, preferably methyl-quaternized difatty acid triethanolamine ester salts, quaternized hydroxyethyl cellulose, modified chitosan with propylene glycol and quaternized with epichlorohydrin, distearyldimethylammonium chloride (DSDMAC), benzalkonium chloride,
  • Cetyltrimethylammonium bromide (cetrimonium bromide), dequalinium chloride. are particularly preferred.
  • the emulsifiers can be added to the external aqueous phase in an amount of about 0.1 to about 10% by weight and preferably about 1 to about 5% by weight, based on the total weight of the external aqueous phase.
  • the microcapsules can be produced continuously or discontinuously. As the viscosity of the aqueous phase increases or the viscosity of the oily phase decreases, the size of the capsules generally decreases.
  • the method according to the invention for the production of the polysaccharide- and protein-based microcapsules can be carried out, for example, according to the "inline" technique.
  • the internal non-aqueous phase and the external aqueous phase are first fed separately to an emulsifying turbine by means of a forced metering pump, in short combined before entering the emulsifying turbine or combined in the emulsifying turbine, with a throughput volume of 1200 to 1500 l/h
  • the process according to the invention for producing the polysaccharide- and protein-based microcapsules can also be carried out in conventional dispersion apparatus or emulsifying devices.
  • the emulsification or dispersion of the external aqueous phase and the internal non-aqueous phase takes place, for example, by means of an emulsifying turbine (IKA Eurostar 20 high-speed stirrer).
  • an emulsifying turbine IKA Eurostar 20 high-speed stirrer
  • the process of emulsifying or dispersing in the method according to the invention is advantageously carried out for a time of 30 seconds to 20 minutes, preferably 1 to 7 minutes and very particularly preferably 1 to 5 minutes, at a stirring speed of 1000 rpm /min to 5000 rpm, preferably at 2000 rpm to 4000 rpm, until a capsule size of 10 to 75 ⁇ m ⁇ 5 ⁇ m (D50) or 75-155 ⁇ 10 ⁇ m (D90) has been established .
  • step (iii) there is an oil-in-water emulsion or dispersion in which the internal oily phase is finely emulsified with the active ingredients to be encapsulated in the form of droplets or dispersed in the external aqueous phase is present.
  • At least one polysaccharide or at least one protein is optionally added in a method step (iv) after the emulsifying or dispersing step (iii), as described above. If the external aqueous phase in process step (ii) is provided with only at least one main protein component, at least one polysaccharide is added in process step (iv). If, on the other hand, the external aqueous phase in process step (ii) is only provided with at least one polysaccharide main component, at least one protein is added in process step (iv).
  • the separate addition results in the formation of multiple layers (“layer-by-layer”), the individual layers of which are crosslinked with one another in the subsequent process step (v). In this way, for example, the charge of the emulsion and thus the aggregation stability can be controlled.
  • step (iv) a further protein and/or polysaccharide which is the same as or different from the at least one protein and/or at least one polysaccharide from step (ii) or has a different charge or with a change of the pH value changes the charge can be added.
  • a further protein and/or polysaccharide which is the same as or different from the at least one protein and/or at least one polysaccharide from step (ii) or has a different charge or with a change of the pH value changes the charge can be added.
  • further layers (“layer-by-layer”) are built up, the individual layers of which are crosslinked with one another in the subsequent process step (v). This leads to a denser and more stable network of the capsule wall components and consequently to more stable capsule shells, which increases the stability of the microcapsule.
  • the additional protein and/or additional polysaccharide is selected from the group of plant proteins and/or polysaccharides, as already defined in detail above for method step (ii). The same applies to the preferred variants or preferred combinations of the plant protein and/or polysaccharide described there.
  • a first crosslinking of the material of the capsule shell or capsule wall is also carried out with stirring.
  • the first crosslinking takes place after the emulsification or dispersing, optionally by adding a catalyst, in order to crosslink the above-described layers (“layer-by-layer)” of capsule wall components and to stabilize the resulting capsule shell.
  • Interfacial polymerization at the interface between the outer aqueous phase and the disperse inner phase, i.e. at the boundary surfaces of the emulsified or dispersed oil droplets that include the active substance to be encapsulated forms catalyzed polymerization reactions between the carboxyl group and/or sulfo group and/or hydroxyl group of polysaccharide and the amino group of protein on the one hand and the isocyanate group of the crosslinking agent on the other.
  • step (v) the first crosslinking takes place to obtain a microcapsule slurry by adding at least one catalyst; wherein the at least one catalyst is selected from the group consisting of diazobicyclo[2.2.2]octane (DABCO), bismuth catalyst and tin catalyst and mixtures of two or more of the aforementioned catalysts.
  • DABCO diazobicyclo[2.2.2]octane
  • first crosslinking units or a first crosslinking matrix for the construction of a capsule shell or capsule wall are formed.
  • the formation of the first crosslinking units in the method according to the invention is based on the polyaddition reaction between polysaccharide and crosslinking agent and/or plant protein and crosslinking agent.
  • the hydroxyl groups of the polysaccharide react with the isocyanate groups of the crosslinking agent to form polyurethane
  • the amino groups of the protein react with the isocyanate groups of the crosslinking agent to form polyurea.
  • soluble or insoluble complexes of vegetable protein and polysaccharide are also formed in the first crosslinking step (v) to constitute the capsule wall matrix or capsule shell.
  • the chain length of the individual capsule wall building blocks also influences the mechanical properties, i. H. the stability of the microcapsules is decisive: for example, the large number of hydroxyl groups in starch enables the formation of spatially particularly pronounced crosslinks; longer-chain capsule wall building blocks, such as polyisocyanates, lead to the formation of more stable capsule walls.
  • the addition of the at least one catalyst to the emulsion or dispersion accelerates the crosslinking reaction between the polysaccharide and/or vegetable protein and the crosslinking agent and catalyzes the reaction in favor of the formation of a first crosslinking matrix or first crosslinking units.
  • the catalyst that can be added in the process according to the invention can preferably be diazabicyclo[2.2.2]octane (DABCO), also called triethylenediamine (TEDA), a bicyclic tertiary amine. DABCO is commonly used as a catalyst in the production of polyurethane plastics.
  • DABCO diazabicyclo[2.2.2]octane
  • TAA triethylenediamine
  • the lone-pair tertiary amine promotes the reaction between the isocyanate groups of the crosslinking agent and the hydroxyl groups of the polysaccharide.
  • catalysts based on bismuth or tin can also be used to catalyze the first crosslinking, for example catalysts based on bismuth(II) salts or bismuth(III) salts, as described in K.C. Fresh & L.P. Rumao, Catalysis in Isocyanate Reactions, Polymer Reviews, 1970, 5:1, pages 103 - 149, DOI:
  • a combination of DABCO and one of the abovementioned catalysts can preferably be used. Such a mixture leads to a multiplication of reactivity as described in K.C. Fresh & L.P. Rumao, Catalysis in Isocyanate Reactions, Polymer Reviews, 1970, 5:1, pages 103-149, DOI: 10.1080/15583727008085365, the disclosure of which in this regard is incorporated in its entirety into the present description.
  • DABCO and the aforementioned catalysts preferably catalyze the polyurethane reaction between the at least one polymerizable aliphatic polyisocyanate having two or more isocyanate groups and the diols or polyols in the process of the invention.
  • the catalyst can be added to the external aqueous phase.
  • the amount in which the catalyst is added to the external aqueous phase is in a range from 0.001 to 2% by weight, preferably in a range from 0.02 to 1.0% by weight and particularly preferably in ranges from 0.05 to 0.8% by weight based on the total weight of the external aqueous phase.
  • the catalyst is preferably added to the emulsion or dispersion either as such, for example as a solid, or in the form of an aqueous solution, preferably in water, with stirring. It can be provided that the amount in which the catalyst is in a range from 0.001 to 2% by weight, preferably in a range from 0.02 to 1.0% by weight and particularly preferably in a range from 0. 05 to 0.8% by weight based on the total weight of the external aqueous phase.
  • the catalyst is present in the aqueous solution in a concentration of 0.5 to 2 mol/l, preferably 1 mol/l.
  • the catalyst is added at a stirring speed of 500 rpm to 2000 rpm, preferably at 1000 rpm to 1500 rpm and at a temperature in the range of 20°C to 30°C, preferably at Temperatures from 22°C to 26°C.
  • Process step (v) first crosslinking is even more preferably carried out by gradually heating the emulsion or dispersion to a temperature in the range from 60° C. to 90° C., preferably to a temperature in the range from 65 to 85° C. most preferably to a temperature in the range 70 to 80°C.
  • the first crosslinking in the method of the invention is for a period of time from about 30 minutes to 90 minutes, preferably for a period of from 40 minutes to 70 minutes, and most preferably for a period of 60 minutes.
  • the first crosslinking can take place at a temperature of 20° C. to 40° C., preferably 20° C. to 30° C., in particular at room temperature.
  • the capsules produced by the process according to the invention are present as raw microcapsules in the form of an aqueous dispersion or a slurry.
  • the microcapsules in the slurry still have a flexible shell that is not particularly stable and therefore breaks open easily.
  • the shell is hardened.
  • the curing in process step (vi) is preferably carried out by gradually heating the microcapsule slurry to a temperature of at least 60° C., preferably to a temperature in the range from 60° C. to 90° C., preferably in the range from 65° C. to 80 °C to a maximum of the boiling point of the microcapsule slurry. Curing is usually carried out over a period of at least 1.5 hours, preferably for a period of between 2 and 5 hours, most preferably for a period of 3 hours.
  • ком ⁇ онентs are used, which, chemically speaking, are proanthocyanidins such as are found in dicotyledonous perennials, shrubs and leaves, particularly in the tropics and subtropics.
  • the terpenes typically have molecular weights in the range of 500 to 3000 KDa.
  • a preferred example of a suitable tannin is corigallin.
  • An aqueous preparation of the tannins is added to the aqueous dispersion containing the raw microcapsules for hardening.
  • the tannins are usually added in amounts of from about 0.1 to about 2% by weight and preferably from about 0.5 to about 1.5% by weight, based on the microcapsules.
  • a further plant protein and/or further polysaccharide can optionally be added to the microcapsule slurry in method step (vi).
  • the additional plant protein and/or additional polysaccharide is selected from the group of proteins and/or polysaccharides as already defined in detail above for method step (ii).
  • the same definitions and preferred embodiments and/or preferred combinations as for the plant protein and/or polysaccharide are also fully valid for the other plant protein and/or polysaccharide.
  • the additional vegetable protein and/or the additional polysaccharide can be the same as or different from the vegetable protein and/or polysaccharide of method step (ii).
  • the curing step (vi) of the method according to the invention is followed by a step of cooling the microcapsule slurry to room temperature and optionally a second crosslinking step of the capsule wall building blocks by adding a further crosslinking agent.
  • At least one further crosslinking agent is used as a further crosslinking agent for further crosslinking in the process according to the invention, which is selected from the group consisting of transglutaminase, peroxidase, phytochemicals selected from the group consisting of polyphenols, in particular tannin, gallic acid, ferulic acid, hesperidin, cinnamaldehyde, vanillin, carvacrol, and mixtures of two or more of the aforementioned Crosslinking agents, as already described above in connection with the first and further crosslinking agents.
  • the same definitions and preferred embodiments as for the first and further crosslinking agent are also fully valid for the further crosslinking agent.
  • Cinnamaldehyde, tannin, ferulic acid and gallic acid are particularly preferred of the other crosslinking agents mentioned above.
  • the at least one further crosslinking agent can be added in the non-aqueous phase. Alternatively or additionally, the at least one further crosslinking agent can be added in the aqueous phase.
  • the content of further crosslinking agent is in a range from 0.1 to 5% by weight, preferably in a range from 0.15 to 2.5% by weight, based on the total weight of the non-aqueous phase.
  • the crosslinking agent is used in the internal non-aqueous phase in a range of 0.1 to 1% by weight based on the total weight of the non-aqueous phase.
  • the further crosslinking agent can be added to the emulsion or dispersion either as such, for example as a solid, or in the form of an aqueous solution.
  • the further crosslinking in process step (vii) is carried out by gradually heating the emulsion or dispersion to a temperature in the range from 20°C to 50°C, preferably to a temperature in the range from 30 to 40°C .
  • the further crosslinking in the invention The process is carried out for a period of about 20 minutes to 10 hours, preferably for a period of about 30 minutes to 8 hours.
  • the pH of the emulsion or dispersion is optionally adjusted to a pH above or below the isoelectric point of the used protein set. At a pH value below the isoelectric point, the net electrostatic charge on a protein is positive; above the isoelectric point, the net charge on a protein is negative.
  • the pH is adjusted to a pH in the range of pH 2.0 to pH 4.0, more preferably to a pH in the range of pH 2.5 to pH 3.5 and most preferably preferably adjusted to a pH in the range of pH 2.9 to pH 3.3 to obtain a positive charge on the protein.
  • the pH is preferably adjusted to a pH in the range of pH 8.0 to pH 12.0, more preferably to a pH in the range of pH 9.0 to pH 10, 0 and most preferably adjusted to a pH in the range of 9.3 to 9.6.
  • an organic acid for example formic acid or acetic acid
  • a base for example sodium hydroxide solution
  • Carrying out the first crosslinking and/or the further crosslinking at a pH above or below the isoelectric point has the advantage that the electrical charge of the protein is changed and electrostatic interactions can thus positively influence the capsule formation.
  • such a modification of the proteins has a positive effect on their emulsifying ability.
  • the stirring power is reduced in each case, for example to a stirring speed of about 800 to 1400 rpm, so that the microcapsules that are forming are not immediately broken up again.
  • microcapsules An important criterion for the usability of the microcapsules is the weight ratio of core material to capsule wall material. While on the one hand the highest possible proportion of core material is sought in order to enable the highest possible utility value of the capsules, on the other hand it is necessary for the capsule to still have a sufficient proportion of capsule wall material to ensure the stability of the capsules.
  • the microcapsules are designed in such a way that the microcapsules have a weight ratio of core material to capsule wall material which is 50:50 to 98:2, preferably 80:20 to 97.5: 2.5 lies.
  • the microcapsules produced by the process according to the invention are in the form of a dispersion in water, which is also referred to as microcapsule dispersion or microcapsule slurry.
  • the microcapsules can already be sold in this form.
  • the suspension In order to prevent such a suspension from separating or creaming and thus to achieve high storage stability, it has proven advantageous for the suspension to have a viscosity of from 12 to 2000 mPas. In order to obtain the desired viscosity of the suspension, a thickening agent is preferably used.
  • xanthan gum diethane gum
  • Carboxymethyl cellulose (CMC), microcrystalline cellulose (MCC) or guar gum is used.
  • CMC Carboxymethyl cellulose
  • MMC microcrystalline cellulose
  • guar gum is used.
  • preservatives are optionally added to the microcapsule slurry, or the microcapsule slurry is dried.
  • the microcapsule slurry is preferably dried.
  • Methods such as lyophilization are suitable for drying the microcapsule slurry, but spray drying, for example in a fluidized bed, is preferred. It has proven advantageous to add further polysaccharides, preferably dextrins and in particular maltodextrins, to the suspension at temperatures of about 20 to about 50° C. and preferably about 40° C., which support the drying process and protect the capsules during this process.
  • the amount of polysaccharides used can be about 50 to about 150% by weight and preferably about 80 to about 120% by weight, based on the capsule mass in the dispersion.
  • the spray drying itself can be carried out continuously or batchwise in conventional spray systems, with the inlet temperature being about 170 to about 200 °C and preferably about 180 to 185 °C and the outlet temperature being about 70 to about 80 °C and preferably about 72 is up to 78 °C.
  • the method according to the invention is further characterized in that plant protein, polysaccharide and aliphatic polyisocyanate(s) are polymerized and/or crosslinked as the main components and thus the production of very stable vegan microcapsules with excellent sensory properties is based biocompatible polymers allows.
  • the polyisocyanates no longer function as the main material in the plant protein-based microcapsules according to the invention, but mainly serve as crosslinking agents for the amino acids and the other components mentioned above. This reduction in the amounts of polyisocyanate to be used is a further advantage of the process according to the invention.
  • the inventive method thus allows to replace part of the polyisocyanate with biodegradable wall materials such as proteins and / or polysaccharides and thus reduce the polyisocyanate content without causing a loss or loss in the functionality of the microcapsules, such as olfactory properties and positive secondary properties such as high stability, namely the ability to retain the active ingredient occurs.
  • the process according to the invention can thus be used to produce microcapsules which, on the one hand, have excellent functionality and, at the same time, are readily biodegradable.
  • the polysaccharide or the at least one other polysaccharide is hyaluronic acid or wherein the polyhydroxyphenol is a tannin. It can be possible here that the polysaccharide is the first polysaccharide according to step (ii). Alternatively or additionally, it may be possible for the polysaccharide to be the further polysaccharide according to step (iv) and/or step (vi).
  • the amount of hyaluronic acid based on the amount of wall-forming agent is 1 to 15 percent by weight, preferably 2 to 13 percent by weight, particularly preferably 2.5 to 6 percent by weight.
  • the content of hyaluronic acid is in a range from 0.1 to 5% by weight, preferably in a range from 0.15 to 2.5% by weight, particularly preferably in a Range from 0.2 to 1.0% by weight based on the total weight of the non-aqueous internal phase and/or in a range from 0.1 to 5% by weight, preferably in a range from 0.15 to 2 5% by weight, particularly preferably in a range from 0.25 to 1.0% by weight, based on the total weight of the aqueous external phase.
  • this allows the amount of aliphatic polyisocyanates for the crosslinking to be reduced, which on the other hand can have a positive effect in terms of environmental pollution.
  • reducing the amount of polyisocyanate can have a positive effect on the biodegradability of the vegetable protein-based microcapsules. It is also advantageous that neither the stability nor the sensory properties of the microcapsules are adversely affected.
  • At least one catalyst is added after the emulsion formation.
  • the present invention relates to a vegetable protein-based microcapsule or a corresponding microcapsule slurry, which is produced by the method according to the invention.
  • a capsule shell comprising or consisting of a crosslinking matrix or crosslinking units of at least one plant protein and at least one aliphatic polyisocyanate as crosslinking agent and optionally at least one polysaccharide; and optionally at least one/one protective colloid and/or optionally at least one/another crosslinking agent.
  • the microcapsule according to the invention comprises a core which is surrounded or enveloped by the capsule shell or capsule wall. Any material that is suitable for inclusion in microcapsules can be used as the core material for producing the microcapsules according to the invention. Materials to be encapsulated are preferably hydrophobic, water-insoluble or water-immiscible liquids or solids, and also suspensions.
  • the core material is a hydrophobic active substance, ie a substance that has a specific effect or evokes a specific reaction, for example a drug, a plant protection product, a cosmetic active substance, a food active substance, etc., as mentioned above was described.
  • hydrophobic active ingredient means that the active ingredient to be encapsulated is in the internal non-aqueous phase during manufacture of the microcapsule and does not mix with the external aqueous phase.
  • polymerization and/or crosslinking of functional groups of plant protein and/or polysaccharide with polyisocyanate results in a stable capsule wall made of alternating and dense and thus stable crosslinking matrices or crosslinking units based on polyurea and polyurethane as well as soluble or insoluble protein complexes and polysaccharide.
  • the capsule shell comprises or consists of: a/a crosslinking matrix or crosslinking units from a polymerization and/or crosslinking of at least one plant protein with the first and optionally the further crosslinking agent and/or a/a crosslinking matrix or crosslinking units a polymerization and/or crosslinking of at least one polysaccharide with the first and optionally the further crosslinking agent.
  • the crosslinking matrix or the crosslinking units from a polymerization and/or crosslinking of at least one plant protein with the first and optionally the further crosslinking agent is predominantly a network based on polyurea and the crosslinking matrix or the crosslinking units from a Polymerization and/or crosslinking of at least one polysaccharide with the first and optionally further crosslinking agent is a network predominantly based on polyurethane and soluble or insoluble complexes of vegetable protein and polysaccharide.
  • the crosslinking steps described above result in by-products, for example urea, allophanate, biuret, uretidione, carbodiimide, uretonimine, etc., as described in MF Sunshine, Introduction to Polyurethane Chemistry, Polyurethanes: Science, Technology, Markets, and Trends, First Edition, 2015, John Wiley & Sons, pages 105 to 126, the relevant disclosure of which is incorporated in the present description in its entirety.
  • These by-products are part of the capsule shell or capsule wall.
  • the capsule shell can optionally comprise a protective colloid and/or optionally another crosslinking agent.
  • the vegetable protein-based microcapsule comprises hyaluronic acid. Surprisingly, it turned out that the stability properties of the vegetable protein-based microcapsule can be significantly improved in this way. In addition, such vegetable protein-based microcapsules surprisingly have improved sensory properties. It has also been found that the amounts of polyisocyanates used can be reduced to produce these vegetable protein-based microcapsules which comprise hyaluronic acid.
  • the microcapsules according to the invention are in the form of a dispersion or slurry, in which the microcapsules are dispersed in the external aqueous phase.
  • the proportion by weight of the microcapsules in the dispersion or slurry is about 20 to 60% by weight, in particular about 25 to 55% by weight, more preferably about 33 to 50% by weight.
  • the vegetable protein-based microcapsule produced by the process according to the invention has a comparable stability and a comparable content of perfume oil escaping unintentionally to microcapsules of the prior art.
  • the plant protein-based microcapsules according to the present invention can be used for a wide range of scenting and flavoring applications.
  • microcapsule according to the invention is also a universal capsule with which, according to the current state of the art, a wide range of fragrances or flavorings can be encapsulated, even fragrances or flavorings that have an aldehyde, carboxylic acid or ester functionality, see above that there are no restrictions on individual active ingredients.
  • the plant protein-based microcapsules according to the invention are suitable for a wide range of applications and in particular for use in household products, textile care products, detergents, fabric softeners, cleaning agents, scent boosters, scent lotion and fragrance enhancers, cosmetics, personal care products, agricultural products, pharmaceutical products, or print coating for paper and the like.
  • the present invention therefore relates to the use of the plant protein-based microcapsules according to the invention or a dispersion of the plant protein-based microcapsules according to the invention (microcapsule slurry) for the production of household products, textile care products, detergents, fabric softeners, cleaning agents, scent boosters, Scent lotion and fragrance enhancers in liquid or solid form, cosmetics, personal care products, agricultural products, pharmaceutical products or print coating for paper.
  • the microcapsules according to the invention are particularly suitable for enclosing hydrophobic fragrances or flavorings which can be used in various household and textile care products.
  • the present invention relates to household products, textile care products, detergents, fabric softeners, cleaning agents, scent boosters, scent lotions and fragrance enhancers, cosmetics, personal care products, agricultural products, pharmaceutical products or print coating for paper and the like, which contain the plant protein-based microcapsules of the invention or a dispersion of the vegetable protein-based microcapsules according to the invention.
  • the proportion of microcapsules in the aforementioned products is 0.05 to 15% by weight, based on the total weight of the product, preferably 0.2 to 5% by weight.
  • the invention further relates to a microcapsule slurry comprising a microcapsule according to the invention in combination with a thickener and/or a preservative.
  • the stability data below relate to a test at 40° C. in a commercial formulation such as Scent Booster or fabric softener.
  • Scent Booster or fabric softener.
  • the non-aqueous internal phase comprises a mixture consisting of TAKENATETM D-120N, STABIO D370N and Desmodur N 3400 as the polyisocyanate. These three polyisocyanates were each used in equal parts.
  • the aqueous external phase includes tannin, CMC and glycerol (86.5% in water).
  • the pH of the aqueous external phase was adjusted to 3.3 with formic acid. After emulsification, hyaluronic acid, maltodextrin and DABCO were added. In the last step, curing took place at 70 °C over a period of 3 hours.
  • the proportion of free oil was measured in isopropanol, ie isopropanol was added to a defined amount of the microcapsule slurry, the mixture was stirred for 30 seconds and a sample was taken from it. The sample taken was measured by GC-MS. The result indicates how much of the encapsulated oil went into the isopropanol or was not completely encapsulated.
  • the free oil content therefore gives an indication of whether the process itself has worked, ie the perfume oil has been completely encapsulated and/or whether the capsule shell is stable enough to prevent the perfume oil from bleeding out in isopropanol. Values of less than 1% are considered an indicator of successful encapsulation and a stable capsule shell.
  • Example 1 Stability of the plant protein-based microcapsules according to the invention in use
  • Polyisocyanate 1 is TAKENATETM D-120N.
  • Polyisocyanate 2 is STABIO D370N.
  • Polyisocyanate 3 is Desmodur N 3400 and
  • Polyisocyanate 4" is 100741 Desmodur 44 M Flakes. As is known, the latter is an aromatic polyisocyanate.
  • the stabilities shown all relate to pea protein-based, which were obtained as described above.
  • the sensory performance i.e. the fragrance or fragrance release
  • a mixture of two or more polyisocyanates as crosslinking agent one of which is a cycloaliphatic and one of which is an aliphatic
  • Polyisocyanate is very good stability can be achieved with very good sensory properties at the same time.
  • the use of two or more polyisocyanates as crosslinking agents in the production of vegetable protein-based microcapsules is preferred.
  • Another advantage of using two or more polyisocyanates as crosslinking agent compared to just one aliphatic crosslinking agent is that the plant protein-based microcapsules according to the invention produced in this way are more readily biodegradable and, moreover, overall reduced amounts of polyisocyanates have to be used.
  • At least one cycloaliphatic polyisocyanate is present. At least one aliphatic polyisocyanate is present for improved sensory properties and biodegradability.
  • molar ratios specified herein can also be replaced by quantitative ratios and vice versa.
  • polyisocyanate 1 named in Table 4 is TAKENATETM D-120N. With “Polyisocyanate 2” STABIO D370N. "Polyisocyanate 3” is Desmodur N 3400 and “Polyisocyanate 4" is 100741 Desmodur 44 M Flakes. The stabilities shown all relate to pea protein-based microcapsules.
  • the developers have further found that the stability of the plant protein-based microcapsules according to the invention can also be increased by the addition other substances can be positively influenced. It was surprisingly found that the addition of hyaluronic acid, in particular the addition of hyaluronic acid after the emulsification step, has a clearly positive effect on the stability of the microcapsules produced, as shown in Table 5 below. In Table 5, the percentages of the isocyanates relate to the total proportion of wall formers in the vegetable protein-based microcapsule.
  • hyaluronic acid accordingly has a positive effect on the stability, with remarkably fewer polyisocyanates being required as crosslinking agents.
  • the use of hyaluronic acid in the method according to the invention for producing plant protein-based microcapsules is also advantageous in that the microcapsules obtained have improved biodegradability.
  • the use of hyaluronic acid improves the sensory properties.
  • Table 5 The results according to Table 5 are also shown in FIG.
  • Table 6 shows results of more extensive investigations into the stability behavior of plant protein-based microcapsules according to the invention.
  • the washing instructions were as follows: The laundry, including the terry towels (cotton cloth), was placed in the washing machine and the fabric softener was added to the softener compartment. The washing program “Express 20; 900 rpm was started.
  • the fragrance was released in three steps.
  • the first step describes the smelling of an untreated cloth.
  • the second step describes the smelling of a lightly kneaded cloth; instead, the cloth was subject to slight mechanical stress by moving it back and forth between the hands several times, which broke the capsules.
  • the third step describes sniffing after the cloths have been rubbed vigorously, breaking the capsules. After each step, the fragrance intensity was rated.
  • plant proteins that are preferably used such as pea protein, pumpkin protein, sunflower protein and hemp protein, each make it possible to provide plant protein-based microcapsules according to the invention, with good sensory properties always being achievable (compare also FIG. 3).
  • the sensory properties of those plant protein-based microcapsules are better if aliphatic polyisocyanates are used as crosslinking agents (see Table 8, lines 2 and 8).

Abstract

La présente invention concerne un procédé de fabrication de microcapsules, en particulier de microcapsules à base de protéines végétales, ainsi que des dispersions de telles microcapsules (suspension de microcapsules), qui renferment au moins un principe actif hydrophobe, de préférence des microcapsules à base de protéines végétales contenant du parfum ou des arômes, qui présentent un équilibre parfait entre stabilité et performance comparativement aux microcapsules de l'état de la technique. La présente invention concerne en outre des microcapsules à base de protéines végétales qui peuvent être obtenues d'après le procédé selon l'invention. Selon un autre aspect, la présente invention concerne l'utilisation des microcapsules et des dispersions à base de protéines végétales selon l'invention comme composants de produits ménagers, de produits d'entretien de textiles, de détergents, d'assouplissants, de nettoyants, de renforçateurs olfactifs ou de renforçateurs de parfum sous forme liquide ou solide, de cosmétiques, de produits de soins corporels, de compositions de parfum, de produits agricoles, de produits pharmaceutiques ou d'un revêtement d'impression pour papier. Au final, la présente invention concerne des produits de consommation, qui comprennent de telles microcapsules ou dispersions de microcapsules selon l'invention.
PCT/EP2022/052501 2022-02-02 2022-02-02 Procédé de fabrication de microcapsules WO2023147855A2 (fr)

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PCT/EP2023/052523 WO2023148253A1 (fr) 2022-02-02 2023-02-02 Procédé de production de microcapsules

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