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WO2002031092A2 - Procede pour incorporer des huiles parfumees dans des lessives et des detergents ou des produits cosmetiques - Google Patents

Procede pour incorporer des huiles parfumees dans des lessives et des detergents ou des produits cosmetiques Download PDF

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Publication number
WO2002031092A2
WO2002031092A2 PCT/EP2001/011675 EP0111675W WO0231092A2 WO 2002031092 A2 WO2002031092 A2 WO 2002031092A2 EP 0111675 W EP0111675 W EP 0111675W WO 0231092 A2 WO0231092 A2 WO 0231092A2
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WO
WIPO (PCT)
Prior art keywords
template particles
liquid
polyelectrolyte
shell
phase
Prior art date
Application number
PCT/EP2001/011675
Other languages
German (de)
English (en)
Other versions
WO2002031092A3 (fr
Inventor
Ute Krupp
Frank Meier
Wolfgang Von Rybinski
Andreas Voigt
Gleb Sukhoroukov
Alexei A. Antipov
Edwin Donath
Helmut MÖHWALD
Horst Seibt
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
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 Henkel Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Priority to PCT/EP2001/011675 priority Critical patent/WO2002031092A2/fr
Priority to AU2002215015A priority patent/AU2002215015A1/en
Publication of WO2002031092A2 publication Critical patent/WO2002031092A2/fr
Publication of WO2002031092A3 publication Critical patent/WO2002031092A3/fr

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Classifications

    • 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
    • A61K9/51—Nanocapsules; Nanoparticles
    • A61K9/5107—Excipients; Inactive ingredients
    • A61K9/513—Organic macromolecular compounds; Dendrimers
    • A61K9/5146—Organic macromolecular compounds; Dendrimers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polyethylene glycol, polyamines, polyanhydrides
    • 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
    • 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
    • A61K9/51—Nanocapsules; Nanoparticles
    • A61K9/5192—Processes
    • 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
    • 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
    • B01J13/10—Complex coacervation, i.e. interaction of oppositely charged particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/20—After-treatment of capsule walls, e.g. hardening
    • B01J13/22—Coating
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/50—Perfumes
    • C11D3/502—Protected perfumes
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/50—Perfumes
    • C11D3/502—Protected perfumes
    • C11D3/505—Protected perfumes encapsulated or adsorbed on a carrier, e.g. zeolite or clay

Definitions

  • the ethers include, for example, benzyl ethyl ether and ambroxan, the aldehydes, for example, the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal, and the ketones include, for example, the jonones, ⁇ -isomethylionone and Me - thylcedryl ketone.
  • Mixtures of different fragrances are preferably used which are coordinated with one another in such a way that they together produce an appealing fragrance.
  • simplex compounds can be used as amphiphilic polyelectrolytes which (a) polycationic polymers and anions, for example monomeric anions such as salts of organic acids, e.g. Carboxylic acids or polymeric anions such as polyacrylates or (b) polyanionic polymers and cations, e.g. contain cationic monomers or polymers.
  • the oleophilic behavior of these types of compounds can be influenced by the selection of the corresponding counterions to the polymer.
  • Polyfunctional zwitterionic surfactants which are also amphiphilic compounds, can also be used. In special cases, combinations of polyfunctional surfactants and polyelectrolyte / counterion pairs can also be used.
  • amphiphilic polyelectrolytes are simplex compounds composed of polycations containing ammonium ions and hydrophobic organic anions such as the salts of organic acids, e.g. Carboxylic acids with 10 or more carbon atoms or polyanions, such as polyacrylate or polymethacrylate.
  • organic acids e.g. Carboxylic acids with 10 or more carbon atoms or polyanions
  • polyacrylate or polymethacrylate such as polyacrylate or polymethacrylate.
  • Specific examples are poly (diallyldimethyl) ammonium stearate, palmitate, oleate or ricinolate, poly (alkyl-methyl-bis (polyoxyethylene) ammonium) polyacrylate or poly (alkyl-dihydroxyethyl-ethyl-ammonium) polyacrylate, where the
  • Suitable surfactants are alkyl bis (polyoxyethylene) ammonium sulfobetaine sulfinate, alkyl bis (polyoxyethylene) ammonium sulfobetaine sulfonate, ethylated alkyl or dialkyl ammonium betaine or alkyl dimethyl ammonium propyl modified polysiloxanes or siloxane sulfobetaine sulfones.
  • the liquid template particles can be a homogeneous liquid. However, they can also comprise a solution, an emulsion or a suspension. Furthermore, the liquid template particles can consist of or contain a liquid-crystalline substance.
  • template particles are encapsulated which contain an additional active ingredient.
  • active ingredients that are dissolved or dispersed in the liquid template particle can be encapsulated.
  • the active ingredient can be selected, for example, from catalysts, polymers, dyes, sensor molecules, flavorings or other oils.
  • organic liquids such as alcohols or hydrocarbons, for example hexanol, octanol, octane or decane
  • Such capsules filled with an organic, water-immiscible liquid can also be used for chemical reactions, for example polymerization reactions.
  • the monomer can be specifically enriched in the interior of the capsules via its distribution equilibrium. If necessary, the monomer solution can be encapsulated in the interior prior to the start of the synthesis.
  • the method according to the invention it is also possible to produce capsules for the inclusion of further active ingredients.
  • the interior can be loaded with molecules by varying the permeability of the shell as a function of the external physical and chemical parameters. A state of high permeability is set for loading. The enclosed material is then retained by changing the external parameters and / or closing the pores, for example by condensation of the shell or chemical and / or thermal modification of the pores or channels.
  • the method according to the invention allows the deposition of charged and / or uncharged components on the template particle.
  • the components required to form the shell contain at least one polyelectrolyte, for example two oppositely charged polyelectrolytes and / or a polyvalent metal cation and a negatively charged polyelectrolyte.
  • Polyelectrolytes are generally understood to mean polymers with ionically dissociable groups which can be part or a substituent of the polymer chain.
  • the number of these ionically dissociable groups in polyelectrolytes is usually so large that the polymers in the dissociated form (also called polyions) are water-soluble.
  • the term polyelectrolytes is also used herein to mean ionomers in which the concentration of the ionic groups is not sufficient for solubility in water, but which have sufficient charges in order to undergo self-assembly.
  • the shell preferably comprises “real” polyelectrolytes.
  • polyelectrolytes are divided into polyacids and polybases. Polyanions are formed from polyacids during dissociation with the elimination of protons, which can be both inorganic and organic polymers.
  • Polyelectrolytes suitable according to the invention are both biopolymers, such as alginic acid, gum arabic, nucleic acids, pectins, proteins and others, and chemically modified biopolymers, such as ionic or ionizable polysaccharides, e.g. Carboxymethyl cellulose, chitosan and chitosan sulfate, lignin sulfonates and synthetic polymers such as polymethacrylic acid, polyvinyl sulfonic acid, polyvinyl phosphonic acid and polyethylene imine.
  • biopolymers such as alginic acid, gum arabic, nucleic acids, pectins, proteins and others
  • chemically modified biopolymers such as ionic or ionizable polysaccharides, e.g. Carboxymethyl cellulose, chitosan and chitosan sulfate, lignin sulfonates and synthetic polymers such as polymeth
  • Suitable polyanions include naturally occurring polyanions and synthetic polyanions.
  • naturally occurring polyanions are alginate, carboxymethyiamylose, carboxymethylcellulose, carboxymethyldextran, carageenan, cellulose sulfate, chondroitin sulfate, chitosan sulfate, dextran sulfate, gum arabic, gum guar, gum gellan, heparin, hyaluronic acid and pectin, a protein corresponding to xant.
  • Examples of synthetic polyanions are polyacrylates (salts of polyacrylic acid), anions of polyamino acids and their copolymers, polymaleinate, polymethacrylate, polystyrene sulfate, polystyrene sulfonate, polyvinyl phosphate, polyvinyl phosphonate, polyvinyl sulfate, polyacrylamide methyl propane sulfonate, polylactate / poly (ethane), mal (polylactate), poly (maleactate), poly (ethane), poly (maleactate), poly (maleactate), poly (maleactate), poly (maleactate), poly (ethane), poly (maleactate), poly (maleactate), poly (ethane), poly (maleactate), poly (maleactate), poly (maleate), poly (maleactate), poly (maleate), poly (maleactate), poly (maleate), poly (maleactate), poly (maleate), poly (maleactate), poly (maleate), poly (maleactate
  • Suitable polybases include naturally occurring polycations and synthetic polycations.
  • suitable naturally occurring polycations are chitosan, modified dextrans, e.g. Diethylaminoethyl-modified dextrans, hydroxymethylcellulose trimethylamine, lysozyme, polylysine, protamine sulfate, hydroxyethylcellulose trimethylamine and proteins at the appropriate pH.
  • synthetic polycations are polyallylamine, polyallylamine hydrochloride, polyamines,
  • Polymethylvinylpyridinium bromide, poly (vinylpyrrolidone / dimethylaminoethyl methacrylate) and polyvinylmethylpyridinium bromide are examples of polyvinylpyridinium bromide.
  • Linear or branched polyelectrolytes can be used.
  • the use of linear polyelectrolytes leads to less compact polyelectrolyte multifilaments with a higher degree of wall porosity.
  • polyelectrolyte molecules can be crosslinked within and / or between the individual layers, e.g. by crosslinking amino groups with aldehydes.
  • Amphiphilic polyelectrolytes e.g. amphiphilic block or random copolymers with partial polyelectrolyte character can be used.
  • amphiphilic copolymers consist of units of different functionality, e.g. on the one hand acidic or basic units and on the other hand hydrophobic units such as styrenes, dienes or siloxanes etc. which can be arranged as blocks or randomly distributed over the polymer.
  • copolymers that change their structure as a function of external conditions the capsule walls can be controlled in terms of their permeability or other properties.
  • Weak polyelectrolytes, polyampholytes or copolymers with a poly (N-isopropyl-acrylamide) component e.g. Poly (N-isopropylacrylamide-acrylic acid), which change their water solubility as a function of temperature via the equilibrium of hydrogen bonds, which is associated with swelling.
  • the dissolution the capsule walls control the release of trapped active substances.
  • conductive polyelectrolytes or polyelectrolytes with optically active groups for example optical brighteners, can also be used as capsule components for certain possible applications. It is also possible to incorporate particles with magnetic properties into the shell. This enables, for example, the identifiability of the end products, which is advantageous for product protection, in particular for preventing brand piracy.
  • the polyelectrolytes By suitable choice of the polyelectrolytes it is possible to set the properties and composition of the polyelectrolyte shell of the capsules according to the invention in a defined manner.
  • the composition of the shells can be varied within wide limits by the choice of substances in the layer structure. In principle, there are no restrictions with regard to the polyelectrolytes or ionomers to be used, as long as the molecules used have a sufficiently high charge and / or have the ability to bind to the underlying layer via other types of interaction, such as hydrogen bonds and / or hydrophobic interactions enter into.
  • Suitable polyelectrolytes are thus both low molecular weight polyelectrolytes or polyions and macromolecular polyelectrolytes, for example polyelectrolytes of biological origin.
  • the permeability of the envelope wall is of particular importance for the use of the capsules.
  • the large number of available polyelectrolytes enables the production of a large number of shell compositions with different properties.
  • the electrical charge of the outer shell can be adapted to the application.
  • the inner shell can be adapted to encapsulated active ingredients, which can, for example, stabilize the active ingredient.
  • the permeability of the envelope wall can also be influenced by the choice of the polyelectrolytes in the envelope and by the wall thickness and the ambient conditions. This is a selective design of the Permeability properties and a defined change of these properties possible.
  • the permeability properties of the shell can be further modified by pores in at least one of the polyelectrolyte layers. With a suitable choice, such pores can be formed by the polyelectrolytes themselves.
  • the shell can also comprise other substances in order to achieve a desired permeability.
  • the permeability for polar components can be reduced by introducing nanoparticles with anionic and / or cationic groups or with surface-active substances such as surfactants and / or lipids.
  • selective transport systems such as Carriers or channels
  • the pores or channels of the envelope wall can be opened or closed in a targeted manner by chemical modification and / or change in the ambient conditions. For example, a high salt concentration of the surrounding medium leads to a high permeability of the envelope wall.
  • a preferred embodiment of the method according to the invention comprises the layered application of polyelectrolytes to the liquid template particles pretreated by adding amphiphilic polyelectrolytes.
  • the layer-by-layer application of polyelectrolytes preferably comprises several, in particular more than four, process steps, wherein oppositely charged polyelectrolytes are deposited on the template particle from the continuous liquid phase.
  • Another preferred embodiment of the method according to the invention comprises complex precipitation of multilayers or coacervation of several, for example two, oppositely charged polyelectrolytes.
  • the coating components are presented in complex form in the coating emulsion, for example as complexes of two oppositely charged Polyelectrolytes, and by changing the media conditions causes a transfer (redistribution) of the components to the interface between the template particles and the continuous phase.
  • the film-forming components are kept in a solution, for example in an alkaline solution, in which both are present simultaneously without reacting with one another.
  • the template particles to be coated are added to this solution. It is then titrated with acid, for example HCl, to the neutral range, the template particles being encapsulated. After the encapsulated particles have been separated from the complexes in the free solution, for example by filtration, centrifugation, sedimentation (creaming) or phase separation, the template particles can, if appropriate, be dissolved.
  • the surface precipitation can be carried out from a solution containing a complex of a low molecular weight ion and an oppositely charged polyelectrolyte.
  • suitable low molecular weight ions are metal cations, inorganic anions such as sulfate, carbonate, phosphate, nitrate etc., charged surfactants, charged lipids and charged oligomers in combination with a correspondingly oppositely charged polyelectrolyte. This creates a distributed source for one polyelectrolyte in the presence of the other polyelectrolyte.
  • the polyelectrolyte of the complex can be both the polycation and the polyanion. The choice depends on the template particle and other requirements.
  • the negatively and positively charged polyelectrolyte can be introduced into an aqueous solution with a high salt content, preferably a salt content of> 0.5 mol / l, for example 1 M NaCl, and stirred. After adding the template particles, they are coated.
  • the coated template particles can, for example, by centrifugation, filtration, sedimentation or other known. Phase separation process and subsequent washing are obtained and, if necessary, dissolved to produce microcapsules.
  • the shell comprises low molecular weight cations, e.g. Metal cations and at least one negatively charged polyelectrolyte.
  • metal cations e.g. Metal cations and at least one negatively charged polyelectrolyte.
  • divalent and in particular trivalent cations are used as cations.
  • suitable cations are alkaline earth metal cations, transition metal cations and
  • Rare earth element cations such as Ca 2+ , Mg 2+ , Y 3+ , Tb 3+ and Fe 3+ .
  • monovalent cations such as Ag + can also be used.
  • the components required to form the shell comprise at least one macromolecule, for example an abiogenic macromolecule, such as an organic polymer, or a biomolecule, such as a nucleic acid, for example DNA, RNA or a nucleic acid analogue, a polypeptide, a glycoprotein or a polysaccharide with a molecular weight of preferably> 5 kD, and particularly preferably> 10 kD.
  • the macromolecules can carry charges, for example like nucleic acids, or they can also be uncharged, such as polysaccharides, for example dextran.
  • the components prescribed to form the shell comprise a mixture of several polyelectrolytes and / or lipids and / or proteins and / or peptides and / or nucleic acids and / or other organic and inorganic compounds of biogenic or abiogenic origin.
  • suitable composition of the liquid continuous phase in terms of salinity, pH, co-solvents, surfactants and by suitable choice of coating conditions, e.g. Temperature, theological conditions, presence of electrical and / or magnetic fields, presence of light, etc. are used to induce the various envelope components to assemble themselves on the templates, forming complex structures with diverse biomimetic properties.
  • step (b) of the method according to the invention is carried out under conditions such that a shell with a defined thickness in the range from 1 to 100 nm, preferably 1 to 50 nm, particularly preferably 5 to 30 nm and most preferably 10 to 20, around the template nm is formed.
  • the wall thickness and the homogeneity of the capsule shell are determined in layers by the number and composition of the layers and in the case of precipitation by their process management, which essentially depends on the concentration of the template particles, the concentration of the coating components and the speed of the solubility change in the liquid phase which causes the precipitation depends.
  • the capsule shell should be as long-term stable as possible so that the active substances are protected when the end products are stored within the capsule structures. If there are no particularly aggressive environmental conditions, this is the case according to the invention Processed washing and cleaning agents or cosmetics also the case. In the case of aggressive environmental conditions, such as high temperatures or low or high pH values, the storage stability can be controlled and improved by varying the wall thickness and the structure of the capsule shell.
  • the perfume oils are then released during or after use.
  • the active substances can be released during use, for example by dissolving or partially dissolving the casing during the washing process.
  • the active ingredients can be released during use, for example, by the capsule shells being destroyed by mechanical pressure when applied to the skin.
  • a release of the active ingredients from stable capsules after use can be regulated by the permeability of the envelope wall.
  • the large number of available polyelectrolytes enables the production of a large number of shell compositions with different properties.
  • precipitation can take place, for example, by introducing part of the components forming the shell in the liquid phase and then adding one or more further shell components.
  • a precipitation step can be used, for example, for a combination of metal cations and oppositely charged polyelectrolytes.
  • Another possibility of precipitation consists in that the components required for the formation of the shell are already completely in the liquid phase and that the liquid phase causes the precipitation.
  • This change in the liquid phase can include, for example, a change in the pH and / or a change in the composition of the liquid phase, for example by adding a solvent component and / or removing a solvent component.
  • precipitation of hydrophilic biopolymers such as DNA or polysaccharides can be effected by adding ethanol to an aqueous liquid phase, while the precipitation of polyelectrolyte combinations can be carried out by evaporating an organic solvent, such as acetone, from the liquid phase.
  • the components used to form the shell can alternatively or additionally also comprise nanoparticles, for example organic or inorganic nanoparticles, in particular nanoparticles with electrical, magnetic or optical properties, for example magnetite or CdTe.
  • the method according to the invention can include carrying out at least one additional coating step before and / or after the precipitation step.
  • Such an additional coating step can include, for example, the application of one or more lipid layers and / or the layer-by-layer application of polyelectrolytes.
  • a modification of the permeability of a shell can be achieved by depositing lipid layers and / or amphiphilic polyelectrolytes on the polyelectrolyte shell. In this way, the permeability of the shells for small and polar molecules can be greatly reduced.
  • lipids that can be deposited on the shells are lipids that carry at least one ionic or ionizable group, e.g. Phospholipids such as dipaimitoylphosphatidic acid or zwitterionic phospholipids such as dipalmitoylphosphatidylcholine or also fatty acids or corresponding long-chain alkylsulfonic acids.
  • Phospholipids such as dipaimitoylphosphatidic acid or zwitterionic phospholipids such as dipalmitoylphosphatidylcholine or also fatty acids or corresponding long-chain alkylsulfonic acids.
  • zwitterionic lipids lipid multilayers can be deposited on the
  • Polyelectrolytes can be applied in layers, for example as described in WO 99/47252.
  • the layer-by-layer structure can be combined with a precipitation step, for example, in such a way that a small number, for example 1 to 4 layers, of polyelectrolytes is first built up on the template particle, followed by a precipitation step.
  • a layer-by-layer deposition of polyelectrolytes on the shell can also take place after the precipitation steps.
  • a chemical reaction can also take place in and / or on the shells.
  • the method according to the invention enables capsules to be produced whose size distribution corresponds to that of emulsions and which, in contrast to surfactant-stabilized systems, show no change in the size distribution in the sense of Ostwald ripening.
  • the capsules are very stable against chemical, biological, mechanical and thermal loads. With a suitable composition, they can be dried and resuspended. They can be stored as a concentrate in aqueous or aqueous gel-like phases.
  • the core / wall ratio of the capsules is preferably 95/5 - 60/40, in particular 90/10 - 75/25.
  • FIG. 1 shows an embodiment of the method according to the invention comprising the one-step formation of a polyelectrolyte / ion shell on colloidal liquid template particles.
  • FIG. 2 shows a further embodiment of the method according to the invention, comprising self-assembly of polymer films on the surface of colloidal liquid particles.
  • FIG. 1 shows a schematic representation of two embodiments of the method according to the invention.
  • a suspension of liquid template particles (2) with amphiphilic polyelectrolytes is produced, which contain a perfume oil and metal ions, for example ions of a polyvalent metal or ions of a noble metal, such as Ag + (4).
  • metal ions for example ions of a polyvalent metal or ions of a noble metal, such as Ag + (4).
  • metal ions for example ions of a polyvalent metal or ions of a noble metal, such as Ag + (4).
  • a solution with negatively charged polyelectrolyte molecules (6) an ion / polyelectrolyte shell is precipitated on the template particles.
  • the coated template particles (8) can be processed further in different ways. In this way the template particles can be dissolved.
  • metal ions receive metal-coated capsules (12).
  • capsules with an anisotropic shell are produced, the inner part being an ion / polyelectrolyte shell and the outer part being a layered polyelectrolyte / polyelectrolyte shell.
  • the template particles can then be dissolved.
  • the inner ion / polyelectrolyte part of the shell can be dissolved, so that the perfume oil and the polymer (6) are encapsulated inside the shell formed from the oppositely charged polyelectrolytes (14a, 14b) (20).
  • FIG. 2 Another embodiment of the method according to the invention is shown in FIG. 2.
  • a suspension of colloidal liquid template particles (32) containing amphiphilic polyelectrolytes and comprising a perfume oil is presented in a liquid phase which contains a polymer, for example a nucleic acid, a protein, a polysaccharide or a synthetic polymer, in dissolved form.
  • a polymer for example a nucleic acid, a protein, a polysaccharide or a synthetic polymer, in dissolved form.
  • perfume oil blends were made:
  • Poly (diallyldimethyl) ammonium stearate (weight ratio of simplex compound to polyfunctional surfactant of 2: 1) is dissolved in 10 g of sweet orange oil.
  • poly (diallyldimethyl) ammonium poly (stearate) and poly (diallyldimethyl) ammonium poly (erucic acid) are each dissolved in 10 g orange oil, sweet.
  • 0.02 g of a mixture of hexadecyl / octadecyl-bis (polyoxyethylene) -3-sulfopropyl-ammonium-betaine and sodium hexadecyl / octadecyl-bis (polyoxyethylene) -2-sulfinato-3-sulfopropyl-ammonium-betaine are mixed of 5 g miglyol (C 8 , C ⁇ 2 triglyceride) and 5 g orange oil, sweet, dissolved.
  • the modified oil phases obtained according to regulations 2.1 to 2.7 are emulsified in aqueous solutions of suitable polyelectrolytes. 2.1, 2.3 and 2.4 should preferably continue with a polyanion and 2.2 preferably with a polycation in the aqueous phase. 2.5 can be further processed in both polycationic and polyanionic systems.
  • the polyelectrolyte complexes obtained in the oil / water phase boundary give the emulsion the necessary temporary stability against coalescence and also stabilize the phase boundary itself, so that it is possible to continue with known step-by-step or one-step processes for producing the polyelectrolyte multilayers.
  • PAH poly (allylamine hydrochloride)
  • the third layer is formed by adding 15 ml of PSS and the fourth layer by adding 20 ml of PAH.
  • a total of 10 layers (tenth layer 50 ml PAH) are produced in this way.
  • a starting solution of the two polyelectrolytes is prepared, in which both are in solution simultaneously without reacting with one another. This is achieved by presenting 100 ml of 0.1% (w / w) NaOH solution with 0.1 M NaCl. 300 mg of PSS (70,000 MW) and 200 mg of PAH (MG 50-65,000) solved. It is shaken until completely dissolved. This solution is stable for several hours. 20 ml of unmodified orange oil or 20 ml of an oil according to formulations 2.1 to 2.7 are added. The Ultraturrax is then used for emulsification and then rapidly tritrated with 10% (w / w) HCl to the neutral range. The emulsion is then cleaned by washing it several times in a separating funnel. The result is an emulsion that is stable for months.
  • Example 5 One-step precipitation from a solution containing a complex of a polyelectrolyte and a polyvalent ion
  • Solution I 1 ml of PSS solution (2 mg / ml) is mixed with 200 ⁇ l of a Y (N0 3 ) 3 solution (2 x 10 "2 M). The resulting charge ratio between sulfate and yttrium is 5: 3.
  • Solution II 400 ⁇ l orange oil are mixed with 1 ml water. The mixture is ultrasonically emulsified in an Ultraturrax for 3 to 4 minutes.
  • Solution I is then quickly added to solution II and the resulting emulsion is vortexed for 2 minutes.
  • the emulsion is stable for more than 20 hours and can optionally serve as a starting system for further coatings.
  • Two fabric softener formulations (for compositions, see Table 1) were each mixed with 0.5% of the microcapsules produced according to Example 4. Textiles made of cotton were then treated with a fabric softener solution for 5 minutes. The quantity ratio of fabric softener to dry laundry was 10.3 g / kg, the liquor ratio 1: 5. Capsules with a) orange oil and b) the perfume oil mixtures according to Example 1.1 and c) according to Example 1.2 were used.
  • Fabric softeners whose free perfume content corresponded to the total perfume content (free and encapsulated) of the agents according to the invention were chosen as comparative agents.
  • the intensity of the perfume oils was perceived after finishing, spinning and hanging for a day, hanging over the scent impression during the subsequent ironing. It was shown here that the textiles finished according to the invention had a significantly stronger fragrance intensity than the reference samples.
  • the basic formulation of the fabric softener examined consists of:
  • Table 1 Formulations for fabric softener, quantities in% by weight
  • Stepantex VL 90 A ® N-methyl-N (2-hydroxyethyl) -N, N- (ditalgacyloxyethyl) ammonium methosulfate, additized with Stepanquat X 9124 ® ex Stephan Europe, 3-tallow amidopropyldimethylammonium methosulfate, 90% in isopropanol.

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Abstract

L'invention concerne un procédé pour incorporer des huiles parfumées dans des lessives et des détergents ou des produits cosmétiques, ledit procédé comprenant les étapes suivantes : (a) préparation d'une émulsion de particules matricielles liquides, contenant au moins une huile parfumée, dans une phase liquide ou gel continue, au moins un polyélectrolyte ou complexe polyélectrolytique amphiphile ou un copolymère de monomères hydrophiles chargés et de monomères solubles dans l'huile étant dissous dans ces particules matricielles liquides et/ou la phase continue et un film étant formé à la limite de phase entre les particules matricielles liquides et la phase continue ; (b) application d'une enveloppe sur le film formé à la limite de phase et (d) incorporation des particules matricielles enveloppées, contenant des huiles parfumées, dans des lessives et des détergents ou des produits cosmétiques.
PCT/EP2001/011675 2000-10-11 2001-10-09 Procede pour incorporer des huiles parfumees dans des lessives et des detergents ou des produits cosmetiques WO2002031092A2 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PCT/EP2001/011675 WO2002031092A2 (fr) 2000-10-11 2001-10-09 Procede pour incorporer des huiles parfumees dans des lessives et des detergents ou des produits cosmetiques
AU2002215015A AU2002215015A1 (en) 2000-10-11 2001-10-09 Method for the inclusion of perfume oils in washing and cleaning agents or cosmetics

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10050382.9 2000-10-11
PCT/EP2001/011675 WO2002031092A2 (fr) 2000-10-11 2001-10-09 Procede pour incorporer des huiles parfumees dans des lessives et des detergents ou des produits cosmetiques

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WO2002031092A3 WO2002031092A3 (fr) 2002-07-25

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002096551A1 (fr) * 2001-05-31 2002-12-05 Novosom Ag Microcapsules et nanocapsules solubles, procede de production associe et utilisation
EP1304160A1 (fr) * 2001-10-19 2003-04-23 Novosom AG Mélanges stabilisés de liposomes et émulsions
WO2004047977A1 (fr) * 2002-11-22 2004-06-10 Capsulution Nanoscience Ag Procede et dispositif pour modifier des microparticules
US7531498B2 (en) 2003-06-13 2009-05-12 Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) Peroxycarboxylic acid-based bleach compositions having a long shelf life
CN104870084A (zh) * 2012-10-25 2015-08-26 奇华顿股份有限公司 胶囊
CN105188906A (zh) * 2012-10-25 2015-12-23 奇华顿股份有限公司 方法
WO2016059349A3 (fr) * 2014-10-15 2016-09-15 Lvmh Recherche Copolymeres acryliques amphiphiles, procede de preparation et produit parfume transparent
WO2016207179A1 (fr) * 2015-06-22 2016-12-29 Givaudan Sa Améliorations apportées ou se rapportant à des compositions de parfum encapsulées
WO2016207180A1 (fr) * 2015-06-22 2016-12-29 Givaudan Sa Améliorations apportées à des compositions parfumées encapsulées ou associées à celles-ci
WO2019120958A1 (fr) * 2017-12-18 2019-06-27 Henkel Ag & Co. Kgaa Fabrication de corps fusibles contenant un parfum
EP3423028B1 (fr) 2016-02-29 2020-04-08 Symrise AG Procédé de production de capsules à stabilité ameliorée à l'égard des tensides, comprenant des parfums

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2750997B1 (fr) * 1996-07-12 2003-04-25 Rhone Poulenc Chimie Granules d'un produit parfume a liberation controlee, leur procede d'obtention et leur utilisation dans les compositions detergentes pour lave-vaisselle
FR2774390B1 (fr) * 1998-02-02 2002-12-13 Rhodia Chimie Sa Parfums encapsules dans des polymeres alcali-hydrosolubles, leur procede de preparation et leur utilisation dans les compositions detergentes
FR2774389B1 (fr) * 1998-02-02 2001-07-27 Rhodia Chimie Sa Granules dispersables dans l'eau comprenant un parfum dans une matrice hydrosoluble ou hydrodispersable et leur procede de preparation

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002096551A1 (fr) * 2001-05-31 2002-12-05 Novosom Ag Microcapsules et nanocapsules solubles, procede de production associe et utilisation
EP1304160A1 (fr) * 2001-10-19 2003-04-23 Novosom AG Mélanges stabilisés de liposomes et émulsions
WO2004047977A1 (fr) * 2002-11-22 2004-06-10 Capsulution Nanoscience Ag Procede et dispositif pour modifier des microparticules
US7531498B2 (en) 2003-06-13 2009-05-12 Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) Peroxycarboxylic acid-based bleach compositions having a long shelf life
CN104870084A (zh) * 2012-10-25 2015-08-26 奇华顿股份有限公司 胶囊
US20150284665A1 (en) * 2012-10-25 2015-10-08 Givaudan Sa Capsules
CN105188906A (zh) * 2012-10-25 2015-12-23 奇华顿股份有限公司 方法
CN105188906B (zh) * 2012-10-25 2018-09-04 奇华顿股份有限公司 方法
WO2016059349A3 (fr) * 2014-10-15 2016-09-15 Lvmh Recherche Copolymeres acryliques amphiphiles, procede de preparation et produit parfume transparent
CN107709534A (zh) * 2015-06-22 2018-02-16 奇华顿股份有限公司 包封的香料组合物中或与之相关的改进
WO2016207180A1 (fr) * 2015-06-22 2016-12-29 Givaudan Sa Améliorations apportées à des compositions parfumées encapsulées ou associées à celles-ci
KR20180018806A (ko) * 2015-06-22 2018-02-21 지보당 에스아 캡슐화된 향료 조성물의 개선 또는 캡슐화된 향료 조성물과 관련된 개선
WO2016207179A1 (fr) * 2015-06-22 2016-12-29 Givaudan Sa Améliorations apportées ou se rapportant à des compositions de parfum encapsulées
JP2018525460A (ja) * 2015-06-22 2018-09-06 ジボダン エス エー カプセル封入された香料組成物における、またはこれに関する改善
US10722857B2 (en) 2015-06-22 2020-07-28 Givaudan S.A. Encapsulated perfume compositions
EP3310893B1 (fr) 2015-06-22 2020-08-05 Givaudan SA Améliorations apportées ou se rapportant à des compositions de parfum encapsulées
US10806683B2 (en) 2015-06-22 2020-10-20 Givaudan Sa Encapsulated perfume compositions
KR102528222B1 (ko) 2015-06-22 2023-05-02 지보당 에스아 캡슐화된 향료 조성물의 개선 또는 캡슐화된 향료 조성물과 관련된 개선
EP3310893B2 (fr) † 2015-06-22 2024-02-28 Givaudan SA Améliorations apportées ou se rapportant à des compositions de parfum encapsulées
EP3423028B1 (fr) 2016-02-29 2020-04-08 Symrise AG Procédé de production de capsules à stabilité ameliorée à l'égard des tensides, comprenant des parfums
WO2019120958A1 (fr) * 2017-12-18 2019-06-27 Henkel Ag & Co. Kgaa Fabrication de corps fusibles contenant un parfum

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AU2002215015A1 (en) 2002-04-22

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