WO2002060573A2

WO2002060573A2 - Capsule-in-capsule system and method for the production thereof

Info

Publication number: WO2002060573A2
Application number: PCT/EP2002/000816
Authority: WO
Inventors: Michael Dreja; Wolfgang Von Rybinski; Ute Krupp
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 2001-02-01
Filing date: 2002-01-26
Publication date: 2002-08-08
Also published as: AU2002250858A1; DE10104841A1; WO2002060573A3

Abstract

The invention relates to capsule-in-capsule systems (1) consisting of an external capsule (outer capsule) (2) with an external capsule envelope (3) and internal capsules (inner capsules) (4) located therein. The invention also relates to a method for the production of said systems. The capsule-in-capsule systems (1) are particularly suitable for use in the field of cosmetics and body care, in the production and processing of adhesives and/or in the field of detergents and washing products.

Description

Capsule-in-capsule system and method for its production

The present invention relates to an active ingredient-containing capsule-in-capsule system and a method for its production and the use of this capsule-in-capsule system, in particular as a delivery or metering system for active ingredients or active ingredients, preferably for use in washing and Detergents, cosmetic products, adhesives and adhesive compositions and the like.

Active substances or active substances such as fragrances, essential oils, perfume oils and care oils, dyes or antibacterial active substances that are used in cosmetic products or in detergents and cleaning agents often lose their activity during storage or directly during use. Some of these substances can also have insufficient stability for use or cause interfering interactions with other product components.

It is therefore of interest to control such substances in a controlled manner and to use them at the desired location with maximum effect.

For this reason, active or active substances such as fragrances, care oils, antibacterial agents and the like are often added to the products in a spatially defined, protected form. Sensitive substances are often enclosed in capsules of various sizes, adsorbed on suitable carrier materials or chemically modified. The release can then be activated with the aid of a suitable mechanism, for example mechanically by shearing, or diffusively directly from the matrix material.

For this reason, systems are often sought which are suitable as encapsulation, transport or presentation vehicles - often also referred to synonymously as "delivery systems" or "carrier systems". There are already numerous commercial delivery systems based on porous polymer particles or liposomes (e.g. Mikrosponges® from Advanced Polymer Systems or Nanotopes® from Ciba-Geigy, see B. Herzog, K. Sommer, W. Baschong, J. Röding "Nanotopes ™; A Surfactant Resistant Carrier System" in SÖFW-Journal, 124th year 10/98, pages 614 to 623).

The disadvantage of these conventional delivery systems known from the prior art is that they have only a low loading potential. Another disadvantage of conventional capsule systems is that they generally have only simple shell structures made of polymeric substances, which can react to only a change in the environmental properties. Furthermore, the encapsulation of active substances can often not take place in situ. Liposomes also have insufficient stability for many applications.

K. Landfester, F. Tiarks, H.-P. Hentze, M. Antonietti "Polyaddition in mini-emulsions: A new mute to polymer dispersions" in Macromol. Chem. Phys. 201, 1-5 (2000) generally describe polyadditions in mini-emulsions. Encapsulation of active substances or active substances is not mentioned there.

A general process for carrying out polyaddition reactions in mini-emulsions is also described in WO 00/29465.

European patent application EP 0 967 007 A2 describes a process for the microencapsulation of solid, biologically active substances, in particular pesticides, by polycondensation of a melamine or phenol / formaldehyde resin or a urea / formalin resin in dispersion in the presence of the active substance to be encapsulated in each case and a nonionic polymeric protective colloid for stabilizing the emulsion, microcapsules having average particle diameters of 0.1 to 300 μm being obtained. This method is only suitable for the encapsulation of solid biological active substances. To stabilize the emulsion, the emulsion must have a polymeric protective colloid be added. Only conventional capsule systems with a simple shell structure are described.

Y. G. Durant "Miniemulsion Polymerization: Applications and Continuous Process" in Polymer. Mater. Be. Closely. 1999, 80, pages 538-540 describes the encapsulation of organically soluble dyes with a polymer shell made of polystyrene by UV-induced radical polymerization of styrene in a miniemulsion. Encapsulation of compounds other than organically soluble dyes is not mentioned. A particular disadvantage of this process is that relatively insensitive compounds cannot be encapsulated by this method, since the radicals formed as intermediates in the radical polymerization are more sensitive compounds, e.g. B. can attack those with double bonds. Only conventional capsule systems with a simple shell structure are described.

B. Erdem et al. "Encapsulation of Inorganic Particles via Miniemulsion Polymerization" in Polymer. Mater. Be. Closely. 1999, 80, pages 583/584 describe the encapsulation of solid, insoluble inorganic particles, namely titanium dioxide particles, with a polymer shell made of polystyrene by UV-induced radical polymerization of styrene in a miniemulsion. Encapsulation of compounds other than insoluble, solid inorganic particles is not mentioned. A disadvantage of this method, too, is that relatively insensitive compounds cannot be encapsulated by this method, since the radicals formed as intermediates in the radical polymerization are more sensitive compounds, eg. B. can attack those with double bonds. Only conventional capsule systems with a simple shell structure are described.

WO 98/02466, DE 196 28 142 A1, DE 196 28 143 A1 and EP 818471 A1 describe the preparation of aqueous polymerization dispersions by free radical polymerization of free-radically polymerizable compounds in the state of the miniemulsion. Encapsulation of active substances is nowhere mentioned. DE 44 36 535 A1 describes a process for the preparation of microcapsule dispersions by means of interfacial polyaddition, which works with a certain minimum solubility in the oil phase using special oil-soluble emulsifiers (fatty acid esters, fatty amides, polyglycol ethers or polypropylene glycol ethers). Only conventional capsule systems with a simple shell structure are described.

US Pat. No. 4,626,471 describes a process for the microencapsulation of colorless organic dye precursor molecules by in-situ polymerization of polyfunctional amines with special multifunctional epoxy resins based on methylolated bisphenol-A or 4-glycidyloxy-N, N-diglycidylaniline. Only conventional capsule systems with a simple shell structure are described.

G.P. Puglisi et al. "Influence of the preparation conditions on poly (ethyl cyanoacrylate) nanocapsule formation" in International Journal of Pharmaceutics 125 (1995), pages 283-287 describe the production of poly (ethyl cyanoacrylate) nanocapsules (PECA nanocapsules) by situ polymerization. The nanocapsules produced are suitable as delivery systems for active ingredients. This involves conventional capsule systems with only a simple shell structure.

F. Caruso "Hollow Capsule Processing through Colloidal Templating and Self-Assembly" in Chem. Eur. J. 2000, 6, No. 3, pages 413-419 describes the production of various nano- and microscale capsule systems, which can be called delivery systems suitable for encapsulated active ingredients in the field of cosmetics and medicine. Here too, only conventional capsule systems with a simple shell structure are described.

K. Hong "Melamine resin microcapsules containing fragrant oil: synthesis and characterization" in Materials Chemistry and Physics 58 (1999), pages 128-131 describe the production of long-life melamine resin microcapsules containing active ingredient, which contain a fragrance oil, by in-situ polymerization of Migrin oil as capsule core material, melamine and formalin as capsule shell material, sodium lauryl sulfate as emulsifier and polyvinyl alcohol as protective colloid. Capsule systems loaded with fragrance oil with a simple shell structure are created.

German Offenlegungsschrift 18 17 316 describes active ingredient-containing capsules with a multi-layer shell and a process for their production. The capsules contain a liquid inside the capsule, in particular a color developer for pressure-sensitive copying material, fertilizer solutions, fragrances or adhesives.

EP 1 020 177 A1 describes a multi-layer soft capsule designed as a capsule-in-capsule system for removing malodorous breath, which contains a first soft capsule and a second soft capsule located therein, both the first and outer capsules the second, inner capsule contain an active ingredient for combating malodorous breath, the second, inner capsule should only dissolve in the stomach.

German Offenlegungsschrift 22 15 441 describes aqueous detergents which contain 1 to 50% of a detersive surfactant, at least 1% electrolyte and capsules which contain a water-soluble polymer in gelled form on their surface, the electrolyte, the concentration of the electrolyte and the polymer the capsules are selected such that the stability of the capsules in the detergent and the dissolution of the capsules when diluted with water are ensured. These are also conventional capsule systems with a simple shell.

The disadvantage of the capsule systems of the prior art is that no complex capsule systems are described which can react to more than one change in the environmental properties.

The object of the present invention is to provide a capsule or delivery system (metering system) which avoids the disadvantages of conventional capsule systems described above. Another object of the present invention is to provide in particular an encapsulation technique which leads to systems which can react in particular to two or more environmental parameters in an application.

Another object of the present invention is to provide an encapsulation system which offers a good to increased protective action for the encapsulated ingredients. Such a system is said to be particularly suitable for applications in detergents and cleaning agents, cosmetics and personal care products and in adhesive technology.

Surprisingly, it has now been found that the problem on which the present invention is based can be solved by using capsules which contain further smaller, preferably active substance-loaded capsules, in particular microcapsules or nanocapsules, or else smaller, active substance-loaded particles ("capsules-in-capsule" Systems "), especially in connection with suitably assembled solid, liquid or gel-like ingredients.

The present invention thus relates to a capsule-in-capsule system 1 with an outer capsule (outer capsule) 2 with an outer capsule shell 3 and an inner capsule (inner capsule) 4 located therein, the capsule-in-capsule system 1 according to the invention contains a plurality of inner capsules 4 which are completely surrounded by the capsule shell 3 of the outer capsule 2.

The outer capsule 2 also includes a first medium 5, in particular a carrier medium, in which the inner capsules 4 are located. This first medium 5 can, for example, be a solid or liquid medium.

In the case of a liquid medium, the first medium 5 can comprise, for example, an oil phase, an aqueous phase, an oil-in-water emulsion or a water-in-oil emulsion. The oil of the oil phase or the emulsion can for example be a higher hydrocarbon, in particular with a carbon atom number of more than twelve, a paraffin oil, a silicone oil, a perfume or Fragrance oil, an essential oil or a care oil or a mixture of at least two such substances.

In the case of a solid medium, the first medium 5 can be designed, for example, as a powder or granulate.

In general, the inner capsules 4 comprise a second medium 6. The second medium 6 can in particular comprise at least one active substance or active substance, either in pure substance or in solution or suspension. The active substance or active substance can be, for example, a substance that is active in washing and / or cleaning. In this case, it is selected in particular from the group of washing and / or cleaning active inorganic and organic acids, in particular carboxylic acids, soil repellent and soil release active substances, bleaching agents such as in particular hypochlorites, bleach activators, washing and cleaning active enzymatic systems and Enzymes such as, in particular, amylases, cellulases, lipases and proteases, fragrances, in particular perfume oils, antimicrobial active substances, in particular antibacterial, antiviral and / or fungicidal active substances, builders and cobuildem, antiredeposition additives, oxidants, graying and discoloration inhibitors, active substances and color additives Laundry care, optical brighteners, foam inhibitors, all types of surfactants such as, in particular, surfactants with fabric softener properties as well as pH adjusting agents and pH buffer substances.

The active ingredient or active ingredient can also be an ingredient for cosmetics or personal care products.

The active ingredient can also be an adhesive or an adhesive component.

In general, the inner capsules contain 4 identical active ingredients. According to a special embodiment of the present invention, the inner capsules 4 can also contain different active substances. In other words, in this case there is a mixture of different inner capsules 4. For example, for detergent applications, part of the inner capsules 4 can contain a detergent enzyme, while the other part of the inner capsules 4 can contain a surfactant with fabric softener properties, the inner capsules 4 filled with different ingredients - after the outer capsule shell 3 has dissolved - the ingredients ( release enzyme or surfactant) specifically at different times of the washing process, for example due to different dissolution behavior of the inner capsules 4 z. B. depending on the ambient temperature.

According to a particular embodiment of the present invention, the second medium 6 of the inner capsules 4 can be designed as a matrix, in particular a solid or gel-like matrix, in which the at least one active substance or active substance is embedded.

The inner capsules 4 can preferably also have a capsule shell 7 which completely encloses the second medium 6.

According to a special embodiment of the present invention, the first medium 5 can also comprise at least one active substance or active substance, either in pure substance or in solution or suspension. This can be an identical active substance or active substance as in the inner capsules 4, or else a different active substance or active substance.

The first medium 5 and the second medium 6 can be identical or different. However, the first medium 5 and the second medium 6 are preferably different from one another.

In general, the average diameter of the inner capsules 4 is at least one order of magnitude smaller than the average diameter of the outer capsule 2.

Preferably, the ratio of the average diameter of the inner capsules 4 to the average diameter of the outer capsule 2 is generally approximately 1:10 to about 1: 100,000, in particular about 1: 100 to about 1: 30,000, preferably about 1: 1,000 to about 1: 20,000.

In particular, the average diameter of the inner capsules 4 is approximately

100 nm to approximately 100 μm, in particular approximately 150 nm to approximately 50 μm, preferably approximately 175 nm to approximately 25 μm.

The mean diameter of the outer capsule 2, on the other hand, is approximately 1 μm to approximately 10 mm, in particular approximately 10 μm to approximately 5 mm, preferably approximately

150 μm to about 2.5 mm.

The capsule shells (3, 7) are generally formed from a polymer or from polymers. The capsule shell material of the capsule shells 7 of the inner capsules 4 can be identical or different with respect to the capsule shell material of the capsule shells 3 of the outer capsules 2. Preferably, the capsule shells 7 of the inner capsules 4 and the capsule shells 3 of the outer capsule 2 are made of different materials, i. H. the capsule shell material of the capsule shells 7 of the inner capsules 4 is preferably different from the capsule shell material of the capsule shell 3 of the outer capsule 2. The capsule shells 7 of the inner capsule 4 formed from polymers can consist, for example, of polyelectrolytes or polyelectrolyte complexes, polystyrenes, epoxy resins, polyurethanes, polyureas, polycyanoacrylates, poly (meth) acrylates, melamine resins, formaldehyde resins, phenolic resins, polyisocyanates, waxes, solid paraffins or polysaccharides. The capsule shell 3 of the outer capsule 2 formed from polymers can also consist, for example, of polyelectrolytes or polyelectrolyte complexes, polystyrenes, epoxy resins, polyurethanes, polyureas, polycyanoacrylates, poly (meth) acrylates, melamine resins, formaldehyde resins, phenolic resins, polyisocyanates, waxes, solid paraffins or polysaccharides.

The capsule-in-capsule system 1 according to the invention generally has an active substance content of 0.001% by weight to 80% by weight, in particular 0.005 to 50% by weight, preferably 0.01 to 30% by weight, on, based on the entire capsule-in-capsule system 1. The weight of the inner capsules 4 generally makes up 0.1 to 50% by weight, in particular 0.1 to 30% by weight, preferably 1 to 10% by weight, of the total weight of the capsule-in-capsule system 1 ,

The weight of the polymer from which the outer shell 3 is made generally represents 0.1 to 10% by weight, in particular 0.1 to 5% by weight, of the total weight of the capsule-in-capsule system 1.

The capsule-in-capsule system 1 according to the invention generally has a content of the first medium 5 of 0.1 to 70% by weight, in particular 0.1 to 50% by weight, preferably 1 to 20% by weight.

According to a particular embodiment of the present invention, the capsule shells 7 of the inner capsules 4 are hydrophobic and the capsule shell 3 of the outer capsule 2 is hydrophilic or vice versa.

According to a further embodiment of the present invention, the capsule shells 7 of the inner capsules 4 can be semipermeable and preferably in particular permeable to water molecules, but impermeable or essentially impermeable to the optionally encapsulated active substance or active ingredient. "Essentially impermeable" in the sense of the present invention means that the capsule shells 7 are designed in particular in such a way that the active substance or active ingredient diffuses through the semipermeable capsule shell (membrane) considerably more slowly, preferably by at least one order of magnitude, than water molecules. The production of capsules with a semipermeable capsule shell is known per se to the person skilled in the art and is described, for example, in German patent application 101 00 689, the content of which is hereby incorporated by reference.

According to another embodiment of the present invention, the capsule shell 3 of the outer capsule 2 can be semipermeable and in particular permeable to water molecules. In the capsule-in-capsule system according to the invention, for example, the capsule shells 7 of the inner capsules 4 and the capsule shell 3 of the outer capsule 2 can dissolve at different temperatures and / or be soluble and / or melt in a given external medium. This effect can be used, for example, in detergents (e.g. for the delayed release of wash-active enzymes or to protect fragrances that should only be released when the laundry is ironed), but also in personal care products, cosmetics and adhesives.

According to a further embodiment of the present invention, the capsule shells 7 of the inner capsules 4 and the capsule shell 3 of the outer capsule 2 can go into solution at different pH values and / or be soluble and / or melt in a given external medium. This effect can be used, for example, in detergents (e.g. for the delayed release of wash-active enzymes or to protect fragrances that should only be released when the laundry is ironed), but also in personal care products, cosmetics and adhesives.

According to a further embodiment of the present invention, the capsule shells 7 of the inner capsules 4 and the capsule shell 3 of the outer capsule 2 can dissolve at different ion concentrations and / or be soluble and / or melt in a given external medium. This effect can be used, for example, in detergents (e.g. for the delayed release of wash-active enzymes or to protect fragrances that should only be released when the laundry is ironed), but also in personal care products, cosmetics and adhesives.

According to a further embodiment of the present invention, the capsule shells 7 of the inner capsules 4 and the capsule shell 3 of the outer capsule 2 can have different degradation times in a given external medium. This effect can be used, for example, in detergents (e.g. to delay the release of wash-active enzymes or to protect fragrances, which should only be released when the laundry is ironed), but also in personal care products, cosmetics and adhesives.

According to a further embodiment of the present invention, the capsule shells 7 of the inner capsules 4 and the capsule shell 3 of the outer capsule 2 can have different strengths. This effect can be used for example in the case of adhesives by z. B. the inner capsules 4 are firmer than the outer shell 3 and contain a catalyst for adhesive curing, which is only released by the action of high shear forces (z. B. by pressing) with destruction of the inner capsules 4.

According to a further embodiment of the present invention, the capsule shells 7 of the inner capsules 4 and the capsule shell 3 of the outer capsule 2 can have different affinities or chemical-physical properties with respect to an external medium. For example, the inner capsules may contain a fragrance and have a high affinity for textiles, while the outer capsule 2 e.g. B. can be temperature sensitive and z. B. dissolves during the washing process, so that the inner capsules 4 are released during the washing process and can attach to the fibers.

Furthermore, the capsule shells 7 of the inner capsules 4 and the capsule shell 3 of the outer capsule 2 can have different thicknesses. The capsule shells 7 of the inner capsules 4 and / or the capsule shell 3 of the outer capsule 2 can consist of single- or multi-layer shells.

According to a further embodiment of the present invention, the inner capsules 4 can have a high affinity for textiles and in particular can adhere to the fibers of the textiles.

The capsule shells 7 of the inner capsules 4 and the capsule shell 3 of the outer capsule 2 can also have several of the aforementioned different properties. For example, the inner capsules 4 can be temperature-stable, in particular up to at least 30 ° C., preferably up to 95 ° C. and / or of a given external medium, in particular a detergent or cleaning agent solution, can be non-dissolvable and have a high affinity for textile fibers, while the outer capsule 2 cannot be temperature-stable and / or dissolved by a given external medium, in particular a detergent or cleaning agent solution can be.

In general, the capsule shells 7 of the inner capsules 4 and / or the capsule shell 3 of the outer capsule 2 are designed to be environmentally friendly, in particular biodegradable.

The present invention also relates to a method for producing the capsule-in-capsule system 1 according to the invention, which comprises the following method steps:

(a) preparation of a dispersion of the inner capsules 4 by polymerization, in particular in-situ polymerization in the presence of an active ingredient to be encapsulated, using methods known per se,

(b) Encapsulation of the dispersion prepared in step (a) and containing the inner capsules 4 by polymerization using methods known per se, in particular by gelation, coacervation, solution dropletization, melt dropletization, emulsion evaporation, spray drying or interfacial polymerization, so that a capsule-in -Capsule system 1, in which several inner capsules 4 are completely surrounded by an outer capsule shell 3, and finally

(c) if appropriate, separation of the capsule-in-capsule system 1 obtained in step (b) using methods known per se.

The very small, in particular active substance-loaded, inner capsules 4 in step (a) can be carried out in particular as follows: Drug-loaded micro- and nanocapsules, microparticles or sponge particles can be produced in a manner known per se, e.g. B. by miniemulsion polymerization, interfacial polymerization of reactive surfactants (see e.g. German patent applications 100 37 656 and 100 31 132), by interfacial polymerization of cyanoacrylates (see e.g. BG Puglisi et al., Int. J. Pharm. 1995, 125 , Pages 283-287), by melamine-formaldehyde resin reactions (see, for example, BK Hong, S. Park, Mater. Chem. Phys. 1999, 58, 128-131) or else by others, by the status of Techniques known in the art. The particles obtained are usually in the form of an aqueous or oil-containing dispersion after their preparation. The shell or matrix material of the inner capsules 4 is selected in particular so that it can produce the desired second switching mechanism when released in later use. Capsules with a delayed release of active ingredient and capsules with a substantial surface quality are particularly interesting.

A method for producing the inner capsules 4 according to step (a) of the method according to the invention is e.g. B. described in German patent application 100 44 635, which relates to a process for the preparation of polymer capsules with encapsulated active ingredients or active ingredients by sol-gel polycondensation of monomeric, trifunctional, surface-active organosilicon compounds polymerizable by polycondensation in emulsion, the organosilicon compound being selected in particular from the group of trifunctional alkylhalosilanes and the corresponding alkylsilanols and trifunctional alkylsiloxanes, each with a long-chain alkyl chain, for. B. trifunctional alkylhalosilanes of the formula RSiX3 with X = halogen (preferably chlorine or bromine) and R = Ci 1-C22-alkyl.

Further methods according to the invention which are suitable for producing active substance or active substance-containing nano and microcapsules according to step (a) of the method according to the invention are e.g. B. described in EP 0 941 761 A2, in EP 0 304 416 A1, in EP 0 934 773 A2, in WO 90/10436, in DE 44 16 857 C1 and in US Pat. No. 5,492 994, the disclosures of which are hereby incorporated by reference. Another method according to the invention for producing the inner capsules 4 of the method according to the invention is described, for example, in German patent application 100 37 656. German patent application 100 37 656 describes the production of polymer capsules containing active substance or active substance by non-radical emulsion polymerization of suitable monomers in the presence of the active substance or active substance to be encapsulated under mini-emulsion polymerization conditions. In particular, the polyaddition of di- or polyfunctional amines, alcohols, carboxylic acid anhydrides and mercaptans to di- and / or polyfunctional epoxides is used. The polyaddition of di- and polyfunctional amines and alcohols onto di- and / or polyfunctional isocyanates is also suitable. Depending on the starting monomers, active ingredient-containing polymer capsules based on epoxy resins, polyurethanes or polyureas are formed as the capsule material.

Further methods suitable according to the invention for carrying out step (a) of the method according to the invention are described in WO 00/29465, in EP 0 967 007 A2, in WO 98/02466, in DE 196 28 142 A1, in DE 196 28 143 A1, in EP 818 471 A1, in DE 44 36 535 A1 and in US-A-4 626 471. Further methods according to the invention for carrying out step (a) of the method according to the invention are described by Landfester et al. "Polyaddition in miniemulsions: A new mute to polymer dispersions" in Macromol. Chem. Phys. 201, pages 1-5 (2000) and by Durant "Miniemulsion Polymerization: Applications and Continuous Process" in Polymer. Mater. Be. Closely. 1999, 80, pages 538-540 and by Erdem et al. "Encapsulation of Inorganic Particles via Miniemulsion Polymerization" in Polymer. Mater. Be. Closely. 1999, 80, pages 583/584.

A further method according to the invention for producing the inner capsules 4 is described in the German patent application 100 31 132. Here the heat, plasma or radiation-induced radical interfacial polymerization in dispersion for the in-situ encapsulation of active substances in polymer capsules produced by interfacial polymerization is described , Another method which is suitable according to the invention is described in German patent application 100 00 689, which describes a method for producing microcapsules with a semipermeable capsule shell with encapsulated detergent and / or cleaning substances by in-situ complexation of suitable polyelectrolytes or polyelectrolyte mixtures. Also suitable according to the invention are the processes mentioned in this application as prior art, in particular EP 0 782 853 A2, DE 195 19 804 A1, WO 99/02252, US-A-4,352,883, US-A- 4,690,682, WO 91/15196, DE 197 12 978 A1, WO 00/46337 and EP 0280 155 B1, the disclosures of which are hereby incorporated by reference.

Further methods according to the invention for producing the inner capsules 4 are, for example, the methods for producing capsule systems with a simple shell structure that were mentioned at the outset in the assessment of the prior art.

The encapsulation of the capsule or particle dispersion or granulate produced in step (a) in step (b) of the method according to the invention is carried out in particular as follows:

The encapsulation carried out in step (b) can be carried out, for example, by dripping the dispersion prepared in step (a) after adding suitable monomers or polymers into a suitable template, in particular an acidic, basic or neutral salt or ion solution.

The capsule or particle dispersion or granulate produced according to step (a) is z. B. via a known method, such as. B. gelation, coacervation, solution drop or melt drop (e.g. with waxes or wax-like substances), emulsion evaporation, spray drying or interfacial polymerization (see e.g. German patent application 100 44 635), as is known from the prior art for "simple" Encapsulation is known, encapsulated again. The outer shell or matrix material becomes the outer one Capsules 2 in particular chosen so that it can generate the desired first switching mechanism in the release in the later application. For this, z. B. water-soluble polymers such as. B. in German Offenlegungsschrift 22 15 441 (z. B. polyvinyl alcohol, cellulose derivatives, polysaccharides, polyacrylates, etc.) are used, which can either melt or which form insoluble complexes with suitable, especially polyvalent ions ("gelling ") or can be salted out or crosslinked (e.g. alginates by dropletization in alkaline earth metal ion solutions or e.g. polyvinyl alcohols by dropletization in solutions which contain alkaline earth metal ions, borates, aluminum ions, etc.). The resulting capsules, which have a switching mechanism for the pH value (for example via polyacrylate casings, e.g. using Eudragit® polymers from Röhm), the temperature (LCST polymers such as poly-N-isopropylacrylamide derivatives) are particularly interesting. or which have ionic strength (for example polyvinyl alcohol, for example from Erkol) and can thus serve to delay or selectively release the smaller capsules 4.

The present invention also relates to the use of the capsule-in-capsule system 1 according to the invention for the field of cosmetics and personal care, for the production and processing of adhesives and / or for the field of detergents and cleaning agents.

In particular, the capsule-in-capsule system 1 according to the invention can be used as a delivery system or dosing system, preferably for the controlled release of active substances or active substances.

The present invention further also relates to cosmetics or personal care products, adhesives or adhesive components or else in particular detergents and cleaning agents which contain the capsule-in-capsule system 1 according to the invention - in one or more phases of the product.

The present invention offers a number of advantages: The present invention provides an encapsulation system 1 or an encapsulation technology that can react to two or more environmental parameters in an application.

At the same time, the system 1 according to the invention provides a good to increased protective effect for the encapsulated ingredients.

The main focus of the applications for the system 1 according to the invention are washing and cleaning agents, cosmetics and personal care products and adhesives.

The present invention readily enables "capsule-in-capsule system 1 to be" tailored "for the respective application. The capsule-in-capsule system 1 according to the invention can, for. B. can be tailored for the respective application by selecting the suitable material for the release on both "size levels" of the capsules in a suitable manner. The release profile of the active ingredients can also be tailored via the "size levels" of the capsules by utilizing surface effects. Small capsules with a thin wall and a large surface area, for example, lead to a faster release than large capsules of the same material.

Z. B. also optical or acoustic effects during the release, such as. B. a color change of an indicator by pH change or the formation of a gas in the reaction of the capsule ingredient with the outer phase. A suitable ingredient of the smaller capsules is selected accordingly.

Particularly preferred polymers for the outer capsule shell 3 are therefore in particular those which protect the enclosed smaller capsules 4 from the surrounding medium, so that a reaction and / or release of the encapsulated ingredient does not occur during storage. In this context, it can be useful to use an oil phase as the carrier phase 6 for the smaller capsules 4 (similar to a w / o / w emulsion), if as the outer phase 5 an aqueous phase and an active ingredient in the inner capsules 4 a water-soluble active ingredient, since the (diffusive) exchange of the phases is thus minimized. Ideally, the oil phase is then in the form of a gel by adding a suitable gelator (low molecular weight or polymer).

Further configurations and variations of the present invention are readily recognizable and realizable for the person skilled in the art on reading the description, without thereby leaving the scope of the present invention.

The present invention is illustrated by means of the following exemplary embodiments, which, however, in no way limit the invention.

WORKING EXAMPLES

Example 1:

By in-situ encapsulation in an aqueous phase which, in addition to the monomers to be polymerized (alkyl cyanoacrylate) and optionally conventional additives such as emulsifiers, contains 10% by weight of an active ingredient (fragrance oil or orange oil), known methods (see Puglisi et al.) a 10% aqueous dispersion of 2 to 20 μm large poly (alkyl cyanoacrylate) capsules (e.g. poly (methyl cyanoacrylate) capsules or poly (ethyl cyanoacrylate) capsules), which contain the fragrance oil in encapsulated form ,

The dispersion of poly (alkyl cyanoacrylate) microcapsules produced in this way is added dropwise to a 20% sodium sulfate solution after the addition of 5% by weight of polyvinyl alcohol. Due to the ion concentration-dependent solubility of polyvinyl alcohol in water, capsules of 100 to 2,000 μm in size form spontaneously with an outer shell made of polyvinyl alcohol, which encapsulate the dispersion with the smaller, active substance-loaded poly (alkyl cyanoacrylate) and can then be filtered off if necessary.

The result is a capsule-in-capsule delivery system according to the invention with an oil-like active ingredient (fragrance oil), which is used, for example, in liquid detergents when diluted, ie. H. in use when washing, e.g. B. in washing machines, the active ingredient-filled inner capsules, which have a substantivity to the tissue, only releases with delay. The inner capsules remain on the fabric treated in this way even after the laundry has dried. This results in an improved fragrance when ironing the laundry.

Example 2:

By in-situ encapsulation in the aqueous phase by means of mini-emulsion polymerizations according to methods of the prior art (see German patent application 100 37 658 and the state cited therein, in particular polyaddition of amines, alcohols or mercaptans on di- and / or polyfunctional epoxides), a 12% aqueous dispersion of approximately 200 nm large, epoxy resin-containing capsules, which are loaded with 10% by weight of a fragrance oil (orange oil) as an encapsulated active ingredient, is produced ,

The dispersion of active substance-loaded nanocapsules produced in this way is added to a solution containing 2% calcium chloride and 0.2% poly-L-lysine after the addition of 1.8% by weight sodium alginate. Due to the complexation of the alginate, 30 to 300 μm capsules with an outer shell made of an alginate complex are formed, which surround the dispersion with the smaller, active substance-loaded nanocapsules and can then be filtered off if necessary.

The result is a capsule-in-capsule delivery system according to the invention with an oil-like active ingredient (fragrance oil) which, for example, as in Example 1, in liquid detergents when diluted, ie. H. in use when washing, e.g. B. in washing machines, the active ingredient-filled inner capsules, which have a substantivity to the tissue, only releases with delay. The inner capsules remain on the fabric treated in this way even after the laundry has dried. This results in an improved fragrance when ironing the laundry.

Example 3:

By in-situ encapsulation in the aqueous phase by means of interfacial polymerization of dodecyl-15EO-acrylate according to methods of the prior art (see German patent application 100 31 132 and prior art cited therein), a 12% oil-containing dispersion of approximately 180 nm capsules is obtained , which are loaded with 10 wt .-% of a vitamin C solution as an encapsulated active ingredient.

The oil-containing dispersion (Cetiol OE) of nanocapsules loaded with active ingredient produced in this way is added after adding 12% by weight of Eudragit®, a Methacrylate polymer from Röhm or Rohm & Haas, dripped into a solution with 5% HCl and 2% sucrose. Due to the solubility of the Eudragit® polymer, which is dependent on the pH of the medium, capsules of 500 to 2,000 μm in size are created with an outer shell made of Eudragit®, which surround the dispersion with the smaller, active ingredient-loaded nanocapsules and can then be filtered off if necessary.

The result is a capsule-in-capsule delivery system according to the invention with a hydrophilic active ingredient which, for example when used in a hair colorant, releases the active ingredient-filled capsules with a delay when applied to the hair and thereby achieves an antioxidative effect on the scalp.

Claims

claims:

1. capsule-in-capsule system (1) with an outer capsule (outer capsule) (2) with an outer capsule shell (3) and an inner capsule (inner capsule) (4) therein,

characterized in that

the capsule-in-capsule system (1) contains a plurality of inner capsules (4) which are completely surrounded by the capsule shell (3) of the outer capsule (2).

2. capsule-in-capsule system (1) according to claim 1, characterized in that the outer capsule (2) also surrounds (envelops) a first medium (5), in particular a carrier medium, in which the inner capsules ( 4).

3. capsule-in-capsule system (1) according to claim 2, characterized in that the first medium (5) is a solid or liquid medium.

4. capsule-in-capsule system (1) according to claim 3, characterized in that the liquid medium comprises an oil phase, an aqueous phase, an oil-in-water dispersion or a water-in-oil dispersion.

5. capsule-in-capsule system (1) according to claim 4, characterized in that the oil of the oil phase or the emulsion is a higher hydrocarbon, in particular with a carbon atom number of more than twelve, a paraffin oil, a silicone oil, a perfume or Fragrance oil, an essential oil or a care oil or a mixture of at least two such substances.

6. capsule-in-capsule system (1) according to claim 3, characterized in that the solid medium is a powder or granules.

7. capsule-in-capsule system (1) according to any one of the preceding claims, characterized in that the inner capsules (4) contain a second medium (6).

8. capsule-in-capsule system (1) according to claim 7, characterized in that the second medium (6) comprises at least one active substance or active substance, either in pure substance or in solution or suspension.

9. capsule-in-capsule system (1) according to claim 8, characterized in that the active substance or active substance is a washing and / or cleaning active substance and is preferably selected from the group of washing and / or cleaning active inorganic and organic Acids, in particular carboxylic acids, soil repellent and soil release active ingredients, bleaching agents such as in particular hypochlorites, bleach activators, washing and cleaning-active enzymatic systems and enzymes such as in particular amylases, cellulases, lipases and proteases, fragrances, in particular perfume oils, antimicrobial agents, in particular antibacterial, antiviral and / or fungicidal active ingredients, builders and cobuilders, anti-redeposition additives, oxidants, graying and discoloration inhibitors, active substances for color protection, substances and additives for laundry care, optical brighteners, foam inhibitors, all types of surfactants, in particular surfactants with fabric softening properties such as pH regulators and pH buffer substances.

10. capsule-in-capsule system (1) according to claims, characterized in that the active substance or active ingredient is an ingredient for cosmetics or personal care products.

11. capsule-in-capsule system (1) according to claims, characterized in that the active substance or active ingredient is an adhesive or an adhesive component.

12. capsule-in-capsule system (1) according to any one of the preceding claims, characterized in that the inner capsules (4) contain different active ingredients.

13. Capsule-in-capsule system (1) according to one of the preceding claims, characterized in that the second medium (6) of the inner capsules (4) is designed as a matrix, in particular a solid or gel-like matrix, into which the at least one active substance or active substance is stored.

14. capsule-in-capsule system (1) according to one of the preceding claims, characterized in that the inner capsules (4) have a capsule shell (7) which completely encloses the second medium (6).

15. capsule-in-capsule system (1) according to any one of the preceding claims, characterized in that the first medium (5) also comprises at least one active substance or active substance, either in pure substance or in solution or suspension.

16. capsule-in-capsule system (1) according to any one of the preceding claims, characterized in that the first medium (5) and the second medium (6) are identical or different.

17. Capsule-in-capsule system (1) according to one of the preceding claims, characterized in that the average diameter of the inner capsules (4) is at least one order of magnitude smaller than the average diameter of the outer capsule (2).

18. Capsule-in-capsule system (1) according to one of the preceding claims, characterized in that the ratio of the average diameter of the inner capsules (4) to the average diameter of the outer capsule (2) is about 1:10 to about 1: 100,000, in particular about 1: 100 to about 1: 30,000, preferably about 1: 1,000 to about 1: 20,000.

19. Capsule-in-capsule system (1) according to one of the preceding claims, characterized in that the average diameter of the inner capsules (4) about 100 nm to about 100 microns, in particular about 150 nm to about 50 microns, preferably about 175 nm to about 25 μm.

20. Capsule-in-capsule system (1) according to one of the preceding claims, characterized in that the average diameter of the outer capsule (2) is about 1 μm to about 10 mm, in particular about 10 μm to about 5 mm, preferably about 150 μm to about 2.5 mm.

21. Capsule-in-capsule system (1) according to one of the preceding claims, characterized in that the capsule shells (3, 7) are formed from a polymer, the capsule shell material of the capsule shells (7) of the inner capsules (4) in can be identical or different with respect to the capsule shell material of the capsule shells (3) of the outer capsules (2).

22. Capsule-in-capsule system (1) according to claim 21, characterized in that the capsule shell material of the capsule shells (7) of the inner capsules (4) is preferably different from the capsule shell material of the capsule shells (3) of the outer capsules (2) ,

23. Capsule-in-capsule system (1) according to claim 21 or 22, characterized in that the capsule shells (7) formed from polymers of the inner capsule (4) made of polyelectrolytes or polyelectrolyte complexes, polystyrenes, epoxy resins, polyurethanes, polyureas, polycyanoacrylates , Poly (meth) acrylates, melamine resins, formaldehyde resins, phenolic resins, polyisocyanates, waxes, solid paraffins or polysaccharides.

24. Capsule-in-capsule system (1) according to one of claims 21 to 23, characterized in that the capsule shell (3) formed from polymers of the outer capsule (2) made of polyelectrolytes or polyelectrolyte complexes, polystyrenes, epoxy resins, polyurethanes, polyureas , Polycyanoacrylates, Poly (meth) acrylates, melamine resins, formaldehyde resins, phenolic resins, polyisocyanates, waxes, solid paraffins or polysaccharides.

25. Capsule-in-capsule system (1) according to one of the preceding claims, characterized in that the capsule shells (7) of the inner capsules (4) are hydrophobic and the capsule shell (3) of the outer capsule (2) is hydrophilic or vice versa.

26. Capsule-in-capsule system (1) according to one of the preceding claims, characterized by an active substance or active substance content of 0.001% by weight to 80% by weight, in particular 0.005 to 50% by weight, preferably 0, 01 to 30% by weight, based on the entire capsule-in-capsule system (1).

27. Capsule-in-capsule system (1) according to one of the preceding claims, characterized in that the weight of the inner capsules (4) 0.1 to 50 wt .-%, in particular 0.1 to 30 wt .-% , preferably 1 to 10% by weight, of the total weight of the capsule-in-capsule system (1).

28. Capsule-in-capsule system (1) according to one of the preceding claims, characterized in that the weight of the polymer from which the outer shell (3) consists is 0.1 to 10% by weight, in particular 0, 1 to 5% by weight of the total weight of the capsule-in-capsule system (1).

29. capsule-in-capsule system (1) according to one of the preceding claims, characterized by a content of the first medium (5) of 0.1 to 70 wt .-%, in particular 0.1 to 50 wt .-%, preferably 1 to 20% by weight.

30. Capsule-in-capsule system (1) according to one of the preceding claims, characterized in that the capsule shells (7) of the inner capsules (4) are semipermeable and preferably in particular permeable to water molecules, but impermeable or essentially are impermeable to the optionally encapsulated active ingredient.

31. Capsule-in-capsule system (1) according to one of the preceding claims, characterized in that the capsule shell (3) of the outer capsule (2) is semipermeable and is in particular permeable to water molecules.

32. Capsule-in-capsule system (1) according to one of the preceding claims, characterized in that the capsule shells (7) of the inner capsules (4) and the capsule shell (3) of the outer capsule (2) at different temperatures in solution go and / or are soluble in the respective external medium and / or melt.

33. Capsule-in-capsule system (1) according to one of the preceding claims, characterized in that the capsule shells (7) of the inner capsules (4) and the capsule shell (3) of the outer capsule (2) at different pH values go into solution and / or are soluble in the respective external medium and / or melt

34. Capsule-in-capsule system (1) according to one of the preceding claims, characterized in that the capsule shells (7) of the inner capsules (4) and the capsule shell (3) of the outer capsule (2) at different ion concentrations in solution go and / or are soluble in the respective external medium and / or melt.

35. capsule-in-capsule system (1) according to any one of the preceding claims, characterized in that the capsule shells (7) of the inner capsules (4) and the capsule shell (3) of the outer capsule (2) in a given external medium different Show dismantling times.

36. Capsule-in-capsule system (1) according to one of the preceding claims, characterized in that the capsule shells (7) of the inner capsules (4) and / or the capsule shell (3) of the outer capsule (2) is environmentally compatible and in particular is biodegradable.

37. capsule-in-capsule system (1) according to one of the preceding claims, characterized in that the capsule shells (7) of the inner capsules (4) and the capsule shell (3) of the outer capsule (2) have different strengths.

38. Capsule-in-capsule system (1) according to one of the preceding claims, characterized in that the capsule shells (7) of the inner capsules (4) and the capsule shell (3) of the outer capsule (2) have different thicknesses.

39. Capsule-in-capsule system (1) according to one of the preceding claims, characterized in that the capsule shells (7) of the inner capsules (4) and / or the capsule shell (3) of the outer capsule (2) made of multi-layer shells consist.

40. capsule-in-capsule system (1) according to any one of the preceding claims, characterized in that the inner capsules (4) are temperature stable, in particular up to at least 30 ° C, preferably up to 95 ° C, and / or of a given external medium, in particular a detergent or cleaning agent solution, are not dissolved, while the outer capsule (2) is not temperature-stable and / or is dissolved by a given external medium, in particular a detergent or cleaning agent solution.

41. Capsule-in-capsule system (1) according to one of the preceding claims, characterized in that the inner capsules (4) have a high affinity for textiles and in particular remain adherent to the fibers of the textiles.

42. A method for producing a capsule-in-capsule system (1) according to claims 1 to 41, characterized by the following process steps:

(a) preparation of a dispersion of the inner capsules (4) by polymerization, in particular in-situ polymerization in the presence of an active ingredient to be encapsulated, using methods known per se,

(b) Encapsulation of the dispersion prepared in step (a) and containing the inner capsules (4) by polymerization using methods known per se, in particular by gelation, coacervation, solution dropletization, melt dropletization, emulsion evaporation, spray drying or interfacial polymerization, so that encapsulation -in capsule system (1), in which several inner capsules (4) are completely surrounded by an outer capsule shell (3), and finally

(c) if appropriate, separation of the capsule-in-capsule system (1) obtained in step (b) using methods known per se.

43. The method according to claim 42, characterized in that the encapsulation carried out in step (b) by dropping the dispersion prepared in step (a) after adding suitable monomers or polymers into a suitable template, in particular an acidic, basic or neutral salt or ion solution, he follows.

44. Use of a capsule-in-capsule system (1) according to claims 1 to 41 in the field of cosmetics and personal care, in the manufacture and processing of adhesives and / or in the field of detergents and cleaning agents.

45. Use according to claim 44 as a delivery system or dosing system, in particular for the controlled release of active substances.

46. Cosmetics or personal care products containing a capsule-in-capsule system (1) according to claims 1 to 41.

47. Adhesives or adhesive components containing a capsule-in-capsule system (1) according to claims 1 to 41.

48. washing and cleaning agent containing a capsule-in-capsule system (1) according to claims 1 to 41.