DE10104841A1 - Capsule-in-capsule system and method for its production - Google Patents

Abstract

Capsule-in-capsule systems (1) consisting of an outer capsule (outer capsule) (2) with an outer capsule shell (3) and inner capsule (inner capsules) (4) located therein, and a method for their production are described. The capsule-in-capsule systems (1) are particularly suitable for use 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.

Description

The present invention relates to an active substance-containing or active substance-containing cap seln-in-capsule system and a process for its manufacture as well as the Use of this capsule-in-capsule system, in particular as a delivery or dosing system for active substances or active substances, preferably for use in detergents and cleaning agents, 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 agents that are used in cosmetic Products or used in detergents and cleaning agents often already during storage or directly when using them Activity. Some of these substances also cannot be used have sufficient stability or interfering interactions with others cause their product components.

It is therefore of interest to control such substances and to achieve them use with maximum effect.

For this reason, active or active substances such as fragrances, care products oils, antibacterial agents and the like often in the products spatially delimited, protected form added. Often become sensitive Liche substances enclosed in capsules of various sizes, on ge suitable carrier materials adsorbed or chemically modified. The freeset tongue can then be activated using a suitable mechanism, for example mechanically by shearing, or diffusively directly from the measure trix material.

For this reason, systems are often sought which can be encapsulated, trans port or presentation vehicle - often synonymous as "delivery systems" or "carrier systems" - suitable.

There are already numerous commercial delivery systems that are based on po based polymer particles or liposomes (e.g. Mikrosponges® from  from Advanced Polymer Systems or Nanotopes® from the company Ciba-Geigy, see in this regard B. Herzog, K. Sommer, W. Baschong, J. Röding "Nanotopes ™: A Surfactant Resistant Carrier System" in the SÖFW Journal, 124th year 10/98, pages 614 to 623).

The disadvantage of this conventional, known from the prior art Delivery systems consist in that they have a low loading potential exhibit. Another disadvantage of conventional capsule systems is in that they usually only simple shell structures made of polymeric sub have stamps that only change the environmental properties can react. Furthermore, the encapsulation of active substances often not done in situ. Liposomes also have one for many types insufficient stability.

K. Landfester, F. Tiarks, H.-P. Hentze, M. Antonietti "Polyaddition in mini emulsions: A new route 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 procedure for performing polyaddition reactions in Mini emulsions are also described in WO 00/29465.

The European patent application EP 0 967 007 A2 describes a method microencapsulation of solid, biologically active substances, in particular other pesticides, by polycondensation of a melamine or phenol / formal dehyde resin or a urea / formalin resin in dispersion in counter was the active substance to be encapsulated and one non-ionic polymeric protective colloid to stabilize the emulsion, microcap can be obtained with average particle diameters of 0.1 to 300 µm. This procedure is only for encapsulating solid biological active substances suitable. To stabilize the emulsion, the emulsion must have a poly meres protective colloid are added. It just becomes conventional Capsule systems described with only a simple shell structure.  

Y. G. Durant "Miniemulsion Polymerization: Applications and Continuous Process "in Polymer. Mater. Sci. Eng. 1999, 80, pages 538-540 encapsulating organically soluble dyes with a polymer shell Polystyrene by UV-induced radical polymerization of styrene in Miniemulsion. Encapsulation of compounds other than organically soluble Che dyes are not mentioned. A particular disadvantage of this method is special that relatively insensitive compounds by this method cannot be encapsulated because of the radical polymerization intermediately formed radicals more sensitive compounds, e.g. B. such with double bonds. It just becomes conventional Capsule systems described with only a simple shell structure.

B. Erdem et al. "Encapsulation of Inorganic Partie / es via Miniemulsion Po lymerization "in Polymer. Mater. Sci. Eng. 1999, 80, pages 583/584 be write the encapsulation of solid, insoluble inorganic particles, näm Lich titanium dioxide particles, with a polymer shell made of polystyrene by UV-in reduced radical polymerization of styrene in a miniemulsion. A ver Encapsulation of other compounds as insoluble, solid inorganic parts kel is not mentioned. A disadvantage of this method is that it is relative insensitive compounds are not encapsulated by this method can, since the intermediates formed in the radical polymerization Radically sensitive compounds, e.g. B. those with double bonds, can attack. There are only conventional capsule systems with only simple envelope structure described.

WO 98/02466, DE 196 28 142 A1, DE 196 28 143 A1 and EP 818 471 A1 write the production of aqueous polymerization dispersions free radical polymerization of radical polymerizable compounds in the state of the miniemulsion. There is an encapsulation of active substances not mentioned anywhere.

DE 44 36 535 A1 describes a method for producing microcapsules dispersions described by interfacial polyaddition, which under Ver use of special oil-soluble emulsifiers (fatty acid esters, fatty amides, poly glycol ether or polypropylene glycol ether) with a certain minimum solubility  works in the oil phase. They are just conventional capsules described with a simple shell structure.

US-A-4 626 471 describes a process for the microencapsulation of colorless organic dye precursor molecules by in-situ polymeri sation of polyfunctional amines with special multifunctional epoxyhar zen based on methylolated bisphenol-A or 4-glycidyloxy-N, N-di glycidyl aniline. There are only conventional capsule systems with only one fold envelope structure described.

GP Puglisi et al. "Influence of the preparation conditions on poly (ethyl cyanoacrylate) nanocapsule formation" in International Journal of Pharmaceuticals 125 ( 1995 ), pages 283-287 describe the production of poly (ethyl cyanoacrylate) nanocapsules (PECA nanocapsules) by in-situ -Poly merisation. 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 Manufacture of various nano and microscale capsule systems that are as delivery systems for encapsulated active ingredients in the field of cosmetics and are suitable for medicine. Again, only conventional capsule systems described with a simple shell structure.

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 active ingredient-containing melamine resin microcapsules with a long service life, 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.

The German laid-open specification 18 17 316 describes active ingredient chap seln with multi-layer casing and a process for their manufacture. The  Capsules contain a liquid inside the capsule, especially color winder for pressure-sensitive copying material, fertilizer solutions, fragrance fabrics or adhesives.

EP 1 020 177 A1 describes a capsule-in-capsule system dete, multilayer soft capsule for the removal of malodorous Breath, which is a first soft capsule and a second soft capsule inside Capsule contains, with both the first, outer capsule and the second, in capsule contains an active ingredient to combat malodorous breath hold, whereby the second, inner capsule should only dissolve in the stomach.

German Offenlegungsschrift 22 15 441 describes aqueous detergents, the 1 to 50% of a detergent surfactant, at least 1% electrolyte as well Capsules contain a water-soluble polymer in their gelled form Surface included, the electrolyte, the concentration of the electrolyte and the polymer of the capsules are selected such that the stability of the Capsules in the detergent and the dissolution of the capsules when diluted are guaranteed with water. 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 that refer to more than one Change in environmental properties can respond.

The object of the present invention is to provide a capsule or Deliverysystems (dosing systems), which have the disadvantages described above avoids conventional capsule systems.

Another object of the present invention is, particularly one To provide encapsulation technology that leads to systems that wel especially two or more environmental parameters in one application can react.

Another object of the present invention is to provide a Encapsulation system, which has a good to increased protective effect for the encapsulated ingredients. Such a system should in particular  for applications in detergents and cleaning agents, cosmetics and Personal care products and in adhesive technology.

Surprisingly, it has now been found that the present invention underlying problem can be solved by using Chap seln, the other smaller, preferably drug-laden capsules, esp special microcapsules or nanocapsules, or smaller, active ingredient contain charged particles ("capsule-in-capsule systems"), especially in Connection with suitably assembled solid, liquid or gelför moderate 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 therein, the capsule-in-capsule according to the invention System 1 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 of such substances.

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

The inner capsules 4 generally 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, for example, be washed and / or cleaned be cleaning active substance. In this case, it is selected in particular from the group of washing and / or cleaning active inorganic and organic acids, especially carboxylic acids, soil repellant and soil re lease active ingredients, bleaching agents such as in particular hypochlorites, bleaching agent telactivators, washing and cleaning active enzymatic systems and Enzymes such as, in particular, amylases, cellulases, lipases and proteases, Fragrances, especially perfume oils, antimicrobial agents, in particular special antibacterial, antiviral and / or fungicidal active ingredients, Buil 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, especially surfactants with fabric softener properties as well as pH adjusting agents and pH buffer substances.

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

In addition, the active ingredient can be an adhesive or a glue be part of the fabric.

In general, the inner capsules contain 4 identical active ingredients. According to a particular embodiment of the present invention, the inner capsules 4 can also contain different active substances or active substances. In other words, in this case there is a mixture of different inner capsules 4 .

For example, the inner Cape clauses 4 contain a detergent active enzyme, a surfactant may be included with fabric softener properties while the other part of the inne ren capsules 4, where in the filled with different ingredients of inner capsules 4 for detergents applications, a part - after dissolution of the outer capsule casing 3 - release the ingredients (ie enzyme or surfactant) specifically at different times during 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.

Preferably, the inner capsules 4 can have a capsule shell 7 which completely encloses the second medium 6 .

According to a particular 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 S 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 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.

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 approximately 2.5 mm.

The capsule shells ( 3 , 7 ) are generally formed from a polymer or from polymers. The capsule shell material of the capsule shell len 7 of the inner capsules 4 can be identical or different with respect to the capsule shell material of the capsule shell 3 of the outer capsules 2 . Before 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, ie 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 formed from polymers of the inner capsule 4 can be made, for example, of polyelectrolytes or polyelectrolyte complexes, polystyrene, epoxy resins, polyurethanes, polyureas, polycyanoacrylates, poly (meth) acrylates, melamine resins, formaldehyde resins, phenolic resins, poly isocyanates, waxes, solid paraffins or polysaccharides consist. The capsule shell 3 formed from polymers of the outer capsule 2 can, for example, also be made of polyelectrolytes or polyelectrolyte complexes, polystyrenes, epoxy resins, polyurethanes, polyureas, polycyanacryla, 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 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. , 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 out.

The weight of the polymer from which the outer shell 3 is made generally makes up 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 out.

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 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 semiper meable capsule shell (membrane) considerably more slowly, preferably by at least an order of magnitude slower 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 be 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. 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 strengths. This effect can be used for example in the case of adhesives by z. B. the inner capsules 4 are more solid than the outer shell 3 and contain a catalyst for curing the adhesive, which is only released by the action of high shear forces (for example, 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 sheath 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-layered shells.

According to a further embodiment of the present invention, the inner capsules 4 can have a high affinity for textiles and in particular stick 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 egg 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 be non-dissolvable from a given external medium, in particular a detergent or cleaning agent solution, and have a high affinity for textile fibers have, while the outer capsule 2 cannot be temperature stable and / or can be dissolved by a given external medium, in particular a detergent or cleaning agent solution.

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 process for producing the capsule-in-capsule system 1 according to the invention, which comprises 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) containing the inner capsules 4 ent by polymerization using methods known per se, in particular by gelation, coacervation, solution droplet ing, 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-form aldehyde resin reactions (see, for example, BK Hong, S. Park, Mater. Chem. Phys. 1999, 58, 128-131) or else by others, by the state of the art Technically known processes. 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 finish are particularly interesting.

A method for producing the inner capsules 4 according to step (a) of the inventive method is, for. B. described in German patent application 100 44 635, which describes a process for the production of polymer capsules with encapsulated active ingredients or active ingredients by sol-gel polycondensation of monomeric, polymerizable by polycondensation, trifunk tional, surface-active organosilicon compounds in emulsion, the organosilicon compound is 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 RSiX ₃ with X = halogen (preferably chlorine or bromine) and R = C ₁₁ -C ₂₂ alkyl.

Further processes according to the invention for producing active ingredient or active ingredient-containing nano and microcapsules according to step (a) of the invention Process according to the invention are, for. B. described in EP 0 941 761 A2, in EP 0 304 416 A1, EP 0 934 773 A2, WO 90/10436, DE 44 16 857 C1 as well as in US-A-5,492,994, the disclosures of which are hereby incorporated by reference are incorporated by reference.

Another method according to the invention which is suitable 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 route to polymer dispersions" in Macromol. Chem. Phys. 201, pages 1-5 ( 2000 ) and by Durant "Miniemulsion Polymerization: Applications and Continuous Process" in Polymer. Mater. Sci. Closely. 1999, 80, pages 538-540 and by Erdem et al. "Encapsulation of Inorganic Particles via Miniemulsion Polymerization" in polymer. Mater. Sci. Closely. 1999, 80, pages 583/584.

Another 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 in-situ encapsulation of active substances in by interfacial polymerization produced polymer capsules be written.

Another method according to the invention is described in US Pat German patent application 100 00 689, which is a method of manufacture of microcapsules with a semipermeable capsule shell with encapsulated washing and / or cleaning-active substances by in-situ complexation describes suitable polyelectrolytes or polyelectrolyte mixtures. Farther according to the invention are suitable as prior art in this application the method mentioned, 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 0 280 155 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 process 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 droplet or melt dropletization (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 of the outer capsules 2 is selected in particular so that it can produce the desired first switching mechanism in the later use when released. For this, z. B. used water-soluble polymers such as z. B. in German Offenlegungsschrift 22 15 441 (e.g., polyvinyl alcohol, cellulose derivatives, polysaccharides, polyacrylates, etc.) are used, which can either be melted or which form insoluble complexes with suitable, in particular polyvalent ions ("gelling" ) or 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 containing 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, for example using Eudragit® polymers from Röhm), the temperature (LCST polymers such as poly-N-isopropylacrylamide derivatives) are particularly interesting. or have the 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 manufacture 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 encapsulation technology that can respond 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 in particular detergents and cleaning agents, cosmetics and personal care agents 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 each application by choosing the suitable material for the release on both "size levels" of the capsules in a suitable manner. On the "size levels" of the capsules, the release profile of the active ingredients can also be tailored 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 the release, e.g. B. a color change of an indicator due to pH Change or formation of a gas in the reaction of the capsule contents with the outer phase. Accordingly, an appropriate content fabric of the smaller capsules selected.

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 an aqueous phase is used as the outer phase 5 and a water-soluble one as the active ingredient in the inner capsules 4 Active ingredient can be used, since the (diffusive) exchange of the phases is 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 apparent to those skilled in the art upon reading the description and feasible without departing from the scope of the present invention leaves.

The present invention is based on the following exemplary embodiments illustrates which, however, in no way limit the invention.  

EMBODIMENTS example 1

By in-situ encapsulation in the aqueous phase, which in addition to that to polymerize Renden monomers (alkyl cyanoacrylate) and, if necessary, usual additive like emulsifiers, 10% by weight of an active ingredient (fragrance oil or orange oil) contains, according to known methods (see Puglisi et al.) a 10% aqueous dispersion of 2 to 20 µm poly (alkyl cyanoacrylate) capsules (e.g. poly (methyl cyanoacrylate) capsules or poly (ethyl cyanoacrylate) capsules seln), which contain the fragrance oil in encapsulated form.

The dispersion of poly (alkyl cyanoacrylate) -Mi prepared in this way Crocapsules is after adding 5 wt .-% polyvinyl alcohol in a 20% Sodium sulfate solution dripped. Due to the ion concentration dependent solubility of polyvinyl alcohol in water, spontaneously form 100 to 2,000 µm capsules with an outer shell made of polyvinyl alcohol, wel che the dispersion with the smaller, drug-laden poly (alkylcyanacry include lat) capsules and then optionally filtered off can.

A capsule-in-capsule delivery system according to the invention is also formed an oil-like active ingredient (fragrance oil), which, for example, in liquid Detergents when diluted, d. H. in use when washing, e.g. B. in washing machines, the active ingredient-filled inner capsules, which contain a sub have a stantivity towards the tissue, only releases with delay. The inner ones Capsules remain on the treated fabric even after drying laundry. This improves the fragrance when ironing of the laundry.  

Example 2

By in-situ encapsulation in the aqueous phase using miniemulsion polymers sations according to methods of the prior art (see German patent message 100 37 658 and the state cited there, in particular polyaddition of Amines, alcohols or mercaptans on di- and / or polyfunctional ones Epoxies) is a 12% aqueous dispersion of about 200 nm in size, epoxy resin-containing capsules containing 10% by weight of a fragrance oil (orange oil) encapsulated active ingredient are made.

The dispersion of active substance-loaded nano produced in this way After adding 1.8% by weight sodium alginate, the capsule is encapsulated in a solution 2% calcium chloride and 0.2% poly-L-lysine dripped. Due to the Complexing the alginate, 30 to 300 gm capsules are formed an outer shell made of an alginate complex, which the dispersion with the surrounded smaller, drug-loaded nanocapsules and then ge can be filtered off if necessary.

A capsule-in-capsule delivery system according to the invention is also formed an oil-like active ingredient (fragrance oil) which, for example, as in Example 1 in liquid detergents when diluted, d. H. in use at Wa to z. B. in washing machines, the drug-filled inner capsules, the have a substantivity to the tissue, only releases with delay. The inner capsules remain on the tissue treated in this way even after Drying the laundry. This will result in an improved fragrance effect Ironing the laundry achieved.

Example 3

By in-situ encapsulation in the aqueous phase using interfacial polymers sation of dodecyl-15EO-acrylate according to methods of the prior art (see German patent application 100 31 132 and state of the art cited there Technology) becomes a 12% oily dispersion of about 180 nm in size  Capsules containing 10% by weight of a vitamin C solution as an encapsulated active ingredient loaded with fabric.

The oil-containing dispersion (Cetiol OE) produced in this way is effective fabric-loaded nanocapsules is made after adding 12% by weight of Eudragit®, a methacrylate polymer from Röhm or Rohm & Haas, into one Solution dripped with 5% HCl and 2% sucrose. Due to the from pH of the medium-dependent solubility of the Eudragit® polymer, ent there are 500 to 2,000 µm capsules with an outer shell made of Eudra git®, which contains the dispersion with the smaller, active ingredient-loaded nanocap surrounded and then optionally filtered off.

A capsule-in-capsule delivery system according to the invention is also formed a hydrophilic active ingredient which, for example, when used in a hair dye when applied to the hair filled with the active ingredient Delays capsules and thus has an antioxidant effect achieved on the scalp.

Claims (48)

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 Kohlenwas serstoff, 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 one of the preceding Ansprü surface, 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 ingredient 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 active ingredients, in particular antibacterial, antiviral and / or funcidal 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, surfactants especially surfactants with fabric softener dough properties as well as pH adjusting agents and pH buffer substances. 10. capsule-in-capsule system ( 1 ) according to claim 8, 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 claim 8, characterized in that the active substance or active ingredient is an adhesive or an adhesive component. 12. Capsule-in-capsule system ( 1 ) according to one of the preceding claims, characterized in that the inner capsules ( 4 ) contain different active substances or active substances. 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, in which the at least one active ingredient is embedded. 14. Capsule-in-capsule system ( 1 ) according to one of the preceding claims, characterized in that the inner capsules ( 4 ) also have a capsule shell ( 7 ) which completely encloses the second medium ( 6 ). 15. Capsule-in-capsule system ( 1 ) according to one of the preceding claims, characterized in that the first medium ( 5 ) comprises at least one active substance or active ingredient, either in pure substance or in solution or suspension. 16. Capsule-in-capsule system ( 1 ) according to 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 mean diameter of the inner capsules ( 4 ) to the mean 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, be. 19. Capsule-in-capsule system ( 1 ) according to one of the preceding claims, characterized in that 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 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 preferably about 1 µm to about 10 mm, in particular about 10 µm to about 5 mm about 150 microns 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 ) with respect to the Kapselhüllenma material of the capsule shells ( 3 ) of the outer capsules ( 2 ) may be identical or different. 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 ) preferably from the capsule shell material of the capsule shells ( 3 ) of the outer capsules ( 2 ) is different. 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, Polycyan acrylates, poly (meth) acrylates, melamine resins, formaldehyde resins, phenolic resins, polyisocyanates, waxes, solid paraffins or poly saccharides exist. 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, poly cyanoacrylates, 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 capsule ( 4 ) are hydrophobic and the capsule shell ( 3 ) of the outer capsule ( 2 ) is hydrophilic or the other way around. 26. Capsule-in-capsule system ( 1 ) according to one of the preceding claims, characterized by an active ingredient or active ingredient content of 0.001% by weight to 80% by weight, in particular 0.005 to 50% by weight, preferably before 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% 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 ). 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 wt .-%, of the total weight of the capsule-in-capsule system ( 1 ) makes. 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% by weight, in particular 0.1 to 50% by weight. , 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 Chen 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 ) are different Temperatures go into solution 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 ) are 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 ) are different Ion concentrations go into solution and / or are soluble in the respective external medium and / or melt. 35. 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 ) in one counter have different 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 ) are environmentally friendly are inert and in particular are 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 ) more layered shells exist. 40. capsule-in-capsule system ( 1 ) according to 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 from 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 from 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, adhere 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 method steps:

• a) preparation of a dispersion of the inner capsules ( 4 ) by polymerisation, in particular polymerisation in situ in the presence of an active substance or active substance 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.

43. The method according to claim 42, characterized in that the in Step (b) encapsulation carried out by dropping the in Step (a) prepared dispersion after adding suitable monomers or polymer in a suitable template, especially an acidic, base cal or neutral salt or ion solution. 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 or Agents. 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.