EP3630049A1

EP3630049A1 - Microcapsule system for polysensory olfactory effects ii

Info

Publication number: EP3630049A1
Application number: EP18727234.9A
Authority: EP
Inventors: Andreas Bauer; André HÄTZELT; Frank Pessel; Andreas Gerigk; Anneliese Wilsch-Irrgang; Klaus Last; Raul AMADO
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 2017-05-24
Filing date: 2018-05-18
Publication date: 2020-04-08
Also published as: US20200093714A1; WO2018215354A1; DE102017111445A1

Abstract

The invention relates to a microcapsule system comprising an outer microcapsule having an outer capsule shell, said outer microcapsule containing enclosed therein at least one inner microcapsule with an inner capsule shell and a first fragrance composition, and the inner microcapsule containing a second fragrance composition that differs from the first fragrance composition. The invention further relates to methods for the production thereof, products that contain said microcapsules, methods for producing polysensory olfactory impressions and to the corresponding use of the microcapsule system.

Description

Microcapsule system for polysensory scent effects II

The invention is in the field of perfume-containing microcapsules, as well as the cosmetic agents, detergents and textiles treating compositions containing perfume-containing microcapsules, and methods for releasing perfumes from these microcapsules in the application of said agents.

A variety of cosmetics, cleansers, and fabric treatment agents contain sensitive ingredients, e.g. Fragrances, essential oils, perfume oils and care oils, dyes or antibacterial agents. The disadvantage is that those ingredients that are used in such agents, often lose their activity already during storage and / or before the desired application time or at least greatly reduced, for example, by chemical reactions due to interaction with other components of the respective funds and / or by physical influences.

In order to control such substances and to use them at the desired site with maximum effect, active substances or active substances such as fragrances, care oils, antibacterial agents and the like are often added to the products in a spatially delimited, protected form. Frequently, sensitive substances are encapsulated in capsules of various sizes, adsorbed on suitable carrier materials, or chemically modified. The release can then be carried out by means of a suitable mechanism, for example mechanically by shearing, or diffusively directly from the matrix material.

There are already numerous commercial encapsulation systems based on natural or artificial polymers. These may enclose an active agent or its solution and then be physically or chemically crosslinked in the shell or precipitated by a coacervation process with another polymer. Microcapsules are known from the prior art, which may contain liquid, solid or gaseous substances as core material. As material for the capsule walls, for example phenol-formaldehyde polymers, melamine-formaldehyde polymers, polyurethane, gelatin, polyamides or polyureas are used. Cosmetic agents, detergents and texturing agents containing microcapsules are known as such. In particular, microcapsules of melamine-formaldehyde resins have been proven in these agents, since they are particularly stable. Thus, European published 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 respectively to be encapsulated Active substance and a nonionic polymeric protective colloid to stabilize the emulsion, wherein microcapsules having average particle diameters of 0.1 to 300 microns are obtained. This procedure is only for Encapsulation of solid biological active substances suitable. To stabilize the emulsion, a polymeric protective colloid must be added to the emulsion. Conventional capsule systems with a simple sleeve structure are described. K. Hong "Elamine Resin Microcapsules Containing Fragrant Oil: Synthesis and Characterization" in Materials Chemistry and Physics 58 (1999), pages 128-131 describe the preparation of long-lasting active-ingredient melamine resin microcapsules containing a fragrance oil by in situ Polymerization of Migrinöl as capsule core material, melamine and formalin as a capsule shell material, sodium lauryl sulfate as an emulsifier and polyvinyl alcohol as a protective colloid. The result is fragrance-oil-loaded capsule systems with a simple shell structure.

However, the known capsule systems do not allow the production of different fragrance profiles over the entire application cycle of a product. This may be desirable or advantageous, in particular, if the fragrance impression of the consumer is to change over time. Above all, a first fragrance impression which is characteristic of the product or its intended use and possibly also causes a certain recognition value is conceivable, for example a predominantly cosmetic odor impression when the product is opened or used, which after use is affected by a different odor impression, For example, a predominantly fruity olfactory impression, is replaced. Thus, for example, it would be possible to combine the odor of a detergent and cleaner product, which is typically intended primarily to impart freshness and cleanliness, to more complex perfumes, which are released at a later time after use.

International Patent Publication WO 2012/032145 A1 describes a formaldehyde-free capsule system based on aromatic alcohols and aldehydic compounds, with phloroglucin / resorcinol-based capsules having the best performance, in particular with regard to boosting properties, compared to alternative technologies, demonstrate. However, the disadvantage of this technology is that the resorcinol & phloroglucin-based capsules discolor the product formulation and are therefore not commercially viable. In addition, after storage, a strong, unacceptable sedimentation of the capsules.

It is an object of the present invention to provide the consumer with an improved scent experience over the entire application cycle of a product. Such an improvement in the perception of odors is to be realized by the change of odoriferous profiles during the application of a product and / or the application of a product-equipped surface, for example a textile.

It has now surprisingly been found that the problem underlying the present invention can be solved by the use of capsules, the other smaller, perfume-loaded Capsules based on aromatic alcohols and aldehydic compounds ("capsule-in-capsule systems") in conjunction with correspondingly formulated perfume compositions.

In a first aspect, therefore, the invention relates to a microcapsule system comprising an outer microcapsule having an outer capsule shell, the outer microcapsule containing:

(a) at least one inner microcapsule enclosed therein with an inner capsule shell; and

(b) a first fragrance composition;

wherein the capsule shell of the outer microcapsule completely surrounds the inner microcapsule and the first perfume composition,

characterized in that

the inner microcapsule contains a second perfume composition completely surrounded by the inner capsule shell of the inner microcapsule and different from the first perfume composition, the capsule shell of the inner microcapsule comprising a resin which is converted by reaction

I. at least one aromatic alcohol or its ether or derivative with

ii. at least one aldehydic component containing at least two carbon atoms per molecule

has, and

iii. optionally in the presence of at least one (meth) acrylate polymer,

is available.

In a further aspect, the invention relates to methods of making the microcapsule systems described herein which comprise (1) providing microcapsules containing the second perfume composition and a first perfume composition, (2) encapsulating the microcapsules containing the second perfume composition, and first perfume composition in an outer microcapsule.

In yet another aspect, the invention relates to means for washing, cleaning, conditioning, conditioning and / or dyeing hard or soft surfaces, such as textiles, dishes, etc., containing the microcapsule system described herein.

Further, the invention relates to a method of producing polysensory fragrance impressions using the microcapsule systems described herein, wherein first the release of the first fragrance composition from the outer microcapsule followed by a time delay of release of the second fragrance composition from the inner microcapsule. Preferably, the release of the first fragrance composition takes place inter alia by diffusion through the capsule wall of the outer microcapsule and optionally additionally by mechanical stress. Preferably, the release of the second fragrance composition by mechanical force, in particular by friction occurs. In these methods, the microcapsule system is preferably made by contact of an agent for washing, cleaning, conditioning, care and / or dyeing of hard or soft surfaces containing the microcapsule system described herein applied to the surface and then the release of the fragrances takes place, preferably by diffusion and then mechanical force, such as by friction. In yet another aspect, the invention relates to the use of the described microcapsule system to produce polysensory fragrance impressions.

For example, capsule-in-capsule systems are generally known from International Patent Publication WO 02/060573 A2. This document describes the encapsulation of various active ingredients in capsule-in-capsule systems that can respond to more than one change in environmental properties and provide good to increased protection for the encapsulated ingredients. The systems described are particularly suitable for applications in detergents and cleaners, cosmetics and personal care products and in adhesive technology. However, no capsule-in-capsule systems are described for encapsulating at least two different perfume compositions that allow for sequential release to produce polysensory fragrance impressions.

These and other aspects, features, and advantages of the invention will become apparent to those skilled in the art from a study of the following detailed description and claims. Any feature of one aspect of the invention may be employed in any other aspect of the invention. Further, it is to be understood that the examples contained herein are intended to describe and illustrate the invention, but not to limit it, and in particular that the invention is not limited to these examples. All percentages are, unless otherwise stated,% by weight and each refer to said composition / capsule / capsule shell. Numeric ranges specified in the format "from x to y" include the above values.If multiple preferred numeric ranges are specified in this format, it is understood that all ranges resulting from the combination of the various endpoints, also be recorded.

"At least one" as used herein refers to 1 or more, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9 or more, more particularly, this indication refers to the type of agent / compound and not the absolute number of molecules. "At least one perfume" therefore means that at least one type of perfume is detected but may also contain 2 or more different types of perfume.

"About" or "approximately" as used herein in reference to a numerical value means the numerical value + 10%, preferably + 5%. "Microcapsule system" as used herein refers to the capsule-in-capsule systems described herein, ie, microcapsules, which in turn include microcapsules. "Icc capsule," as used herein, refers to micron-scale capsules having core-shell morphology that include a capsule shell that completely encloses a core "fully encloses" or "completely surrounds" as used herein with respect to the microcapsules. means that the core is completely surrounded by the shell, ie in particular is not embedded in a matrix so that it is exposed in one place It is further preferred that the capsule shell is such that the release of the contents is controlled, ie For this reason, the capsule shell is preferably substantially impermeable to the encapsulated contents. "Substantially impermeable," as used in this context, means that the contents of the capsule or ingredients, respectively, are substantially unpermissive can not spontaneously penetrate the envelope, but the Freisetzu ng can be done only by opening the capsule or optionally via a running over a long period of diffusion process. The core may be solid, liquid and / or gaseous, but is preferably solid and / or liquid. The microcapsules are preferably substantially spherical and have diameters in the range of 0.01 to 1000 μιη, in particular 0.1 to 500 μηη. Capsule shell and capsule core are made of different materials, in particular, the capsule shell is preferably solid under standard conditions (20 ° C, 1013 mbar), the core preferably solid and / or liquid, in particular liquid.

When referring generally to "microcapsules" below, it will be understood that the same applies to both the outer and inner microcapsules, unless it is explicitly stated that the statement applies to one of the two types of microcapsules used it is to be understood that while the capsule system of the present invention will be described herein with reference to an outer microcapsule, the microcapsule system employed will usually contain a plurality of such microcapsules, typically> 100, preferably> 1000, or substantially (ie 20 wt. % or more, preferably 30% or more by weight, more preferably 50% by weight or more) or completely (ie to 00% by weight) In addition to the microcapsules, the microcapsule system may also be a liquid carrier medium, for example aqueous carrier medium in which the outer microcapsules are dispersed, u For example, to form a capsule slurry. In such capsule lutes, the microcapsules of the invention typically constitute 10 to 80% by weight, preferably 20 to 50% by weight.

As a capsule material for the outer microcapsules according to the invention can very generally z. B. high molecular weight compounds of animal or vegetable origin, eg. B. protein compounds (gelatin, albumin, casein), cellulose derivatives (methylcellulose, ethylcellulose, cellulose acetate, cellulose nitrate, carboxymethylcellulose) and in particular synthetic polymers (eg., Polyamides, polyolefins, polyesters, polyurethanes, epoxy resins, silicone resins and condensation products of carbonyl and NH group-containing compounds) can be used. Concretely, the shell material may be selected, for example, from polyacrylates; polyethylene; polyamides; polystyrenes; polyisoprenes; polycarbonates; polyesters; polyureas; polyurethanes; polyolefins; polysaccharides; epoxy resins; Vinyl polymers; Urea crosslinked with formaldehyde or glutaraldehyde; Melamine cross-linked with formaldehyde; Gelatin-polyphosphate coacervates, optionally crosslinked with glutaraldehyde; Gelatin Gum Arabic Coacervates; Silicone resins; polyamines reacted with polyisocyanates; by free radical polymerization of polymerized acrylate monomers; Silk; Wool; Gelatin; cellulose; proteins; and mixtures and copolymers of the foregoing. Particular preference is given to polyacrylates, polyethylene, polyamides, polystyrenes, polyisoprenes, polycarbonates, polyesters, polyureas, polyurethanes, polyolefins, epoxy resins, vinyl polymers and urea and / or melamine crosslinked with formaldehyde or glutaraldehyde. For the preparation of the outer microcapsules according to the invention, the known microencapsulation processes are suitable in principle in which z. For example, the encapsulation of the phase to be encapsulated by coating with film-forming polymers (such as those mentioned above), which are reflected on the material to be enveloped after emulsification and coacervation or interfacial polymerization. With respect to the present invention, the phase to be encapsulated is preferably a perfume composition, usually in the form of a perfume oil. For the preparation of the outer microcapsules, the inner microcapsules are preferably dispersed in the first perfume composition, usually once again a perfume oil, which differs from that in the inner capsules, and this dispersion is then encapsulated in film-forming polymers.

The microcapsules may release the contained fragrance compositions by various environmental agents, preferably changing the pH or ionic strength of the environment, changing temperature, exposure to light, diffusion and / or mechanical stress. It may be preferred that the outer microcapsule, ie the capsule shell of the outer microcapsule, and the inner microcapsule, ie the capsule shell of the inner microcapsule, differ in their construction or composition, so that different release mechanisms are used or, if the same Release mechanism is used, different release conditions are used. "Different release conditions" as used herein also refers to different permeabilities of the capsule shells as defined above In various embodiments, it is preferred that the outer and inner microcapsules exhibit in their release behavior, ie the release of the encapsulated material, e.g. Such a difference in release behavior refers to the capsules as such in direct comparison, ie, in such a comparison, the inner capsules are in free, unencapsulated form with the outer capsules as such, ie without encapsulated inner capsules In various embodiments, inner and outer capsules differ in their release behavior upon investigation of a given release mechanism, such as diffusivity by means of thermogravimetric analysis (TGA) at a heating rate of 1 K / min coupled with Fast Fourier Infrared Spectroscopy (FFIR) in a temperature range of Room temperature (20 ° C) to 350 ° C under a nitrogen atmosphere (for example, 1, 8 I N2 / h) take place. The capsules are weighed in the range of 10-12 mg and examined in AI crucibles. Both types of capsules are filled with the same perfume mixture for the purposes of this comparative test. Before each measurement, a background measurement is performed, whereby the signals of the measurement spectrum are always corrected immediately around the background. When it is referred to herein that inner and outer capsules differ in their release behavior, this means, unless stated otherwise, that the capsules differ in their permeability to the encapsulated substances such that during the dynamic phase (ie during heating ) the TGA-FFIR under the above conditions at any time, for example in the temperature range between 80 and 300 ° C, at the same temperature results in a difference in weight loss relative to the initial weight of at least 1%. In various embodiments, the weight loss of the outer capsules under the same conditions at the same temperature (for example, after 250 minutes of heating at 1 K / min and a temperature of 280 °) is at least 1% by weight greater than that of the inner capsules. This means, for example, that after a period of 250 minutes and at a temperature of 280 ° C, the weight loss (relative to the initial weight) of the outer capsule is 86.6%, while that of the inner capsule is 82.3% (ie a difference of 4.3%).

It is particularly preferred that the release of the first fragrance composition from the outer microcapsules by diffusion and optionally additional mechanical release, and the release of the second fragrance composition from the inner microcapsules by a different release mechanism, in particular only by mechanical stress. For this it is necessary that the capsule materials for outer and inner capsule shell are accordingly different. In such embodiments, therefore, the outer and inner microcapsules differ by their release behavior. In general, it is preferred that the outer microcapsules slowly release the first fragrance composition, for example by having the capsule shell diffusively permeable, whereas the inner microcapsules are retained and are broken up until a later stimulus. The release of the inner microcapsules is usually carried out, even if the outer microcapsules are diffusively permeable, not by diffusion, but by the outer microcapsule being broken by one of the other release mechanisms mentioned above. In this case, the difference in the diffusivity can also be effected by encapsulating the inner capsules themselves and therefore limiting the diffusibility even with the same structure of the shell by the encapsulation in the outer capsules. In various embodiments, this difference is further reinforced by the fact that the capsule shell of the inner capsules is different from that of the outer capsules, ie there is a difference in the release behavior as described above. Thus, when referring to the release mechanism by diffusion, this phrase always refers to the fragrances, not the internal microcapsules. By "diffusely permeable" with respect to the outer capsules herein is meant permeability to the perfume molecules by diffusion is greater than the corresponding permeability of the inner capsules. The term is therefore used herein essentially as a relative term.

The diffusivity (permeability to diffusion) of the capsules can be adjusted for example via the degree of crosslinking of the shell materials and the wall thickness of the capsules.

The microcapsules according to the invention may be water-soluble and / or water-insoluble microcapsules. However, the outer microcapsules are preferably water-insoluble microcapsules. The water insolubility of the outer microcapsules has the advantage that, by using appropriate detergents or cleaning agents, it is possible to permit the separation of fragrances from the application, and also that the fragrance release from the microcapsules can take place after the application.

Also, the inner microcapsules are preferably water-insoluble for the reasons mentioned above.

The wall material of the outer microcapsules preferably comprises polyacrylates, polyurethanes, polyolefins, polyamides, polyesters, polysaccharides, epoxy resins, silicone resins and / or polycondensation products of carbonyl compounds and compounds containing NH groups. This corresponds to a preferred embodiment of the invention. Preference is given to using, for example, melamine-urea-formaldehyde microcapsules or melamine-formaldehyde microcapsules or urea-formaldehyde microcapsules. Particularly preferred are microcapsules based on melamine-formaldehyde resins. in preferred embodiments, the outer microcapsules are thus those based on melamine-formaldehyde resins.

The general procedure in microcapsule preparation as such has long been well known to those skilled in the art. Particularly suitable methods for microcapsule production are in principle z. In US Pat. No. 3,516,941, in US Pat. No. 3,415,758 or also in EP 0 026 914 A1. The latter describes, for example, the production of microcapsules by acid-induced condensation of melamine-formaldehyde precondensates and / or their C1-C4-alkyl ethers in water, in which the hydrophobic material forming the capsule core is dispersed, in the presence of a protective colloid.

In particularly preferred embodiments, the outer microcapsules are those based on melamine-formaldehyde resins, and the release of the encapsulated fragrances occurs at least partially by a diffusive route. In such embodiments, the capsule shell for the encapsulated perfume composition or components thereof is permeable such that a, preferably persistent, diffusion of the fragrance molecules into the ambient air occurs. In addition, the outer microcapsule is preferably breakable by mechanical stress, in particular drivable (English, "friable.") The latter mechanism leads to the breaking of the outer capsule shell and thus to the release of the inner microcapsules.

As already described above, the capsule wall of the inner microcapsule comprises a resin which is converted by reaction

i. at least one aromatic alcohol or its ethers or derivatives with

ii. at least one aldehydic component having at least two carbon atoms per molecule, and

iii. optionally in the presence of at least one (meth) acrylate polymer,

is available. The capsule wall of the inner microcapsule may preferably be substantially, i. at least 50, preferably at least 75, more preferably at least 90 wt .-% or consist entirely of one or more such resins.

As aromatic alcohols a) aryloxyalkanols, arylalkanols and oligoalkanol aryl ethers are preferred in the context of the present invention. Also preferred are aromatic compounds in which at least one free hydroxy group, particularly preferably at least two free hydroxy groups, are directly aromatically bonded, it being particularly preferred if at least two free hydroxy groups are bonded directly to an aromatic ring and very particularly preferred are arranged in meta position to each other. It is preferred that the aromatic alcohols are selected from phenols, o-cresol, m-cresol, p-cresol, α-naphthol, β-naphthol, thymol, catechol, resorcinol, hydroquinone and 1,4-naphthohydroquinone, phloroglucinol, pyrogallol , Hydroxyhydroquinone and mixtures thereof.

Aromatic alcohols which are preferred according to the invention are also those which are used in the production of polycarbonate plastics and epoxy resin paints, in particular 2,2-bis- (4-hydroxyphenyl) -propane (bisphenol A). It is very particularly preferred if the aromatic alcohol present in accordance with the invention is selected from phenols having two or more hydroxyl groups, preferably from catechol, resorcinol, hydroquinone and 1,4-naphthohydroquinone, phloroglucinol, pyrogallol, hydroxyhydroquinone and mixtures thereof, resorcinol in particular (1 , 3-dihydroxybenzene) and / or phloroglucinol (1, 3,5-trihydroxybenzene) are preferred as aromatic alcohols, most preferred is phloroglucinol.

In a further embodiment of the present invention, in the preparation of the internal microcapsules, the aromatic alcohol a) is used as ether, the ether in a preferred embodiment being a derivative of the respective free form of the aromatic alcohol a) to be reacted. The free alcohol can also be present; then there is a mixture. In this case, the molar ratio between the free form of the aromatic alcohol to be reacted according to the invention and the said additional component (ether form of an aromatic alcohol) may be between 0: 100, preferably 1: 1, or 1: 2 or 1: 4. The advantage of mixing the aromatic alcohol with an ether form is that it can influence the reactivity of the system. In particular, with the appropriate choice of ratio, a system can be created whose reactivity balances with the storage stability of the system. As derivatives of the aromatic alcohols, their esters are preferred. The term "derivative" as used herein therefore preferably includes the esters of said alcohols.

In various embodiments, various internal microcapsules may be employed, which may then differ from one another in the reacted component a).

Particularly stable internal microcapsules are obtained with the preferred aromatic alcohols a) phloroglucinol and / or resorcinol. It is also possible to use mixtures of internal microcapsules, in each of which one of phloroglucin and resorcinol is used as component a). As aldehydes b) having at least 2 carbon atoms, both aliphatic and aromatic aldehydes are preferred according to the present invention. Particularly preferred aldehydes are one or more selected from the following group valeraldehyde, caproic aldehyde, caprylaldehyde, decanal, succinic dialdehyde, cyclohexanecarbaldehyde, cyclopentanecarbaldehyde, 2-methyl-1-propanal, 2-methylpropionaldehyde, acetaldehyde, acrolein, aldosterone, antimycin A, 8 '-Apo-β-caroten-8'-al, benzaldehyde, butanal, chloral, citral, citronellal, crotonaldehyde, dimethylaminobenzaldehyde, folinic acid, fosmidomycin, furfural, glutaraldehyde, glutaric dialdehyde, glyceraldehyde, glyceraldehyde, glyoxal, glyoxylic acid, heptanal, 2 -Hydroxybenzaldehyde, 3-hydroxybutanal, hydroxymethylfurfural, 4-hydroxynonenal, isobutanal, isobutyraldehyde, methacrolein, 2-methylundecanal, mucochloric acid, N-methylformamide, 2-nitrobenzaldehyde, nonanal, octanal, oleocanthal, orlistat, pentanal, phenylethanal, phycocyanin, piperonal , Propanal, propenal, protocatechualdehyde, retinal, salicylaldehyde, secologanin, streptomycin, strophanthinidin, tylosin, vanillin, cinnamic aldehyde and mixtures it. Particularly stable microcapsules were obtained with the preferred aldehydic components b) glutaric dialdehyde and / or succinic dialdehyde. For the purposes of the present invention, the aldehydic component may have at least one or two, particularly preferably two, three or four, in particular two, free aldehyde groups per molecule. Accordingly, of the above-mentioned compounds, those having at least two aldehyde groups are preferred. Preferred aldehydic components are the dia-dehydehydes derived from linear C 2-8 alkanes, more preferably glyoxal, glutaric and / or succinic dialdehyde, glutaric dialdehyde being particularly preferred.

In the internal microcapsules which can be used according to the invention, the molar ratio of a) the at least one aromatic alcohol or (ether or derivative thereof) to b) the at least one aldehydic component can generally be between 1: 1 and 1: 5, more preferably between 1: 1 2 and 1 to 3 and most preferably at resorcinol / phloroglucin is about 1 to 2.6. The Weight ratio of the components a) + b) to c), ie the ratio of the weight sum of a) + b)) to the weight of component c) is generally between 1: 1 and 1: 0.01, more preferably between 1: 0.2 and 1: 0.05. If different internal microcapsules are used, they may differ from each other in a particular embodiment in the reacted components b).

The optionally used (meth) acrylate polymers may be homo- or copolymers of methacrylate monomers and / or acrylate monomers. The term "(meth) acrylafis in this invention refers to both methacrylates and acrylates. The (meth) acrylate polymers are e.g. Homopolymers or copolymers, preferably copolymers, of one or more polar-functionalized (meth) acrylate monomers, such as sulfonic acid-containing, carboxylic acid-containing, phosphoric acid-containing, nitrile-containing, phosphonic acid-containing, ammonium group-containing, amine-containing or nitrate groups containing (meth) acrylate monomers. The polar groups can also be present in salt form. The (meth) acrylate polymers are suitable as protective colloids and can be advantageously used in the production of microcapsules.

For example, (meth) acrylate copolymers may consist of two or more (meth) acrylate monomers (eg, acrylate + 2-acrylamido-2-methylpropanesulfonic acid) or one or more (meth) acrylate monomers and one or more of ( Meth) acrylate monomers of various monomers (eg methacrylate + styrene).

Examples of (meth) acrylate polymers are homopolymers of sulfonic acid groups-containing (meth) acrylates (for example, 2-acrylamido-2-methyl-propanesulfonic acid or salts thereof (AMPS), commercially available as Lupasol ^® PA 140, BASF), or copolymers thereof , copolymers of acrylamide and (meth) acrylic acid, copolymers of alkyl (meth) acrylates and N-vinylpyrrolidone (commercially available as Luviskol ^® K15, K30 or K90, BASF), copolymers of (meth) acrylates with polycarboxylates or polystyrene sulfonates, copolymers of (Meth) acrylates with vinyl ethers and / or maleic anhydride, copolymers of (meth) acrylates with ethylene and / or maleic anhydride, copolymers of (meth) acrylates with isobutylene and / or maleic anhydride, or copolymers of (meth) acrylates with styrene-maleic anhydride.

Preferred (meth) acrylate polymers are homopolymers or copolymers, preferably copolymers, of 2-acrylamido-2-methylpropanesulfonic acid or its salts (AMPS). Preference is given to copolymers of 2-acrylamido-2-methylpropanesulfonic acid or its salts, for example copolymers with one or more comonomers from the group of (meth) acrylates, vinyl compounds such as vinyl esters or styrenes, unsaturated di- or polycarboxylic acids such as maleic acid esters, or the salts of amyl compounds or allyl compounds. Hereinafter, preferred comonomers for AMPS are mentioned, but these comonomers can also be copolymerized with other polar-functionalized (meth) acrylate monomers: 1) vinyl compounds, for example vinyl esters such as vinyl acetate, vinyl laurate, vinyl propionate or vinyl esters of neononanoic acid, or aromatic vinyl compounds such as styrene comonomers, for example styrene, alpha- ethylstyrene or polar functionalized styrenes such as styrenes with hydroxyl, amino, nitrile, carboxylic acid, Phosphonic acid, phosphoric acid, nitro or sulfonic acid groups and their salts, wherein the styrenes are preferably polar functionalized in the para position.

2) Unsaturated di- or polycarboxylic acids, e.g. Maleic acid esters such as dibutylmicinate or dioctylmaleinate, as salts of allyl compounds e.g. Sodium allylsulfonate, as salts of amyl derivatives e.g. Natriumamylsulfonat.

3) (meth) acrylate comonomers, these are esters of acrylic acid and methacrylic acid, the ester groups e.g. saturated or unsaturated, straight-chain, branched or cyclic

Hydrocarbon radicals are those which may contain one or more heteroatoms such as N, O, S, P, F, Cl, Br, I. Examples of such hydrocarbon radicals are straight-chain, branched or cyclic alkyl, straight-chain, branched or cyclic alkenyl, aryl such as phenyl or heterocylyl such as tetrahydrofurfuryl.

Suitable (meth) acrylate comonomers, preferably for AMPS, are for example:

a) acrylic acid, Ci-Ci4-alkyl-acrylic acid such as methacrylic acid.

b) (meth) acrylamides such as acrylamide, methacrylamide, diacetone-acrylamide, diacetone-methacrylamide, N-butoxymethyl-acrylamide, N-isobutoxymethyl-acrylamide, N-butoxymethyl-methacrylamide, N-isobutoxymethyl-methacrylamide, N-methylol Acrylamide, N-methylol-methacrylamide.

c) heterocyclyl (meth) acrylates such as tetrahydrofurfuryl acrylate and tetrahydrofurfuryl methacrylate or carbocyclic (meth) acrylates such as isobornyl acrylate and isobornyl methacrylate.

d) Urethane (meth) acrylates such as diurethane diacrylate and diurethane methacrylate (CAS: 72869-86-4).

e) Ci-Ci4-alkyl acrylates such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, tert. Butyl, n-pentyl, isopentyl, hexyi (e.g., n-hexyl, isohexyl or cyclohexyl), heptyl, octyl (e.g.

Ethylhexyl), nonyl, decyl (e.g., 2-propylheptyl or iso-decyl), undecyl, dodecyl, tridecyl (e.g., iso-tridecyl), and tetradecyl acrylate; the alkyl groups may optionally be substituted with one or more halogen atoms (e.g., fluoro, chloro, bromo or iodo), e.g. Trifluoroethyl acrylate, or with one or more amino groups, e.g. Diethylaminoethyl acrylate, or with one or more alkoxy groups such as methoxypropyl acrylate, or with one or more aryloxy groups such as phenoxyethyl acrylate.

f) C 2 -C 4 alkenyl acrylates such as ethenyl, n-propenyl, iso-propenyl, n-butenyl, sec-butenyl, iso-butenyl, tert. Butenyl, n-pentenyl, iso-pentenyl, hexenyl (eg n-hexenyl, iso-hexenyl or cyclohexenyl), heptenyl, octenyl (eg 2-ethylhexenyl), nonenyl, decenyl (eg 2-propenylheptyl or iso-decenyl!), undecenyl, dodecenyl, tridecenyl (eg, iso-tridecenyl), and tetradecenyl acrylate, and their epoxides, such as glycidyl acrylate or aziridines, such as aziridine acrylate.

g) C 1 -C 4 -hydroxyalkyl acrylates such as hydroxymethyl, hydroxyethyl, hydroxy-n-propyl, hydroxy-isopropyl, hydroxy-n-butyl, hydroxy-sec-butyl, hydroxy-isobutyl, Hydroxy-tert-butyl, hydroxy-n-pentyi, hydroxy-iso-pentyl, hydroxyhexyl (eg hydroxy-n-hexyl, hydroxy-iso-hexyl or hydroxy-cyclohexyl), hydroxyheptyl, hydroxyoctyl ( eg 2-ethylhexyl), hydroxynonyl, hydroxydecyl (eg Hydroxy-2-propylheptyl or hydroxy-iso-decyl), hydroxydecyl-, hydroxydodecyl-, hydroxytridecyl- (eg hydroxy-iso-tridecyl), and hydroxytetradecyl-acrylate, where the hydroxy group is preferably in the terminal position (ω- Position) (eg, 4-hydroxy-n-butyl acrylate) or in the (co-I) position (eg, 2-hydroxy-n-propyl acrylate) of the alkyl group.

h) alkylene glycol acrylates containing one or more alkylene glycol units. Examples are i) monoalkylene glycol acrylates, such as acrylates of ethylene glycol, propylene glycol (eg 1, 2 or 1, 3-propanediol), butylene glycol (eg 1, 2, 1, 3 or 1, 4-butanediol, pentylene glycol (eg 1, 5-pentanediol) or hexylene glycol (eg 1,6-hexanediol) in which the second hydroxy group is etherified or esterified, for example by sulfuric acid, phosphoric acid, acrylic acid or methacrylic acid, or ii) polyalkylene glycol acrylates such as polyethylene glycol acrylates, polypropylene glycol acrylates, polybutylene glycol acrylates, polypentylene glycol acrylates or Polyhexylenglykolacrylate whose second hydroxy group may be optionally etherified or esterified, eg by sulfuric acid, phosphoric acid, acrylic acid or methacrylic acid. Examples of (poly) alkylene glycol units having etherified hydroxy groups are C 1 -C 4 -alkyloxy (poly) alkylene glycols (eg C 1 -C 4 -alkyloxy (poly) alkylene glycol acrylates), examples of (poly) alkylene glycol units having esterified hydroxy groups Sulfonium (poly) alkylene glycols (eg sulfonium (poly) alkylene glycol acrylates) and their salts, (poly) alkylene glycol diacrylates such as 1,4-butanediol diacrylate or 1,6-hexanediol diacrylate or (poly) alkylene glycol dimethacrylate acrylates such as 1,4-butanediol meth acrylate acrylate or 1,6-hexanediol methacrylate acrylate;

The polyalkylene glycol acrylates may carry an acrylate group (e.g., polyethylene glycol monoacrylate, polypropylene glycol monoacrylate, polybutylene glycol monoacrylate, polypentylene glycol monoacrylate, or polyhexylene glycol monoacrylate) or two or more, preferably two, acrylate groups such as polyethylene glycol diacrylate, polypropylene glycol diacrylate, polybutylene glycol diacrylate,

Polyalkylene glycol diacrylate or polyhexylenglycol diacrylate;

The polyalkylene glycol acrylates may also contain two or more different polyalkylene glycol blocks, e.g. Blocks of polymethylene glycol and polyethylene glycol or blocks of polyethylene glycol and polypropylene glycol;

The degree of polymerization of the polyalkylene glycol units or polyalkylene glycol blocks is generally in the range from 1 to 20, preferably in the range from 3 to 10, particularly preferably in the range from 3 to 6. i) C 1 -C 4 -alkyl methacrylates, such as methyl, ethyl , n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, tert. Butyl, n-pentyl, iso-pentyl, hexyl (eg n-hexyl, isohexyl or cyclohexyl), heptyl, octyl (eg 2-ethylhexyl), nonyl, decyl (eg 2-propylheptyl or iso-decyl), undecyl, dodecyl, tridecyl (eg, iso-tridecyl), and tetradecyl methacrylate; the alkyl groups may optionally be substituted by one or more halogen atoms (eg fluorine, chlorine, bromine or iodine), eg trifluoroethyl methacrylate, or with one or more amino groups, for example diethylaminoethyl methacrylate, or with one or more alkoxy groups, such as methoxypropyl methacrylate, or with one or more aryloxy groups, such as phenoxyethyl methacrylate. j) C 2 -C 4 alkenyl methacrylates such as ethenyl, n-propenyl, iso-propenyl, n-butenyl, sec-butenyl, iso-butenyl, tert. Butenyl, n-pentenyl, iso-pentenyl, hexenyl (eg n-hexenyl, iso-hexenyl or cyclohexenyl), heptenyl, octenyl (eg 2-ethylhexenyl), nonenyl, decenyl (eg 2-propenyl heptyl or iso-decenyl), undecenyl, dodecenyl, tridecenyl (eg iso-tridecenyl), and tetradecenyl methacrylate, and their epoxides such as glycidyl methacrylate or aziridines such as aziridine methacrylate. k) C 1 -C 4 -hydroxyalkyl methacrylates, such as hydroxymethyl, hydroxyethyl, hydroxy-n-propyl, hydroxyisopropyl, hydroxy-n-butyl, hydroxy-sec-butyl, hydroxy-isobutyl, Hydroxy-tert-butyl, hydroxy-n-pentyl, hydroxy-iso-pentyl, hydroxyhexyl (eg hydroxy-n-hexyl, hydroxy-iso-hexyl or hydroxy-cyclohexyl), hydroxyheptyl, hydroxyoctyl (eg 2-ethylhexyl), hydroxynonyl, hydroxydecyl (eg, hydroxy-2-propylheptyl or hydroxy-iso-decyl), hydroxyundecyl, hydroxydodecyl, hydroxytridecyi (eg, hydroxyiso-tridecyl), and hydroxytetradecyl methacrylate, wherein the hydroxy group is preferably in the terminal position (ω position) (eg 4-hydroxy-n-butyl methacrylate) or in the (ω-1) position (eg 2-hydroxy-n-propyl methacrylate) of the alkyl radical. I) Alkylenglykolmethacrylate containing one or more Alkyienglykoi units. Examples are i) monoalkylene glycol methacrylates, such as methacrylates of ethylene glycol, propylene glycol (eg 1, 2 or 1, 3-propanediol), butylene glycol (eg 1, 2, 1, 3 or 1, 4-butanediol, pentylene glycol (eg 1, 5-pentanediol) or hexylene glycol (for example 1,6-hexanediol) in which the second hydroxyl group is etherified or esterified, for example by sulfuric acid, phosphoric acid, acrylic acid or methacrylic acid, or ii) polyalkylene glycol methacrylates such as polyethylene glycol methacrylates, polypropylene. Glycol methacrylates, polybutylene glycol methacrylates, polypentylene glycol methacrylates or polyhexylenglycol methacrylates whose second hydroxy group may optionally be etherified or esterified, for example by sulfuric acid, phosphoric acid, acrylic acid or methacrylic acid. Examples of (poly) alkylene glycol units having etherified hydroxy groups are C 1 -C 4 -alkyloxy (poly) alkylene glycols (for example C 1 -C 4 -alkyloxy (poly) alkylene glycol methacrylates), examples of (poly) alkylene glycol units having esterified hydroxy groups are sulfonium (poly) alkylglycols (eg sulfonium (poly) alkylene glycol methacrylates) and their salts or (poly) alkylene glycol dimethacrylates such as 1,4-butanediol dimethacrylate.

The polyalkylene glycol methacrylates may carry a methacrylate group (eg polyethylene glycol monomethacrylate, polypropylene glycol monomethacrylate, polybutylene glycol monomethacrylate, polypentylene glycol mono methacrylate or polyhexylenglycol monomethacrylate) two or more, preferably two, bear methacrylate groups, such as polyethylene glycol dimethacrylate, Polypropylene glycol di-methacrylate, polybutylene glycol diacrylate, polypentylene glycol di-methacrylate or polyhexylenglycol dimethacrylate.

The polyalkylene glycol methacrylates may also contain two or more different polyalkylene glycol blocks, e.g. Blocks of polymethylene glycol and polyethylene glycol or blocks of polyethylene glycol and polypropylene glycol (e.g., Bisomer PE 63PHD (Cognis), CAS 58916-75-9).

The degree of polymerization of the polyalkylene glycol units or polyalkylene glycol blocks is generally in the range of 1 to 20, preferably in the range of 3 to 10, more preferably in the range of 3 to 6.

Examples of preferred (meth) acrylate comonomers are 4-hydroxybutyl acrylate, 2-hydroxypropyl methacrylate, ammonium sulfatoethyimethacrylate, pentapropylene glycol methacrylate, acrylic acid, hexaethylene glycol methacrylate, hexapropylene glycol acrylate, hexaethylene glycol acrylate, hydroxyethyl methacrylate, polyalkylene glycol methacrylate (CAS No. 589-75-9), Bisomer PEM63PHD, methoxy polyethylene glycol methacrylate, 2-propylheptyl acrylate (2-PHA), 1,3-butanediol dimethacrylate (BDDMA), triethylene glycol dimethacrylate (TEGDMA), hydroxyethyl acrylate (HEA), 2-hydroxypropyl acrylate (HPA), ethylene glycol dimethacrylate (EGDMA), glycidyl methacrylate (GMA ) and / or allyl methacrylate (ALMA).

The A PS copolymers generally have a proportion of AMPS units of more than 50 mol%, preferably in the range of 60-95 mol%, particularly preferably from 80 to 99 mol%, the proportion of comonomers is generally less than 50 mol%, preferably in the range of from 5 to 40 mol%, particularly preferably from 1 to 20 mol%.

The copolymers can be obtained by methods known per se, for example in the batch or in the semibatch process. For example, first appropriate amounts of water and monomers are passed into a temperature-controlled reactor and placed under an inert gas atmosphere. The original then stirred, brought to reaction temperature (preferably in the range of about 70 - 80 ° C) and initiator added, preferably in the form of an aqueous solution. Suitable initiators are known initiators for free-radical polymerizations, for example sodium, potassium or ammonium peroxodisulfate, or H2O2-based mixtures, for example mixtures of H2O2 with citric acid. The maximum temperature is waited for and as soon as the temperature in the reactor decreases either a) the addition of the remaining monomers and then a post-reaction (semibatch Ver-drive), or b) directly the post-reaction (batch process). Thereafter, the resulting reaction mixture is cooled to room temperature and the Copoiymer isolated from the aqueous solution, for example by extraction with organic solvents such as hexane or methylene chloride and then distilling off the solvent. Thereafter, the copolymer may be washed with organic solvent and dried. The resulting reaction mixture can also be used directly be further processed, in this case it is advantageous to add a preservative to the aqueous copolymer solution.

The AMPS copolymers are useful as protective colloids in the preparation of the internal microcapeins useful in the present invention.

The preparation of the internal microcapsules, for example in the form of microcapsule dispersions, is preferably effected by the at least one aromatic alcohol to be reacted and the at least one aldehydic component to be reacted according to the invention having at least two carbon atoms per molecule, optionally in the presence of at least one (meth) Acrylatpolymer, in the presence of the substance to be encapsulated (Kernmateriai), ie the second fragrance composition, are brought together and reacted and by subsequent increase in temperature, the curing of the capsules. It is particularly preferred that the pH is increased in the course of the process.

Preferably, in the context of such a procedure first

a) the at least one aromatic alcohol and / or its derivative or ether and the at least one aldehydic component and optionally at least one (meth) acrylate polymer and at least one substance to be encapsulated at a temperature of 40 to 65 ° C and a pH between 6 and 9, preferably 7 and 8.5 brought together and

b) in a later process step at a temperature of 40 to 65 ° C, the pH raised to above 9, preferably between 9.5 and 11, wherein

c) later the curing of the capsules by increasing the temperature to 60 ° C to 110 ° C, preferably 70 ° C to 90 ° C, in particular 80 ° C is performed.

However, when phloroglucin is used as the alcohol component, it is more advantageously cured in acid form; Preferably, the pH is then at most 4, more preferably between 3 and 4, for example between 3.2 to 3.5. The producible inner capsules are formaldehyde-free and can be processed as stable core / shell microcapsules out of the aqueous slurry without problems to a dry flowable powder.

In further preferred embodiments, the release from the inner microcapeins takes place by mechanical stress, in particular the inner microcapeins are drivable. The inner microcapeins in such embodiments are preferably substantially impermeable to the encapsulated perfume composition, ie, the diffusion of the encapsulated perfume molecules is limited such that no or only a very small portion, usually below the perceptual limit, of the perfume molecules permeates the capsule shell. In preferred embodiments, the capsule shell of the outer microcapsule for the encapsulated first fragrance composition is more permeable than the encapsulation shell of the inner microcapsule for the encapsulated second fragrance composition. "Permeable" in this context means that the absolute amount of the fragrance molecules passing through the closed shell exceeds a predetermined one For example, the amount diffused is at least a factor of 2, at least a factor of 10, or at least a factor of 100 or 1000. When referring to permeability or diffusion, this information always refers to the capsules after use, ie for example after they have been applied to a surface, such as a textile, for example, diffusion preferably takes place into the ambient air, preferably from a capsule which is already largely free from the other constituents of the composition it was formulated, is separate.

In such preferred embodiments, both the outer and inner microcapsules are broken by mechanical stress and the contents released, but the capsules differ in that the outer microcapsules are partially permeable to the fragrances encapsulated therein, i. at least more permeable than the inner microcapsules, so that they can be gradually released by diffusion while the inner microcapsules are largely impermeable, i. less permeable than the outer microcapsules for which fragrances are encapsulated therein, so that their release occurs only after the breaking of the inner capsule shell. However, the outer microcapsules preferably do not allow the release of the inner microcapsules before the outer shell is broken by mechanical stress. Since the outer microcapsules are broken by mechanical stress, the inner microcapsules are released, which in turn are also broken by mechanical stress. This results in the release of the first fragrance composition not already released by diffusion and at the same time the release of the second fragrance composition. The differences in the permeability between outer and inner microcapsules are, for example, as defined above and measurable by means of TGA-FFIR.

The term "drippable microcapsules" means those microcapsules which can be opened or wiped out by mechanical rubbing or by pressure, such as when drying hands with a towel, so that a release of content essentially only as a result of mechanical Exposure results, for example, from drying hands with a towel on which such microcapsules are deposited The preferred melamine-formaldehyde resin-based outer microcapsules and the inner microcapsules described herein are typically such reusable microcapsules.

In various embodiments, capsules for which permeability by diffusion is largely undesirable, such as the inner capsules,> 10 to 20% wall material, preferably 12 to 18, more preferably 13-17, most preferably 14-16% wall material (= sheath). or shell material) based on the total weight of the capsule, the remainder through the Core material is formed. In conjunction with a customary, suitable degree of crosslinking, for example, this leads to a sufficient diffusion barrier of the inner capsule. The inner capsules, therefore, in various embodiments have a proportion of> 10 to 20% wall material, preferably 12 to 18, more preferably 13 to 7, most preferably 14 to 16% wall material relative to the total weight of the capsules.

In various other embodiments, a reduction of the wall material of the capsule of> 10% results in increased, faster and perceptible diffusion of the core material. Accordingly, the outer capsules are distinguished in various embodiments in that the proportion of the wall material in the total weight of the capsules compared to the inner capsules by more than 10%, for example> 10 to 30%, is reduced. For example, the inner capsule may have a proportion of wall material of 14-16%, in which case the outer capsule has a proportion of wall material of 13% or less, for example 10-12%. The release behavior may also be regulated by the degree of cross-linking of the capsules, depending on the wall material (the terms "wall material", "shell material" and "shell material" being used interchangeably herein), in addition to the reaction conditions (eg pH, time, Temperature) also - in melamine-formaldehyde capsules - determined by the molar ratio of formaldehyde to melamine.

Here it has been found in various embodiments that the molar ratio of formaldehyde to melamine can be adjusted to achieve the desired differences in the release behavior. These differences can be quantified using TGA-FFIR as described above.

In various embodiments, these features are combined in terms of the amount of wall material and degree of crosslinking, for example, by means of the ratio of formaldehyde-melamine, to achieve the desired differences in release behavior. In various embodiments, the outer microcapsule wall material comprises a polyacrylate, polyurethane, polyolefin, polyamide, polyester, polysaccharide, epoxy, silicone resin, and / or a polycondensation product of carbonyl compounds and NH group-containing compounds. The latter corresponds to a preferred embodiment of the invention. For example, it is possible to use as external microcapsules, for example, melamine-urea-formaldehyde microcapsules or melamine-formaldehyde microcapsules or urea-formaldehyde microcapsules. Particularly preferred are microcapsules based on melamine-formaldehyde resins. In various embodiments, the capsule shell of the outer microcapsules consist essentially, ie at least 50, preferably at least 75, more preferably at least 90 wt .-%, or completely of the aforementioned polymers, ie one or a mixture of different polymers of the same class or different classes , especially one of them. The Internal microcapsules are as described above, in particular those based on phlorogiucin and / or resorcinol, most preferably based on phlorogiucin, as component a). It is preferred that the capsule shell of the outer microcapsules be substantially free of material which falls within the definition herein of the material for the inner capsule shell. "Substantially free" means a content of less than 5% by weight, preferably less than 3% by weight, more preferably less than 1% by weight, based in each case on the total weight of the capsule shell, most preferably none Contain material (= below the detection limit).

It has surprisingly been found in the use of the capsule systems according to the invention that the change in odor leads to a synergistic effect and the fragrance intensity is rated higher. Furthermore, these capsule-in-capsule systems allow for a sharper separation of the different fragrances, since the release of the fragrances from the inner capsule, especially if it is already substantially impermeable to the fragrances, further impeded by the encapsulation in an outer microcapsule becomes. Thus, the odor profile of such capsule-in-capsule systems differs from systems in which two different microcapsules each have perfumes and capsule morphologies corresponding to the first and second perfume compositions (ie, one capsule is diffusely permeable while the other is substantially impermeable) The use of two separate capsules always leads to a degree of mixing of the individual perfume compositions, whereas this mixing of the odor impressions by the claimed capsule-in-capsule systems is significantly reduced so that the various odors can be perceived as sharply separated.

Another technical effect of the capsule systems according to the invention is that the inner capsules are indeed high performance, but have the disadvantage that they show an undesirable discoloration and strong sedimentation when used in conventional means. This disadvantage is due to the encapsulation of the inner capsules in an outer capsule

Preferred microcapsules according to the invention have average diameters (median of the size distribution) in the range from 0.1 to 500 μm, preferably between 1 and 150 μm, in particular between 1 and 100 μm, eg. B. 10 to 80 pm. The shell of the microcapsules surrounding the core or (filled) cavity has an average thickness in the range between advantageously about 1 nm and 1000 nm, preferably between about 10 nm and about 500 nm, more preferably between about 30 nm and about 300 nm, more preferably 30 nm to 200 nm, in particular about 50 nm to about 150 nm.

The outer microcapsules according to the invention preferably have average diameters (median size distribution) of 5 to 500 .mu.m, preferably 10 to 150 .mu.m, more preferably 15 to 100 .mu.m with shell thicknesses of 30 nm to 200 nm and the inner microcapsules average diameters of 1 to 30 pm, preferably 2 to 25 pm, more preferably 5 to 20 pm, with shell thicknesses of 30 nm to 200 nm. Among other things, the permeability of the shell, ie the diffusivity, can be controlled via the shell thickness. Low shell thicknesses require a higher diffusive permeability than larger shell thicknesses. In various embodiments, the shell thickness of the outer microcapsule is approximately equal to or smaller than that of the inner microcapsule.

In preferred embodiments of the invention, the outer microcapsule contains on average more than one, preferably at least 2, more preferably at least 3, most preferably 4 or more internal microcapsules entrapped therein. In various embodiments, the outer microcapsule may contain up to 20, preferably up to 15, more preferably up to 10, inner microcapsules.

In various embodiments, the mean diameter of the inner capsules may be at least a factor of 2 smaller than the average diameter of the outer capsules, preferably this is smaller by a factor of 2-10, in particular 2-5. The outer microcapsules have, for example, a mean diameter of 20 to 80 μητι, the inner of 1 to 20 μιτη.

The inner microcapsules are preferably dispersed in the first perfume composition also encapsulated in the outer microcapsules. Both the capsule shell of the outer and inner microcapsules are therefore insoluble in the first fragrance composition.

The first and second fragrance compositions each contain at least one fragrance. As fragrances or fragrances or perfume oils, all known substances and mixtures can be used. For the purposes of this invention, the terms "fragrance (s)", "fragrances" and "perfume oil (s)" are used interchangeably, meaning in particular all those substances or their mixtures which are perceived by humans and animals as odor, in particular by People are perceived as a fragrance.

As fragrance components, perfumes, perfume oils or perfume oil ingredients can be used. Perfume oils or fragrances can according to the invention individual fragrance compounds, eg. As the synthetic products of the ester type, ethers, aldehydes, ketones, alcohols and hydrocarbons.

Fragrance compounds of the aldehyde type are, for example, adoxal (2,6,10-trimethyl-9-undecenal), anisaldehyde (4-methoxybenzaldehyde), cymal (3- (4-isopropyl-phenyl) -2-methylpropanal), ethylvanillin, florhydral ( 3- (3-isopropylphenyl) butanal), helional (3- (3,4-methylenedioxyphenyl) -2-methylpropanal), heliotropin, hydroxycitronellal, lauraldehyde, lyral (3- and 4- (4-hydroxy-4-methylpentyl) - 3-cyclohexene-1-carboxaldehyde), methylnonylacetaldehyde, lilial (3- (4-tert-butylphenyl) -2-methylpropanal), phenyiacetaldehyde, undecylenealdehyde, vanillin, 2,6,10-trimethyl-9-undecenal, 3-dodecene 1-al, alpha-n-amylcinnamaldehyde, melonal (2,6-dimethyl-5-heptenal), 2,4-dimethyl-3- cyclohexene-1-carboxaldehyde (Triplal), 4-metoxybenzaldehyde, benzaldehyde, 3- (4-tert-butylphenyl) propanal, 2-methyl-3- (para-methoxyphenyl) propanal, 2-methyl-4- (2, 6,6-Timethyl-2 (1) -cyclohexene-1-yl) butanal, 3-phenyl-2-propenal, cis- / trans-3,7-dimethyl-2,6-octadiene-1-al, 3, 7-dimethyl-6-octene-1-al, [(3,7-dimethyl-6-octenyl) oxy] acetaldehyde, 4-isopropylbenzyl aldehyde, 1, 2, 3, 4, 5, 6, 7, 8-octahydroxy 8,8-dimethyl-2-naphthaldehyde, 2,4-dimethyl-3-cyclohexene-1-carboxaldehyde, 2-methyl-3-

(isopropylphenyl) propanal, 1-decanal, 2,6-dimethyl-5-heptenal, 4- (tricyclo [5.2.1.0 (2,6)] decylidene-8) -butanai, octahydro-4,7-methane-1 H-indenecarboxaidehyde, 3-ethoxy-4-hydroxybenzaldehyde, para-ethyl-alpha.aipha-dimethylhydrocinnamaldehyde, alpha-methyl-3,4- (methylenedioxy) -hydrocinnamaldehyde, 3,4-methylenedioxybenzaldehyde, alpha-n-hexylcinnamaldehyde, m- Cymene-7-carboxaldehyde, alpha-methylphenylacetaldehyde, 7-hydroxy-3,7-dimethyl octanal, undecenal, 2,4,6-trimethyl-3-cyclohexene-1-carboxaldehyde, 4- (3) (4 Methyl 3-pentenyl) -3-cyclohexene carboxaldehyde, 1-dodecanal, 2,4-dimethylcyclohexene-3-carboxaldehyde, 4- (4-hydroxy-4-methylpentyl) -3-cyclohexene-1-carboxaldehyde, 7-methoxy 3,7-dimethyloctan-1-al, 2-methyl undecanal, 2-methyl decanal, 1-nonanal, 1-octanal, 2,6,10-trimethyl-5,9-undecadieno !, 2-methyl-3- ( 4-tert-butyl) propanal, dihydrocinnamaldehyde, 1-methyl-4- (4-methyl-3-pentenyl) -3-cyclohexene-1-carboxaldehyde, 5- or 6-methoxy-hexahydro-4,7-methanindan-1 - or 2-carboxaldehyde, 3,7-di methyloctan-1-al, 1-undecanal, 10-undecene-1-al, 4-hydroxy-3-methoxybenzaldehyde, 1-methyl-3- (4-methylpentyl) -3-cyclohexenecarboxaldehyde, 7-hydroxy-3J-dimethyl octanal, trans-4-decenal, 2,6-nonadienal, para-tolylacetaldehyde, 4-methylphenylacetaldehyde, 2-methyl-4- (2,6,6-trimethyl-1-cyclohexen-1-yl) -2-butenal, ortho-methoxycinnamaldehyde, 3,5,6-trimethyl-3-cyclohexene carboxaldehyde, 3J-dimethyl-2-methylene-6-octenal, phenoxyacetaldehyde, 5,9-dimethyl-4,8-decadienal, peonyaldehyde (6,10- Dimethyl-3-oxa-5,9-undecadiene-1-al), hexahydro-4,7-methanindan-1-carboxaldehyde, 2-methyloctanal, alpha-methyl-4- (1-methylethyl) -benzylacetaldehyde, 6,6- Dimethyl-2-norpinen-2-propionaldehyde, para-

Methylphenoxyacetaldehyde, 2-methyl-3-phenyl-2-propene-1-al, 3,5,5-trimethylhexanal, hexahydro-8,8-dimethyl-2-naphthaldehyde, 3-propyl-bicyclo- [2.2.1] - hept-5-en-2-carbaldehyde, 9-decenal, 3-methyl-5-phenyl-1-pentanal, methylnonylacetaldehyde, hexanal and trans-2-hexenal.

Ketone-type perfume compounds are, for example, methyl-beta-naphthyl ketone, muskedanone-1-one (2,3,3,6,7-hexahydro-1,1,3,3,3-pentamethyl-4H-inden-4-one), Tonalid (6-acetyl-1,1,1,4,4,7-hexamethyltetralin), alpha-damascone, beta-damascone, delta-damascone, iso-damascone, damascenone, methyldihydrojasmonate, menthone, carvone, camphor, koavon (3 , 4,5,6,6-pentamethylhept-3-en-2-one), fenchone, alpha-ionone, beta- lonone, gamma-methyl-ionone, fleuramon (2-hepty! Cyclopentanone), dihydrojasmon, cis -Jasmon, iso-E-Super (1- (1,2,3,4,5,6J, 8-octahydro-2,3,8,8-tetramethyl-2-naphthalenyl) -ethan-1-one (and Isomers), methyl cetrenyl ketone, acetophenone, methyl acetophenone, para-methoxy acetophenone, methyl beta-naphthyl ketone, benzyl acetone, benzophenone, para-hydroxyphenyl butanone, celery ketone (3-methyl-5-propyl-2-cyclohexenone), 6-isopropyl decahydro-2 -naphtone, dimethyloctenone, frescomenthe (2-butan-2-yl-cyclohexan-1-one), 4- (1-ethoxyvinyl) -3,3,5,5-tetramethylcyclohexanone, methylheptenone, 2- (2- (4 -Methyl-3-cyclohexen-1-yl) -propyl) cyclopentanone, 1- (p-menthene-6 (2) yl) -1-propanone, 4- (4-hydroxy-3-methoxyphenyl) -2-butanone, 2 Acetyl-3,3-dimethylnorbornane, 6,7-dihydro-1,1,3,3,3-pentamethyl-4 (5H) -indanone, 4-damascol, Dulcinyl (4- (1,3-benzodioxol-5-yl) butan-2-one), hexalon (1- (2,6,6-trimethyl-2-cyclohexene-1-yl) -1, 6-heptadiene 3-οη), isocyclone (2-acetonaphthone-1, 2,3,4,5,6,7,8-cx, tahydro-2,3,8,8-tetrarnethyl), methylnonyl ketone, methylcyclocitron, methyllavedelketone, orivone ( 4-tert-amyl-cyclohexanone), 4-tert-butylcyclohexanone, 2-peniyl-cyciopentanone (Delphon), Muscon (CAS 541-91-3), neobutenone (1- (5,5-dimethyl-1-cyclohexenyl) pent 4-en-1-one), Plicaton (CAS 41724-19-0), Veloutone (2,2,5-trimethyl-5-pentylcyclopentan-1-one), 2,4,4-J-tetramethyl-oct-6 -en-3-one and tetrameran (6,10-dimethylundecen-2-one).

Fragrance compounds of the alcohol type are, for example, 10-undecen-1-ol, 2,6-dimethylheptan-2-ol, 2-methylbutanol, 2-methylpentanol, 2-phenoxyethanol, 2-phenylpropanol, 2-tert-butycyclohexanol, 3,5,5-trimethylcyclohexanol, 3-hexanol, 3-methyl-5-phenyl-pentanol, 3-octanol, 3-phenyl-propanol, 4-heptenol, 4-isopropylcyclohexanol, 4-tert-butycyclohexanol, 6 , 8-dimethyl-2-nonanol, 6-nonene-1-ol, 9-decen-1-ol, α-methylbenzyl alcohol, α-terpineol, amyl salicylate, benzyl alcohol, benzyl salicylate, β-terpineol, butyl salicylate, citronellol, cyclohexyl salicylate , Decanol, di-hydromyrcenol, dimethylbenzylcarbinol, dimethylheptanol, dimethyloctanol, ethyl salicylate, ethylvaniline, eugenol, farnesol, geraniol, heptanol, hexyl salicylate, isoborneol, isoeugenol, isopulegol, linalool, menthol, myrtenol, n-hexanol, nerol, nonanol, octano! p-menthan-7-ol, phenylethyl alcohol, phenol, phenyl salicylate, tetrahydrogeraniol, tetrahydrolinalool, thymol, trans-2-cis-6-nonadicnol, trans-2-nonen-1-ol, trans-2-octeno !, undecanol, vanillin, champiniol, hexenol and cinnamyl alcohol.

Fragrance type ester compounds are e.g. Benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate (DMBCA), phenylethylacetate, benzylacetate, ethylmethylphenylglycinate, allylcyclohexylpropionate, styrallylpropionate, benzylsalicylate, cyclohexylsalicylate, floramate, melusate and jasmacyclate.

Ethers include, for example, benzyl ethyl ether and ambroxan. The hydrocarbons mainly include terpenes such as limonene and pinene.

Preference is given to using mixtures of different fragrances which together produce an attractive fragrance. Such a mixture of perfumes may also be referred to as perfume or perfume oil. Such perfume oils may also contain natural perfume mixtures as are available from plant sources.

Fragrances of plant origin include essential oils such as angelica root oil, aniseed oil, arnica blossom oil, basil oil, bay oil, champacilla oil, citrus oil, fir pine oil, pinecone oil, elemi oil, eucalyptus oil, fennel oil, pine needle oil, galbanum oil, geranium oil, ginger grass oil, guaiac wood oil, gurdy balm oil, helichrysum oil, ho oil , Ginger oil, iris oil, jasmin oil, cajeput oil, calamus oil, chamomile oil, camphor oil, kanaga oil, cardamom oil, cassia oil, pine oil, copaiba balsam, coriander oil, spearmint oil, caraway oil, cumin oil, labdanum oil, lavender oil, lemongrass oil, lime blossom oil, lime oil, tangerine oil, lemon balm oil, mint oil, musk kernel oil , Muscatel oil, Myrrh oil, Clove oil, Neroli oil, Niaouli oil, Olibanum oil, Orange blossom oil, Orange peel oil, Origanum oil, Palmarosa oil, Patchouli oil, Peruvian balsam oil, Petitgrain oil, Pepper oil, Peppermint oil, Pimento oil, Pine oil, Rose oil, Rosemary oil, Sage oil, Sandalwood oil, Celery oil, Spik oil, Star aniseed oil, Turpentine oil, Thuja oil, Thyme oil, Verbena oil, Vetiver oil, Juniper berry oil, Vermouth oil, Wintergreen oil, Ylang Ylang oil, hyssop oil, cinnamon oil, cinnamon leaf oil, citronella oil, lemon oil and cypress oil and ambrettolide, ambroxan, alpha-amylcinnamaldehyde, anethole, anisaldehyde, anisalcohol, anisole, anthranilate, acetophenone, benzylacetone, benzaldehyde, ethyl benzoate, benzophenone, benzyl alcohol, benzyl acetate, Benzyl benzoate, benzyl formate, benzyl valerate, borneol, bornyl acetate, Boisambrene forte, alpha-bromostyrene, n-decyl aldehyde, n-dodecyl aldehyde, eugenol, eugenol methyl ether, eucalyptol, farnesol, fenchone, fenchyl acetate, geranyl acetate, geranyl formate, heliotropin, heptincarboxylic acid methyl ester, heptaldehyde, Hydroquinone dimethyl ether, hydroxy cinnamaldehyde, hydroxy cinnamyl alcohol, In dol, Iran, isoeugenol,! oligonylmethyl ether, isosafrole, jasmone, camphor, karvakrol, karvon, p-cresol methyl ether, coumarin, p-methoxyacetophenone, methyl n-amyl ketone,

Methyl anthranilate, p-methylacetophenone, methylchavikole, p-methylquinoline, methylnaphthylketone, methyln-nonylacetaldehyde, methyln-nonylketone, muscon, beta-naphtholethyl ether, beta-naphthol methyl ether, nerol, n-nonylaldehyde, nonyl alcohol, n-octylaldehyde, p-oxy-acetophenone, pentadecanolide, beta-phenylethyl alcohol, phenylacetic acid, pulegone, safrole, salicylic acid isoamyl ester, salicylic acid methyl ester, salicylic acid hexyl ester,

Salicylic acid cyclohexyl esters, santalol, sandelice, skatole, terpineol, thymes, thymol, troenan, gamma-undelactone, vanillin, veratrumaldehyde, cinnamaldehyde, cinnamyl alcohol, cinnamic acid, cinnamic acid ethyl ester, cinnamic acid benzyl ester, diphenyloxide, limonene, linalool, linalyl acetate and propionate, melusate, menthol, menthone , Methyl-n-heptenone, pinene, phenylacetaldehyde, terpinyl acetate, citral, citronellal, and mixtures thereof.

In order to be perceptible, a fragrance must be volatile, whereby besides the nature of the functional groups and the structure of the chemical compound, the molecular weight also plays an important role. For example, most odorants have molecular weights up to about 200 daltons, while molecular weights of 300 daltons and above are more of an exception. Due to the different volatility of fragrances, the smell of a perfume or fragrance composed of several fragrances changes during evaporation, whereby the odor impressions in "top note", "middle note or body" and "base note" (end note or dry out) Analogously to the description in international patent publication WO 2016/200761 A2, head, heart and base notes can be determined on the basis of their vapor pressure (by means of the test methods described in WO 2016/200761 ) as classified below:

Top note: Vapor pressure at 25 ° C:> 0.0133 kPa

Middle note: Vapor pressure at 25 ° C: 0.0133 to 0.000133 kPa

Base note: Vapor pressure at 25 ° C: <0, 000133 kPa

Adhesive-resistant fragrances which can be used in the context of the present invention include, for example, the essential oils such as angelica root oil, aniseed oil, arnica blossom oil, basil oil, bay oil, bergamot oil, champacilla oil, fir pine oil, pinecone oil, elemi oil, eucalyptus oil, fennel oil, pine needle oil, galbanum oil, geranium oil, Ginger Grass Oil, Guaiac Wood Oil, Gurjun Balm Oil, Helichrysum Oil, Ho oil, ginger oil, iris oil, cajeput oil, calamus oil, chamomile oil, camphor oil, kanga oil, cardamom oil, cassia oil, pine needle oil, copalva balsam oil, coriander oil, spearmint oil, caraway oil, cumin oil, lavender oil, lemongrass oil, lime oil, tangerine oil, lemon balm oil, musk oil, myrrh oil, clove oil, Neroli Oil, Niaouli Oil, Olibanum Oil, Orange Oil, Origanum Oil, Palmarosa Oil, Patchouli Oil, Peru Balsam Oil, Petitgrain Oil, Pepper Oil, Peppermint Oil, Pimento Oil, Pine Oil, Rose Oil, Rosemary Oil, Sandalwood Oil, Celery Oil, Spik Oil, Star Aniseed Oil, Turpentine Oil, Thuja Oil, Thyme Oil, Verbena Oil, Vetiver Oil, Juniper berry oil, wormwood oil, wintergreen oil, ylang-ylang oil, hyssop oil, cinnamon oil, cinnamon oil, lemon oil, lemon oil and cypress oil.

Higher-boiling or solid fragrances of natural or synthetic origin include, for example: ambrettolide, α-amylcinnamaldehyde, anethole, anisaldehyde, anisalcohol, anisole, methyl anthranilate, acetophenone, benzylacetone, benzaldehyde, ethyl benzoate, benzophenone, benzyl alcohol, benzyl acetate, benzyl benzoate, benzyl formate, benzyl valerate, Borneol, bornyl acetate, α-bromostyrene, n-decyl aldehyde, n-dodecyl aldehyde, eugenol, eugenol methyl ether, eucalyptol, farnesol, fenchone, fenchyl acetate, geranyl acetate, geranyl formate, heliotropin, heptincarboxylic acid methyl ester, heptaldehyde, hydroquinone dimethyl ether, hydroxycinnamaldehyde, hydroxycinnamyl alcohol, Indole, Iran, isoeugenol, isoeugenol methyl ether, isosafrole, jasmone, camphor, karvakrol, karvon, p-cresol methyl ether, coumarin, p-methoxyacetophenone, methyl n-amyl ketone, methyl anthranilate, p-methylaceto-phenone, methylchavikole, p-methylquinoline , Methyl-ß-naphthyl ketone, methyl-n-nonylacetaldehyde, methyl n-nonyl ketone, Muscone, β-naphtholethyl ether, β-naphthol methyl ether, nerol, nitrobenzene, n-nonylaldehyde, nonyl alcohol, n-octylaldehyde, p-oxyacetophenone, pentadecanolide, β-phenylethyl alcohol, phenylacetaldehyde dimethyacetal, phenylacetic acid, pulegone, safrol, Isoamyl salicylate, methyl salicylate, hexyl salicylate, cyclohexyl salicylate, santalol, skatole, terpineol, thymes, thymol, γ-undelactone, vaniline, veratrum aldehyde, cinnamaldehyde, cinnamyl alcohol, cinnamic acid, ethyl cinnamate, cinnamic acid cinnamate

The more volatile fragrances include in particular the lower-boiling fragrances of natural or synthetic origin, which can be used alone or in mixtures. Examples of more volatile fragrances are alkyl isothiocyanates (alkylmustard oils), butanedione, limonene, linalool, linayl acetate and propionate, menthol, menthone, methyl-n-heptenone, phellandrene, phenylacetaldehyde, terpinyl acetate, citral, citronellal.

Preferred fragrance compounds of the aldehyde type are hydroxycitronellal (CAS 107-75-5), helional (CAS 1205-17-0), citral (5392-40-5), bourgeonal (18127-01-0), triplal (CAS 27939 - 60-2), Ligustral (CAS 68039-48-5), Vertocitral (CAS 68039-49-6), Florhydral (CAS 125109-85-5), Citronellal (CAS 106-23-0), Citronellyloxyacetaldehyde (CAS 7492 -67-3).

In addition or as an alternative to the abovementioned fragrances, it is also possible to use the fragrances described in WO 2016/200761 A2, in particular the fragrances mentioned in Tables 1, 2 and 3, and the modulators listed in Tables 4a and 4b. This publication is incorporated herein by reference in its entirety. The icc capsules according to the invention may comprise other oils in addition to perfumes. In particular, the microcapsules may also contain active ingredients in oil form, which are suitable for washing, cleaning, care and / or finishing purposes, in particular (a) textile care substances, such as preferably silicone oils, and / or

(b) skin care ingredients, such as preferably vitamin E, natural oils and / or cosmetic oils.

Skin-care active substances are all those active substances which give the skin a sensory and / or cosmetic advantage. Skin-care active substances are preferably selected from the following substances:

a) waxes such as carnauba, spermaceti, beeswax, lanolin and / or derivatives thereof and others.

b) Hydrophobic plant extracts

c) hydrocarbons such as squalene and / or squalane

d) Higher fatty acids, preferably those having at least 12 carbon atoms, for example lauric acid, stearic acid, behenic acid, myristic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid, isostearic acid and / or polyunsaturated fatty acids and others.

e) Higher fatty alcohols, preferably those having at least 12 carbon atoms, for example lauryl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, behenyl alcohol, cholesterol and / or 2-hexadecanol and others.

f) esters, preferably such as cetyloctanoates, lauryl lactates, myristyl lactates, cetyl lactates, isopropyl myristates, myristyl myristates, isopropyl palmitates, isopropyl adipates, butyl stearates, decyl oleates, cholesterol stearates, glycerol monostearates, glyceryl distearates, glycerol tristearates, alkyl lactates, alkyl citrates and / or alkyl tartrates and others.

g) lipids such as cholesterol, ceramides and / or sucrose esters and others.

h) vitamins such as vitamins A, C and E, vitamin C esters, including vitamin C alkyl esters and others.

i) sunscreen

j) phospholipids

k) derivatives of alpha hydroxy acids

I) Germicides for cosmetic use, both synthetic and, for example, salicylic acid and / or others, as well as natural ones such as neem oil and / or others,

m) silicones

n) natural oils, e.g. almond oil

as well as mixtures of any of the aforementioned components.

In various embodiments, the microcapsules additionally contain Pfianzenxtrakte as an active ingredient. Usually these extracts are produced by extraction of the whole plant. However, in individual cases it may also be preferred to prepare the extracts exclusively from flowers and / or leaves of the plant. According to the invention are especially the extracts of green tea, oak bark, nettle, witch hazel, hops, henna, chamomile, burdock, horsetail, hawthorn, linden, almond, aloe vera, spruce needle, horse chestnut, sandalwood, juniper, coconut, mango, apricot, lime , Wheat, kiwi, melon, orange, grapefruit, sage, rosemary, birch, mallow, meadowfoam, quenelle, yarrow, thyme, lemon balm, toadstool, coltsfoot, marshmallow, meristem, ginseng and ginger root. Especially preferred are extracts of aloe vera.

As extraction medium for the preparation of said plant extracts, water, alcohols and mixtures thereof can be used. Among the alcohols are lower alcohols such as ethanol and isopropanol, but especially polyhydric alcohols such as ethylene glycol and propylene glycol, both as sole extractant and in admixture with water, are preferred. Plant extracts based on water / propylene glycol in a ratio of 1:10 to 10: 1 have proven to be particularly suitable.

The plant extracts can be used according to the invention both in pure and in diluted form. If they are used in diluted form, they usually contain about 2 to 80 wt .-% of active substance and as a solvent used in their extraction agent or extractant mixture.

Furthermore, it may be preferable to use several active plant extracts, in particular two different plant extracts.

It may be advantageous for the outer / inner microcapsules usable according to the invention to be applied particularly well to the treated textile. This is achieved, for example, by the use of aminoplast capsules, such as those based on melamine-formaldehyde. After the washing process, in particular such Aminoplast capsules then usually have a certain brittleness, so that by the action of mechanical force, a targeted release of active ingredient, in particular fragrance release, can take place from the capsule, z. B. when rubbing the skin with a towel, which has been washed with an appropriate detergent. In this way, even after prolonged storage of the laundry targeted z. B. a fragrance be caused. This deliberately induced fragrance differs from the odor of the product, which is also caused by the conventional perfuming or by the use of diffusively permeable outer microcapsules and the first fragrance composition, as this of the released from the inner microcapsule second perfume composition, optionally in combination is dominated by the residues of the first fragrance composition released simultaneously from the outer microcapsules. This allows a polysensory fragrance experience, ie an odor sensation which is characteristic of the product as such and which occurs when it is opened or applied, is subsequently explained by a later odor experience, which only occurs after the Application occurs detached. The consumer is thus enabled to produce specific fragrances that differ from the smell of the detergent.

In particular, the separation of the different fragrance compositions into different icc capsules offers the advantage of enabling a comparatively sharp separation of the fragrance sensation of the different compositions and is far superior to known processes based on the mixture of different volatile fragrances.

The first and second fragrance compositions differ, for example, in terms of their fragrance profile and / or the volatility of the fragrances contained and / or the substantivity of the fragrances contained. It is particularly preferred that the fragrance profile of the first and second fragrance composition for the consumer differs sensory perceived. Fragrance profiles may be described, for example, as fresh, green, ozone, floral, rose, lily of the valley, fruity, apple, berry, citrus, woody, cosmetic, balsamic, amber, musk, fougere or others. Additionally or alternatively, the two perfume compositions in outer and inner capsule may also differ in physicochemical composition, i. the perfumes / perfume mixtures used differ in composition and physical parameters, such as vapor pressure, boiling point, hydrophobicity (clogP value), etc. In various embodiments, the first and second perfume compositions differ in that the first perfume composition comprises at least one perfume, preferably two Perfumes, more preferably three perfumes, most preferably four or more fragrances that are not included in the second perfume composition. Likewise, it may be preferred that the second perfume composition contains at least one perfume, preferably two perfumes, more preferably three perfumes, most preferably four or more perfumes not included in the first perfume composition. However, it is not excluded that both fragrance compositions contain the same fragrances, as long as the composition in at least one fragrance and / or the amounts of the fragrances used differ.

Generally, in various embodiments it is preferred that the second perfume composition, i. the composition in the inner capsule is higher performing than the first fragrance composition. This has the consequence that the odor profile of the second fragrance composition, even with partial simultaneous release, for example, when by friction residues of the first released together with the second fragrance composition, dominates. Methods as to how this can be achieved, for example via the selection of fragrances via their vapor pressures, are known to the person skilled in the art.

The microcapsule systems described herein preferably contain the perfume compositions in an amount of 0.1 to 95% by weight, more preferably 1 to 90% by weight, more preferably 5 to 85 wt .-% based on the total microcapsule system. The first perfume composition preferably comprises at least 30, preferably at least 50, preferably up to, for example, 80% by weight, or up to 70% by weight of the total amount of perfume compositions in the capsule system. In various embodiments, the weight of the internal microcapsules constitutes up to 60% by weight, preferably 1 to 50% by weight, more preferably 2 to 40% by weight of the total microcapsule system. In various embodiments, the weight of the polymer from which the outer capsule shell is made is from 1 to 25% by weight, especially from 5 to 20% by weight, of the total weight of the microcapsule system. The microcapsule systems of the present invention may be in known forms, for example, as a slurry in an aqueous carrier medium or as a powder.

The middle according to the invention preferably contain! for washing, cleaning, conditioning, care and / or dyeing of hard or soft surfaces, microcapsules in amounts of 0.0001 to 50 wt .-%, preferably 0.01 to 20 wt .-%, and in particular 0, 1 to 5 Wt .-%, based on the total agent.

The agents for washing, cleaning, conditioning, care and / or dyeing of hard or soft surfaces in the context of this application are detergents, cleaners, aftertreatment agents and / or cosmetic agents.

The compositions according to the invention are used for washing, cleaning, conditioning, care and / or dyeing of hard or soft surfaces. Hard surfaces in the context of this application are windows, mirrors and other glass surfaces, surfaces of ceramic, plastic, metal or wood and lacquered wood, which are found in household and commercial, such as bathroom ceramics, cooking and dining utensils, kitchen surfaces or floors. Soft surfaces in the context of this application are textile fabrics, skin and hair.

Agents for washing hard or soft surfaces in the context of this application are textile detergents, e.g. in the form of powders, granules, beads, tablets, pastes, gels, tissues, pieces or liquids.

Agents for cleaning hard or soft surfaces in the context of this application include all cleaners for hard or soft surfaces, especially dishwashing detergents, all-purpose cleaners, toilet cleaners, sanitary cleaners and glass cleaners, toothpastes, skin detergents such as Duschgeie, or shampoos.

For the purposes of this application, agents for conditioning hard or soft surfaces are fabric softeners, scavengers, conditioning wipes for use in the tumble dryer, hygiene rinse aids, deodorants, antiperspirants, hair conditioners, styling agents and / or hair fixatives. Agents for the care of hard or soft surfaces in the context of this application are textile care products, hair care products or skin treatment agents, such as, for example, creams, lotions or gels.

For the purposes of this application, agents for dyeing hard or soft surfaces are hair dyeing and hair toning agents and agents for lightening keratinic fibers.

In addition to the capsule-in-capsule systems described herein, the agents may additionally contain conventional perfuming. This preferably differs from both the first and second fragrance compositions of the systems of the invention, for example in the parameters discussed above. This conventional perfuming can give the product as such the actual odor which is perceived during opening / use. In addition, the compositions may also contain other conventional perfume microcapsules containing the same or different perfumes.

The means for washing, cleaning, conditioning, conditioning and / or dyeing hard or soft surfaces preferably allow the targeted release of fragrances stored in the outer / inner capsules, but at the same time have their own odor, typically by a conventional Perfuming of the product is determined. The outer / inner capsules are preferably stable within the middle matrix and can be opened by targeted stimulus, in particular mechanical force, wherein the outer capsules additionally allow release of the fragrances by means of diffusion. For the purposes of the present invention, mechanical force is understood to mean any type of force applied to the microcapsule, such as e.g. Shearing forces, pressure and / or friction. In the application of the agent, e.g. in textile washing or skin cleansing, the outer microcapsules deposit on the hard or soft surface. The release of the fragrances from the outer microcapsules is then preferably by diffusive route, i. the fragrances migrate through the polymeric shell material and are thereby slowly released. After drying the surface, the microcapsules may then be e.g. be easily opened by friction, the friction also opens the thereby released from the outer microcapsules inner microcapsules. In this way, a targeted release of the fragrance (s) of the residues of the first fragrance composition from the outer capsules (the part that has not already been released by diffusion) and the second fragrance composition from the inner capsules, so that the performance profile of the entire By means of increased. In particular, the scent effect is of particular importance, since the product performance is judged in many cases by the consumer proportionally to the fragrance.

The means described herein for washing, cleansing, conditioning, conditioning and / or dyeing hard or soft surfaces enables a long-lasting perfume release, in particular a long-lasting scenting and care of hard or soft surfaces (by the release from the outer microcapsule) and a targeted release of fragrance (by the release from the inner microcapsule and optionally also the outer microcapsule), even after long periods by using the microcapsule systems described herein. In a preferred embodiment, the surface is a textile surface. When the surface is a textile surface, it is particularly preferred if the means for washing, cleaning, conditioning, conditioning and / or dyeing hard or soft surfaces is a washing, cleaning or aftertreatment agent. In a further embodiment, the surface is a body site, in particular skin and / or hair. When the surface is a body site, especially skin and / or hair, it is preferred if the means for washing, cleansing, conditioning, conditioning and / or dyeing hard or soft surfaces is a cosmetic composition.

The contact of the microcapsules with the skin and / or the hair can be done either by direct contact of the skin and / or the hair with a cosmetic composition comprising microcapsules and / or by transferring the microcapsules through textiles carrying such microcapsules on the surface.

In the methods also described herein for preparing the microcapsule systems of the invention, first, the internal microcapsules containing the second perfume composition are prepared by methods known in the art. These are then mixed with the first perfume composition, preferably dispersed therein, and the resulting mixture is encapsulated by known methods to form the outer microcapsules.

The microcapsules containing the second perfume composition may be surface modified to facilitate encapsulation in the outer microcapsule. For this purpose, the microcapsules containing the second perfume composition (inner microcapsules) are suspended in water, for example with one or more preferably hydrophobic modifiers. The modifiers can be at least one compound selected from the group consisting of polyethyleneimides, quaternary ammonium compounds, preferably those having hydrophobic hydrocarbon radicals, quaternary polyvinylpyrrolidones, and unsaturated fatty acids such as oleic acid. Examples of suitable quaternary ammonium compounds are betaine, choline chloride, benzalkonium chloride and di (Ce-ie alkyl) dimethylammonium chloride, such as didecyldimethylammonium chloride. Suitable polyethyleneimide compounds are multifunctional ethyleneimide-based cationic polymers having molecular weights in the range of 600 to 2,500,000 Da. Such polymers are commercially available, for example, under the trade name Lupasol from BASF SE. Likewise, suitable quaternary PVPs are under the trade name Luviquat of BASF SE commercially available. In general, corresponding surface modification and encapsulation processes are described, for example, in EP 2 732 803 A1 for "disintegrants" and are readily transferable to the internal microcapsules of the present invention After modification, the microcapsules may be dried before being mixed with the first perfume composition combined and encapsulated in the outer microcapsule.

It goes without saying that the surface-modified internal microcapsules described above in the context of the process according to the invention can also be used in the microcapsule systems according to the invention. In various embodiments of the invention, the inner microcapsules are therefore surface-modified microcapsules as described above, in particular those which have been hydrophobically modified, particularly preferably those modified with at least one modifier selected from the group consisting of polyethyleneimides, quaternary ammonium compounds, quaternary polyvinylpyrrolidones and oleic acid were modified.

By selecting and controlling the reaction conditions in the formation of the shells, for example control of shell thickness, their permeability to the encapsulated fragrances can be controlled. This can be used, for example, to produce internal microcapsule shells that are impermeable to the encapsulated fragrances and outer microcapsule shells that allow release by diffusion through the capsule shell.

Also within the scope of the invention are methods of generating polysensing fragrance impressions using the microcapsule systems described herein. In these processes, first the release of the first fragrance composition from the outer microcapsule and then delayed release of the second fragrance composition from the inner microcapsule occurs. As a result, the fragrance profile can be modified and a polysensory fragrance impression produced by the consumer. The scenting experience may be enhanced by adding to the agent, in addition, a conventional, i. not encapsulated perfuming, is used. This results in the opening and the application of the product, a first fragrance impression is essentially caused by the conventional perfuming, in the further course of application, it comes to the release of the first fragrance composition from the outer microcapsules by diffusion and finally by mechanical stress release of the second perfume composition from the inner microcapsules. In these methods, the agent containing the perfuming and the microcapsules is brought into contact with a surface on which the fragrances / microcapsules deposit / deposit and then release the encapsulated fragrances following the appropriate stimulus.

In various embodiments of this method, the agent in which the capsule system described herein is employed is a textile treatment agent, such as a detergent or fabric softener, which additionally contains a conventional perfume. The The capsule system used is preferably based on melamine-formaldehyde-resin-based outer microcapsules and the internal microcapsules based on aromatic alcohols described herein, in particular phloroglucinol and / or resorcinol, most preferably phloroglucinol, wherein the outer capsule is diffusely permeable and the inner capsule is closed , both are however drivable. In a first step, before the product is used, the top and middle notes of the conventional perfuming are released, thus providing a first fragrance impression. After application, a moist textile is obtained, which is olfactorily characterized by the top and bottom notes of conventional perfuming and the diffusely released fragrance composition from the outer capsule. The dry textile is characterized by the heart and base notes of conventional perfuming and the diffusely released fragrance composition from the outer capsule and after mechanical stress, for example by friction or the wearing of the fabric, the perfume comes from the inner capsule or outweighs. It goes without saying that in the course of the application cycle, the odor profile of the conventional perfume rapidly weakens and is gradually replaced by the fragrance released by means of diffusion fragrances from the outer microcapsule. These are then removed from the inner microcapsule under mechanical stress, ie when wearing or using the dry textile of the fragrances.

In such a way, the microcapsule systems described herein can be used to generate polysensory fragrance impressions.

The claimed agents for washing, cleaning, conditioning, care and / or dyeing of hard or soft surfaces may, in addition to the microcapsules described contain other ingredients, such as surface-active substances.

Suitable surface-active substances are, in particular, anionic surfactants, nonionic surfactants, cationic, zwitterionic, amphoteric surfactants and / or emulsifiers. However, it is particularly preferred if the means for washing, cleaning, conditioning, care and / or dyeing of hard or soft surfaces, anionic, nonionic and / or cationic surfactants. In particular, the use of a mixture of anionic and nonionic surfactants is advantageous. The agent preferably contains 0.05% by weight to 50% by weight, advantageously 1% to 40% by weight, more preferably 3% to 30% by weight and in particular 5% by weight to 20% by weight. % surface-active substance, in particular from the groups of anionic surfactants, nonionic surfactants, cationic, zwitterionic, amphoteric surfactants and / or emulsifiers. This corresponds to a preferred embodiment of the invention and enables optimum cleaning performance.

It is particularly preferred if the agent for washing, cleaning, conditioning, care and / or dyeing of hard or soft surfaces contains anionic surfactant, advantageously in amounts of from 0.1 to 25% by weight, more preferably from 1 to 20% by weight. %, in particular in amounts of 3 to 15 wt .-%, based on the total agent. This corresponds to a preferred embodiment of Invention and allows particularly advantageous cleaning performance. A particularly suitable anionic surfactant is alkylbenzenesulfonate, preferably linear alkylbenzenesulfonate (LAS). If the agent contains alkylbenzenesulfonate, preferably in amounts of from 0.1 to 25% by weight, more preferably from 1 to 20% by weight, in particular in amounts of from 3 to 15% by weight, based on the total agent a preferred embodiment of the invention.

Particularly suitable anionic surfactants are also the alkyl sulfates, especially the fatty alcohol sulfates (FAS), e.g. Ci2-CI8 fatty alcohol sulfate. Cs-Cis-alkyl sulfates can preferably be used, C 1 -alkyl-alkyl sulfate and C 13 -is-alkylsulfate and C 13 -alkyl-alkyl sulfate, advantageously branched, in particular alkyl-branched C 13 -17-alkyl sulfate, are particularly preferred. Particularly suitable fatty alcohol sulfates are derived from lauryl and myristyl alcohol, ie fatty alcohol sulfates with 12 or 14 carbon atoms. The long-chain FAS types (Cie to de) are very suitable for washing at higher temperatures. Particular preference is given to alkyl sulfates which have a lower Krafft point, preferably with a Krafft point of less than 45, 40, 30 or 20 ° C.

Krafft point is the term for the temperature at which the solubility of surfactants greatly increases due to the formation of micelles. The Krafft point is a triple point at which the solid or hydrated crystals of the surfactant are in equilibrium with its dissolved (hydrated) monomers and micelles. The Krafft point is determined by a turbidity measurement in accordance with DIN EN 13955: 2003-03. If the agent for washing, cleaning, conditioning, care and / or dyeing of hard or soft surfaces contains alkyl sulfate, in particular C 12 -C 16 fatty alcohol sulfate, advantageously in amounts of 0.1-25% by weight, more preferably 1% 20% by weight, in particular in amounts of 3-15 wt .-%, based on the total agent, so is a preferred embodiment of the invention.

Other preferred anionic surfactants are e.g. Alkanesulfonates (eg C13-C18 secondary alkanesulfonate), methyl ester sulfonates (eg α-C12-C18 methyl ester sulfonate) and α-olefin sulfonates (eg α-C14-C18 olefin sulfonate) and alkyl ether sulfates (eg C12-C14 fatty alcohol 2EO ether sulfate) and / or soaps. Further suitable anionic surfactants will be described below. However, FAS and / or LAS are particularly suitable.

The anionic surfactants, including soaps, may be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine. The anionic surfactants are preferably present in the form of their sodium or potassium salts, in particular in the form of the sodium salts.

It is particularly preferred if the means for washing, cleaning, conditioning, care and / or dyeing of hard or soft surfaces contains nonionic surfactant, advantageously in amounts of from 0.01 to 25% by weight, more preferably from 1 to 20% by weight. %, in particular in amounts of 3 to 15 wt .-%, based on the total agent. This corresponds to a preferred embodiment of Invention. Particularly preferred is the use of alkylpolyglycol ethers, in particular in combination with anionic surfactant, such as preferably LAS.

Further suitable nonionic surfactants are alkyiphenol polyglycol ethers (APEO), (ethoxylated) sorbitan fatty acid esters (sorbitans), alkyl polyglucosides (APG), fatty acid glucamides, fatty acid ethoxylates, amine oxides, ethylene oxide-propylene oxide block polymers, polyglycerol fatty acid esters and / or fatty acid alkanolamides. Other suitable nonionic surfactants will be described below. Sugar-based nonionic surfactants, in particular APG, are particularly preferred. In a further preferred embodiment, the surface-active substances are emulsifiers. Emulators cause at the phase interface the formation of water- or oil-stable adsorption layers, which protect the dispersed droplets against Koaieszenz and thus stabilize the emulsion. Emulsifiers are therefore surfactants like a hydrophobic and a hydrophilic molecule! built up. Hydrophilic emulsifiers preferably form O W emulsions and hydrophobic emulsifiers preferably form W / O emulsions. An emulsion is to be understood as meaning a droplet-like distribution (dispersion) of a liquid in another liquid under the expense of energy in order to create stabilizing phase interfaces by means of surfactants. The selection of these emulsifying surfactants or emulsifiers depends on the substances to be dispersed and the respective outer phase and the fineness of the emulsion. Emulsifiers which can be used according to the invention are, for example

Addition products from 4 to 30 Mo! Ethyfenoxid and / or 0 to 5 moles of propylene oxide to linear fatty alcohols having 8 to 22 carbon atoms, to fatty acids having 12 to 22 carbon atoms and to alkylphenols having 8 to 15 carbon atoms in the alkyl group,

C12-C22 fatty acid mono- and diesters of addition products of from 1 to 30 moles of ethylene oxide onto polyols having from 3 to 6 carbon atoms, in particular to glycerol,

Ethylene oxide and polyglycerol addition products to methyl glucoside fatty acid esters, fatty acid alkanolamides and fatty acid glucamides,

C 8 -C 22 -alkylmono- and -oligoglycosides and their ethoxylated analogues, preference being given to degrees of oligomerization of from 1.1 to 5, in particular from 1.2 to 2.0, and glucose as the sugar component,

Addition products of from 5 to 60 mol of ethylene oxide onto castor oil and hydrogenated castor oil, partial esters of polyols having 3-6 carbon atoms with saturated fatty acids having 8 to 22 carbon atoms,

Sterols. Sterols are understood to mean a group of steroids which carry a hydroxyl group on C-atom 3 of the steroid skeleton and are isolated both from animal tissue (zoosterines) and from vegetable fats (phytosterols). Examples of zoosterols are cholesterol and lanosterol. Examples of suitable phytosterols are ergosterol, stigmasterol and sitosterol. Mushrooms and yeasts are also used to isolate sterols, the so-called mycosterols. Phospholipids. These include, in particular, the glucose phospholipids which are obtained, for example, as lecithins or phosphatidylchiolines from, for example, egg yolks or plant seeds (for example soybeans).

Fatty acid esters of sugars and sugar alcohols, such as sorbitol,

Polyglycerols and polyglycerol derivatives such as, for example, polyglycerol poly-12-hydroxystearate (commercial product Dehymu! S® PGPH),

Linear and branched fatty acids with 8 to 30 C atoms and their Na, K, ammonium, Ca, Mg and Zn salts. When the means for washing, cleaning, conditioning, conditioning and / or dyeing hard or soft surfaces is a washing, cleaning or post-treatment agent, it may contain, in addition to the essential ingredients, other ingredients which have the performance and / or aesthetic properties of the washing, cleaning or post-treatment further improve. In the context of the present invention, the washing, cleaning or post-treatment agent preferably additionally contains one or more substances from the group of builders, bleaching agents, bleach catalysts, bleach activators, enzymes, electrolytes, non-aqueous solvents, pH adjusters, perfume compositions, perfume carriers, fluorescence agents, dyes , Hydrotropes, foam inhibitors, silicone oils, soil release polymers, grayness inhibitors, shrinkage inhibitors, anti-crease agents, color transfer inhibitors, other antimicrobial agents, germicides, fungicides, antioxidants, preservatives !, corrosion inhibitors, antistatic agents, bittering agents, ironing auxiliaries, repellents and impregnating agents, swelling agents Slip-resistant agents, softening components and UV absorbers.

Particularly preferred additional ingredients for washing, cleaning or post-treatment agents are builders, enzymes, electrolytes, nonaqueous solvents, pH adjusters, perfume compositions, fluorescers, dyes, hydrotropes, foam inhibitors, soil release polymers, grayness inhibitors, dye transfer inhibiting agents, softening components, UV Absorber and mixtures thereof. In a preferred embodiment, the washing, cleaning or post-treatment agents are in liquid form and contain water as the main solvent.

The invention also relates to the use of a washing, cleaning or aftertreatment agent in the washing, cleaning and / or pretreatment of textile fabrics.

When the means for washing, cleaning, conditioning, conditioning and / or dyeing hard or soft surfaces is a cosmetic composition, it may contain other ingredients in addition to the essential ingredients. Preferably, the cosmetic composition further comprises at least one cosmetic active ingredient selected from the group consisting of the oxidation dye precursors, the substantive dyes, the oxidizing agent selected from Hydrogen peroxide and its attachment compounds to solid carriers, hair conditioning agents, deodorizing and / or antiperspirant active ingredients, skin-lightening and / or skin-calming and / or moisturizing agents, inorganic and / or organic UV filter substances, sebum-regulating agents, mechanical Exfoliationmittei , the antimicrobial agents, the hair setting or hair styling agents, the anti-caries agents, the anticalculus agents and the mixtures of these agents. These cosmetic agents are preferably contained at 0.01 to 70 wt .-% based on the total weight of the ready-to-use agent. The embodiments described in connection with the capsule systems according to the invention are also transferable to processes for the preparation thereof, the agents containing them and the uses and processes described herein, and vice versa.

The invention is illustrated below by means of examples, but is not limited to these.

Examples

Example 1 AMPS hydroxybutyl acrylate

891 g of demineralized water along with 585 g of AM PS (50% aqueous solution) and 7.5 g of 4-hydroxybutyl acrylate (HBA) were charged to the reactor and placed under a protective gas atmosphere. The reaction mixture was heated to 75 ° C. with stirring (400 rpm). From the water-soluble initiator sodium peroxodisulfate, 0.03 g was dissolved in 15 g of water and injected into the reactor by syringe when the reaction temperature was reached. After reaching the maximum temperature, one hour of post-reaction started. The mixture was then cooled to room temperature and treated with 1, 5 g of preservative.

The aqueous solution was characterized by viscosity, solid content and pH. The viscosity was 540 mPas (measured at 20 rpm Brookfield), the solids content was 21% and the pH was 3.3. 3 g of copolymer were placed on a Petri dish and dried for 24 hours at 160 ° C in a drying oven. The weight is 0.69 g, which corresponds to a yield of 21, 6%.

Resorcinol capsule

In a 400 ml beaker 5.5 g of resorcinol were dissolved with stirring (stirring speed: about 1500 U / min) in 70 g of water and then with 2.0 g of sodium carbonate solution (20 wt.%), Whereupon the pH Value was around 7.9. This solution was heated to a temperature of about 52 ° C. Then, 25.5 g of glutaric dialdehyde was added. The mixture was stirred for a further approximately 10 minutes at a stirring speed of approximately 1500 rpm and a temperature of approximately 52 ° C. (precondensation time). Thereafter, about 20 g of water were added and about 2 minutes later, 1 g of the protective colloid AMPS hydroxybutyl acrylate (see above) and again about 2 minutes later added the perfume composition. Immediately thereafter, the stirring speed was increased to about 4,000 rpm and at about the same time, 20.0 g of sodium carbonate solution (20% by weight) was added. Thereafter, the pH of the mixture was about 9.7. In the subsequent period, the viscosity and the volume of the mixture increased. It was further stirred at a stirring speed of about 4000 U / min until the viscosity had dropped again. Only then was the stirring speed lowered to about 1500 rpm. At a temperature of about 52 ° C and about the same stirring speed, the mixture was stirred for about 60 minutes. Thereafter, the mixture was heated to about 80 ° C and the capsules cured at this temperature over a period of 3 hours.

Capsule size distribution - D (90) 5 - 10 ym; Encapsulation efficiency approx. 90%;

Drying yield>90%; Solids of the slurry about 40% by weight. Phloroglucinol capsule

Analogously to the above method, the 5.5 g of resorcinol used there were completely replaced by 6.3 g of pholoroglucinol. In this way phloroglucin microcapsules were obtained.

Characterization of the microcapsule systems

A commercially available fabric softener (Vernel conc.) Was closed with a capsule system according to the invention (sample 2, 0.3% by weight of capsule slurry according to the invention: inner phloroglucin capsule, drivable and loaded with perfume 3, outer melamine-formaldehyde capsule diffuse, can be drenched and loaded with perfume 2) or a conventional capsule system (sample 1, 0.15% by weight of phloroglucin capsule slurry: capsule closed, can be drummed and loaded with perfume 3) and the discoloration by the microcapsules and the sedimentation of Microcapeins on a scale of 0-3 (0 = no discoloration / sedimentation, 1 = faint discoloration / sedimentation, 2 = medium

Discoloration / sedimentation; 3 = strong discoloration / sedimentation) assessed by a panel of trained experts.

Assessment of discoloration / sedimentation Phloroglucin capsules

It was found that the disadvantageous discoloration / sedimentation of the high-performance phloroglucin capsules can be markedly reduced by use in the capsule-in-capsule system according to the invention.

The same experiment was carried out with resorcinol capsules, with the following result:

Assessment discoloration / sedimentation resorcinol capsules

Here, a similar effect was seen as in the phloroglucin capsule.

Claims

claims

A microcapsule system comprising an outer microcapsule having an outer capsule shell, the outer microcapsule containing:

(b) a first fragrance composition;

characterized in that

the inner microcapsule contains a second fragrance composition completely surrounded by the inner capsule shell of the inner microcapsule and different from the first fragrance composition, and

the capsule shell of the inner microcapse! comprising a resin, which by reacting

i. at least one aromatic alcohol or its ether or derivative with ii. at least one aldehydic component having at least two carbon atoms per molecule, and

iii. optionally in the presence of at least one (meth) acrylate polymer,

is available.

2. microcapsule system according to claim 1, characterized in that

(A) the at least one aromatic alcohol a) is selected from phenols, o-cresol, m-cresol, p-cresol, et-naphthol, ß-naphthol, thymol, catechol, resorcinol, hydroquinone and 1, 4-naphthohydroquinone, phloroglucin , Pyrogallol, hydroxyhydroquinone and mixtures thereof, preferably resorcinol and / or phloroglucinol, more preferably phloroglucinol; and or

(b) the aldehydic component b) is selected from valeraldehyde, capronaldehyde, caprylaldehyde, decanal, succinic dialdehyde, cyclohexanecarbaldehyde, cyclopentanecarbaldehyde, 2-methyl-1-propanal, 2-methylpropionaldehyde, acetaldehyde, acrolein, aldosterone, antimycin A, 8 ' -Apo-β-caroten-8'-al, benzaldehyde, butanal, chloral, citral, citronellal, crotonaldehyde, dimethylaminobenzaldehyde, foiic acid, fosmidomycin, furfural, glutaraidehyde, glutaric dialdehyde, glyceraldehyde, glycolaldehyde, glyoxal, glyoxylic acid, heptanal, 2-hydroxybenzaldehyde, 3-hydroxybutanal, hydroxy molybdenum 1, 4-hydroxynonenal, isobutanal, isobutyraldehyde, methacrolein, 2-methylundecanai, mucochloric acid, N-methylformamide, 2-nitrobenzaldehyde, nonanal, octanal, oleocanthal, orlistat, pentanal, phenylethanal , Phycocyanin, piperonal, propanal, propenal, protocatechualdehyde, retinal, acylaldehyde, secologanin, streptomycin, strophanthinidin, tylosin, vanillin, cinnamic aldehyde and mixtures thereof, preferably min at least two free aldehyde groups per molecule, more preferably succinic dialdehyde and / or glutaric dialdehyde.

A microcapsule system according to claim 1 or 2, characterized in that the at least one (meth) acrylate polymer is a copolymer of 2-acrylamido-2-methylpropanesulfonic acid or its salts with one or more further (meth) acrylate monomers, wherein the other (meth) acrylate monomers are preferably selected from acrylic acid, Ciu-alkyl acrylic acid, (meth) acrylamides, heterocyclyl (meth) acrylates, urethane (meth) acrylates, C1-14 alkyl acrylates, C2-14 alkenyl Acrylates, Ci-i4-hydroxyalkyl acrylates, alkylene glycol acrylates, C1-14-alkyl methacrylates, C2-14 alkenyl methacrylates, Ci-i4-hydroxyalkyl methacrylates and alkylene glycol methacrylates.

Microcapsule system according to one of claims 1 -3, characterized in that the outer capsule shell

(A) comprises a resin which is selected from polyacrylates, polyurethanes, polyolefins, polyamides, polyesters, polysaccharides, epoxy resins, silicone resins and / or polycondensation products of carbonyl compounds and NH-containing compounds, preferably melamine-urea-formaldehyde or melamine-formaldehyde or urea-formaldehyde, more preferably melamine-formaldehyde resins; and or

(b) is partially permeable to at least portions of the first perfume composition and released by diffusion.

A microcapsule system according to any one of claims 1 to 4, characterized in that the inner capsule shell for the second fragrance composition is less permeable than the outer capsule shell for the first fragrance composition.

Microcapsule system according to one of claims 1 to 5, characterized in that the release of the perfume composition from the inner and optionally also the outer microcapsule is carried out by mechanical stress.

Microcapsule system according to one of the preceding claims, characterized in that the first and second fragrance composition differ with regard to their fragrance profile and / or the physicochemical properties.

A process for producing a microcapsule system according to any one of claims 1-7, characterized in that the process comprises (1) providing microcapsules containing the second perfume composition and a first perfume composition, (2) encapsulating the microcapsules containing the second perfume composition, and first perfume composition in an outer microcapsule.

Agent for washing, cleaning, conditioning, care and / or dyeing of hard or soft surfaces containing the microcapsule system according to one of claims 1-7.

10. Use of the microcapsule system according to any one of claims 1-7 for generating polysensory fragrance impressions.