DE102015217981A1 - Release of fragrances from microcapsules - Google Patents

Abstract

The present invention relates to the release of fragrances from microcapsules. This allows a long-lasting fragrance experience.

Description

The present invention relates to the release of fragrances from microcapsules. This allows a long-lasting fragrance experience.

In different areas of everyday life the consumer is confronted with fragrances. One of the problems associated with this is the relatively rapid loss of odor intensity of the corresponding compounds due to their low volatility. Furthermore, some fragrances can not be incorporated stably in the application products.

For example, washing or cleaning agents, cosmetics but also, for example, adhesives, usually contain fragrances which give the compositions a pleasant odor. Here, the smell of other ingredients is masked by the fragrances, so that the consumer creates a pleasant smell impression.

In addition, detergents and cosmetic products contain fragrances that ensure that the laundry or the body of a person should have a pleasant fragrance. In the detergent sector, not only the moist but also the dry laundry should have the longest possible fresh fragrance. In general, however, fragrances are volatile substances, so that a long-lasting scent effect is difficult to achieve. Especially with fragrances that represent the fresh and light notes of the perfume and evaporate very quickly due to their relatively high vapor pressure, the desired longevity of the fragrance impression is hardly achievable.

Fragrance storage molecules (fragrance storage substances) are now described in the prior art. These are one way to release fragrances delayed. Depending on the chemical structure of the molecule, the incorporated fragrance is released by the action of heat or reaction with chemicals. This can be done, for example, by breaking a covalent bond in the fragrance storage molecule. However, the fragrance intensity is low in known fragrance storage molecules and the scent effect obtained only for a short time.

Also known in the prior art is the incorporation of additives into detergents. These are introduced in the form of microcapsules in the detergent. During washing, the microcapsules are deposited on the textiles to be cleaned and then, for example, during use of the textile diffused or by friction, so by breaking the capsules when using or wearing the textile, released. The use of microcapsules improves the performance of the additives over direct incorporation of the additive into the detergent, especially when the capsule surface is such that it has a greater affinity for the substrate, garment or fabric than the additive itself.

Surprisingly, it has now been found that, when using special fragrance storage molecules release of the fragrances from capsules also takes place under special and thus controlled conditions. This allows a controlled release of a fragrance over a longer period of time, so that a pleasant and fresh scent persists over a longer period of time.

wobei R¹ und/oder R² jeweils unabhängig voneinander in alpha-Position zu C' ein abstrahierbares H-Atom aufweisen.In a first embodiment, the object underlying the present invention is achieved by microcapsules comprising a core and a shell, wherein the core comprises at least one compound of general formula (I)

wherein R ¹ and / or R ² each independently of one another in the alpha position to C 'have an abstractable hydrogen atom.

According to the invention, the terms "capsules" and "microcapsules" are used synonymously in the present application. According to the invention, the capsules have a core and a shell, so that hereinafter Also the term "core-shell-capsule" is used. Suitable microcapsules are those capsules which have an average diameter X _50.3 (volume average) of from 1 to 100 μm, preferably from 1 to 80 μm, particularly preferably from 1 to 50 μm and in particular from 1 to 40 μm. The mean particle size diameter X _50.3 is determined by sieving or by means of a particle size analyzer Camsizer from Retsch.

Core-shell capsules in the context of the present invention are those capsules which have as external shell a wall material preferably solid at room temperature. At its core is the compound of the invention of the general formula (I) shown above. This compound is a fragrance-based material. According to the invention, it is also possible that a plurality of different compounds of the general formula (I) shown above are included. According to the invention, the core can both have a solid form and be liquid or viscous. Also conceivable are waxy structures. It is possible that the at least one fragrance storage substance according to the general formula (I) is substantially contained as a pure substance in the capsule. Alternatively, those capsules are also conceivable in which the core comprises, in addition to the at least one fragrance storage material, further ingredients, such as solvents, stabilizers or other fragrances or olfactorily active substances, etc. Particularly preferred for the purposes of the present invention are capsules in which the core of the capsules is liquid, viscous or at least meltable at temperatures of 120 ° C or less, in particular 80 ° C and below, especially 40 ° C and below. This makes it possible to provide the fragrance storage material represented by a compound of the general formula (I) shown above in the core of the capsule at the desired time and enables a homogeneous distribution thereof in the core.

The core preferably comprises the fragrance storage substance of the general formula (I) in a proportion of 0.001 to 50 wt .-%, in particular from 0.05 to 45 wt .-%, particularly from 0.1 to 40 wt .-%, preferably from 1 to 38 wt .-% or from 5 to 35 wt .-%, particularly preferably from 5 to 30 wt .-%, based on the total weight of the core. It has been shown that a more fragrance storage material does not lead to a significantly longer fragrance experience, since the capsule is completely emptied when breaking the shell. At lower levels, the fragrance experience is no longer so noticeable to humans that he finds it beneficial.

The compounds of the general formula (I) according to the invention are fragrance storage substances. If corresponding compounds are exposed to light, such as daylight or artificial light, in particular light having a wavelength in the range from 100 nm to 1000 nm, in particular from 150 nm to 700 nm, preferably from 200 nm to 500 nm, the stored fragrance becomes as well as N ₂ released.

Surprisingly, it has been found that upon exposure to light, a fragrance is released from this compound. At the same time, N _{2 is formed} . The shell of the microcapsules according to the invention is not permeable to N ₂ . This leads to an increase in pressure inside the microcapsules. If a certain pressure is exceeded, the capsule breaks, releasing the material of the core. In the microcapsules of the invention, the fragrance which has been formed by elimination of N ₂ from the compound of the invention of the general formula (I) shown above, is released, whereby a long-lasting fragrance experience is made possible.

Advantageously, a force of 0.1 to 5 mN, in particular from 0.2 to 3 mN, preferably from 0.5 to 2 mN necessary to cause bursting of the capsules according to the invention.

In an equally preferred embodiment, the capsules are not thermally stable. If the capsules are exposed to a temperature of at least 70 ° C., preferably of at least 60 ° C., preferably of at least 50 ° C. and in particular of at least 40 ° C., the compound according to the invention is of the general formula (I) shown above, which is located inside the capsules is released.

The capsules which can be used according to the invention are preferably water-insoluble capsules. The water insolubility of the capsules has the advantage that they can thereby outlast the washing or cleaning process and thus are able to absorb the fragrance only after the aqueous washing or cleaning process - for example, when drying by mere temperature increase or for example by sunlight during the Wear clothes or rubbing the surface - release.

In particular, it is preferred if the water-insoluble capsules are capsules in which the wall material (shell) is preferably polyurethanes, polyolefins, polyamides, polyacrylates, polyesters, polysaccharides, epoxy resins, silicone resins and / or polycondensation products of carbonyl compounds and NH 4. Group containing compounds such as melamine-urea-formaldehyde capsules or melamine-formaldehyde capsules or urea-formaldehyde capsules contains.

In a preferred embodiment, the capsules are inflatable capsules. The term drittable capsules means those capsules, which, when they adhere to a surface treated with it, can be opened by mechanical rubbing or by pressure, so that a release of content results only as a result of a mechanical action, for example when dealing with a Towel on which such capsules are deposited, dries hands. The shell of the capsules enclosing the core or (filled) cavity has an average thickness in the range from about 0.01 to 5 μm, preferably from about 0.05 μm to about 3 μm, in particular from about 0.05 μm to 1.5 μm is preferably about 80 nm to 150 nm, in particular 90 nm to 120 nm. Capsules are in particular readily drivable if they are within the ranges specified above concerning the mean diameter and the average thickness.

Suitable materials for the capsules are usually high molecular weight compounds such as protein compounds such as gelatin, albumin, casein and others, cellulose derivatives such as methylcellulose, ethylcellulose, cellulose acetate, cellulose nitrate, carboxymethylcellulose and others and especially synthetic Polymers such as polyamides, polyethylene glycols, polyurethanes, polyacrylates, epoxy resins and others. The wall material (shell) used is preferably, for example, melamine-urea-formaldehyde or melamine-formaldehyde or urea-formaldehyde or polyacrylate copolymer. With particular preference, such capsules are used according to the invention, as in US 2003/0125222 A1 . DE 10 2008 051 799 A1 or WO 01/49817 are described.

Preferred melamine-formaldehyde microcapsules are prepared by reacting melamine-formaldehyde precondensates and / or their C ₁ -C ₄ -alkyl ethers in water in which a hydrophobic material is emulsified, the at least one fragrance and / or. other ingredients, such as at least one oil, condenses in the presence of a protective colloid. As the hydrophobic material that can be used in the core material (among others, as an additive) for the production include all kinds of oils, such as fragrances, vegetable oils, animal oils, mineral oils, paraffins, silicone oils and other synthetic oils. Suitable protective colloids are, for example, cellulose derivatives, such as hydroxyethylcellulose, carboxymethylcellulose and methylcellulose, polyvinylpyrrolidone, copolymers of N-vinylpyrrolidone, polyvinyl alcohols, partially hydrolyzed polyvinyl acetates, gelatin, gum arabic, xanthan gum, alginates, pectins, degraded starches, casein, polyacrylic acid, polymethacrylic acid, copolymers of acrylic acid and methacrylic acid, sulfonic acid-containing water-soluble polymers containing sulfoethyl acrylate, sulfoethyl methacrylate or sulfopropyl methacrylate, and polymers of N- (sulfoethyl) -maleimide, 2-acrylamido-2-alkylsulfonic acids, styrenesulfonic acids and formaldehyde and condensates of phenolsulfonic acids and formaldehyde.

It is preferred in accordance with the invention to coat the microcapsules used according to the invention wholly or partly on their surface with at least one cationic polymer. Accordingly, at least one cationic polymer of polyquaternium-1, polyquaternium-2, polyquaternium-4, polyquaternium-5, polyquaternium-6, polyquaternium-7, polyquaternium-8, polyquaternium-9, polyquaternium-10 is suitable as cationic polymer for coating the microcapsules , Polyquaternium-11, Polyquaternium-12, Polyquaternium-13, Polyquaternium-14, Polyquaternium-15, Polyquaternium-16, Polyquaternium-17, Polyquaternium-18, Polyquaternium-19, Polyquaternium-20, Polyquaternium-22, Polyquaternium-24, Polyquaternium -27, Polyquaternium-28, Polyquaternium-29, Polyquaternium-30, Polyquaternium-31, Polyquaternium-32, Polyquaternium-33, Polyquaternium-34, Polyquaternium-35, Polyquaternium-36, Polyquaternium-37, Polyquaternium-39, Polyquaternium-43 , Polyquaternium-44, Polyquaternium-45, Polyquaternium-46, Polyquaternium-47, Polyquaternium-48, Polyquaternium-49, Polyquaternium-50, Polyquaternium-51, Polyquaternium-56, Polyquaternium-57, Polyquaternium-61, Polyquaternium-69, Polyquater nium-86th Very particular preference is given to polyquaternium-7. The polyquaternium nomenclature of cationic polymers used in the context of this application is taken from the declaration of cationic polymers according to the International Nomenclature of Cosmetic Ingredients (INCI Declaration) of cosmetic raw materials.

Particularly preferred in the present invention are the core-shell capsules in which the shell comprises a wall material selected from melamine-urea-formaldehyde or melamine-formaldehyde or urea-formaldehyde or polyacrylate copolymer. It has been shown that in particular those capsules N ₂ , which in the release of fragrances from the compounds of the invention general formula (I) is formed, can not diffuse. Rather, it comes to building a pressure inside the microcapsules, causing them to be destroyed above a certain threshold.

If the microcapsules are part of a washing or cleaning agent, they may also be in the form of a microcapsule granulate. To obtain a microcapsule granule, the microcapsules are contacted with a particulate carrier material. Support materials in the sense of the present invention are materials which have a very good absorption property. The carrier material preferably detects an oil absorption capacity ISO 787-5 of at least 125 ml / 100 g, preferably of at least 150 ml / 100 g, more preferably of at least 175 ml / 100 g and in particular of at least 200 ml / 100 g. The oil absorption capacity serves as a measure of the absorption properties of a material. It is expressed in milliliters of oil per 100 grams of sample. For determination, a sample amount of the particulate material to be examined is placed on a plate. Lacquer oil is slowly added dropwise from a burette and rubbed with a knife spatula into the particulate material after each addition of the oil. The addition of the oil is continued until clumps of solid and oil have formed. From this point on, only one drop of lake oil is added and, after each addition of the oil, thoroughly distributed with the knife spatula. When a soft paste is formed, we stop the addition of oil. The paste should just be able to spread without, however, tear or crumble and even stick to the plate.

Preferred microcapsule granules thus contain carrier material loaded with microcapsules, the carrier material having an oil absorption capacity ISO 787-5 of at least 125 ml / 100 g, preferably of at least 150 ml / 100 g, more preferably of at least 175 ml / 100 g and in particular of at least 200 ml / 100 g. In this case, the oil absorption coefficient of the pure support material is determined prior to assembly with microcapsules as described above.

For the purposes of the present invention, the particulate carrier material may be a single particulate component or a mixture of a plurality of different components. It is crucial that the sum of all carrier materials after one hour of heating in the dry state have an oil absorption capacity of 100 ml / 100 g or more.

The BET surface area after DIN ISO 9277: 2003-05 of the support material is preferably at least 10 m ² / g, preferably at least 40 m ² / g, in particular at least 70 m ² / g, especially at least 100 m ² / g and particularly preferably at least 130, independently of the values of the oil absorption capacity m ² / g.

The mean particle size X _{50.3 of} the support material is preferably below 100 mm, preferably below 75 mm, more preferably below 50 mm, more preferably below 25 mm, in particular below 10 mm and in particular below 5 mm.

The support material preferably comprises amorphous aluminosilicates. Among these amorphous compounds with different proportions of alumina (Al ₂ O ₃ ) and silicon dioxide (SiO ₂ ) are understood to contain other metals. Preferably, the amorphous aluminosilicate used in the process according to the invention can be described by means of one of the following formulas (I) or (II): x (M ₂ O) Al ₂ O ₃ y (SiO ₂ ) w (H ₂ O) (Formula (I)) x (MeO) y (M ₂ O) Al ₂ O ₃ z (SiO ₂ ) w (H ₂ O) (Formula (II))

In the formula (I), M represents an alkali metal, preferably sodium or potassium. With particular preference x takes values from 0.2 to 2.0, y the values from 0.5 to 10.0 and w all positive values including 0.

In the formula (II) Me stands for an alkaline earth metal, M for an alkali metal, moreover preferably x for values of 0.001 to 0.1, y for values of 0.2 to 2.0, z for values of 0.5 to 10 , 0 and w for positive values including 0.

Furthermore, instead of the amorphous aluminosilicates or in addition to these clays, the support material may preferably comprise bentonites, alkaline earth metal silicates, preferably calcium silicate, alkaline earth metal carbonates, in particular calcium carbonate and / or magnesium carbonate and / or silica.

Silicas are particularly preferably contained in the support material, the term silica here as a collective name for compounds of general formula (SiO ₂ ) _m · nH ₂ O stands. Precipitated silicas are prepared from an aqueous alkali silicate solution by precipitation with mineral acids. This forms colloidal primary particles, which agglomerate with progressive reaction and finally grow into aggregates. The powdery, voluminous forms have BET surface areas of 30 to 800 m ² / g.

The term pyrogenic silicas combines highly disperse silicas which are prepared by flame hydrolysis. In this case, silicon tetrachloride is decomposed in a blast gas flame. Pyrogenic silicic acids have significantly less OH groups on their surface than precipitated silicas. Because of their silanol-related hydrophilicity, the synthetic silicas are often subjected to chemical aftertreatment processes in which the OH groups react with, for example, organic chlorosilanes. This results in modified, for example, hydrophobic surfaces, which significantly extend the performance properties of silicas. Also chemically modified silicas fall within the scope of the present invention under the term "silicas".

Particularly advantageous embodiments provide this Sipernat ^® 22 S, Sipernat ^® 50 or Sipernat ^® 50 S from Evonik (Germany) is spray-dried and then milled silicas in particular, as these have proven to be highly absorbent. However, preference is likewise given to the other silicas known from the prior art.

Corresponding microcapsule granules are in WO 2010/118959 A1 described in detail. The production process of corresponding granules described there in particular beginning on page 12 is hereby expressly incorporated by reference.

According to the invention, a plurality of different fragrance storage materials, ie at least one or at least one fragrance storage material, may also be present in the core of a microcapsule.

"At least one" or "at least one" or "one or more" as used herein refers to 1 or more, for example, 2, 3, 4, 5, 6, 7, 8, 9 or more. In the context of constituents of the compound described herein, this indication does not refer to the absolute amount of molecules but to the nature of the constituent. "At least one compound of formula (I)" therefore means, for example, one or more different compounds of formula (I), d. H. one or more different types of compounds. Together with quantities, the quantities refer to the total amount of the corresponding designated type of ingredient as defined above.

wobei R¹ und/oder R² jeweils unabhängig voneinander in alpha-Position zu C' ein abstrahierbares H-Atom aufweisen.The microcapsules according to the invention have in the core at least one compound of the general formula (I)

wherein R ¹ and / or R ² each independently of one another in the alpha position to C 'have an abstractable hydrogen atom.

According to the invention, R ¹ and R ^{2 are} each independently selected from a linear, aliphatic, olefinic or open-chain organic radical having 2 to 20 carbon atoms, in particular 2 to 12 carbon atoms, and 0 to 10 heteroatoms selected from N, O, S and Si; or
a branched or cyclic organic radical having 3 to 20 carbon atoms, especially 3 to 12 carbon atoms, and 0 to 10 heteroatoms selected from N, O, S and Si; or
an aromatic or heteroaromatic organic radical having 4 to 20 carbon atoms, especially 4 to 12 carbon atoms, and 0 to 10 heteroatoms selected from N, O, S and Si; or
R ¹ and R ² are connected to each other with ring closure via a bridge Q and form a bridging part -R ¹ -QR ² -, wherein R ¹ and R ² each independently represent a radical having 1 to 5 carbon atoms; and Q is a bridging substituted or unsubstituted group having 1 or 2 to 20 carbon atoms, especially 2 to 12 carbon atoms, and 0 to 10 heteroatoms selected from N, O, S and Si.

In this case, R ¹ and / or R ² each independently of one another in the alpha position to C 'on an abstractable H atom. Thus, for example, if R ^{1 has} an abstractable H atom in the alpha position, the structure (Ia) shown below results; if R ² has an abstractable hydrogen atom in the alpha position relative to C ', the structure (Ib) shown below results; if both R ¹ and R ^{2 have} a corresponding H atom, this results in structure (Ic).

• a. ein Rest der Formel -CH(OH)-R³, -CH₂-C(O)-R³, -Aryl, -Heteroaryl, -CH₂-Aryl oder -CH₂-Heteroaryl, wobei R³ ausgewählt ist aus der Gruppe bestehend aus Wasserstoff, substituiertem oder unsubstituiertem, linearem oder verzweigtem Alkyl, Alkenyl oder Alkinyl mit bis zu 20, vorzugsweise bis 10 Kohlenstoffatomen, substituiertem oder unsubstituiertem, linearem oder verzweigtem Heteroalkyl, Heteroalkenyl oder Heteroalkinyl mit bis zu 20, vorzugsweise bis 10 Kohlenstoffatomen, und 1 bis 6, vorzugsweise 1 bis 4 Heteroatomen ausgewählt aus O, S und N, substituiertem oder unsubstituiertem Aryl mit bis zu 20, vorzugsweise 6 bis 10 Kohlenstoffatomen, substituiertem oder unsubstituiertem Heteroaryl mit bis zu 20, vorzugsweise 4 bis 10 Kohlenstoffatomen, und 1 bis 6, vorzugsweise 1 bis 4 Heteroatomen ausgewählt aus O, S und N, Cycloalkyl oder Cycloalkenyl mit bis zu 20, vorzugsweise 5 bis 10 Kohlenstoffatomen, und Heterocycloalkyl oder Heterocacloalkenyl mit bis zu 20, vorzugsweise 4 bis 10 Kohlenstoffatomen, und 1 bis 6, vorzugsweise 1–4 Heteroatomen ausgewählt aus O, S und N; oder
• b. ein substituiertes oder unsubstituiertes, lineares Alkyl mit 1 oder 2 bis 5 Kohlenstoffatomen, oder ein substituiertes oder unsubstituiertes verzweigtes Alkyl mit 3 bis 5 Kohlenstoffatomen.

In preferred embodiments, therefore, R ¹ and / or R ^{2 are} each independently

• a. a radical of formula -CH (OH) -R ³ , -CH ₂ -C (O) -R ³ , -aryl, -Heteroaryl, -CH ₂ -aryl or -CH ₂ -Heteroaryl, wherein R ^{3 is} selected from A group consisting of hydrogen, substituted or unsubstituted, linear or branched alkyl, alkenyl or alkynyl having up to 20, preferably to 10 carbon atoms, substituted or unsubstituted, linear or branched heteroalkyl, heteroalkenyl or heteroalkynyl having up to 20, preferably to 10 carbon atoms, and 1 to 6, preferably 1 to 4 heteroatoms selected from O, S and N, substituted or unsubstituted aryl having up to 20, preferably 6 to 10 carbon atoms, substituted or unsubstituted heteroaryl having up to 20, preferably 4 to 10 carbon atoms, and 1 to 6, preferably 1 to 4 heteroatoms selected from O, S and N, cycloalkyl or cycloalkenyl having up to 20, preferably 5 to 10 carbon atoms, and heterocycloalkyl or heterocacloalkenyl having up to 20, preferably 4 bi s is 10 carbon atoms, and 1 to 6, preferably 1-4, heteroatoms selected from O, S and N; or
• b. a substituted or unsubstituted linear alkyl having 1 or 2 to 5 carbon atoms, or a substituted or unsubstituted branched alkyl having 3 to 5 carbon atoms.

"Alkyl" refers to a saturated aliphatic hydrocarbon including straight and branched chain groups. Preferably, the alkyl group has 1 to 10 carbon atoms, and when a numerical range, for example, "1 to 10" is given herein, it is meant that this group, in this case the alkyl group, is 1 carbon atom, 2 carbon atoms, 3 carbon atoms, etc. up to and including May have 10 carbon atoms. In particular, the alkyl may be a middle alkyl having 1 to 6 carbon atoms or a lower alkyl having 1 to 4 carbon atoms, for example, methyl, ethyl, n-propyl, isopropyl, butyl, iso-butyl, tert-butyl etc., act.

In the present application, "alkenyl" refers to an alkyl group as defined herein which consists of at least two carbon atoms and at least one carbon-carbon double bond, for example ethenyl, propenyl, butenyl or pentenyl and their structural isomers such as 1- or 2- Propenyl, 1-, 2-, or 3-butenyl, etc.

"Alkynyl" refers to an alkyl group as defined herein which consists of at least two carbon atoms and at least one carbon-carbon triple bond, for example, ethynyl (acetylene), propynyl, butynyl or pentynyl and their structural isomers as described above.

"Heteroalkyl", "heteroalkenyl" and "heteroalkynyl" as used herein refers to alkyl, alkenyl or alkynyl groups as defined above in which 1 or more carbon atoms are represented by heteroatoms, especially selected from O, S, N and Si , are replaced, for example, ethoxyethyl, ethoxyethenyl, isopentoxypropyl, etc.

A "cycloalkyl" group refers to mono-, di- or polycyclic groups, especially from 3 to 8 carbon atoms, in which the ring is made of carbon atoms which are linked together by carbon-carbon single bonds, carbon-carbon double bonds and / or carbon Carbon triple bonds are interconnected. The ring may have none, one, two or more double and / or triple bonds. However, it does not have a complete conjugated pi-electron system. For example, a cycloalkyl radical is cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclobutenyl, Cyclopentenyl, cyclohexenyl, etc. Examples of cycloalkyl groups are cyclopropane, cyclobutane, cyclopentane, cyclopentene, cyclohexane, adamantane, cyclohexadiene, cycloheptane and cycloheptatriene.

"Aryl" refers to monocyclic or polycyclic, d. H. Rings, which have adjacent carbon pairs in common, groups, in particular 6 to 14 carbon ring atoms which have a fully conjugated pi-electron system. Examples of aryl groups are phenyl, naphthalenyl and anthracenyl.

A "heteroaryl" group refers to mono-, or dicyclic or polycyclic, that is rings which share an adjacent ring atomic aromatic ring, in particular from 5 to 10 ring atoms, where one, two, three or four ring atoms are nitrogen, oxygen or sulfur and the rest is carbon. Examples of heteroaryl groups are pyridyl, pyrrolyl, furyl, thienyl, imidazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, pyrazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, 1,2,3-oxadiazolyl, 1, 2,4-oxadiazolyl, 1,2,5-oxadiazolyl, 1,3,4-oxadiazolyl, 1,3,4-triazinyl, 1,2,3-triazinyl, benzofuryl, isobenzofuryl, benzothienyl, benzotriazolyl, isobenzothienyl, indolyl, Isoindolyl, 3H-indolyl, benzimidazolyl, benzothiazolyl, benzoxazolyl, quinolizinyl, quinazolinyl, pthalazinyl, quinoxalinyl, cinnolinyl, naphthyridinyl, quinolyl, isoquinolyl, tetrazolyl, 5,6,7,8-tetrahydroquinolyl, 5,6,7,8-tetrahydroisoquinolyl, Purinyl, pteridinyl, pyridinyl, pyrimidinyl, carbazolyl, xanthenyl or benzoquinolyl.

A "heterocycloalkyl" group refers to a monocyclic or fused ring of 5 to 10 ring atoms containing one, two or three heteroatoms selected from N, O and S, with the remainder of the ring atoms being carbon atoms. A "heterocycloalkenyl" group additionally contains one or more double bonds. However, the ring does not have a complete conjugated pi-electron system. Examples of heteroalicyclic groups include pyrrolidine, piperidine, piperazine, morpholine, imidazolidine, tetrahydropyridazine, tetrahydrofuran, thiomorpholine, tetrahydropyridine, and the like.

Wasserstoffatome, Methylgruppen, Methylengruppen, Methingruppen oder quartäre Kohlenstoffatome der Reste R¹ R², oder R³ können grundsätzlich beliebig durch Heteroatome substituiert werden, jedoch werden mit Ausnahme von Di- oder Polysulfiden keine zwei direkt benachbarten Gruppen gleichzeitig durch Heteroatome substituiert.In the present invention, substituted means that one or more of hydrogen atoms, methyl groups, methylene groups, methine groups or quaternary carbon atoms of R ¹ , R ² , or R ^{3 of} the scavenging agent may each be independently replaced by heteroatoms. Heteroatoms in the context of the present invention are selected from the group consisting of nitrogen, oxygen, sulfur, silicon, selenium, phosphorus, fluorine, chlorine, bromine or iodine. One or more hydrogen atoms or methyl groups can be substituted by a heteroatom selected from the group consisting of nitrogen, oxygen, sulfur, silicon, selenium, phosphorus, fluorine, chlorine, bromine or iodine, one or more methylene groups can be selected from the group by a heteroatom Nitrogen, oxygen, sulfur, selenium, phosphorus, or silicon, one or more methine groups may be substituted by a heteroatom selected from the group consisting of nitrogen, phosphorus, or silicon, and one or more quaternary carbon atoms may be substituted by silicon. Should free valences arise through the substitution of hydrogen atoms, a methyl group, a methylene group or a methine group, these are in principle saturated with hydrogen. Thus, for example, a terminal methyl group besides a methylene group can be replaced by a hydroxy group or a sulfanyl group to give a methylene hydroxy group or a methylene thiol group. Similarly, an isopropyl group which is a radical having two methyl groups and a methine group or a derivative of the isopropyl group which is a group having a methyl group, a methylene group and a quaternary carbon atom may have, for example, the following substitution patterns:

Hydrogen atoms, methyl groups, methyl groups, methine or quaternary carbon atoms, R ³ may in principle be substituted arbitrarily by heteroatoms, however, the radicals R ¹ R ^2, or be substituted, with the exception of di- or polysulphides no two immediately adjacent groups simultaneously by heteroatoms.

According to the invention it is also possible that R ¹ and R ² are connected to each other with ring closure via a bridge element Q. In this case, the compound of the present invention has the following formula (II).

It is preferred for the bridging moiety -R ¹ -QR ² -, when the radicals R ¹ and R ^{2 are} independently a radical having 1 to 5 carbon atoms, wherein at least one atom of the radicals R ¹ and R ² in the alpha position to C 'is a secondary, tertiary, or quaternary C atom, and Q is a bridging substituted or unsubstituted group having 1 or 2 to 20 carbon atoms, especially 2 to 12 carbon atoms, and 0 to 10 heteroatoms selected from N, O, S and Si is standing. Preferably, the radicals R ¹ and R ² independently of one another represent a radical having 1 to 5 carbon atoms, wherein Q is an R ¹ and R ² are substituted or unsubstituted bridging group having 1 to 10 carbon atoms.

In a further preferred embodiment of the invention, R ¹ and R ² in formula (II) are independently a radical having 1 to 5 carbon atoms, wherein at least one atom of the radicals R ¹ and R ² in the alpha position to C 'is a secondary or tertiary carbon atom. In a very particularly preferred embodiment of the invention, one of the two radicals R ¹ and R ^{2 is} a radical having 1 to 3 carbon atoms, where at least one atom of the radicals R ¹ and R ² in the alpha position to C 'is a secondary carbon atom, while the respective other radical R ¹ or R ^{2 is} a radical having 1 to 3 carbon atoms, wherein at least one atom of the radicals R ¹ and R ² in the alpha position to C 'is a tertiary carbon atom.

In a further preferred embodiment of the invention, Q stands for a substituted or unsubstituted group bridging R ¹ and R ² , where the R ¹ and R ² bridging part of Q is chosen such that one four, five, six, seven or eight-membered ring. Q is particularly preferred when the R ¹ and R ² bridging portion of Q is selected to be a five- or six-membered ring. Q preferably represents a hydrocarbon.

The bridging moiety -R ¹ -QR ² - is preferably a hydrocarbon.

The radical R ¹ and / or the radical R ² or the bridging part R ¹ -QR ² is particularly preferably radical derived from a perfume alkane. "Derived radical" refers to the radical which forms when the unsaturated group of a formally Fragrance alkane nitrogen N ₂ binds and one of the two carbon atoms of the double bond of the alkene bonds to the nitrogen as shown in formula (I).

In a preferred embodiment, the fragrance alkene contains a semi-cyclic or exocyclic double bond in the event that R ¹ or R ^{2 are} cyclic compounds or R ^{1 is} connected to R ² with ring closure via Q. For the purposes of the present invention, the term "endocyclic double bond" / "cyclic double bond" is to be understood as meaning a double bond in which both of the linked atoms represent ring atoms. For the purposes of the present invention, the term "exocyclic double bond" is to be understood as meaning a double bond in which none of the two atoms linked by the double bond represent ring atoms. For the purposes of the present invention, the term "semicyclic double bond" is to be understood as meaning a double bond in which one of the two atoms linked together by the double bond represents one ring atom and the other lies outside the ring:

The formation of the diazirine can take place via this double bond. Under the action of light, nitrogen is split off, which then releases the fragrance.

The exposure can be carried out in natural light or light generated by household lamps, in particular light having a wavelength in the range of 100 nm to 1000 nm, in particular from 150 nm to 700 nm, preferably from 200 nm to 500 nm. Exposure of just a few minutes is sufficient to release the fragrances.

When Q is substituted, Q is substituted with one or more groups independently attached to Q preferably by C and / or N atoms included in the group, preferably by C atoms included in the group. When Q is bonded directly to a carbon atom contained in the group, the group is preferably a straight-chained or branched, saturated or unsaturated hydrocarbon group having up to 6 carbon atoms. When Q is substituted, Q may be substituted with an isopropenyl group.

When R ¹ and / or R ² and / or Q are substituted, the substitutions can give rise to stereocenters. Such stereocenters may include the (R), the (S), and mixtures of the (R) and (S) configurations.

In a preferred embodiment, the fragrance storage material according to the invention is derived from limonene and has the following structure (III):

Here, the perfume storage molecule may be in various configurations, as exemplified by the following formulas (IIIa) and (IIIb):

If nitrogen (N ₂ ) breaks down from these fragrance storage substances, limonene is released as a fragrance. Limonen represents in this preferred embodiment, the Duftalalken, from which the fragrance storage material according to the invention is derived. Limonene is one of the most important scents in the field of detergents and cleaners. The smell of lime is often associated with freshness, which is synonymous with cleanliness and purity.

According to the invention, the fragrance storage material can be derived from conventional fragrances which have an unsaturated CC bond, ie a double bond or a triple bond. Suitable perfume alkenes include benzyl cinnamate, cinnamyl alcohol, ambrettolide, isoeugenol acetate, hexenyl benzoate, phenylethyl cinnamate, aldehyde C11en, amyl cinnamaldehyde, dipentene, cinnamic aldehyde, undecylene, 2-hexenol, dihydromyrcenol, hexylcinnamaldehyde, acyl, propidyl, 9-decenol, citral diethyl acetal, citrusal, geranial, neral , Lyral, allyljonone, hexenyl salicylate, allylamyl glycolate, brahmanol, phenylacetate, citronellol, citronellylacetate, cyclomethylenecitronellol, cinnamylacetate, linalool, linalylformate, linalylacetate, jasmone, undecavertol, Myrcenyl acetate, bacdanol, nerolidol, allylhexanoate, allylheptanoate, ethyllinalool, epiton, gyran, neolavandate, iso-E-super, prepcyclone, polysantol, benzylideneacetone, isoeugenol, eugenol, geraniol, triplal, allylphenylacetate, 3-dodecenal, alpha-methylionone, alpha- Jonon, beta-ionone, Farenal, Sandalore, Tangerinol, Karanal, Dihydroisojasmon, Leguminal, Diantheme, Hexenylcapronate, Hexenylisovalerate, Nerylacetate, Maltol, Cyclopidene, Citronellal, Ebanol, Vetiverylacetate, Farnesol, Butylcinnamaldehyde, Roseoxide, Isopentyrate, Dupical, Vernaldehyde, Isobutylangelate, Isobutyltiglate, melonal, ambrinol, dynascon, coavone, neroloxide, nectaryl, anethole, spiroflor, cyclovertal, fleuroxen, vertosine, myrcene, isopulegol, gamma-terpinene, 4-terpinene-1-ol, ocimen, valencene, gamma-cadinen, delta Carene, alpha, cedrene, carveol, farnesene, perillaaldehyde, myrtenal, myrtenol, germacren, citronellyl formate, geranyl formate, citronellyl propionate, geranyl butyrate, geranyl propionate, carveol, propylangelate, alpha-pinene, alpha-terpinene, limonene, beta-bisabolene, humulene, terpinolene, phellandrene, trichodiene, beta-asarone, alpha-thujen, beta-methylionone, vetiverol, beta-vetiven, gamma-vetiven, methyl jasmonate, methylcinnamaldehyde, 2,6-nonadienal, Sandalmysor, Gergamal, alpha, Patchoulene, Dihydrolinalool, Clariton, Prenylisobutyrate, Terrestral, Liminal, Octalynol, Azarbre, Azuril, Bigaradoxide, Dimethyloctanone, Givescon, Isocyclocitral, Geranylethylether, Isoamylcinnamate, Dihydrolinalylacetate, Isofreshal, Floral Super, Terpinylmethylether, Greenylisobutyrate.

The compound of the general formula (I) present in the core of the capsules according to the invention can be prepared, for example, by dehydrogenation of a diaziridine of the general formula (IV).

The diazidines (IV) according to the invention can be obtained by reacting aldehydes, the general formula (Va) and (Vb), or ketones, the general formula (Vc), or.

In this case, ketones or aldehydes can be reacted by known methods, for example with ammonia and hydroxylamine sulfonic acid. The diaziridines can then be dehydrated with mild oxidants to diazirines. Suitable oxidizing agents are, for example, chromium trioxide / sulfuric acid, iodine, silver oxide or t-butyl hypochlorite.

In a preferred embodiment, a ketone is used as the starting material. The reaction then corresponds to the following reaction scheme:

The ketones (Vc) or aldehydes (Va), (Vb) according to the invention may be fragrance ketones or fragrance aldehydes. As fragrance aldehydes or fragrance ketones, it is possible to use all customary fragrance aldehydes and fragrance ketones which are typically used to produce a pleasant scent sensation. Suitable fragrance aldehydes and fragrance ketones are well known to those skilled in the art. The fragrance ketones can all comprise ketones which can impart a desired fragrance or freshness. It is also possible to use mixtures of different ketones. Insertable ketones are for example, alpha-Damascon, delta-damascone, iso-damascone, carvone, gamma-methylionone, iso-E-super, 2,4,4,7-tetramethyl-oct-6-en-3-one, benzylacetone, beta damascone, Damascenone, methyldihydrojasmonate, methylcedrylon, hedione and mixtures thereof. Suitable fragrance aldehydes may be any aldehydes which, in accordance with the fragrance ketones, impart a desired fragrance or sensation of freshness. In turn, they may be individual aldehydes or aldehyde mixtures. Suitable aldehydes include Melonal, Triplal, Ligustral, Adoxal, Lilial and so on. The fragrance aldehydes and fragrance ketones may have an aliphatic, cycloaliphatic, aromatic, ethylenically unsaturated structure or a combination of these structures. There may also be other heteroatoms or polycyclic structures. The structures may have suitable substituents such as hydroxyl or amino groups. Suitable fragrances of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate and so on. Fragrance compounds of the hydrocarbon type are, for example, terpenes such as limonene and pinene. Suitable fragrances of the ether type are, for example, benzyl ethyl ether and ambroxan. Suitable perfume alcohols are, for example, 10-undecen-1-ol, 2,6-dimethylheptan-2-ol, 2-methylbutanol, 2-methylpentanol, 2-phenoxyethanol, 2-phenylpropanol and so on. Perfumes or perfume oils can also be natural perfume mixtures, as they are accessible from plant sources. The fragrances or perfume oils can also be essential oils, such as, for example, angelica root oil, aniseed oil, arnica blossom oil and so on.

In a preferred embodiment of the invention, the perfume ketone of the general formula (Vc) is dihydrocarvone (5-isopropenyl-2-methylcyclohexanone). Dihydrocarvone has two stereogenic centers. The ketone of the general formula (Vc) is preferably selected from the group consisting of (2S, 5S) -5-isopropenyl-2-methylcyclohexanone ((-) - dihydrocarvone), (2S, 5R) -5-isopropenyl-2- methylcyclohexanone ((+) - isodihydrocarvone), (2R, 5R) - 5-isopropenyl-2-methylcyclohexanone ((+) - dihydrocarvone, (2R, 5S) -5-isopropenyl-2-methylcyclohexanone ((-) - isodihydrocarvone), or mixtures thereof In a particularly preferred embodiment, the ketone is of the general formula (Vc) (2S, 5R) -5-isopropenyl-2-methylcyclohexanone ((+) - isodihydrocarvone), or (2R, 5R) -5-isopropenyl- 2-methylcyclohexanone ((+) - dihydrocarvone), or mixtures thereof.

From (+) - dihydrocarvone and / or (+) - Isodihydrocarvon is obtained by the process according to the invention, a fragrance material of the general formula (I), which lends on irradiation with light limonene, which is one of the most important fragrances in the field of washing and Cleaning agent is. The smell of lime is often associated with freshness, which is synonymous with cleanliness and purity.

The microcapsules of the invention can be stably incorporated into conventional detergents or cleaners, in cosmetics or other fragrance-containing compositions. They allow an immediate but also a delayed release of the stored perfume alcohols and alkenes. A preferred perfume is limonene. These fragrances give usual washing or cleaning agents as well as cosmetics a particularly long lasting freshness impression. In particular, the dried, washed textile benefits from the good long-term freshness effect.

In another aspect, the present invention relates to a laundry or cleaning composition containing microcapsules as described herein.

In this case, it is possible according to the invention that the washing or cleaning agent, or other agents which comprise the microcapsules according to the invention, have different microcapsules. This means that the capsules, for example, have a different wall thickness, so that at different pressures bursting of the capsules and thus a release of the stored fragrance occurs. This allows a release of the stored fragrance over a longer period of time and thus a long-lasting fragrance experience.

Another object of the invention is a cosmetic agent comprising the microcapsules of the invention.

Yet another object of the invention is an air freshener containing the microcapsules described herein.

Finally, the present invention is also directed to a process for the long-lasting scenting of surfaces.

An object of the present invention is a washing or cleaning agent, preferably a detergent, fabric softener or washing aid, containing at least one microcapsule according to the invention. In various embodiments, microcapsules are in amounts between 0.01 and 10 wt .-%, advantageously between 0.05 and 8 wt .-%, more preferably between 0.05 and 5 wt .-%, in particular between 0.1 and 3 Wt .-%, each based on the total agent included. Suitable cleaning agents are, for example, hard surface cleaners, such as dishwashing detergents. It may also be detergents such as household cleaners, all-purpose cleaners, window cleaners, floor cleaners, etc. Preferably, it can be a product for cleaning toilet bowls and urinals, advantageously a rinsing cleaner for hanging in the toilet bowl.

According to a preferred embodiment of the invention, the washing or cleaning agent according to the invention comprises at least one surfactant selected from anionic, cationic, nonionic, zwitterionic, amphoteric surfactants or mixtures thereof.

According to a further preferred embodiment of the invention, the agent according to the invention is in solid or liquid form.

Another object of the invention is a cosmetic composition containing microcapsules according to the invention, which the microcapsules preferably in amounts between 0.01 and 10 wt .-%, advantageously between 0.05 and 8 wt .-%, more preferably between 0.05 and 5 wt .-%, in particular between 0.1 and 3 wt .-%, each based on the total agent contains.

Another object of the invention is an air care agent (for example, air freshener, room deodorant, room spray, etc.), containing microcapsules according to the invention, wherein the microcapsules preferably in amounts between 0.01 and 10 wt .-%, advantageously between 0.05 and 8 wt. %, more preferably between 0.05 and 5 wt .-%, in particular between 0.1 and 3 wt .-%, each based on the total weight of the composition, are included.

According to a further preferred embodiment of the invention, an agent according to the invention (ie washing or cleaning agent, cosmetic or air care agent) contains additional fragrances, in particular selected from the group comprising fragrances of natural or synthetic origin, preferably more volatile fragrances, higher-boiling fragrances, solid Fragrances and / or adherent fragrances.

Adherent fragrances which are advantageously used in the present invention are, for example, essential oils such as angelica root oil, aniseed oil, arnica blossom oil, basil oil, bay oil, bergamot oil, Champacablütenöl, Edeltannöl, Edeltannenzapfen oil, Elemiöl, eucalyptus oil, fennel oil, spruce oil, galbanum oil, geranium oil, gingergrass oil , Guaiac wood oil, gurdy balm oil, helichrysum oil, ho oil, ginger oil, iris 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, lavender oil, lemongrass oil, lime oil, tangerine oil, lemon balm oil , Musk Grain 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.

But also higher-boiling or solid fragrances of natural or synthetic origin can be used in the context of the present invention as adherent fragrances or fragrance mixtures, ie fragrances. These compounds include the following compounds and mixtures thereof: ambrettolide, alpha-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, 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, hydroxycinnamaldehyde, hydroxycinnamyl alcohol, indole, iron, isoeugenol, isoeugenol methyl ether , Isosafrole, Jasmon, Camphor, Karvakrol, Karvon, p-cresol methyl ether, coumarin, p-methoxyacetophenone, methyl n-amyl ketone, methyl anthranilate, p-methylacetophenone, methylchloraval, p-methylquinoline, methyl-beta-naphthyl ketone, methyl-n nonylacetaldehyde, methyl n-nonyl ketone, Musk on, beta-naphtholethylether, beta-naphtholmethylether, nerol, nitrobenzene, n-nonylaldehyde, nonyl alcohol, n-octylaldehyde, p-oxy-acetophenone, pentadecanolide, beta-phenylethylalcohol, phenylacetaldehyde-dimethylacetal, phenylacetic acid, Pulegone, safrole, salicylic acid isoamyl ester, methyl salicylate, hexyl salicylate, cyclohexyl salicylate, santalol, skatole, terpineol, thymes, thymol, gamma undecalactone, vanillin, veratrum aldehyde, cinnamaldehyde, cinnamyl alcohol, cinnamic acid, cinnamic acid ethyl ester, cinnamic acid benzyl ester. 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.

According to a further preferred embodiment, the agent according to the invention (ie washing or cleaning agent, cosmetic agent, or air care agent), at least one, preferably more, active components, in particular washing, care, cleaning active and / or cosmetic components, advantageously selected from the group comprising anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, acidifiers, alkalizing agents, anti-wrinkle compounds, antibacterial agents, antioxidants, anti redeposition agents, antistatics, builders, bleaches, bleach activators, bleach stabilizers, bleach catalysts, ironing aids, cobuilders, fragrances, Anti-shrinkage agents, electrolytes, enzymes, colorants, colorants, dyes, color transfer inhibitors, fluorescers, fungicides, germicides, odor-complexing substances, adjuvants, hydrotropes, rinse aids, complexing agents, preservatives l, corrosion inhibitors, water-miscible organic solvents, optical brighteners, perfumes, perfume carriers, pearlescers, pH adjusters, repellents and impregnating agents, polymers, swelling and anti-foaming agents, foam inhibitors, phyllosilicates, stain-resistant substances, silver protectants, silicone oils, soil release agents, UV protection substances, viscosity regulators, thickeners, discoloration inhibitors, grayness inhibitors, vitamins and / or fabric softeners. For the purposes of this invention, amounts in wt .-%, unless otherwise stated, relate to the total weight of the composition according to the invention.

The amounts of the individual ingredients in the compositions according to the invention, ie washing or cleaning agents, cosmetic or air care, are each based on the intended use of the agent in question and the skilled person is basically familiar with the orders of magnitude of the ingredients to be used or can refer to the corresponding technical literature , Depending on the intended use of the compositions according to the invention, for example, the surfactant content will be higher or lower. Usually, for example, the surfactant content of detergents can be between 10 and 50% by weight, preferably between 12.5 and 30% by weight and in particular between 15 and 25% by weight, while, for example, automatic dishwashing detergents are between 0 and 1 and 10 wt .-%, preferably between 0.5 and 7.5 wt .-% and in particular between 1 and 5 wt .-% surfactants may contain.

The compositions according to the invention (that is to say detergents or cleaners, cosmetic compositions or air-care compositions) may contain surfactants, preference being given to anionic surfactants, nonionic surfactants and mixtures thereof, but also cationic surfactants. Suitable nonionic surfactants are in particular ethoxylation and / or propoxylation of alkyl glycosides and / or linear or branched alcohols each having 12 to 18 carbon atoms in the alkyl moiety and 3 to 20, preferably 4 to 10 alkyl ether groups. Also suitable are ethoxylation and / or propoxylation products of N-alkylamines, vicinal diols, fatty acid esters and fatty acid amides which correspond to said long-chain alcohol derivatives with respect to the alkyl moiety and alkylphenols having from 5 to 12 carbon atoms in the alkyl moiety.

Suitable anionic surfactants are in particular soaps and those which contain sulfate or sulfonate groups with preferably alkali ions as cations. Useful soaps are preferably the alkali salts of the saturated or unsaturated fatty acids having 12 to 18 carbon atoms. Such fatty acids can also be used in incompletely neutralized form. Useful surfactants of the sulfate type include the salts of the sulfuric acid half-esters of fatty alcohols having 12 to 18 carbon atoms and the sulfation products of said nonionic surfactants having a low degree of ethoxylation. Suitable sulfonate-type surfactants include linear alkylbenzenesulfonates having 9 to 14 carbon atoms in the alkyl moiety, alkanesulfonates having 12 to 18 carbon atoms, and olefin sulfonates having 12 to 18 carbon atoms resulting from the reaction of corresponding monoolefins with sulfur trioxide, and alpha-sulfofatty acid esters arise in the sulfonation of fatty acid methyl or ethyl esters.

Cationic surfactants are preferably selected from esterquats and / or quaternary ammonium compounds (QAV) according to the general formula (R ^I ) (R ^II ) (R ^III ) (R ^IV ) N ⁺ X ^- in which R ^I to R ^{III represent} identical or different C _1-22 alkyl radicals, C _7-28 -Arylalkylreste or heterocyclic radicals, wherein two or in the case of an aromatic inclusion as in the pyridine even three radicals together with the Nitrogen atom form the heterocycle, for example a pyridinium or imidazolinium compound, and X ^{- represents} halide ions, sulfate ions, hydroxide ions or similar anions. QACs can be prepared by reacting tertiary amines with alkylating agents, such as, for example, methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide. The alkylation of tertiary amines with a long alkyl radical and two methyl groups succeeds particularly easily, and the quaternization of tertiary amines with two long radicals and one methyl group can be carried out with the aid of methyl chloride under mild conditions. Amines which have three long alkyl radicals or hydroxy-substituted alkyl radicals are less reactive and are quaternized, for example, with dimethyl sulfate. Examples of suitable QACs are benzalkonium chloride (N alkyl-N, N-dimethylbenzylammonium chloride), benzalkone B (m, p-dichlorobenzyldimethyl-C ₁₂ -alkylammonium chloride, benzoxonium chloride (benzyldodecyl-bis (2-hydroxyethyl) -ammonium chloride), Cetrimonium bromide (N-hexadecyl-N, N-trimethyl-ammonium bromide), Benzetonium chloride (N, N-dimethyl-N [2- [2- [p- (1,1,3,3-tetramethyl-butyl) -phenoxy] -ethoxy] -ethyl ] benzyl-ammonium chloride), dialkyldimethylammonium chlorides such as di-n-decyldimethylammonium chloride, didecyldimethylammonium bromide, dioctyldimethylammonium chloride, 1-cetylpyridinium chloride and thiazoline iodide and mixtures thereof Preferred QACs are the benzalkonium chlorides having C ₈ -C ₂₂ -alkyl radicals , in particular C ₁₂ -C ₁₄ -alkyl-benzyl-dimethylammonium chloride.

Preferred ester quats are methyl N- (2-hydroxyethyl) -N, N-di (tallowacyl oxyethyl) ammonium methosulfate, bis (palmitoyl) ethyl hydroxyethyl methyl ammonium methosulfate or methyl N, N bis (acyloxyethyl) -N- (2-hydroxyethyl) ammonium methosulfate. Commercial examples are sold by Stepan under the trade name Stepantex® ^® methylhydroxyalkyldialkoyloxyalkylammonium or those known under the trade name Dehyquart® products from BASF SE or the known under the name Rewoquat products by manufacturer Evonik.

Surfactants are present in the compositions according to the invention as detergents or cleaners, cosmetic compositions or air care agents, in proportions of preferably from 5% by weight to 50% by weight, in particular from 8% by weight to 30% by weight. In particular, in laundry aftertreatment agents are preferably up to 30 wt .-%, in particular 5 wt .-% to 15 wt .-% of surfactants, among these preferably at least partially cationic surfactants used.

An agent according to the invention, in particular washing or cleaning agent, preferably contains at least one water-soluble and / or water-insoluble, organic and / or inorganic builder. The water-soluble organic builder substances include polycarboxylic acids, in particular citric acid and sugar acids, monomeric and polymeric aminopolycarboxylic acids, in particular methylglycinediacetic acid, nitrilotriacetic acid and ethylenediaminetetraacetic acid and polyaspartic acid, polyphosphonic acids, in particular aminotris (methylenephosphonic acid), ethylenediaminetetrakis (methylenephosphonic acid) and 1-hydroxyethane-1,1-diphosphonic acid, polymeric hydroxy compounds such as dextrin and polymeric (poly) carboxylic acids, polymeric acrylic acids, methacrylic acids, maleic acids and copolymers thereof, which may also contain polymerized small amounts of polymerizable substances without carboxylic acid functionality. Suitable, although less preferred, compounds of this class are copolymers of acrylic or methacrylic acid with vinyl ethers, such as vinylmethyl ethers, vinyl esters, ethylene, propylene and styrene, in which the acid content is at least 50% by weight. The organic builder substances can be used, in particular for the preparation of liquid agents, in the form of aqueous solutions, preferably in the form of 30 to 50 percent by weight aqueous solutions. All of the acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali metal salts.

Organic builders may, if desired, be included in amounts of up to 40% by weight, more preferably up to 25% by weight, and preferably from 1% to 8% by weight. Quantities close to the stated upper limit are preferably used in paste-form or liquid, in particular water-containing, agents according to the invention. Laundry washes according to the invention, such as, for example, softeners, may optionally also be free of organic builder.

Suitable water-soluble inorganic builder materials are, in particular, alkali metal silicates and polyphosphates, preferably sodium triphosphate. As water-insoluble, water-dispersible inorganic builder materials, in particular crystalline or amorphous alkali metal aluminosilicates, if desired, in amounts of up to 50 wt .-%, preferably not more than 40 wt .-% and in liquid agents, in particular from 1 wt .-% to 5 wt. -%, are used. Among these, preferred are the detergent grade crystalline sodium aluminosilicates, especially zeolite A, P and optionally X. Amounts near the above upper limit are preferably used in solid, particulate agents. Suitable aluminosilicates have In particular, no particles with a particle size greater than 30 microns and preferably consist of at least 80 wt .-% of particles having a size less than 10 microns.

Suitable substitutes or partial substitutes for the said aluminosilicate are crystalline alkali silicates which may be present alone or in a mixture with amorphous silicates. The alkali metal silicates useful as builders in the compositions according to the invention preferably have a molar ratio of alkali metal oxide to SiO ₂ below 0.95, in particular from 1: 1.1 to 1:12, and may be present in amorphous or crystalline form. Preferred alkali metal silicates are the sodium silicates, in particular the amorphous sodium silicates, with a molar ratio of Na ₂ O: SiO ₂ of 1: 2 to 1: 2.8. The crystalline silicates which may be present alone or in admixture with amorphous silicates, are crystalline layer silicates with the general formula Na ₂ Si _x O 2 _{+ x 1} · yH ₂ O are used in which x, the so-called module, a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4. Preferred crystalline phyllosilicates are those in which x in the abovementioned general formula assumes the values 2 or 3. In particular, both beta- and delta-sodium disilicates (Na ₂ Si ₂ O ₅ .yH ₂ O) are preferred. Also prepared from amorphous alkali silicates, practically anhydrous crystalline alkali silicates of the abovementioned general formula in which x is a number from 1.9 to 2.1, can be used in inventive compositions. In a further preferred embodiment of the composition according to the invention, a crystalline sodium layer silicate with a modulus of 2 to 3 is used, as can be prepared from sand and soda. Crystalline sodium silicates with a modulus in the range from 1.9 to 3.5 are used in a further preferred embodiment of compositions according to the invention. If alkali metal aluminosilicate, in particular zeolite, is also present as an additional builder substance, the weight ratio of aluminosilicate to silicate, based in each case on anhydrous active substances, is preferably 1:10 to 10: 1. In agents containing both amorphous and crystalline alkali metal silicates, the weight ratio of amorphous alkali metal silicate to crystalline alkali metal silicate is preferably 1: 2 to 2: 1 and especially 1: 1 to 2: 1.

Builders are, if desired, in the inventive compositions preferably in amounts of up to 60 wt .-%, in particular from 5 wt .-% to 40 wt .-%, included. Laundry aftertreatment agents according to the invention, such as fabric softeners, are preferably free of inorganic builder.

Suitable peroxygen compounds are, in particular, organic peracids or peracid salts of organic acids, such as phthalimidopercaproic acid, perbenzoic acid or salts of diperdodecanedioic acid, hydrogen peroxide and inorganic salts which release hydrogen peroxide under the conditions of use, such as perborate, percarbonate and / or persilicate. If solid peroxygen compounds are to be used, they can be used in the form of powders or granules, which can also be enveloped in a manner known in principle. Particular preference is given to using alkali percarbonate, alkali perborate monohydrate or, in particular, in liquid media, hydrogen peroxide in the form of aqueous solutions which contain 3% by weight to 10% by weight of hydrogen peroxide, if appropriate. If an agent according to the invention contains bleaches, such as preferably peroxygen compounds, they are present in amounts of preferably up to 50% by weight, in particular from 5% by weight to 30% by weight. The addition of small amounts of known bleach stabilizers such as phosphonates, bristles or metaborates and metasilicates and magnesium salts such as magnesium sulfate may be useful.

As bleach activators, it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups. Preference is given to polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate, 2,5- Diacetoxy-2,5-dihydrofuran and enol esters; and acetylated sorbitol and mannitol or mixtures thereof (SORMAN), acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetyl fructose, tetraacetylxylose and octaacetyl lactose and acetylated, optionally N-alkylated glucamine and gluconolactone, and / or N -acylated lactams, for example N-benzoyl-caprolactam. Hydrophilic substituted acyl acetals and acyl lactams are also preferably used. Combinations of conventional bleach activators can also be used. Such bleach activators may be present in the customary amount range, preferably in amounts of from 1% by weight to 10% by weight, in particular from 2% by weight to 8% by weight, based on the total agent.

In addition to the conventional bleach activators listed above or in their place, sulfone imines and / or bleach-enhancing transition metal salts or transition metal complexes can also be present as so-called bleach catalysts.

Suitable enzymes which can be used in the compositions are those from the class of proteases, cutinases, amylases, pullulanases, hemicellulases, cellulases, lipases, oxidases and peroxidases and mixtures thereof. Particularly suitable are from fungi or bacteria, such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus, Humicola lanuginosa, Humicola insolens, Pseudomonas pseudoalcaligenes or Pseudomonas cepacia derived enzymatic agents. The optionally used enzymes may be adsorbed to carriers and / or embedded in encapsulants to protect against premature inactivation. If desired, they are preferably present in the compositions according to the invention in amounts of not more than 5% by weight, in particular from 0.2% by weight to 2% by weight.

The agents may optionally contain, for example, derivatives of diaminostilbenedisulfonic acid or their alkali metal salts as optical brighteners. Suitable salts are, for example, salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulphonic acid or compounds of similar construction which, instead of the morpholino Group carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group.

Suitable foam inhibitors include, for example, organopolysiloxanes and mixtures thereof with microfine, optionally silanized silica and paraffin waxes and mixtures thereof with silanated silicic acid or bis-fatty acid alkylenediamides. It is also advantageous to use mixtures of various foam inhibitors, for example those of silicones, paraffins or waxes. The foam inhibitors, in particular silicone and / or paraffin-containing foam inhibitors, are preferably bound to a granular, water-soluble or dispersible carrier substance. In particular, mixtures of paraffin waxes and bistearylethylenediamides are preferred.

In addition, the compositions may also contain components which positively influence the oil and Fettauswaschbarkeit from textiles, so-called soil release agents. This effect becomes particularly evident when a textile is soiled which has previously been washed several times with an agent according to the invention containing this oil and fat-dissolving component. The preferred oil and fat dissolving components include, for example, nonionic cellulose ethers such as methylcellulose and methylhydroxypropylcellulose having a proportion of methoxyl groups of 15 to 30 wt .-% and hydroxypropoxyl groups of 1 to 15 wt .-%, each based on the nonionic cellulose ethers, and the known from the prior art polymers of phthalic acid and / or terephthalic acid or derivatives thereof with monomeric and / or polymeric diols, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionic modified derivatives thereof ,

The compositions may also color transfer inhibitors, preferably in amounts of from 0.1 wt .-% to 2 wt .-%, in particular 0.1 wt .-% to 1 wt .-%, containing in a preferred embodiment of the invention polymers Vinylpyrrolidone, vinylimidazole, vinylpyridine N-oxide or copolymers of these are.

Graying inhibitors have the task of keeping suspended from the textile fiber dirt suspended in the fleet. Water-soluble colloids of mostly organic nature are suitable for this purpose, for example starch, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or of cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Also, water-soluble polyamides containing acidic groups are suitable for this purpose. Furthermore, other than the above-mentioned starch derivatives can be used, for example aldehyde starches. Preference is given to using cellulose ethers, such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose and mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof, for example in amounts of from 0.1 to 5% by weight, based on the compositions.

Among the agents according to the invention, in particular when they are in liquid or pasty form, usable organic solvents include alcohols having 1 to 4 carbon atoms, in particular methanol, ethanol, isopropanol and tert-butanol, diols having 2 to 4 carbon atoms, in particular ethylene glycol and Propylene glycol, and mixtures thereof and derived from the above classes of compounds ether. Such water-miscible solvents are preferably present in the compositions according to the invention in amounts of not more than 30% by weight, in particular from 6% by weight to 20% by weight.

In order to establish a desired pH, which does not result from the mixture of the other components, the compositions according to the invention can contain system- and environmentally compatible acids, in particular citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and / or adipic acid. but also mineral acids, in particular sulfuric acid, or bases, in particular ammonium or alkali metal hydroxides. Such pH regulators are optionally in the inventive compositions preferably not more than 20 wt .-%, in particular from 1.2 wt .-% to 17 wt .-%, included.

The preparation of solid compositions according to the invention (i.e., especially detergents or cleaners) presents no difficulties and can in principle be carried out by known methods, for example by spray-drying or granulation, with optional peroxygen compound and optional bleach catalyst optionally added later. For the preparation of inventive compositions having an increased bulk density, in particular in the range from 650 g / L to 950 g / L, a process comprising an extrusion step is preferred. The preparation of liquid inventive means also presents no difficulties and can also be done in a known manner.

The preparation of the compounds of the formula (I) according to the invention is described in the example part by way of example with reference to the preparation of a citronellol and geraniol-containing fragrance storage substance. The other compounds of the general formula (I) and in particular the compounds of the formulas (11) to (XIII) can also be prepared via this basic synthesis route.

According to a preferred embodiment, the teaching according to the invention can be used to significantly reduce the perfume fraction in washing, cleaning and personal care products. This makes it possible to offer perfumed products even for those particularly sensitive consumers who can not use normally perfumed products due to special intolerances and irritations, or only to a limited extent.

In various embodiments of the present invention, the detergents or cleaners are in liquid or solid form.

• – Aniontenside, wie vorzugsweise Alkylbenzolsulfonat, Alkylsulfat, beispielsweise in Mengen von vorzugsweise 5 bis 30 Gew.-%
• – Nichtionische Tenside, wie vorzugsweise Fettalkoholpolyglycolether, Alkylpolyglucosid, Fettsäureglucamid beispielsweise in Mengen von vorzugsweise 0,5 bis 15 Gew.-%
• – Gerüststoffe, wie beispielsweise Zeolith, Polycarboxylat, Natriumcitrat, in Mengen von beispielsweise 0 bis 70 Gew.-%, vorteilhafterweise 5 bis 60 Gew.-%, vorzugsweise 10 bis 55 Gew.-%, insbesondere 15 bis 40 Gew.-%,
• – Alkalien, wie beispielsweise Natriumcarbonat, in Mengen von beispielsweise 0 bis 35 Gew.-% vorteilhafterweise 1 bis 30 Gew.-%, vorzugsweise 2 bis 25 Gew.-%, insbesondere 5 bis 20 Gew.-%,
• – Bleichmittel, wie beispielsweise Natriumperborat, Natriumpercarbonat, in Mengen von beispielsweise 0 bis 30 Gew.-% vorteilhafterweise 5 bis 25 Gew.-%, vorzugsweise 10 bis 20 Gew.-%,
• – Korrosionsinhibitoren, beispielsweise Natriumsilicat, in Mengen von beispielsweise 0 bis 10 Gew.-%, vorteilhafterweise 1 bis 6 Gew.-%, vorzugsweise 2 bis 5 Gew.-%, insbesondere 3 bis 4 Gew.-%,
• – Stabilisatoren, beispielsweise Phosphonate, vorteilhafterweise 0 bis 1 Gew.-%,
• – Schauminhibitor, beispielsweise Seife, Siliconöle, Paraffine vorteilhafterweise 0 bis 4 Gew.-%, vorzugsweise 0,1 bis 3 Gew.-%, insbesondere 0,2 bis 1 Gew.-%,
• – Enzyme, beispielsweise Proteasen, Amylasen, Cellulasen, Lipasen, vorteilhafterweise 0 bis 2 Gew.-%, vorzugsweise 0,2 bis 1 Gew.-%, insbesondere 0,3 bis 0,8 Gew.-%, Vergrauungsinhibitor, beispielsweise Carboxymethylcellulose, vorteilhafterweise 0 bis 1 Gew.-%,
• – Verfärbungsinhibitor, beispielsweise Polyvinylpyrrolidon-Derivate, vorzugsweise 0 bis 2 Gew.-%,
• – Stellmittel, beispielsweise Natriumsulfat, vorteilhafterweise 0 bis 20 Gew.-%, Optische Aufheller, beispielsweise Stilben-Derivat, Biphenyl-Derivat, vorteilhafterweise 0 bis 0,4 Gew.-%, insbesondere 0,1 bis 0,3 Gew.-%,
• – ggf. weitere Duftstoffe
• – ggf. Wasser
• – ggf. Seife
• – ggf. Bleichaktivatoren
• – ggf. Cellulosederivate
• – ggf. Schmutzabweiser,

Gew.-% jeweils bezogen auf das gesamte Mittel.In addition to the compound according to the invention, a preferred solid, in particular powdered, detergent according to the invention may contain, in particular, components which are selected, for example, from the following:

• Anionic surfactants, such as preferably alkylbenzenesulfonate, alkylsulfate, for example in amounts of preferably 5 to 30% by weight
• Nonionic surfactants, such as, preferably, fatty alcohol polyglycol ethers, alkyl polyglucoside, fatty acid glucamide, for example, in amounts of preferably from 0.5 to 15% by weight
• Builders, such as zeolite, polycarboxylate, sodium citrate, in amounts of, for example, from 0 to 70% by weight, advantageously from 5 to 60% by weight, preferably from 10 to 55% by weight, in particular from 15 to 40% by weight,
• Alkalis, for example sodium carbonate, in amounts of, for example, from 0 to 35% by weight, advantageously from 1 to 30% by weight, preferably from 2 to 25% by weight, in particular from 5 to 20% by weight,
• Bleaching agents, for example sodium perborate, sodium percarbonate, in amounts of, for example, from 0 to 30% by weight, advantageously from 5 to 25% by weight, preferably from 10 to 20% by weight,
• Corrosion inhibitors, for example sodium silicate, in amounts of, for example, from 0 to 10% by weight, advantageously from 1 to 6% by weight, preferably from 2 to 5% by weight, in particular from 3 to 4% by weight,
• Stabilizers, for example phosphonates, advantageously 0 to 1% by weight,
• Foam inhibitor, for example soap, silicone oils, paraffins, advantageously 0 to 4% by weight, preferably 0.1 to 3% by weight, in particular 0.2 to 1% by weight,
• Enzymes, for example proteases, amylases, cellulases, lipases, advantageously 0 to 2% by weight, preferably 0.2 to 1% by weight, in particular 0.3 to 0.8% by weight, of grayness inhibitor, for example carboxymethylcellulose, advantageously 0 to 1% by weight,
• Discoloration inhibitor, for example polyvinylpyrrolidone derivatives, preferably 0 to 2% by weight,
• - Adjusting agent, for example sodium sulfate, advantageously 0 to 20 wt .-%, optical brightener, for example stilbene derivative, biphenyl derivative, advantageously 0 to 0.4 wt .-%, in particular 0.1 to 0.3 wt .-% .
• - If necessary, other fragrances
• - If necessary water
• - if necessary, soap
• - optionally bleach activators
• - If necessary, cellulose derivatives
• - if necessary dirt deflector,

% By weight, based in each case on the total agent.

In another preferred embodiment of the invention, the agent is in liquid form, preferably in gel form. Preferred liquid washing or cleaning agents and cosmetics have water contents of, for example, 10 to 95% by weight, preferably 20 to 80% by weight and in particular 30 to 70% by weight, based on the total agent. In the case of liquid concentrates, the water content may also be particularly low, for example <30% by weight, preferably <20% by weight, in particular <15% by weight, in each case based on the total agent. The liquid agents may also contain non-aqueous solvents.

• – Aniontenside, wie vorzugsweise Alkylbenzolsulfonat, Alkylsulfat, beispielsweise in Mengen von vorzugsweise 5 bis 40 Gew.-%
• – Nichtionische Tenside, wie vorzugsweise Fettalkoholpolyglycolether, Alkylpolyglucosid, Fettsäureglucamid beispielsweise in Mengen von vorzugsweise 0,5 bis 25 Gew.-%
• – Gerüststoffe, wie beispielsweise Zeolith, Polycarboxylat, Natriumcitrat, vorteilhafterweise 0 bis 15 Gew.-%, vorzugsweise 0,01 bis 10 Gew.-%, insbesondere 0,1 bis 5 Gew.-%,
• – Schauminhibitor, beispielsweise Seife, Siliconöle, Paraffine, in Mengen von beispielsweise 0 bis 10 Gew.-%, vorteilhafterweise 0,1 bis 4 Gew.-%, vorzugsweise 0,2 bis 2 Gew.-%, insbesondere 1 bis 3 Gew.-%,
• – Enzyme, beispielsweise Proteasen, Amylasen, Cellulasen, Lipasen, in Mengen von beispielsweise 0 bis 3 Gew.-%, vorteilhafterweise 0,1 bis 2 Gew.-%, vorzugsweise 0,2 bis 1 Gew.-%, insbesondere 0,3 bis 0,8 Gew.-%,
• – Optische Aufheller, beispielsweise Stilben-Derivat, Biphenyl-Derivat, in Mengen von beispielsweise 0 bis 1 Gew.-%, vorteilhafterweise 0,1 bis 0,3 Gew.-%, insbesondere 0,1 bis 0,4 Gew.-%,
• – ggf. weitere Duftstoffe
• – ggf. Stabilisatoren,
• – Wasser
• – ggf. Seife, in Mengen von beispielsweise 0 bis 25 Gew.-%, vorteilhafterweise 1 bis 20 Gew.-%, vorzugsweise 2 bis 15 Gew.-%, insbesondere 5 bis 10 Gew.-%,
• – ggf. Lösungsmittel (vorzugsweise Alkohole), vorteilhafterweise 0 bis 25 Gew.-%, vorzugsweise 1 bis 20 Gew.-%, insbesondere 2 bis 15 Gew.-%,

Gew.-% jeweils bezogen auf das gesamte Mittel.In addition to the compound according to the invention, a preferred liquid, in particular gel detergent according to the invention may contain, in particular, components which are selected, for example, from the following:

• Anionic surfactants, such as preferably alkylbenzenesulfonate, alkylsulfate, for example in amounts of preferably from 5 to 40% by weight
• Nonionic surfactants, such as preferably fatty alcohol polyglycol ethers, alkyl polyglucoside, fatty acid glucamide, for example, in amounts of preferably from 0.5 to 25% by weight
• Builders, such as, for example, zeolite, polycarboxylate, sodium citrate, advantageously from 0 to 15% by weight, preferably from 0.01 to 10% by weight, in particular from 0.1 to 5% by weight,
• Foam inhibitor, for example soap, silicone oils, paraffins, in amounts of, for example, from 0 to 10% by weight, advantageously from 0.1 to 4% by weight, preferably from 0.2 to 2% by weight, in particular from 1 to 3% by weight. -%
• - Enzymes, for example, proteases, amylases, cellulases, lipases, in amounts of, for example, 0 to 3 wt .-%, advantageously 0.1 to 2 wt .-%, preferably 0.2 to 1 wt .-%, in particular 0.3 up to 0.8% by weight,
• Optical brighteners, for example stilbene derivative, biphenyl derivative, in amounts of, for example, from 0 to 1% by weight, advantageously from 0.1 to 0.3% by weight, in particular from 0.1 to 0.4% by weight .
• - If necessary, other fragrances
• - stabilizers if necessary,
• - Water
• Optionally soap, in amounts of, for example, from 0 to 25% by weight, advantageously from 1 to 20% by weight, preferably from 2 to 15% by weight, in particular from 5 to 10% by weight,
• Optionally solvent (preferably alcohols), advantageously 0 to 25 wt .-%, preferably 1 to 20 wt .-%, in particular 2 to 15 wt .-%,

% By weight, based in each case on the total agent.

• – Kationische Tenside, wie insbesondere Esterquats, beispielsweise in Mengen von 5 bis 30 Gew.-%,
• – Cotenside, wie beispielsweise Glycerolmonostearat, Stearinsäure, Fettalkohole, Fettalkoholethoxylate, beispielsweise in Mengen von 0 bis 5 Gew.-%, vorzugsweise 0,1 bis 4 Gew.-%,
• – Emulgatoren, wie beispielsweise Fettaminethoxylate, beispielsweise in Mengen von 0 bis 4 Gew.-%, vorzugsweise 0,1 bis 3 Gew.-%,
• – ggf. weitere Duftstoffe
• – Farbstoffe, vorzugsweise im ppm-Bereich (Gew.-ppm)
• – Stabilisatoren, vorzugsweise im ppm-Bereich (Gew.-ppm)
• – Lösemittel, wie beispielsweise Wasser, in Mengen von vorzugsweise 60 bis 90 Gew.-%

Gew.-% jeweils bezogen auf das gesamte Mittel.In addition to the ketone according to the invention, a preferred liquid fabric softener according to the invention may in particular also contain components which are selected from the following:

• Cationic surfactants, in particular esterquats, for example in amounts of from 5 to 30% by weight,
• Cosurfactants, for example glycerol monostearate, stearic acid, fatty alcohols, fatty alcohol ethoxylates, for example in amounts of from 0 to 5% by weight, preferably from 0.1 to 4% by weight,
• Emulsifiers, for example fatty amine ethoxylates, for example in amounts of from 0 to 4% by weight, preferably from 0.1 to 3% by weight,
• - If necessary, other fragrances
• Dyes, preferably in the ppm range (ppm by weight)
• Stabilizers, preferably in the ppm range (ppm by weight)
• Solvents, such as water, in amounts of preferably 60 to 90% by weight

% By weight, based in each case on the total agent.

Another object of the invention is a method for scenting surfaces, wherein a compound according to the invention of formula (I) or a detergent or cleaner according to the invention, cosmetic or air care agent is applied to the surface to be scented (for example, textile, dishes, floor) and the compound or agent is then exposed to light.

All embodiments described herein in connection with the compounds of formula (I) are equally applicable to the means, methods and uses described, and vice versa. Other embodiments can be found in the following examples, but the invention is not limited to these.

In the context of the present invention, all previously described and also preferred embodiments or the features described in each case can also be combined individually. Moreover, in the context of the present invention, the term "comprising" also covers the alternative in which the products / methods / uses, with respect to which the term "comprising" is used, consist exclusively of the elements described below.

Embodiment:

Exposure of (4R, 7R) -4-methyl-7- (prop-1-en-2-yl) -1,2-diazaspiro [2.5] oct-1-ene

washing conditions

In a Softronic W 1734 washing machine from Miele, cotton terry goods having a size of 30 cm × 30 cm and a total weight of 3.5 kg were rinsed in a rinse at a temperature of 20 ° C. The spin number was 1200 rpm; Water with a water hardness of 12 ° dH was used. After washing you dried at 20 ° C and 50% to 60% relative humidity.

In the rinse, a fabric conditioner was added. This fabric softener contained microcapsules according to the invention. The amount of fabric softener was 35 ml.

Following the drying process, an olfactory evaluation was performed by a panel of smokers. The following values are mean values from 6 evaluations (n = 6). This means Product: conventional fabric softener containing perfume microcapsules of the invention or unencapsulated perfume FW: wet laundry TW1 / TW7 dark: dry laundry stored after 1 day / dry laundry after 7 days in the dark and evaluated TW1 / TW7 bright: dry laundry after 1 day / dry laundry after 7 days stored in daylight and evaluated in daylight DOS. capsules DOS. (%) Intensity (1-10) product FW TW1 dark TW1 light TW7 dark TW7 light 36 Capsules 1, with 1% diazirine and perfume A 0.20% 4 4 3 3 2 3 36 Capsules 2, with 5% diazirine and perfume A 0.20% 5 3 4 4 2 3 36 Capsules 3, with 10% diazirine and perfume A 0.20% 5 4 4 5 3 4 36 Capsules 4, with 15% diazirine and perfume A 0.20% 5 4 3 5 2 4 36 Capsules 5, with 20% diazirine and perfume A 0.20% 5 4 3 6 3 4 36 Capsules 6, with 25% diazirine and perfume A 0.20% 6 5 4 6 3 6 36 Capsules 7, with 30% diazirine and perfume A 0.20% 6 5 4 7 3 6 36 Capsules 8, with 20% diazirine and perfume B 0.20% 5 4 4 6 2 5 36 Capsules 9, with 25% diazirine and perfume B 0.20% 5 5 3 6 3 5 36 Capsules 10, with 30% diazirine and perfume B 0.20% 6 5 3 6 3 6 36 Capsules 11 *, Perfume A 0.20% 5 4 4 3 3 36 Capsules 12 *, Perfume B 0.20% 5 4 4 3 3 2 * Comparative Examples

Column 1 ("Dos.") Indicates the amount of fabric softener in grams. Column 2 describes the added capsules; in column 3 ("Dos. (%)"), the proportions of capsules according to the invention are given in% by weight, based on the total weight of the composition.

Perfume A and Perfume B are different perfume compositions commonly found in fabric softeners or fabric cleaners. The choice of perfume composition has no influence on the olfactory evaluation.

In the last two embodiments with capsule 11 and capsule 12 no erfindungsmäße composition was included. Here, the olfactory impression was significantly worse than with the capsules according to the invention.

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• US 2003/0125222 Al [0019]
• DE 102008051799 A1 [0019]
• WO 01/49817 [0019]
• WO 2010/118959 A1 [0035]

Cited non-patent literature

• ISO 787-5 [0023]
• ISO 787-5 [0024]
• DIN ISO 9277: 2003-05 [0026]

Claims (12)

Microcapsules comprising a core and a shell, wherein the core comprises at least one compound of general formula (I)

wherein R ¹ and / or R ² each independently of one another in the alpha position to C have an abstractable hydrogen atom. Microcapsules according to claim 1, characterized in that the shell comprises a wall material selected from melamine-urea-formaldehyde or melamine-formaldehyde or urea-formaldehyde or polyacrylate copolymer. Microcapsules according to claim 1 or 2, characterized in that they have a full-area or partial surface coating with a cationic polymer. Microcapsules according to one of claims 1 to 3, characterized in that the core, the compound of general formula (I) in an amount of 0.001 to 50 wt .-%, in particular from 0.05 to 45 wt .-%, especially of 0 , 1 to 40 wt .-%, particularly preferably from 5 to 30 wt .-%, based on the total weight of the core. Microcapsules according to one of claims 1 to 4, characterized in that R ¹ and R ^{2 are} each independently selected from a linear, aliphatic, olefinic or open-chain organic radical having 2 to 20 carbon atoms, in particular 2 to 12 carbon atoms, and 0 to 10 Heteroatoms selected from N, O, S and Si; or a branched or cyclic organic radical having 3 to 20 carbon atoms, especially 3 to 12 carbon atoms, and 0 to 10 heteroatoms selected from N, O, S and Si; or an aromatic or heteroaromatic organic radical having 4 to 20 carbon atoms, especially 4 to 12 carbon atoms, and 0 to 10 heteroatoms selected from N, O, S and Si; or R ¹ and R ² are connected to each other with ring closure via a bridge Q and form a bridging part -R ¹ -QR ² -, wherein R ¹ and R ² each independently represent a radical having 1 to 5 carbon atoms; and Q is a bridging substituted or unsubstituted group having 1 or 2 to 20 carbon atoms, especially 2 to 12 carbon atoms, and 0 to 10 heteroatoms selected from N, O, S and Si. Microcapsules according to one of claims 1 to 5, characterized in that the bridging part -R ¹ -QR ² - is a hydrocarbon. Microcapsules according to any one of claims 1 to 6, characterized in that R ¹ or R ² or the bridging part -R ¹ -QR ² - is a radical derived from a perfume alkane and the perfume alkane is in particular limonene. Detergents or cleaning compositions containing microcapsules according to one of claims 1 to 7. Washing or cleaning agent according to claim 8, characterized in that a. the microcapsules in amounts between 0.01 and 10 wt .-%, advantageously between 0.05 and 8 wt .-%, more preferably between 0.05 and 5 wt .-%, in particular between 0.1 and 3 wt. %, in each case based on the total agent, and / or b. the agent contains at least one surfactant selected from the group consisting of anionic, cationic, nonionic, zwitterionic, amphoteric surfactants and mixtures thereof, and / or c. it is in liquid or solid form. An air-care composition containing at least one compound according to any one of claims 1 to 7, wherein the agent contains the compound in particular in amounts between 0.01 and 10 wt .-%, advantageously between 0.05 and 8 wt .-%, more preferably between 0, 05 and 5 wt .-%, in particular between 0.1 and 3 wt .-%, each based on the total agent contains. Cosmetic composition containing at least one compound according to any one of claims 1 to 7, wherein the agent in particular the compound in amounts between 0.01 and 10 wt .-%, advantageously between 0.05 and 8 wt .-%, more preferably between 0 , 05 and 5 wt .-%, in particular between 0.1 and 3 wt .-%, each based on the total agent contains. Process for the scenting of surfaces, characterized in that microcapsules according to one of claims 1 to 7 are applied to the surface to be scented and the microcapsules are subsequently exposed to light.