EP4004170A1

EP4004170A1 - Shaped products that contain an active substance and production method thereof

Info

Publication number: EP4004170A1
Application number: EP20725134.9A
Authority: EP
Inventors: Andre Haetzelt; Boray TORUN; Peter Schmiedel; Andreas Bauer
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 2019-07-23
Filing date: 2020-05-06
Publication date: 2022-06-01
Anticipated expiration: 2040-05-06
Also published as: DE102019210899A1; WO2021013394A1; EP4004170B1

Abstract

The invention relates to shaped products, comprising a) a first gel-type phase and b) at least a second gel-type phase that is different from the first gel-type phase and is at least partially surrounded by the first gel-type phase, the second gel-type phase containing active substance particles having a maximum diameter of between 1 and 200 µm. The invention also relates to the use thereof and to a method for producing same.

Description

Moldings containing active substances and processes for their production

The present invention relates to active substance-containing moldings and a method for producing active substance-containing moldings.

When using detergents and cleaning agents, the consumer not only pursues the goal of washing and cleaning the objects to be treated, but also wishes to care for these objects to be treated, such as textiles, at the same time. A particularly relevant maintenance procedure is the scenting of the objects to be treated. For this reason in particular, most commercially available detergents and cleaning agents contain fragrances.

However, many of the care products used are volatile or chemically or physically unstable in a detergent or cleaning agent formulation. For this reason, when using conventional detergents or cleaning agents, only a small proportion of the care agent used remains on the treated object after use, in particular after washing. As a result, for example, the treated object, such as laundry in particular, often emits only a weak scent, which then becomes weaker and weaker after a short time. The pleasant feeling of freshness of the treated object disappears after a short time.

Fragrances, as a group of particularly relevant care products, are either used as an integral component of a detergent or cleaning agent, or are dosed into the washing drum in a separate form at the start of a wash cycle in the form of fragrance lozenges. In this way, the consumer can control the scenting of the laundry to be washed through individual dosing.

Such fragrance lozenges are usually produced from melt dispersions, the main component of which is a water-soluble or water-dispersible carrier material with a suitable melting temperature. In addition to the fragrance components and optionally other auxiliaries such as detergent substances, solids can also be added to such melt dispersions in order, for example, to influence the viscosity of the dispersion to be processed. The production of the pastilles requires the uninterrupted provision of such a melt dispersion.

In the prior art, manufacturing processes are common in which a melt consisting of the carrier material and optionally solids and other constituents is first produced and the melt obtained in this way is mixed directly with the fragrance component and optionally other constituents such as dyes. The finished melt dispersion is then shaped into lozenges. At Such a production process, which is described, for example, in European patent EP 2 496 679 B1, must, however, have the aforementioned disadvantages.

Customary carrier materials for the scented lozenges described in the prior art are inorganic salts or synthetic polymers, with polyethylene glycol being particularly important. From a sustainability point of view, the use of large quantities of carrier material, especially synthetic polymers, is in need of improvement. There is accordingly a need for alternative carrier systems and carrier materials for scented lozenges.

Such alternative carrier systems should not only be suitable for the packaging of fragrances such as perfume oils or fragrance capsules or alternative care or auxiliary substances, but should also be processable in a variable process which, in addition to uncomplicated process management, offers the possibility of a quick product change. In the context of the usual process management, as well as with a product changeover, only the smallest quantities of goods that are not suitable for sale and not in accordance with the specification (waste material) should arise.

The above objects were achieved by means of specific multiphase gel-shaped bodies. A first subject of this application is a molded body comprising

a) a first gel phase

b) at least one second gel-like phase which is different from the first gel-like phase and which is at least partially enclosed by the first gel-like phase, the second gel-like phase containing active substance particles with a maximum diameter between 1 and 200 μm.

The weight of the molding can vary and is preferably between 200 mg and 35 g, preferably between 1 and 20 g and in particular between 2 and 10 g.

It is also preferred that the shaped body has a spatial extent of between 2 to 100 mm, in particular 5 to 70 mm and particularly preferably 10 to 50 mm, in any spatial direction. The ratio of the longest diameter determined in any spatial direction to the shortest diameter determined in any spatial direction is preferably between 3: 1 and 1: 1, preferably between 2.5: 1 and 1.2: 1 and in particular between 2.2: 1 and 1, 4: 1.

Even if the three-dimensional shape of the molded bodies can be varied in further areas, a cubic or spherical three-dimensional shape is preferred for reasons of manufacturability and product optics.

Particularly preferred molded bodies comprise a translucent and / or transparent, particularly preferably a transparent, first gel-like phase. Has a gel phase in the spectral Range between 380 nm and 780 nm has a residual light power (transmission) related to the reference measurement of at least 20%, it is considered transparent within the meaning of the invention.

The transparency of the first gel phase can be determined using various methods. The nephelometric turbidity unit (nephelometric turbidity value; NTU) is often used as a measured value for transparency. It is a unit used e.g. in water treatment for turbidity measurements e.g. in liquids. It is the unit of turbidity measured with a calibrated nephelometer. High NTU values are measured for opaque compositions, whereas low values are determined for clear compositions.

The HACH Turbidimeter 2100Q from the Hach Company, Loveland, Colorado (USA) is used using the calibration tools StabICal Solution HACH (20 NTU), StabICal Solution HACH (100 NTU) and StabICal Solution HACH (800 NTU) , all can also be ordered from Hach Company. The measurement is filled in a 10 ml measuring cuvette with a cap with the composition to be examined and the measurement is carried out at 20 ° C.

At an NTU value (at 20 ° C.) of 60 or more, gel-like phases have a perceptible cloudiness that can be recognized by the naked eye within the meaning of the invention. It is therefore preferred if the first gel-like phase have an NTU value (at 20 ° C.) of at most 120, more preferably at most 110, more preferably at most 100, particularly preferably at most 80.

In the context of the present invention, the transparency of the first gel-like phase is determined by a transmission measurement in the visual light spectrum over a wavelength range from 380 nm to 780 nm at 20.degree. For this purpose, a reference sample (water, fully demineralized) is first measured in a photometer (Specord S 600 from AnalytikJena) with a cuvette (layer thickness 10 mm) that is transparent in the spectrum to be examined. The cuvette is then filled with a sample of the shaped body according to the invention and measured again. In the course of sample production, the sample is filled in a liquid state at 80 ° C and solidified in the cuvette and then measured.

It is preferred if the first gel-like phase has a transmission (20 ° C.) of more preferably at least 25%, more preferably at least 30%, more preferably at least 40%, in particular at least 50%, particularly preferably at least 60%.

It is very particularly preferred if the first gel-like phase has a transmission (at 20 ° C.) of at least 30% (in particular of at least 40%, more preferably of at least 50%, particularly preferably of at least 60%) and an NTU value (at 20 ° C) of at most 120 (more preferably at most 1 10, more preferably at most 100, particularly preferably at most 80).

The shaped bodies comprise at least two gel-like phases. With regard to the production and appearance of the shaped bodies, it has proven to be advantageous if the proportion by weight of the first gel phase is 80 to 99% by weight, preferably 86 to 98% by weight, of the total weight of the molding.

A first essential component of the molded body is the first gel phase. This first gel phase in turn preferably comprises, in addition to a solvent, a gel former from the group of hydrocolloids.

The proportion by weight of the solvent in the total weight of the first gel-like phase is preferably from 60 to 99% by weight and in particular from 80 to 99% by weight.

In addition to water, non-aqueous solvents or mixtures of water and non-aqueous solvents can in principle also be used as solvents for the first gel phase. However, the use of water and mixtures of water with non-aqueous solvents, but in particular water, is particularly preferred.

It has proven to be technically advantageous if the proportion by weight of the gelling agent from the group of hydrocolloids in the total weight of the first gel phase is 0.05 to 10% by weight and in particular 0.2 to 4% by weight. The resulting gel phases are distinguished by good producibility, storability and good usage properties, in particular an advantageous dissolution behavior.

Preferred molded bodies are characterized in that the first gel phase

a1) 40 to 99% by weight of solvent

a2) 0.01 to 15 wt .-% gel former from the group of hydrocolloids

includes.

"Hydrocolloids" ("hydrophilic colloids") are macromolecules that have a largely linear shape and intermolecular interaction forces that enable secondary and main valence bonds between the individual molecules and thus the formation of a network-like structure. They are partially water-soluble natural or synthetic polymers that form gels or viscous solutions in aqueous systems. They increase the viscosity of the water by either binding water molecules (hydration) or by absorbing and enveloping the water in their interwoven macromolecules, while at the same time restricting the mobility of the water.

The synthetic and natural hydrocolloids suitable according to the invention include, for example

organic, fully synthetic compounds, such as. B. polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides, organic, natural compounds such as agar-agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, carob gum, starch, dextrins, gelatine and / or casein,

organic, modified natural substances, such as B. carboxymethyl cellulose and other cellulose ethers, hydroxyethyl and -propyl cellulose etc. and

inorganic compounds, such as. B. polysilicic acids, clay minerals such as montmorillonites, zeolites, silicas.

A first group of particularly preferred hydrocolloids are the synthetic hydrocolloids, preferably from the group of polyacrylic polymers and polymethacrylic polymers, particularly preferably from the group of crosslinked polyacrylic acid polymers.

Polyacrylic and polymethacrylic polymers advantageous according to the invention are to be understood as meaning crosslinked or uncrosslinked polyacrylic acid and / or polymethacrylic acid polymers, such as those from 3V Sigma under the trade names Synthalen K or Synthalen M or from Lubrizol under the trade names Carbopol ( for example Carbopol 980, 981, 954, 2984, 5984 and / or Silk 100), each with the INCI name Carbomer, is available. The product marketed by BASF under the trade name Cosmedia SP (INCI name: SODIUM POLYACRYLATE) can also be mentioned as a preferred acrylic acid homopolymer in this context.

Copolymers of acrylic acid and / or methacrylic acid can also be used as suitable polyacrylic and polymethacrylic polymers. A suitable polymer in this context is the polymer known under the INCI name Acrylates / C 10-30 Alkyl Acrylate Crosspolymer, which is available under the trade name Carbopol 1382 from Noveon. A further suitable polymer is that is sold for example under the trade name Aculyn ^® 88 from the company Rohm & Haas under the INCI name of Acrylates / Steareth-20 Methacrylate Crosspolymer known polymer. Polymers with the INCI nomenclature Acrylates / Palmeth-25 Acrylate Copolymer or Acrylates / Palmeth-20 Acrylate Copolymer can also be used. Such polymers are, as available from 3 V Sigma, for example, under the trade name Synthalen ^® W 2000th

It is also preferable to use a copolymer of at least one anionic acrylic acid or methacrylic acid monomer and at least one nonionic monomer. Preferred nonionic monomers in this connection are acrylamide, methacrylamide, acrylic acid esters, methacrylic acid esters, vinyl pyrrolidone, vinyl ethers and vinyl esters.

Further preferred polyacrylic and polymethacrylic polymers are, for example, copolymers of acrylic acid and / or methacrylic acid and their C 1 -C 6 -alkyl esters, as sold under the INCI declaration Acrylates Copolymer. A preferred commercial product is, for example, Aculyn ^® 33 from Rohm & Haas. However, copolymers of acrylic acid and / or are also preferred Methacrylic acid, the Ci-C6-alkyl esters of acrylic acid and / or methacacrylic acid and the esters of an ethylenically unsaturated acid and an alkoxylated fatty alcohol. Suitable ethylenically unsaturated acids are, in particular, acrylic acid, methacrylic acid and itaconic acid; suitable alkoxylated fatty alcohols are, in particular, steareth-20 or ceteth-20. Such copolymers are sold by Rohm & Haas under the tradename Aculyn ^® 22 (INCI Name: / Acrylates Steareth-20 Methacrylate Copolymer) expelled.

A second group of particularly preferred hydrocolloids are the natural hydrocolloids, preferably hydrocolloids from the group of gelatine, agar, gum arabic, guar gum, gellan gum, alginates, carrageenan, carrageenate and pectins, particularly preferably from the group of gelatine and agar.

The first gel-like phase contains, as an essential component, active ingredient particles with a maximum diameter between 1 and 200 μm. The active ingredient particles are enclosed by the second gel phase. The maximum diameter of the active ingredient particles is preferably from 1 to 80 μm, preferably from 5 to 40 μm. The proportion by weight of the active ingredient particles in the total weight of the second gel-like phase is preferably 0.1 to 20% by weight, more preferably 0.2 to 10% by weight and in particular 0.5 to 8% by weight.

Preferred molded bodies are characterized in that the first gel phase

a1) 40 to 99% by weight of solvent

a2) 0.01 to 15 wt .-% gel former from the group of hydrocolloids

a3) 0.1 to 20% by weight of active ingredient particles

includes.

The active ingredient particles contain fragrance as a particularly preferred active ingredient. A fragrance is a chemical substance that stimulates the sense of smell. In order to stimulate the sense of smell, the chemical substance should at least partially be dispersible in the air, i.e. the fragrance should be at least slightly volatile at 25 ° C. If the fragrance is now very volatile, the odor intensity then quickly subsides again. If the volatility is lower, however, the odor impression is more lasting, i.e. it does not disappear as quickly. In one embodiment, the fragrance therefore has a melting point which is in the range from -100 ° C to 100 ° C, preferably from -80 ° C to 80 ° C, even more preferably from -20 ° C to 50 ° C, in particular from - 30 ° C to 20 ° C. In a further embodiment, the fragrance has a boiling point which is in the range from 25 ° C. to 400 ° C., preferably from 50 ° C. to 380 ° C., more preferably from 75 ° C. to 350 ° C., in particular from 100 ° C. to 330 ° C.

Overall, a chemical substance should not exceed a certain molecular mass in order to function as a fragrance, since if the molecular mass is too high, the required volatility can no longer be guaranteed. In one embodiment, the fragrance has a molecular weight of 40 to 700 g / mol, more preferably 60 to 400 g / mol. Most people find the smell of a fragrance pleasant and often corresponds to the smell of, for example, flowers, fruits, spices, bark, resin, leaves, grasses, mosses and roots. For example, fragrances can also be used to mask unpleasant odors or to provide a non-odorous substance with a desired odor. Individual fragrance compounds, for example synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type, can be used as fragrances.

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), phenylacetaldehyde, undecylenealdehyde, vanillin, 2,6,10-trimethyl-9-undecenal, 3- dodecen 1 -al, alpha-n-amylcinnamaldehyde, melonal (2,6-dimethyl-5-heptenal), 2,4-dimethyl-3-cyclohexene-1-carboxaldehyde (triplal), 4-methoxybenzaldehyde, benzaldehyde, 3- (4-tert-butylphenyl) propanal, 2-methyl-3- (para-methoxyphenyl) propanal, 2-methyl-4- (2,6,6-timethyl-2 (1) -cyclohexen-1-yl) butanal , 3-phenyl-2-propenal, cis- / trans-3,7-dimethyl-2,6-octadien-1 -al, 3,7-dimethyl-6-octen-1 -al, [(3,7- Dimethyl-6-octenyl ) oxy] acetaldehyde, 4-isopropylbenzylaldehyde, 1,2,3,4,5,6,7,8-octahydro-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) - butanal, octahydro-4,7-methane 1 H-indene carboxaldehyde, 3-ethoxy-4-hydroxybenzaldehyde, para-ethyl-alpha.alpha-dimethylhydrocinnamaldehyde, alpha-methyl-3,4- (methylenedioxy) -hydrocinnamaldehyde, 3,4-methylenedioxybenzaldehyde, alpha-n-hexylcinnamaldehyde, m -Cymen-7-carboxaldehyde, alpha-methylphenylacetaldehyde, 7-hydroxy-3,7-dimethyloctanal, undecenal, 2,4,6-trimethyl-3-cyclohexene-1-carboxaldehyde, 4- (3) (4-methyl-3 -pentenyl) -3-cyclohexenecarboxaldehyde, 1 -dodecanal, 2,4-dimethylcyclohexene-3-carboxaldehyde, 4- (4-hydroxy-4-methylpentyl) -3-cyclohexen-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-undecadienal, 2-methyl-3- (4-tert- butyl) propanal, dihydrocinnamaldehyde, 1-methyl-4- (4-methyl-3-pentenyl) -3-cyclohexene-1-carboxaldehyde, 5- or 6-methoxyhexahydro-4,7-methanindane-1 - or -2-carboxaldehyde , 3,7-dimethy 1-octane-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, peony aldehyde (6,10- Dimethyl-3-oxa-5,9- undecadien-1 -al), hexahydro-4,7-methanindan-1-carboxaldehyde, 2-methyloctanal, alpha-methyl-4- (1 - methylethyl) benzene acetaldehyde, 6,6- Dimethyl-2-norpinene-2-propionaldehyde, para

Methylphenoxyacetaldehyde, 2-methyl-3-phenyl-2-propen-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. Fragrance compounds of the ketone type are, for example, methyl beta-naphthyl ketone, musk indanone (1, 2, 3,5,6, 7-hexahydro-1, 1, 2,3,3-pentamethyl-4H-inden-4-one), Tonalid (6-acetyl-1, 1, 2,4,4,7-hexamethyltetralin), alpha-damascone, beta-damascone, delta-damascone, iso-damascone, damascenone, methyl dihydrojasmonate, menthone, carvone, camphor, coavone (3 , 4, 5,6,6-pentamethylhept-3-en-2-one), fenchone, alpha-ionone, betalonone, gamma-methyl-ionone, fleuramone (2-heptylcyclopen-tanone), dihydrojasmone, cis-jasmone , 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 cedrenyl ketone, acetophenone, methylacetophenone, para-methoxyacetophenone, methyl-beta-naphthyl ketone, benzylacetone, benzophenone, para-hydroxyphenylbutanone, celery ketone (3-methyl-5-propyl-2-cyclohexenone), 6-isopropyldecahydro- , 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-menthen-6 (2) yl) -1-propanone, 4- (4-hydroxy-3-methoxyphenyl) -2-butanone, 2-acetyl-3,3-dimethylnorbornane, 6,7-dihydro-1, 1, 2,3,3-pentamethyl-4 (5H) -indanone, 4-damascol, dulcinyl (4- (1 , 3-benzodioxol-5-yl) butan-2-one), hexalone (1 - (2,6,6-trimethyl-2-cyclohexene-1-yl) -1,6-heptadien-3-one), isocyclemonE (2-acetonaphthon-1, 2,3,4,5,6,7,8-octahydro-2,3,8,8-tetramethyl), methyl nonyl ketone, methylcyclocitron, methyl lavender ketone, orivon (4-tert-amyl-cyclohexanone) , 4-tert-butylcyclohexanone, Delphon (2-pentyl-cyclopentanone), Muscon (CAS 541-91-3), neobutenone (1 - (5,5-dimethyl-1-cyclohexenyl) pent-4-en-1 -one ), Plicaton (CAS 41724-19-0), Velouton (2,2,5-trimethyl-5-pentylcyclopentan-1-one), 2,4,4,7-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-methyl-butanol, 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-isopropyl-cyclohexanol, 4-tert.-butycyclohexanol, 6 , 8-dimethyl-2-nona-nol, 6-nonene-1 -ol, 9-decen-1 -ol, α-methylbenzyl alcohol, α-terpineol, amyl salicylate, benzyl alcohol, benzyl salicylate, ß-terpineol, butyl salicylate, citronellol, cyclohexyl salicyl , decanol, dihydromyrcenol, dimethylbenzylcarbinol, dimethylheptanol, dimethyloctanol, ethyl salicylate, ethylvanillin, eugenol, farnesol, geraniol, heptanol, hexyl salicylate, isoborneol, isoeugenol, isopulegol, linalool, menthol, myrtenol, n-hexanol, nerol, nonanol, octanol, p -Menthan-7-ol, phenylethyl alcohol, phenol, phenyl salicylate, tetrahydrogeraniol, tetrahydrolinalool, thymol, trans-2-cis-6-nonadicnol, trans-2-nonene-1 -o l, trans-2-octenol, undecanol, vanillin, champiniol, hexenol and cinnamon alcohol.

Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate (DMBCA), phenylethyl acetate, benzyl acetate, ethylmethylphenyl glycinate, allylcyclohexylpropionate, allylcyclohexylpropionate, allylcyclohexylpropionate, allylcyclohexylpropionate, allylcyclohexylpropionate, benzylcyclohexylpropionate, benzoylcyclohexylpropionate, benzacylate, benzacylpropionate, benzacylate and jasacylate.

The ethers include, for example, benzyl ethyl ether and ambroxan. The hydrocarbons mainly include terpenes such as limonene and pinene. Mixtures of different fragrances are preferably used, which together produce an appealing fragrance note. Such a mixture of fragrances can also be referred to as perfume or perfume oil. Such perfume oils can also contain natural fragrance mixtures, such as are available from vegetable sources.

The fragrances of vegetable origin include essential oils such as angelica root oil, anise oil, arnica flower oil, basil oil, bay oil, champaca flower oil, citrus oil, noble fir oil, noble fir cone oil, elemi oil, eucalyptus oil, fennel oil, spruce needle oil, guajun oil, gourd oil, gjajun oil, galbanum oil, gourd oil, gjajun oil , Ginger oil, iris oil, jasmine oil, kajeput oil, calamus oil, chamomile oil, camphor oil, kanaga oil, cardamom oil, cassia oil, pine needle oil, copaiva balsam oil, coriander oil, spearmint oil, caraway oil, cumin oil, labdanum oil, lavender oil, lemon linden oil, almond blossom 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, Peru balsam oil, petitgrain oil, pepper oil, peppermint oil, allspice oil, celery oil, sage oil, starch oil, rosemary oil, sandstone oil, rosemary oil , Turpentine oil, thuja oil, thyme oil, verbena oil, vetiver oil, juniper oil, W ermut oil, wintergreen oil, ylang-ylang oil, hyssop oil, cinnamon oil, cinnamon leaf oil, citronella oil, lemon oil and cypress oil as well as ambrettolide, ambroxan, alpha-amylcinnamaldehyde, anethole, anisaldehyde, anisalcohol, anisole, anthranilic acid methyl ester, benzyl acetophenone, methyl ester, benzyl acetophenone Benzophenone, benzyl alcohol, benzyl acetate, benzyl benzoate, benzyl formate, benzyl valerianate, borneol, bornyl acetate, boisambrene forte, alpha-bromostyrene, n-decyl aldehyde, n-dodecyl aldehyde, eugenol, eugenol methyl ether, eucalyptyl acetate, geranium acid ethyl acetate, geranium acid ethyl acetate, geranium acetyl acetate, fenchone, fencheptanyol , Heptaldehyde, hydroquinone dimethyl ether, hydroxycinnamaldehyde, hydroxycinnamic alcohol, indole, Iran, isoeugenol, isoeugenol methyl ether, isosafrol, jasmone, camphor, karvakrol, karvon, p-cresol methyl ether, coumarin, p-methoxyacetophenone, methyl-n-amyl ketone,

Methyl anthranilic acid methyl ester, p-methylacetophenone, methylchavikol, p-methylquinoline, methyl-betanaphthyl ketone, methyl-n-nonylacetaldehyde, methyl-n-nonyl ketone, muskon, beta-naphthol ethyl ether, beta-naphthol methyl ether, nerol, n-nonyl aldehyde, nonyl alcohol n-octylaldehyde, p-oxy-acetophenone, pentadecanolide, beta-phenylethyl alcohol, phenylacetic acid, pulegone, safrole, isoamyl salicylate, methyl salicylate, hexyl salicylate,

Salicylic acid cyclohexyl ester, santalol, sandelice, skatol, terpineol, thymen, thymol, troenan, gamma- undelactone, vanillin, veratrumaldehyde, cinnamaldehyde, cinnamic alcohol, cinnamic acid, ethyl cinnamate, lenthic acid benzyl ester, lentonate, benzyl acetate, limonate, methylate, prophenionate, prophenionate, prophenionate, prophenionyl acetate, prophenionyl acetate, prophenionate, prophenyl acetate, troenan, gamma- undelacton , Methyl-n-heptenone, pinene, phenylacetaldehyde, terpinylacetate, citral, citronellal, and mixtures thereof.

For the extension of the active substance effect, in particular the extended fragrance effect, it has proven advantageous to encapsulate the fragrance substance. Core-shell particles are therefore used with particular preference as active ingredient particles. Corresponding particles known to the person skilled in the art have an active substance-containing core and a shell material surrounding this core. Preferred envelope materials for the active ingredient particles, materials from the group consisting of polyurethane, polylactic acid, polyurea, polyamide and melamine-formaldehyde resin.

In a corresponding embodiment, at least part of the fragrance is used in encapsulated form (fragrance capsules), in particular in microcapsules. However, the entire fragrance can also be used in encapsulated form. The microcapsules can be water-soluble and / or water-insoluble microcapsules. For example, melamine-urea-formaldehyde microcapsules, melamine-formaldehyde microcapsules, urea-formaldehyde microcapsules or starch microcapsules can be used. “Fragrance precursors” refers to compounds that only release the actual fragrance after chemical conversion / cleavage, typically through exposure to light or other environmental conditions, such as pH, temperature, etc. Such compounds are often referred to as fragrance storage substances or “pro-fragrance”.

Preferred molded bodies are characterized in that a core-shell particle is used as the active substance particle and the core-shell particles are based on their total weight

i) 10 to 60% by weight, preferably 20 to 40% by weight of perfume

ii) 5 to 30% by weight, preferably 10 to 25% by weight, of shell material.

In addition to the first gel-like phase described above, the shaped body furthermore comprises at least one second gel-like phase that is different from the first gel-like phase. This second gel-like phase is preferably completely enclosed by the first gel-like phase.

Like the shaped body, the second gel-like phase also preferably has a cubic or spherical three-dimensional shape. In preferred embodiments, for example, a spherical core is surrounded by a spherical shell. However, polyhedral cores, in particular cubic (cube-shaped) cores which are surrounded by a polyhedral shell, in particular a cubic (cube-shaped) shell, are also conceivable.

The proportion by weight of the second gel-like phase in the total weight of the shaped body is preferably 0.9 to 19% by weight, preferably 1.9 to 13% by weight.

The second gel-like phase preferably has a spatial extent between 0.5 to 8 mm, in particular 0.8 to 5 mm and particularly preferably 1 to 3 mm, in any spatial direction.

The second gel-like phase is preferably translucent or transparent, preferably transparent. With regard to the definition of transparency and suitable methods for determining transparency, in order to avoid repetitions, reference is made to the statements relating to the shaped body above in the text, which apply mutatis mutandis to the second gel-like phase.

Preferred moldings are characterized in that the second gel-like phase b1) 40 to 99% by weight of solvent

b2) 0.01 to 15% by weight of gel former

includes.

As in the case of the first gel phase, water and non-aqueous solvents are suitable as solvents for the second gel phase. In the case of the second gel phase, however, non-aqueous solvents and their mixtures with water are particularly preferred.

The solvent for the second gel phase is preferably selected from the group consisting of ethanol, n-propanol, i-propanol, butanols, glycol, propanediol, butanediol, methylpropanediol, glycerol, propylene carbonate, diglycol, propyl diglycol, butyl diglycol, hexylene glycol, diethylene glycol ethylene glycol, diethylene glycol ethylene glycol -n-butyl ether, diethylene glycol hexyl ether, diethylene glycol n-butyl ether acetate, ethylene glycol propyl ether, ethylene glycol n-butyl ether, ethylene glycol hexyl ether, ethylene glycol n-butyl ether acetate, triethylene glycol, triethylene glycol methyl ether,

Triethylene glycol ethyl ether, triethylene glycol n-butyl ether, ethylene glycol phenyl ether,

Propylene glycol methyl ether, dipropylene glycol methyl ether, tripropylene glycol methyl ether,

Propylene glycol methyl ether acetate, dipropylene glycol methyl ether acetate, propylene glycol n-propyl ether, dipropylene glycol n-propyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, tripropylene glycol n-butyl ether, propylene glycol phenyl ether, propylene glycol phenyl ether,

Dipropylene glycol dimethyl ether, methoxytriglycol, ethoxytriglycol, butoxytriglycol, glycerine carbonate, propylene carbonate, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, 2-methylpropane-1, 3-diol, propylene glycol t-butyl ether, di-n- octyl ether, preferably from the group consisting of glycerol, propylene glycol, ethanol, isoporpanol, methylpropanoldiol, triethylene glycol, propylene carbonate, glycerol carbonate, 3-methyl-3-methoxybutanol and 2-methylpropane-1,3-diol.

It was found that the producibility, packaging and handling of the active substance-containing moldings can be influenced in an advantageous manner not only by the preferred gel formers described above, but also by the selection of specific solvents.

A first group of particularly preferred moldings is characterized in that in the second gel-like phase a solvent from the group of polyalkylene glycols liquid at room temperature (20 ° C), in particular the polyalkylene glycols liquid at room temperature (20 ° C), particularly preferably from the PEG group 200 and PEG 400 is used.

A second group of particularly preferred molded bodies is characterized in that in the second gel-like phase a solvent from the group of organic polyols liquid at room temperature (20 ° C.), in particular diols liquid at room temperature (20 ° C.), particularly preferably from the group 2-methyl-1,3-propanediol (MPDiol) and 3-methyl-1,3-butanediol (isopentyldiol) is used. Further groups of particularly preferred molded bodies include glycerol or triacetin or water as solvents.

Mixtures of solvents have proven to be technically particularly advantageous, in particular the combination of water and 3-methyl-1,3-butanediol (isopentyldiol), but in particular the combination of water, glycerol and 3-methyl-1,3-butanediol are called.

The proportion by weight of solvent in the total weight of the second gel-like phase is preferably 10 to 98% by weight, particularly preferably 40 to 97% by weight and in particular 60 to 96% by weight.

The second gel-like phase preferably comprises less than 10% by weight, more preferably less than 8% by weight, particularly preferably less than 4% by weight and in particular less than 1% by weight surfactant. It is very particularly preferred if the first gel-like phase does not comprise any surfactant.

The second gel phase comprises gel formers as a second essential component. This gelling agent is preferably different from the gelling agent of the first gel phase. The use of gel formers with a molar mass below 2000 g / mol, preferably below 1000 g / mol, is preferred.

The proportion by weight of the gel former in the total weight of the second gel-like phase is preferably 0.1 to 10% by weight and in particular from 1 to 4% by weight.

In a preferred embodiment, the gel former of the second gel phase has a solubility in water of less than 0.1 g / L (20 ° C.). The solubility of the organic gelator compound is determined at 20 ° C in double-distilled, demineralized water.

Furthermore, gel formers are preferably suitable which have a structure containing at least one hydrocarbon structural unit with 6 to 20 carbon atoms (preferably at least one carbocyclic, aromatic structural unit) and in addition an organic structural unit covalently bonded to the aforementioned hydrocarbon unit, the at least two groups selected from -OH, -NH-, or mixtures thereof.

Particularly preferred second gel phases are characterized in that said gel phase contains at least one benzylidene alditol compound of the formula (GB-I) as a gel former * - stands for a covalent single bond between an oxygen atom of the alditol backbone and the intended residue,

n is 0 or 1, preferably 1,

m is 0 or 1, preferably 1,

R ¹ , R ² and R ³ independently of one another represent a hydrogen atom, a halogen atom, a C1-C4-alkyl group, a cyano group, a nitro group, an amino group, a carboxyl group, a hydroxyl group, a group -C (= 0) -NH -NH ₂ , a group -NH-C (= 0) - (C ₂ -C ₄ -alkyl), a C1-C4-alkoxy group, a Ci-C ₄ -alkoxy-C ₂ -C ₄ -alkyl group, two of the Residues form a 5- or 6-membered ring together with the residual molecule,

R ⁴ , R ⁵ and R ⁶ independently stand for a hydrogen atom, a halogen atom, a C1- C ₄ alkyl group, a cyano group, a nitro group, an amino group, a carboxyl group, a hydroxyl group, a group -C (= 0) - NH-NH ₂ , a group -NH-C (= 0) - (C ₂ -C ₄ -alkyl), a C1-C4- alkoxy group, a Ci-C ₄ -alkoxy-C ₂ -C ₄ -alkyl group, two of the residues together with the remainder of the molecule form a 5- or 6-membered ring.

On the basis of the stereochemistry of the alditols, it should be mentioned that both said benzylidene alditols in the L configuration or in the D configuration or a mixture of both are suitable according to the invention. Because of their natural availability, the benzylidene alditol compounds in the D configuration are preferably used according to the invention. It has been found to be preferred if the alditol basic structure of the benzylidene alditol compound according to formula (GB-I) contained in the molded body is derived from D-glucitol, D-mannitol, D-arabinitol, D-ribitol, D-xylitol, L -Glucitol, L-mannitol, L-arabinitol, L-ribitol or L-xylitol.

Gel formers which are particularly preferred are those which are characterized in that R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ^6, according to the benzylidene alditol compound of the formula (GB-I), independently of one another are a hydrogen atom, methyl, ethyl, chlorine , Fluorine or methoxy, preferably a hydrogen atom. According to the benzylidene alditol compound of the formula (GB-I), n is preferably 1. According to the benzylidene alditol compound formula (GB-I), m preferably represents 1. The molding according to the invention very particularly preferably contains at least one compound of the formula (GB-11) as the benzylidene alditol compound of the formula (GB-I)

wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ^{6 are} as defined in formula (I). Most preferably, according to formula (GB-11), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ independently of one another represent a hydrogen atom, methyl, ethyl, chlorine, fluorine or methoxy, preferably a hydrogen atom.

Most preferably the benzylidene alditol compound of formula (GB-I) is selected from 1, 3: 2,4-di-O-benzylidene-D-sorbitol; 1, 3: 2,4-di-0- (p-methylbenzylidene) -D-sorbitol; 1, 3: 2,4-di-0- (p-chlorobenzylidene) -D-sorbitol; 1, 3: 2,4-di-0- (2,4-dimethylbenzylidene) -D-sorbitol; 1, 3: 2,4-di-0- (p-ethylbenzylidene) -D-sorbitol; 1, 3: 2,4-di-0- (3,4-dimethylbenzylidene) -D-sorbitol or mixtures thereof.

Preferred moldings contain at least one 2,5-diketopiperazine compound of the formula (GB-II) as a gel former

wherein

R ¹ , R ² , R ³ and R ⁴ independently of one another represent a hydrogen atom, a hydroxyl group, a (Ci-C6) -alkyl group, a (C2-C6) -alkenyl group, a (C2-C6) -acyl group, a ( C2-C6) - acyloxy group, a (Ci-C6) -alkoxy group, an amino group, a (C2-C6) -acylamino group, a (Ci-C6) -alkylaminocarbonyl group, an aryl group, an aroyl group, an aroyloxy group, an aryloxy group, a Aryl (Ci-C ₄ ) alkyloxy group, an aryl (Ci-C3) alkyl group, a heteroaryl group, a heteroaryl (Ci-C3) alkyl group, a (Ci-C ₄ ) hydroxyalkyl group, a (Ci- C ₄ ) aminoalkyl group, a carboxy (Ci-C3) alkyl group, where at least two of the radicals R ¹ to R ⁴ can form a 5 or 6-membered ring together with the remainder of the molecule,

R ⁵ stands for a hydrogen atom, a linear (Ci to C6) -alkyl group, a branched (C3 to C10) -alkyl group, a (C3 to C6) -cycloalkyl group, a (C2-C6) -alkenyl group, a (C2-C6 ) Alkynyl group, a (Ci-C ₄ ) -hydroxyalkyl group, a (Ci-C ₄ ) -alkoxy- (Ci-C ₄ ) -alkyl group, a (Ci-C ₄ ) -acyloxy- (Ci- C ₄ ) - alkyl group, an aryloxy (Ci-C ₄ ) -alkyl group, an 0- (aryl- (Ci-C ₄ ) -alkyl) oxy- (Ci-C ₄ ) -alkyl group, a (Ci-C ₄ ) -Alkylsulfanyl- (Ci-C ₄ ) -alkylgruppe, an aryl group, an aryl- (Ci-C3) -alkylgruppe, a heteroaryl group, a heteroaryl- (Ci-C3) -alkylgruppe, a (Ci -C ₄ ) -hydroxyalkyl group, a (C1-C4) - aminoalkyl group, an N- (Ci-C ₄ ) -alkylamino- (Ci-C ₄ ) -alkyl group, an N, N- (Ci-C ₄ ) -dialkylamino - (Ci- C4) -alkyl group, an N- (C2-C8) -acylamino- (Ci-C4) -alkyl group, an N- (C2-C8) -acyl-N- (Ci-C4) - alkylamino- ( Ci-C ₄ ) -alkyl group, an N- (C ₂ -C8) aroyl-N- (Ci-C ₄ ) -alkylamino- (Ci-C ₄ ) -alkyl group, an N, N- (C ₂ -C8 ) -Diacylamino- (Ci-C ₄ ) -alkyl group, an N- (aryl- (Ci-C ₄ ) -alkyl) amino- (Ci-C ₄ ) -alkyl group, an N, N-di (aryl- (Ci -C ₄ ) -alkyl) amino (Ci-C ₄ ) -alkyl group, a (Ci-C ₄ ) -carboxyalkyl group, a (C1- C ₄ ) -alkoxycarbonyl- (Ci-C3) -alkyl group, a (Ci- C ₄ ) -Acyloxy- (Ci-C3) -alkyl group, a guanidino- (Ci- C3) -alkyl group, an aminocarbonyl- (Ci-C4) -alkyl group, an N- (Ci-C4) -Alkylaminocarbonyl- (Ci- C4) - alkyl group, an N, N-Di ((Ci-C ₄ ) -Alkyl) aminocarbonyl- (Ci-C ₄ ) -alkyl group, an N- (C2-Cs) - acylaminocarbonyl- (Ci-C ₄ ) -alkyl group, an N, N- (C ₂ -C8) -diacylaminocarbonyl- (Ci-C ₄ ) -alkyl group, an N- ( C ₂ -C 8) acyl-N- _(Ci-C4) alkylaminocarbonyl (Ci-C alkyl _4), an N- (aryl _(Ci-C4) - alkyl) aminocarbonyl (Ci-C ₄ ) -alkyl group, an N- (aryl- (Ci-C ₄ ) -alkyl) -N- (Ci-C6) -alkylaminocarbonyl- (Ci- C ₄ ) -alkyl group or an N, N-di (aryl- (Ci -C ₄ ) -alkyl) aminocarbonyl- (Ci-C ₄ ) -alkyl group.

It is preferred according to the invention if R ³ and R ⁴ according to formula (GB-II) represent a hydrogen atom. It is particularly preferred according to the invention if R ² , R ³ and R ⁴ according to formula (GB-II) represent a hydrogen atom. Therefore, particularly preferred moldings according to the invention contain at least one 2,5-diketopiperazine compound according to formula (GB-Ila)

wherein R ¹ and R ^{5 are} as defined under formula (GB-II) (vide supra).

It has been found to be preferred if the radical R ¹ according to formula (GB-II) and according to formula (GB-Ila) binds in the para position of the phenyl ring. For the purposes of the present invention, therefore, those moldings according to the invention are preferred which contain at least one 2,5-diketopiperazine compound of the formula (GB-IIb),

wherein R ¹ and R ^{5 are defined} as above under formula (GB-II) (vide supra). The numbers 3 and 6 positioned on the ring atoms in formula (GB-IIb) only mark the positions for the purpose of illustration 3 and 6 of the diketopiperazine ring, as they are generally used in the context of the invention for naming all 2,5-diketopiperazines according to the invention.

The 2,5-diketopiperazine compounds of the formula (GB-II) have centers of chirality at least on the carbon atoms in positions 3 and 6 of the 2,5-diketopiperazine ring. The numbering of the ring positions 3 and 6 was illustrated by way of example in formula (GB-Ilb). The 2,5-diketopiperazine compound of the formula (GB-II) of the compositions according to the invention is preferably the configuration isomer 3S, 6S, 3R, 6S, 3S based on the stereochemistry of the carbon atoms at the 3- and 6-position of the 2,5-diketopiperazine ring , 6R, 3R, 6R or mixtures thereof, particularly preferably 3S, 6S.

Preferred second gel phases contain at least one 2,5-diketopiperazine compound of the formula (GB-II) as gel former, selected from 3-benzyl-6-carboxyethyl-2,5-diketopiperazine and 3-benzyl-6-carboxymethyl-2,5 -diketopiperazine, 3-benzyl-6- (p-hydroxybenzyl) -2,5-diketopiperazine, 3-benzyl-6-isopropyl-2,5-diketopiperazine, 3-benzyl-6- (4-aminobutyl) -2 , 5-diketopiperazine, 3,6-di (benzyl) -2,5- diketopiperazine, 3,6-di (p-hydroxybenzyl) -2,5-diketopiperazine, 3,6-di (p- (benzyloxy) benzyl) -2,5- diketopiperazine, 3-benzyl-6- (4-imidazolyl) methyl-2,5-diketopiperazine, 3-benzyl-6-methyl-2,5-diketopiperazine, 3-benzyl-6- (2- ( benzyloxycarbonyl) ethyl) -2,5-diketopiperazine or mixtures thereof. In turn, compounds with the aforementioned configurational isomers are preferably suitable for selection.

It is also possible for the second gel phases to contain at least one diarylamidocystine compound of the formula (GB-III) as gel former a)

wherein

X ⁺ independently represent a hydrogen atom or an equivalent of a cation,

R ¹ , R ² , R ³ and R ⁴ independently of one another represent a hydrogen atom, a halogen atom, a C1-C4 alkyl group, a Ci-C ₄ alkoxy group, a C ₂ -C ₄ hydroxyalkyl group, a hydroxyl group, an amino group, an N- (Ci-C ₄ -alkyl) amino group, an N, N-di (Ci-C ₄ -alkyl) amino group, an N- (C ₂ -C ₄ - hydroxyalkyl) amino group, an N, N-di ( C ₂ -C ₄ -hydroxyalkyl) amino group or R ¹ with R ² or R ³ with R ⁴ forms a 5- or 6-membered fused ring, which in turn each with at least one group from Ci-C ₄ -alkyl group, Ci-C ₄ -alkoxy group, C ₂ -C ₄ -hydroxyalkyl group, hydroxyl group, amino group, N- (Ci-C ₄ -alkyl) amino group, N, N-di (Ci-C ₄ -alkyl) amino group, N- (C ₂ -C ₄ -hydroxyalkyl) amino group, N, N-di (C ₂ -C ₄ -hydroxyalkyl) amino group can be substituted. Each of the stereocenters contained in the compound of the formula (GB-III) can, independently of one another, stand for the L or D stereoisomer. It is preferred according to the invention if the said cystine compound of the formula (GB-III) is derived from the L-stereoisomer of cysteine.

Said shaped bodies can contain at least one compound of the formula (GB-III) in which R ¹ , R ² , R ³ and R ⁴ independently of one another represent a hydrogen atom, a halogen atom, a Ci-C ₄ -alkyl group, a Ci-C ₄ -Alkoxy group, a C ₂ -C ₄ -hydroxyalkyl group, a hydroxyl group, or R ¹ with R ² or R ³ with R ⁴ forms a 5- or 6-membered fused ring, which in turn each with at least one group from Ci-C ₄ -Alkyl group, Ci-C ₄ alkoxy group, C ₂ -C ₄ hydroxyalkyl group, hydroxyl group can be substituted. In particular, those moldings are particularly suitable which are used as the diarylamidocystine compound of the formula (GB-III) N, N'-dibenzoylcystine (R ¹ = R ² = R ³ = R ⁴ = hydrogen atom; X ⁺ = independently of one another for hydrogen atom or a equivalent of a cation), in particular N, N'-dibenzoyl-L-cystine.

Have suitable as gelling agent N- (C8-C ₂₄₎ -Hydrocarbylglyconamid compounds preferably of the formula (GB-IV) on

in which

n is 2 to 4, preferably 3 or 4, especially 4;

R ^{1 is} selected from hydrogen, C1-C16 alkyl radicals, C1-C3 hydroxy or methoxyalkyl radicals, preferably C1-C3 alkyl, hydroxyalkyl or methoxyalkyl radicals, particularly preferably methyl;

R ² is selected from Cs-C ₂₄ alkyl, Cs-C ₂₄ -Monoalkenylresten, Cs-C ₂₄ -Dialkenylresten, Cs C ₂₄ -Trialkenylresten, Cs-C ₂₄ -hydroxyalkyl, Cs-C ₂₄ -Hydroxyalkenylresten, C1-C3 Hydroxyalkyl radicals or methoxy-Ci-C3-alkyl radicals, preferably Cs-Cis alkyl radicals and mixtures thereof, more preferably C10, C12, C14, C16 and Cis-alkyl radicals and mixtures thereof, most preferably C12 and C14 alkyl radicals or a mixture thereof. In particularly preferred embodiments, the HO-CH2- (CHOH) _n -C- radical is one of one

II

O

Glycuronic acid, in particular the glycuronic acid of a hexose (n = 4), derived radical. Glucuronic acid in particular is to be mentioned as a preferred radical. R ¹ is preferably H or a short-chain alkyl radical, in particular methyl. R ² is preferably a long-chain alkyl radical, for example a Cs-Cis alkyl radical.

Compounds of the formula (GB-IV1) are therefore very particularly preferred

where R ^{2 has} the meanings given for formula (GB-IV). In a particularly preferred embodiment, the gel former of the second gel phase is selected from the group consisting of benzylidene alditol compound, hydroxystearic acid, hydrogenated castor oil, diarylamidocystine compound, N- (C8-C ₂₄ ) -hydrocarbylglyconamide, diketopiperazine compound, 2-methyl-acrylic acid -2-ureido-ethyl ester and mixtures thereof. Due to its technical effect, the at least one gelling agent N, N'-dibenzoylcystine (DBC) or dibenzylidene sorbitol (DBS), but in particular dibenzylidene sorbitol (DBS), is particularly preferred.

To improve the producibility, storability and use properties of the shaped bodies, the second gel-like phase can comprise the combination of two or more gel formers. A group of preferred gel formers which can be used in combination with the gel formers described above are the polymeric gel formers with a molar mass of 10,000 g / mol to 200,000 g / mol. Shaped bodies in which the second gel-like phase comprises a low molecular weight gel former with a molar mass of up to 2000 g / mol and a polymeric gel former with a molar mass of 10,000 g / mol to 200,000 g / mol are particularly preferred.

It has proven to be particularly advantageous in relation to the production, packaging and handling of the shaped bodies to use polymeric gel formers with a molar mass of 10,000 to 40,000 g / mol.

The proportion by weight of polymeric compound in the total weight of the second gel-like phase is preferably from 0.01 to 15% by weight, more preferably from 0.1 to 12% by weight and in particular from 1 to 10% by weight.

Polymeric gel formers from the group of

- Celluloses and cellulose derivatives, in particular methyl cellulose, hydroxypropylmethyl cellulose and hydroxypropyl cellulose;

- Starch, in particular potato starch, corn starch, wheat starch, pea starch or tapioca starch;

- polyacrylates;

- polyvinylpyrrolidones;

- polyvinyl alcohols

proven. The use of polyvinyl alcohols is particularly advantageous.

Suitable polyacrylates are homopolymers and copolymers of acrylic acid, in particular acrylic acid copolymers such as acrylic acid-methacrylic acid copolymers, and polysaccharides, especially heteropolysaccharides, and other customary polymer thickeners.

Suitable acrylic acid polymers are, for example, high molecular weight homopolymers crosslinked with a polyalkenyl polyether, in particular an allyl ether of sucrose, pentaerythritol or propylene acrylic acid (INCI Carbomer), which are also referred to as carboxyvinyl polymers. Such polyacrylic acids are available inter alia from the company. BF Goodrich under the trade names Carbopof ^®.

Particularly suitable polymers, however, are the following acrylic acid copolymers: (i) Copolymers of two or more monomers from the group of acrylic acid, methacrylic acid and their simple esters, preferably formed with Ci- ₄ alkanols (INCI Acrylates Copolymers), to which about the copolymers of methacrylic acid, butyl acrylate and methyl methacrylate and include (CAS 25035-69-2) or of butyl acrylate and methyl methacrylate (CAS 25852-37-3) is the example of the company. Rohm & Haas under the trade names Aculyn ^® and Acusol ^®, as well as Degussa (Goldschmidt) are available under the trade name ^Tego® Polymer; (ii) crosslinked high molecular weight acrylic acid copolymers, including the copolymers of Cio-3o-alkyl acrylates crosslinked with an allyl ether of sucrose or pentaerythritol with one or more monomers from the group of acrylic acid, methacrylic acid and their simple, preferably Ci ₄ -alkanols , esters (INCI acrylates / C10-30 alkyl acrylate Crosspolymer) and which are obtainable, for example, by the company BF Goodrich under the trade name Carbopol ^®. Suitable acrylate are also available under the trade name Skålan ^® AT 120 and AT 120 Rheovis ^® by the company BASF. If acrylic acid polymers and especially acrylic acid esters are used as polymeric thickeners, the pH is preferably more than 7, in particular at least 7.5, preferably 8 or more.

Preferred polyvinyl alcohols have a molecular weight of 10,000 g / mol to 150,000 g / mol, particularly preferably 10,000 g / mol to 80,000 g / mol and in particular 10,000 g / mol to 40,000 g / mol. The degree of hydrolysis of preferred polyvinyl alcohols is 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%

Due to the advantages in their production, storage and use, those moldings are preferred which contain dibenzylidene sorbitol and polyvinyl alcohol, the weight ratio of dibenzylidene sorbitol to polyvinyl alcohol being 10: 1 to 1:20, preferably 8: 1 to 1:15 and in particular 6: 1 up to 1:10.

The shaped bodies enable complete washing or cleaning agents to be packaged, but also washing or cleaning aids, for example fragrance additives, care aids or detergent boosters such as enzymes. Corresponding aids can in turn be made up independently or in combination with detergents or cleaning agents. Another preferred subject matter is detergent or cleaning agent combination products which, in addition to a solid or liquid detergent or cleaning agent, also comprise at least one of the shaped bodies described above.

Further particularly preferred formulations can be found in the tables below (data in% by weight based on the total weight of the first or second phase). The moldings have a weight of 1 to 20 g and the second gel-like phase is at least partially enclosed by the first gel-like phase.

Additional particularly preferred formulations can be found in the tables below (data in% by weight based on the total weight of the first or second phase). The shaped bodies have a weight of 1 to 20 g and the second gel-like phase is completely enclosed by the first gel-like phase.

Another object of this application is a method for producing a molded body according to one of the preceding points, comprising the steps: a) introduction of active substance particles with a maximum diameter between 1 and 200 μm into a liquid phase with the formation of a suspension;

b) hardening of the resulting suspension with the formation of a first gel-like shaped body;

c) applying a second liquid phase different from the first liquid phase to the surface of the first gel-like molded body;

d) hardening of the second liquid phase with the formation of a gel-like shaped body which at least partially surrounds the first gel-shaped shaped body.

For shaping, the suspension can be introduced into a mold in step b). In order to accelerate the solidification and, if necessary, to simplify the shaping, the suspension is preferably cooled in such a process variant.

In an alternative and preferred variant of the method, the mixture produced in step a) is dripped into a hardening bath in step b) for hardening.

The second liquid phase in step c) preferably has a temperature between 30 ° C and 180 ° C, preferably between 60 ° C and 160 ° C.

To accelerate the hardening process, the second liquid phase is preferably cooled in step d).

As stated at the outset, the shaped bodies are particularly suitable as active substance carriers for substances with active washing or cleaning properties. The use of the moldings described above in processes for cleaning or caring for textile surfaces are therefore further subjects of this application. In these processes it is preferred to introduce a shaped body into the washing liquor of a textile washing machine.

In an alternative procedure, the shaped bodies described above can be used for cleaning a glass, metal or ceramic surface.

In summary, the following means and procedures are provided:

1. Shaped body comprising

a) a first gel phase

b) at least one second gel-like phase different from the first gel-like phase, the first gel-like phase containing active ingredient particles with a maximum diameter between 1 and 200 μm and being at least partially enclosed by the second gel-like phase.

2. Shaped body according to one of the preceding points, the shaped body having a weight between 200 mg and 35 g, preferably between 1 g and 20 g and in particular between 2 g and 10 g. 3. Shaped body according to one of the preceding points, the shaped body having a spatial extent between 2 to 100 mm, in particular 5 to 70 mm and particularly preferably 10 to 50 mm, in any spatial direction.

4. Shaped body according to one of the preceding points, wherein the ratio of the longest diameter determined in any spatial direction to the shortest diameter determined in any spatial direction is between 3: 1 and 1: 1, preferably between 2.5: 1 and 1.2: 1 and in particular between 2.2: 1 and 1.4: 1.

5. Shaped body according to one of the preceding points, wherein the shaped body has a cubic three-dimensional shape.

6. Shaped body according to one of the preceding points, wherein the shaped body has a spherical three-dimensional shape.

7. Shaped body according to one of the preceding points, the first gel-like phase being transparent.

8. Shaped body according to one of the preceding points, the first gel phase

a1) 40 to 99% by weight of solvent

a2) 0.01 to 15 wt .-% gel former from the group of hydrocolloids

includes.

9. Shaped body according to one of the preceding points, the first gel-like phase having a weight fraction of solvent of 60 to 99% by weight and in particular 80 to 99% by weight, based on its total weight.

10. Shaped body according to one of the preceding points, wherein the first gel phase contains water as the solvent.

1 1. Shaped body according to one of the preceding points, the first gel-like phase having, based on its total weight, a proportion by weight of formers from 0.05 to 10% by weight and in particular from 0.2 to 4% by weight.

12. Shaped body according to one of the preceding points, wherein the first gel-like phase is a gel former from the group of synthetic hydrocolloids, preferably from the group of polyacrylic polymers and polymethacrylic polymers, particularly preferably from the group of crosslinked ones

Contains polyacrylic acid polymers. 13. Shaped body according to one of the preceding points, wherein the first gel-like phase contains a gel former from the group of natural hydrocolloids, preferably from the group of gelatine, agar, gum arabic, guar gum, gellan gum, alginates, carrageenan carrageenate and pectins.

14. Shaped body according to one of the preceding points, the proportion by weight of the first gel-like phase in the total weight of the shaped body being 80 to 99% by weight, preferably 86 to 98% by weight.

15. Shaped body according to one of the preceding points, the second gel-like phase being completely enclosed by the first gel-like phase.

16. Shaped body according to one of the preceding points, the second gel-like phase having a spatial extension between 0.5 to 8 mm, in particular 0.8 to 5 mm and particularly preferably 1 to 3 mm, in any spatial direction.

17. Shaped bodies according to one of the preceding points, the second gel-like phase having a cubic three-dimensional shape.

18. Shaped body according to one of the preceding points, wherein the second gel-like phase has a spherical three-dimensional shape.

19. Shaped body according to one of the preceding points, the second gel-like phase being transparent.

20. Shaped body according to one of the preceding points, wherein the second gel-like phase

b1) 10 to 98% by weight of solvent

b2) 0.01 to 15% by weight of gel former

includes.

21st Shaped body according to item 20, the solvent of the second gel-like phase being selected from the group consisting of ethanol, n-propanol, i-propanol, butanols, glycol, propanediol, butanediol, methylpropanediol, glycerol, propylene carbonate, diglycol, propyldiglycol, butyldiglycol, hexylene glycol, diethylene glycol ethyl ether , Diethylene glycol methyl ether, diethylene glycol n-butyl ether,

Diethylene glycol hexyl ether, diethylene glycol n-butyl ether acetate, ethylene glycol propyl ether, ethylene glycol n-butyl ether, ethylene glycol hexyl ether, ethylene glycol n-butyl ether acetate, triethylene glycol, triethylene glycol methyl ether, triethylene glycol butyl ethyl ether,

Ethylene glycol phenyl ether, propylene glycol methyl ether, dipropylene glycol methyl ether,

Tripropylene glycol methyl ether, propylene glycol methyl ether acetate, dipropylene glycol methyl ether acetate, propylene glycol n-propyl ether, dipropylene glycol n-propyl ether, propylene glycol n-butyl ether,

Dipropylene glycol n-butyl ether, tripropylene glycol n-butyl ether, propylene glycol phenyl ether,

Propylene glycol diacetate, dipropylene glycol dimethyl ether, methoxy triglycol, ethoxy triglycol, butoxy triglycol, glycerine carbonate, propylene carbonate, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, 2-methylpropane-1, 3-diol, propylene glycol-t- n-octyl ether, preferably from the group of glycerol, propylene glycol, ethanol, isoporpanol, methylpropanoldiol, triethylene glycol, propylene carbonate, glycerol carbonate, 3-methyl-3-methoxybutanol and 2-methylpropane-1,3-diol.

22. Shaped body according to one of the preceding points, wherein the second gel-like phase, based on its total weight, has a weight fraction of solvent of

22. Shaped body according to one of points 20 or 21, the gelling agent of the second gel-like phase having a molar mass below 2000 g / mol, preferably below 1000 g / mol.

23. Shaped body according to one of the preceding points, the second gel-like phase having, based on its total weight, a proportion by weight of formers of 0.1 to 10% by weight and in particular 1 to 4% by weight.

24. Shaped body according to one of the preceding points, wherein the gelling agent of the second gel-like phase is selected from the group of benzylidene alditol compounds, hydroxystearic acid, hydrogenated castor oil, diarylamidocystine compound, N- (C8-C ₂₄ ) -hydrocarbylglyconamide, diketopiperazine compound, 2 -Methyl-acrylic acid-2-ureido-ethyl ester and mixtures thereof.

25. Shaped body according to one of the preceding points, wherein the gel former of the second gel-like phase is N, N‘-dibenzoylcystine.

26. Shaped body according to one of the preceding points, wherein the gelling agent of the second gel-like phase is dibenzylidene sorbitol.

27. Shaped body according to one of the preceding points, the second gel-like phase comprising a low molecular weight gel former with a molar mass of up to 2000 g / mol and a polymeric gel former with a molar mass of 10,000 g / mol to 200,000 g / mol.

28. Shaped body according to items 28, wherein the second gel-like phase comprises a polymeric gel former with a molar mass of 10,000 g / mol to 40,000 g / mol.

29. Shaped body according to one of points 27 or 28, wherein the second gel-like phase, based on its total weight, has a weight fraction of polymeric forming agent of 0.01 to 15% by weight, preferably 0.1 to 12% by weight and in particular of 1 to 10% by weight.

30. Shaped body according to one of items 27 to 29, wherein the polymeric gel former is selected from the group of

Celluloses and cellulose derivatives, in particular methyl cellulose, hydroxypropylmethyl cellulose and hydroxypropyl cellulose;

Starch, in particular potato starch, corn starch, wheat starch, pea starch or tapioca starch; Polyacrylates;

Polyvinyl pyrrolidones;

Polyvinyl alcohols.

31. Shaped body according to one of items 27 to 30, wherein the polymeric gel former is selected from the group of polyvinyl alcohols.

32. Shaped body according to one of items 27 to 31, the weight ratio of dibenzylidene sorbitol to polyvinyl alcohol being 10: 1 to 1:20, preferably 8: 1 to 1:15 and in particular 6: 1 to 1:10.

33. Shaped body according to one of the preceding points, the proportion by weight of the second gel-like phase in the total weight of the shaped body being 0.9 to 19% by weight, preferably 1.9 to 13% by weight.

34. Shaped body according to one of the preceding points, the active ingredient particle having a maximum diameter of 1 to 80 μm, preferably 5 to 40 μm.

35. Shaped body according to one of the preceding points, the proportion by weight of the active ingredient particles in the total weight of the second gel-like phase being 0.1 to 20% by weight, preferably 0.2 to 10% by weight and in particular 0.5 to 8% by weight % is.

36. Shaped body according to one of the preceding points, a core-shell particle being used as the active material particle.

37. Shaped body according to one of the preceding points, wherein the active ingredient particle contains fragrance.

38. Shaped body according to one of the preceding points, wherein a core-shell particle is used as the active material particles and the core-shell particles are based on their total weight

i) 10 to 60% by weight, preferably 20 to 40% by weight of perfume

ii) 5 to 30% by weight, preferably 10 to 25% by weight, of shell material.

39. Shaped body according to one of the preceding points, wherein a core-shell particle is used as the active material particle and the shell comprises a material from the group consisting of polyurethane, polylactic acid, polyurea, polyamide and melamine-formaldehyde resin.

40. Washing or cleaning agent combination product, comprising a solid or liquid washing or cleaning agent and at least one shaped body according to one of the preceding points.

41. Method for producing a molded body according to any one of items 1 to 39, comprising the steps: a) introduction of active substance particles with a maximum diameter between 1 and 200 μm into a liquid phase with the formation of a suspension;

42. The method according to item 41, wherein the mixture produced in step a) is dripped into a hardening bath for hardening.

43. The method according to any of the preceding points, wherein the second liquid phase in step d) has a temperature between 30 ° C and 180 ° C, preferably between 60 ° C and 160 ° C.

44. A method for cleaning a textile surface using a molded body according to any one of items 1 to 39.

45. A method for maintaining a textile surface using a molded body according to one of items 1 to 39.

46. The method according to one of items 44 or 45, wherein a molded body according to one of items 1 to 39 is introduced into the washing liquor of a textile washing machine.

47. Process for cleaning a glass, metal or ceramic surface using a shaped body according to one of points 1 to 39.

Claims

1 . Shaped body comprising

a) a first gel phase

b) at least one second gel-like phase different from the first gel-like phase, the first gel-like phase containing active substance particles with a maximum diameter between 1 and 200 μm and being at least partially enclosed by the second gel-like phase.

2. Shaped body according to claim 1, wherein the first gel-like phase is transparent.

3. Shaped body according to one of the preceding claims, wherein the first gel phase

a1) 40 to 99% by weight of solvent

a2) 0.01 to 15 wt .-% gel former from the group of hydrocolloids

includes.

4. Shaped body according to one of the preceding claims, wherein the second gel-like phase is completely enclosed by the first gel-like phase.

5. Shaped body according to one of the preceding claims, wherein the second gel-like phase is transparent.

6. Shaped body according to one of the preceding claims, wherein the second gel-like phase

b1) 10 to 98% by weight of solvent

b2) 0.01 to 15% by weight of gel former

includes.

7. Shaped body according to one of the preceding claims, wherein a core-shell particle is used as the active material particle.

8. Shaped body according to one of the preceding claims, wherein the active ingredient particle contains fragrance.

9. A method for producing a molded body according to any one of claims 1 to 8, comprising the steps:

a) introduction of active substance particles with a maximum diameter between 1 and 200 μm in a liquid phase with the formation of a suspension;

c) applying a second liquid phase different from the first liquid phase to the surface of the first gel-like molded body; d) hardening of the second liquid phase with the formation of a gel-like shaped body which at least partially encloses the first gel-shaped shaped body.

10. A method for cleaning or caring for a textile surface using a shaped body according to any one of claims 1 to 8.