Multilayer system comprising compositions having specific perfume compositions

Abstract

The invention relates to a multilayer system comprising (a) a first layer and (b) a second layer, each layer comprising or consisting of a composition having at least one specific perfume composition. The invention also relates to a means comprising the multilayer system according to the invention. The invention further relates to a method for fragrancing a toilet, wherein a multilayer system according to the invention is used in at least one method step. Furthermore, a method for producing the multilayer system according to the invention and the use of the multilayer system according to the invention for fragrancing a toilet are aspects of the invention.

Description

[0001] The invention relates to a multilayer system comprising (a) a first layer and (b) a second layer, wherein each layer comprises or consists of a composition that includes at least one specific perfume composition. The invention further relates to an agent comprising the multilayer system according to the invention. The invention also relates to a method for scenting a toilet, wherein a multilayer system according to the invention is used in at least one method step. Furthermore, a method for producing the multilayer system according to the invention and the use of the multilayer system according to the invention for scenting a toilet are aspects of the invention.

[0002] NECA (Non-electrical-continuous-action) air fresheners, or liquid, gel, or solid active ingredient preparations for the toilet, are formulated with high concentrations of perfume oils to create a fresh atmosphere and combat unpleasant odors. These air fresheners or toilet additives are typically formulated with a single perfume composition. Due to their intended use, air fresheners and toilet additives, or their perfume compositions, are usually formulated to deliver the same intensity and fragrance impression for weeks after activation. Both NECAs and other technical systems are designed to always release a complete "perfume composition" consisting of top, middle, and base notes into the room, where it is perceived. The FMCG (Fast-moving consumer goods) market...(fast-moving consumer goods) shows the need for products that never smell the same and that are constantly changing, i.e., products that always smell different and new, without a habituation effect like with classic room fragrances.

[0003] The individual components of a classically composed perfume evaporate at different rates. The temporal progression in the perception of a perfume's scent is called its development. This development is subdivided into fragrance notes, which usually blend seamlessly into one another. A distinction is made between three fragrance notes: top note, heart note, and base note. Perfumes usually contain all three notes. The top note of a perfume is responsible for the 'first impression' it conveys. The top note typically consists of intense, light, and highly volatile fragrance substances with a maximum perception duration of several minutes. The heart note is the scent that becomes perceptible once the top notes have evaporated. The heart note of a perfume is responsible for its actual fragrance character. The heart note consists of fragrance substances with a maximum perception duration of several hours. The base note is the scent that is perceived last.It typically contains long-lasting, heavy fragrances that can linger for days.

[0004] Due to significant variations in the processing of ceramic materials, toilets exhibit a high degree of diversity in their flushing behavior. Nevertheless, toilet additives typically show an olfactory delta, i.e., a perceived increase in the intensity of the fragrance, due to the flushing water overflowing or flowing around them. This is caused by the dissolution of the soap-like or gel-like active ingredient preparation, in which these toilet additives are usually formulated, and by turbulence and air movement generated by the flushing water in the toilet. These fragrances are classically composed in the same way as NECA air fresheners. Fragrances are used that are released well to very well into the surrounding air at room temperature. EP 3331982 A2 and EP 1051477 B1 both feature multi-layered toilet blocks in which the fragrance impression changes over time.

[0005] It has now been surprisingly discovered that systems consisting of two or more layers, each preferably containing a different perfume composition, preferably air fresheners or toilet additives, especially liquid or gel-based toilet rim blocks, repeatedly produce a new and / or changing fragrance experience over time. Preferably, the individual layers are liquid or gel-based. Particularly when flushing water is released in a toilet and the (gel) layers are washed away during use, an olfactory delta occurs; that is, the perceived intensity and fragrance impression / scent progression, achieved over the entire life cycle of the toilet additive, changes once or several times during use. In the context of this invention, this change is also referred to as a perception lift.

[0006] Thus, in a first aspect, the invention relates to a multi-layer system comprising (a) a first layer comprising or consisting of a composition comprising at least one perfume composition, wherein the perfume composition comprises (i) 0.01 wt% to 30 wt% of at least one fragrance having a vapor pressure at 25 °C of >0.0133 kPa and a ClogP ≤2.5; and (ii) less than 15 wt% of at least one fragrance having a vapor pressure at 25 °C of <0.000133 kPa and a ClogP ≥4.0; (b) a second layer comprising or consisting of a composition comprising at least one perfume composition, wherein the perfume composition comprises (i) 0.01 wt% to 20 wt% of at least one fragrance having a vapor pressure at 25 °C of >0.0133 kPa and a ClogP ≤2.5; and (ii) more than 55 wt.% of at least one fragrance ingredient having a vapor pressure at 25 °C of <0.000133 kPa and a ClogP ≥4.0; comprises.

[0007] Particularly preferably, the first and / or second layer of the multilayer system are liquid or gel-like at room temperature (20°C and standard pressure (1 bar)). In various embodiments, the first and second layers are directly adjacent, i.e., they abut each other with at least one surface. Typically, the first layer is located below or above the second layer. In various embodiments of the invention, the layers are water-soluble or water-dispersible, i.e., they dissolve or their components disperse upon contact with water. This property refers to the behavior under standard conditions, i.e., at room temperature (20°C) and standard pressure (1 bar). In various embodiments, the first and second layers, and optionally each subsequent layer, are arranged such that they come into contact with the environment, and in particular water, only sequentially.This is typically achieved by arranging the layers one on top of the other in a container, so that only the uppermost layer comes into contact with the environment, such as the ambient air or rinse water. Only when the uppermost layer has gradually dissolved or dispersed in the rinse water does the next, underlying layer come into contact with the environment, usually the rinse water. This successive dissolution of the various layers creates a changing fragrance impression. The altered fragrance impression is caused by the different perfume compositions contained in the respective layers.

[0008] In a further aspect, the invention relates to an agent comprising the multi-layer system according to the invention. The multi-layer system can also be such an agent. Examples of such agents are toilet cleaners or toilet blocks, particularly those in gel form.

[0009] Another aspect of the invention is a method for scenting a toilet, wherein the inventive multi-layer system or the inventive agent is used in at least one process step. It is particularly preferred that the scent impression changes over time.

[0010] In a further aspect, the invention relates to a method for producing the multilayer system according to the invention. Preferably, the compositions of the first layer and / or the second layer are melted at a minimum of 50 °C and then cast in layer form.

[0011] In a final aspect, the invention relates to the use of the multi-layer system or the means according to the invention for scenting a toilet, wherein the scent impression preferably changes over time.

[0012] These and other aspects, features, and advantages of the invention will become apparent to the person skilled in the art upon studying the following detailed description and claims. Each feature from one aspect of the invention can be incorporated into any other aspect of the invention. Furthermore, it is understood that the examples contained herein are intended to describe and illustrate the invention, but do not limit it, and in particular, the invention is not limited to these examples.

[0013] All percentages are weight percentages unless otherwise stated. Numerical ranges specified in the format "from x to y" include the stated values. If multiple preferred numerical ranges are specified in this format, it is understood that all ranges resulting from the combination of the different endpoints are also included. Numerical values ​​stated herein without decimal places refer to the full stated value with one decimal place. For example, "99%" means "99.0%".

[0014] "At least one," as used herein, includes but is not limited to 1, 2, 3, 4, 5, 6, and more. When referring to an ingredient, the statement refers to the type of ingredient and not the absolute number of molecules. Thus, "at least one fragrance" means, for example, at least one type of fragrance, i.e., it may refer to one type of fragrance or a mixture of several different fragrances. When used with weight specifications, the statement refers to all compounds of the specified type contained in the composition / mixture, i.e., the composition contains no further compounds of that type beyond the specified quantity of the relevant compounds.

[0015] According to the invention, the multilayer system described in more detail below is characterized by the fact that it comprises at least a first and a second layer, wherein (a) the first layer comprises or consists of a composition comprising at least one perfume composition, wherein the perfume composition comprises (i) 0.01 wt% to 30 wt% of at least one fragrance having a vapor pressure at 25 °C of >0.0133 kPa and a ClogP ≤2.5; and (ii) less than 15 wt% of at least one fragrance having a vapor pressure at 25 °C of <0.000133 kPa and a ClogP ≥4.0; (b) the second layer comprises or consists of a composition comprising at least one perfume composition, wherein the perfume composition comprises (i) 0.01 wt% to 20 wt% of at least one fragrance having a vapor pressure at 25 °C of >0.0133 kPa and a ClogP ≤2.5; and (ii) more than 55 wt.% of at least one fragrance ingredient having a vapor pressure at 25 °C of < 0.000133 kPa and a ClogP ≥4.0; comprises.

[0016] In the context of the present invention, the term "perfume composition" refers to mixtures of two or more fragrance compounds and thus includes, for example, synthetic products of the type of esters, ethers, aldehydes, ketones, alcohols and hydrocarbons, as well as natural fragrance mixtures such as those obtainable from plant sources.

[0017] The scent of an odorant / fragrance is perceived as pleasant by most people and often corresponds to the smell of, for example, flowers, fruits, spices, bark, resin, leaves, grasses, mosses, and roots. Thus, odorants / fragrances can also be used to mask unpleasant smells or to imbue an odorless substance with a desired scent.

[0018] Typically, the structure of perfume compositions is described as classified below (see also the international patent application WO2016 / 200761 A2): Top note: Vapor pressure at 25°C: > 0.0133kPa Heart note: Vapor pressure at 25°C: 0.0133 - 0.000133kPa Base note: Vapor pressure at 25°C: < 0.000133kPa.

[0019] The vapor pressure is determined, for example, using the commercially available program EPI-Suite 4.11 (MPBPWIN v 1.43 (modified grain method)). Unless otherwise stated, the values ​​given herein were calculated using this program.

[0020] In addition, it was found that the ClogP value of odorants, which is a measure of a compound's hydrophilicity, is also a crucial factor in odor perception. Depending on the ClogP value, certain odorants are washed away at different rates, thus further enhancing the multisensory effect. For example, odorants with ClogP values ​​of 2.5 or less are washed away more quickly and dispersed more effectively in the room than, for example, odorants with a ClogP of 4 or greater. The ClogP value is the n-octanol-water partition coefficient of a chemical compound and can be calculated for any chemical compound. Suitable programs for performing such calculations, or lists of corresponding ClogP values, are known in the art and readily available to those skilled in the art. One suitable program is, for example, EPI-Suite 4.11 (KOWWIN v 1.68).Unless otherwise stated, the values ​​mentioned herein were calculated using this program.

[0021] In various embodiments, the fragrance (i) of the first layer has a vapor pressure at 25 °C of >0.05 kPa, for example >0.1 kPa, >0.5 kPa, >1 kPa, or >10 kPa. The ClogP is ≤2.0 in various embodiments, for example ≤1.5, ≤1, or ≤0.5. In various embodiments, the fragrance (ii) of the first layer has a vapor pressure at 25 °C of <0.00001 kPa, for example <0.000001 kPa. The ClogP is ≥4.5 in various embodiments, for example ≥5. In various embodiments, the fragrance (i) of the second layer has a vapor pressure at 25 °C of >0.05 kPa, for example >0.1 kPa, >0.5 kPa, >1 kPa, or >10 kPa. The ClogP is ≤2.0 in various embodiments, for example ≤1.5, ≤1 or ≤0.5. In various embodiments, the fragrance (ii) of the second layer has a vapor pressure at 25 °C of <0.00001 kPa, for example <0.000001 kPa.The ClogP is ≥4.5 in various embodiments, for example ≥5.

[0022] In preferred embodiments, the multilayer system is a liquid / gel-like multilayer system. In particular, the individual layers can be present as homogeneous solutions or suspensions.

[0023] "Liquid," as used herein, includes liquids and gels as well as pasty compositions. It is preferred that the liquid compositions are free-flowing and pourable at room temperature, but it is also possible that they have a yield point. It is particularly preferred that the first and / or the second layer be liquid or gel-like. Preferably, both the first and the second layer are liquid or gel-like. Particularly preferred are all layers of the multilayer system being liquid or gel-like, i.e., in particular, all being liquid or all being gel-like, preferably exhibiting substantially the same viscosities and flow properties. The layers should preferably have a consistency that prevents mixing of the layers during manufacture, storage, use, or application. Although not preferred, it is not excluded that at least one layer is solid at room temperature.

[0024] In various embodiments, the first layer in the multilayer system is first placed in a container, and then the second layer is added on top. In other embodiments, the arrangement of the layers is exactly the opposite. Then, the composition for the second layer is placed in a container first, and then the composition for the first layer is added on top.

[0025] It is further preferred that the at least one perfume composition of the first layer and / or the perfume composition of the second layer comprises at least one additional fragrance ingredient with a vapor pressure at 25 °C of 0.0133 to 0.000133 kPa. Such an additional fragrance ingredient may, in various embodiments, have a ClogP value in the range of 2 to 4. In particularly preferred embodiments, both the first layer and the second layer comprise such an additional fragrance ingredient.

[0026] At least one fragrance ingredient of the multilayer system according to the invention can, for example, be an aldehyde, preferably selected from Adoxal (2,6,10-Trimethyl-9-undecenal), Anisaldehyde (4-Methoxybenzaldehyde), Cymal (3-(4-Isopropylphenyl)-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, Undecylenaldehyde, Vanillin, 2,6,10-Trimethyl-9-undecenal, 3-Dodecen-1-al, alpha-n-amylcinnamaldehyde, Melonal (2,6-dimethyl-5-heptenal), 2,4-di-methyl-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]acetaldehyd, 4-Isopropylbenzylaldehyd, 1,2,3,4,5,6,7,8-Octahydro-8,8-dimethyl-2-naphthaldehyd, 2,4-Dimethyl-3-cyclohexen-1-carboxaldehyd, 2-Methyl-3-(isopropylphenyl)propanal, 1-Decanal, 2,6-Dimethyl-5-heptenal, 4-(Tricyclo[5.2.1.0(2,6)]-decyliden-8)-butanal, Octahydro-4,7-methan-1H-indencarboxaldehyd, 3-Ethoxy-4-hydroxybenzaldehyd, para-Ethyl-alpha,alpha-dimethylhydrozimtaldehyd, alpha-Methyl-3,4-(methylendioxy)-hydrozimtaldehyd, 3,4-Methylendioxybenzaldehyd, alpha-n-Hexylzimtaldehyd, m-Cymen-7-carboxaldehyd, alpha-Methylphenylacetaldehyd, 7-Hydroxy-3,7-dimethyloctanal, Undecenal, 2,4,6-Trimethyl-3-cyclohexen-1-carboxaldehyd, 4-(3)(4-Methyl-3-pentenyl)-3-cyclohexencarboxaldehyd, 1-Dodecanal, 2,4-Dimethylcyclohexen-3-carboxaldehyd, 4-(4-Hydroxy-4-methylpentyl)-3-cylohexen-1-carboxaldehyd, 7-Methoxy-3,7-dimethyloctan-1-al, 2-Methylundecanal, 2-Methyldecanal, 1-Nonanal, 1-Octanal, 2,6,10-Trimethyl-5,9-undecadienal, 2-Methyl-3-(4-tert-butyl)propanal, Dihydrozimtaldehyd, 1-Methyl-4-(4-methyl-3-pentenyl)-3-cyclohexen-1-carboxaldehyd, 5- oder 6-Methoxyhexahydro-4,7-methanindan-1- oder -2-carboxaldehyd, 3,7-Dimethyloctan-1-al, 1-Undecanal, 10-Undecen-1-al, 4-Hydroxy-3-methoxybenzaldehyd, 1-Methyl-3-(4-methylpentyl)-3-cyclohexencarboxaldehyd, 7-Hydroxy-3J-dimethyl-octanal, trans-4-Decenal, 2,6-Nonadienal, para-Tolylacetaldehyd, 4-Methylphenylacetaldehyd, 2-Methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal, ortho-Methoxyzimtaldehyd, 3,5,6-Trimethyl-3-cyclohexen-carboxaldehyd, 3J-Dimethyl-2-methylen-6-octenal, Phenoxyacetaldehyd, 5,9-Dimethyl-4,8-decadienal, Päonienaldehyd (6,10-Dimethyl-3-oxa-5,9-undecadien-1-al), Hexahydro-4,7-methanindan-1-carboxaldehyd, 2-Methyloctanal, alpha-Methyl-4-(1-methylethyl)benzolacetaldehyd, 6,6-Dimethyl-2-norpinen-2-propionaldehyd, para-Methylphenoxyacetaldehyd, 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-ene-2-carbaldehyde, 9-Decenal, 3-Methyl-5-phenyl-1-pentanal, Methylnonylacetaldehyde, Hexanal and / or trans-2-Hexenal. Mixtures of the aforementioned substances may also be used.

[0027] In various embodiments, at least one fragrance ingredient of the multilayer system according to the invention can be a ketone, preferably selected from 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, koavone (3,4,5,6,6-pentamethylhept-3-en-2-one), fenchone, alpha-ionone, beta-ionone, gamma-methyl-ionone, fleuramone (2-heptylcyclopentanone), 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)), methylcedrenyl ketone, acetophenone, methylacetophenone, para-methoxyacetophenone, methyl-beta-naphtylketone, benzylacetone, Benzophenone, para-hydroxyphenylbutanone, celery ketone (3-methyl-5-propyl-2-cyclohexenone), 6-isopropyldecahydro-2-naphtone, dimethyl octenone,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-acetonaphthone-1,2,3,4,5,6,7,8-octahydro-2,3,8,8-tetramethyl), methyl nonyl ketone, methyl cyclocitron, methyl lavender ketone, Orivon (4-tert-amyl-cyclohexanone), 4-tert-butylcyclohexanone, Delphon (2-pentyl-cyclopentanone), Muscone (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 / or tetrameran (6,10-dimethylundecen-2-one). Mixtures of the aforementioned substances may also be used.

[0028] In a further embodiment, at least one fragrance ingredient of the multilayer system according to the invention can be an alcohol, preferably selected from 10-Undecen-1-ol, 2,6-Dimethylheptan-2-ol, 2-Methylbutanol, 2-Methylpentanol, 2-Phenoxyethanol, 2-Phenylpropanol, 2-tert-Butycyclohexanol, 3,5,5-Trimethylcyclohexanol, 3-Hexanol, 3-Methyl-5-phenylpentanol, 3-Octanol, 3-Phenyl-propanol, 4-Heptenol, 4-Isopropylcyclohexanol, 4-tert.-Butycyclohexanol, 6,8-dimethyl-2-nona-nol, 6-nonen-1-ol, 9-decen-1-ol, α-methylbenzyl alcohol, α-terpineol, amyl salicylate, benzyl alcohol, benzyl salicylate, β-terpineol, butyl salicylate, citronellol, cyclohexyl salicylate, decanol, Dihydromyrcenol, dimethylbenzylcarbinol, dimethylheptanol, dimethyloctanol, ethyl salicylate, ethyl vaniline, 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-nonen-1-ol, trans-2-octenol, undecanol, vanillin, champiniol, hexenol and / or cinnamyl alcohol. Mixtures of the aforementioned substances may also be used.

[0029] Examples of ester-type fragrance compounds include benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate (DMBCA), phenylethyl acetate, benzyl acetate, ethylmethylphenylglycinate, allylcyclohexyl propionate, styralylli propionate, benzyl salicylate, cyclohexyl salicylate, Floramate, Melusate, and Jasmacyclate. Ethers include, for example, benzyl ethyl ether and ambroxane, while hydrocarbons mainly include terpenes such as limonene and pinene. However, mixtures of different fragrance compounds are preferred, as they combine to create an appealing scent.

[0030] In a further embodiment, at least one fragrance ingredient of the multilayer system according to the invention can be an essential oil, such as angelica root oil, anise oil, arnica flower oil, basil oil, bay oil, champaca flower oil, citrus oil, silver fir oil, silver fir cone oil, elemi oil, eucalyptus oil, fennel oil, spruce needle oil, galbanum oil, geranium oil, ginger grass oil, guaiac wood oil, gurjun balsam oil, helichrysum oil, ho oil, ginger oil, iris oil, jasmine oil, cajeput oil, calamus oil, chamomile oil, camphor oil, kanaga oil, cardamom oil, cassia oil, pine needle oil, copaiba balsam oil, coriander oil, spearmint oil, caraway oil, cumin oil, labdanum oil, lavender oil, lemongrass oil, linden flower oil, lime oil, mandarin oil, lemon balm oil, mint oil, musk seed oil, muscatel oil. Myrrh oil, clove oil, neroli oil, niaouli oil, frankincense oil, orange blossom oil, orange peel oil, oregano oil, palmarosa oil, patchouli oil, Peruvian balsam oil, petitgrain oil, pepper oil, peppermint oil, pimento oil, pine oil, rose oil, rosemary oil, sage oil, sandalwood oil, celery oil, spikenard oilStar anise 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 leaf oil, citronella oil, lemon oil, cypress oil, ambrettolide, ambroxan, alpha-amylcinnamaldehyde, anethole, anisaldehyde, anisic alcohol, anisole, methyl anthranilate, acetophenone, benzylacetone, benzaldehyde, ethyl benzoate, benzophenone, benzyl alcohol, benzyl acetate, benzyl benzoate, benzyl formate, benzyl valerianate, borneol, bornyl acetate, Boisambrene forte, alpha-bromostyrene, n-decylaldehyde, n-dodecylaldehyde, eugenol, eugenol methyl ether, eucalyptol, farnesol, fenchone, fenchyl acetate, geranyl acetate Geranyl formate, heliotropin, heptyne carboxylic acid methyl ester, heptaldehyde, hydroquinone dimethyl ether, hydroxycinnamaldehyde, hydroxycinnamaldehyde alcohol, indole, iron, isoeugenol, isoeugenol methyl ether, isosafrole, jasmon, camphor, carvacrol, carvone, p-cresol methyl ether, coumarin, p-methoxyacetophenone, methyl n-amyl ketone, methyl anthranilic acid esterp-Methylacetophenone, Methyl chavicol, p-Methylquinoline, Methyl beta-naphthyl ketone, Methyl n-nonylacetaldehyde, Methyl n-nonyl ketone, Muscone, beta-naphthol ethyl ether, beta-naphthol methyl ether, Nerol, n-nonylaldehyde, Nonyl alcohol, n-octylaldehyde, p-oxyacetophenone, Pentadecanolide, beta-phenylethyl alcohol, Phenylacetic acid, Pulegone, Safrole, Isoamyl salicylate, Methyl salicylate, Hexyl salicylate, Cyclohexyl salicylate, Santalol, Sandelice, Skatole, Terpineol, Thymene, Thymol, Troenane, Gamma-Undelactone, Vanillin, Veratraldehyde, Cinnamaldehyde, Cinnamyl alcohol, Cinnamic acid, Ethyl cinnamic acid, Benzyl cinnamic acid, Diphenyl oxide Limonene, linalool, linalyl acetate and propionate, melusate, menthol, menthone, methyl n-heptenone, pinene, phenylacetaldehyde, terpinyl acetate, citral and / or citronellal. Mixtures of the aforementioned substances may also be used.

[0031] In preferred embodiments, the at least one perfume composition is contained in the composition of the first layer and / or the composition of the second layer in an amount of 0.001 to 30 wt.%, preferably 0.01 to 20 wt.%, more preferably 0.1 to 10 wt.%, even more preferably 0.5 to 7 wt.%, even more preferably 1 to 5 wt.%, in particular 2 to 4 wt.%, based on the total weight of the respective composition.

[0032] For example, d-limonene can be included as a perfume component. In a particularly preferred embodiment, the mixture contains adhesive fragrance substances, especially essential oils. Pine, citrus, jasmine, patchouli, rose, or ylang-ylang oils, for example, can be used as such within the meaning of this invention. Also suitable are clary sage oil, chamomile oil, lavender oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, frankincense oil, galbanum oil, and labdanum oil, as well as orange blossom oil, neroliol, orange peel oil, and sandalwood oil. Other adhesive fragrance substances, such as the higher-boiling or...Solid fragrances of natural or synthetic origin, or also more volatile fragrances, in particular the lower boiling fragrances of natural or synthetic origin, which can be used alone or in mixtures, are advantageously usable within the scope of the present invention.

[0033] In various embodiments, the at least two layers contain very different fragrances, creating a scent change from, for example, hygienic to floral. Once the first layer is used up, the scent changes. This allows for precise, olfactory formulation. This means that the consumer receives a product where it can be precisely defined that a scent change will occur and what that change will be.

[0034] The thickness or volume of the layer preferably determines how long a scent impression should last before it changes. The scent change can be continuous or, preferably, abrupt and sudden.

[0035] Preferably, a layer has a thickness of 0.01 to 10 cm, more preferably 0.05 to 5 cm, for example up to 3 cm, and even more preferably 0.1 to 1.5 cm, for example 1 cm.

[0036] In general, besides the thickness of the layer, water solubility or water dispersibility is also a factor that determines the dissolution rate. The individual layers are consumed through dissolution or dispersion in the rinse water. Typical products are formulated so that, with a normal number of rinse cycles, the product lasts approximately four weeks before it is completely consumed, i.e., all layers are used up.

[0037] According to the invention, the multilayer system comprises at least two layers. However, it can also comprise further layers, for example three or more layers, four or more layers, five or more layers, six or more layers, or eight or more layers. In various embodiments in which more than two layers are used, the perfume-containing layers can be separated by an unscented barrier layer or several such barrier layers.

[0038] However, multi-layer systems with two layers (two-layer system), as described herein, or multi-layer systems with three or four layers are particularly preferred. In such multi-layer systems, the first and second layers are as described herein; all subsequent layers can be structured similarly to the first or second layer and contain a perfume, optionally another different perfume, or alternatively, be perfume-free and then serve, for example, the purpose of separating the perfume-containing layers from one another and thereby ensuring the sharpest possible separation of the different fragrance impressions.

[0039] Preferably, the composition of the at least one further layer comprises at least one perfume composition, wherein the perfume composition (i) at least one fragrance ingredient with a vapor pressure at 25 °C of >0.0133 kPa and a ClogP ≤2.5; and (ii) at least one fragrance ingredient with a vapor pressure at 25 °C of <0.000133 kPa and a ClogP ≥4.0; and (iii) optionally a further fragrance ingredient with a vapor pressure at 25 °C of 0.0133 kPa to 0.000133 kPa; comprising.

[0040] The fragrances can be those described above and are furthermore preferably used in quantities as described above for the first or second layer. Preferred quantity ranges for fragrances in such a further layer are 0.001 to 30 wt.%, preferably 0.01 to 20 wt.%, more preferably 0.1 to 10 wt.%, even more preferably 0.5 to 7 wt.%, and still more preferably 1 to 5 wt.%, in particular 2 to 4 wt.%, in each case based on the total weight of the layer.

[0041] It is preferred that each subsequent layer is also liquid or gel-like at room temperature.

[0042] Another aspect of the invention is a means comprising a multilayer system according to the invention, as described herein.

[0043] The agent according to the invention is particularly preferably a home care product, more preferably a toilet additive product, even more preferably an air freshener or a cleaner, even more preferably a toilet cleaner or a toilet freshener, and in particular a (liquid or gel-like) toilet air freshener, for example in the form of a toilet block, which can also be liquid or gel-like and is used in a special holder.

[0044] Figure 1 Figure 1 shows a cross-section of a two-layer system which was cast in an approximately hemispherical shape into a corresponding mold. Such a mold may be preferred according to the invention. Figure 2 shows the cross-section of an arrangement of four such two-layer systems arranged side by side. Figure 3The figure shows a side cross-section of such a two-layer system in a holder and the state before and after rinsing off the top layer, thus exposing the layer below. It also shows how rinsing off the top layer results in a change of fragrance.

[0045] According to the invention, it is particularly preferred if the compositions of the individual layers are melted into a gel, i.e., liquefied, especially by the application of heat, so that they have a gel-like consistency. Preferably, the compositions are then filled layer by layer into a container or, more preferably, into a multi-chamber container. Furthermore, the compositions could be filled layer by layer into an applicator suitable for dispensing the agent, particularly onto the toilet bowl, for example by stamping or spraying.

[0046] In addition to the described perfume compositions, the multi-layer system or the agent according to the invention may contain further ingredients. In particular, typical ingredients for air fresheners, toilet blocks or toilet bowl fresheners are preferred.

[0047] In various embodiments, the composition of the first layer and / or the composition of the second layer and / or the composition of a further layer of the multilayer system or the agent according to the invention contains, in addition to the at least one perfume composition, at least one further component, preferably two or more further components, wherein the components are preferably selected from the group consisting of surfactants, dyes, rinsing regulators, humectants, bleaching agents, builders, acids, bases, solvents, antimicrobial agents, polymers, salts, thickeners, preservatives, complexing agents, odor-reducing agents, perfume boosters, fillers, bleaching agents, corrosion inhibitors, rinsing regulators, enzymes, microorganisms, biofilm-removing agents, limescale-inhibiting agents, and dirt-adherent agents.Active ingredients to improve processability and active ingredients to reduce stickiness. Mixtures of the aforementioned components may also be included. Typical main components of such coatings, besides fragrances, are water and surfactants, in particular non-ionic and anionic surfactants. These ingredients constitute at least 70% by weight, preferably at least 80% by weight, and particularly preferably at least 90% by weight of the respective coating in various embodiments.

[0048] In various embodiments of the invention, the different layers of the multilayer system are colored differently and visually distinguishable by the use of different dyes.

[0049] Preferably, at least one surfactant is included in the composition of the first layer and / or second layer and / or further layers. This surfactant is selected from the group consisting of anionic surfactants, nonionic surfactants, amphoteric or zwitterionic surfactants, cationic surfactants, and mixtures thereof. Preferably, at least one anionic surfactant is included; more preferably, at least one anionic and at least one nonionic surfactant are included.

[0050] The multilayer system according to the invention, or at least one composition thereof, contains the at least one surfactant preferably in an amount of 10 to 80 wt.%, preferably 20 to 60 wt.%, particularly preferably 25 to 55 wt.%.

[0051] Within the scope of the present invention, fatty acids or fatty alcohols or their derivatives—unless otherwise specified—are representative of branched or unbranched carboxylic acids or alcohols or their derivatives, preferably with 6 to 22 carbon atoms, more preferably 8 to 20 carbon atoms, particularly preferably 10 to 18 carbon atoms, most preferably 12 to 16 carbon atoms, for example 12 to 14 carbon atoms. The former are preferred for ecological reasons, particularly because of their plant-based origin as they are derived from renewable raw materials, without, however, limiting the teaching of the invention to them. In particular, oxo alcohols obtainable, for example, by the Roelen oxo synthesis are also considered.whose derivatives preferably have 7 to 19 carbon atoms, in particular 9 to 19 carbon atoms, especially preferably 9 to 17 carbon atoms, most preferably 11 to 15 carbon atoms, for example 9 to 11, 12 to 15 or 13 to 15 carbon atoms, can be used accordingly.

[0052] Furthermore, the compositions may contain at least one alkylbenzenesulfonate and / or at least one olefinsulfonate. They may also contain other surfactants, in particular from the group of anionic and / or nonionic surfactants.

[0053] Further anionic surfactants that can be used in the multilayer system according to the invention include aliphatic sulfates such as fatty alcohol sulfates, fatty alcohol ether sulfates, dialkyl ether sulfates, monoglyceride sulfates, and aliphatic sulfonates such as alkanesulfonates, ethersulfonates, n-alkyl ethersulfonates, estersulfonates, and lignosulfonates. Also usable within the scope of the present invention are fatty acid cyanamides, sulfosuccinates (sulfosuccinic acid esters), in particular sulfosuccinic acid mono- and di-C8-C18 alkyl esters, sulfosuccinamates, sulfosuccinamides, fatty acid isethionates, acylaminoalkanesulfonates (fatty acid taurides), fatty acid sarcosinates, ether carboxylic acids and alkyl (ether) phosphates, as well as α-sulfofatisfied acid salts, acylglutamates, monoglyceride disulfates, and alkyl ethers of glycerin disulfate.

[0054] Preferably, within the scope of the present invention, are fatty alcohol sulfates and / or fatty alcohol ether sulfates. Fatty alcohol sulfates are products of sulfation reactions on corresponding alcohols, while fatty alcohol ether sulfates are products of sulfation reactions on alkoxylated alcohols. Those skilled in the art generally understand alkoxylated alcohols to be the reaction products of alkylene oxides, preferably ethylene oxide, with alcohols, and, within the meaning of the present invention, preferably with longer-chain alcohols. Typically, from n moles of ethylene oxide and one mole of alcohol, depending on the reaction conditions, a complex mixture of addition products with varying degrees of ethoxylation is formed. Another embodiment of the alkoxylation involves the use of mixtures of alkylene oxides, preferably the mixture of ethylene oxide and propylene oxide.Preferred fatty alcohol ether sulfates are the sulfates of low ethoxylated fatty alcohols with 1 to 4 ethylene oxide units (EO), in particular 1 to 2 EO, for example 1,3 EO.

[0055] The anionic surfactants are preferably used as sodium salts, but can also be present as other alkali or alkaline earth metal salts, for example magnesium salts, as well as in the form of ammonium or mono-, di-, tri- or tetraalkylammonium salts, and in the case of sulfonates also in the form of their corresponding acid, e.g. dodecylbenzenesulfonic acid.

[0056] In various embodiments, the composition contains at least one alkylbenzenesulfonic acid, preferably in the form of its sodium salt, in an amount of approximately 10 to 30 wt.%, preferably approximately 20 to 25 wt.%, in each case based on the total weight of said composition.

[0057] Nonionic surfactants within the scope of the invention can be alkoxylates such as polyglycol ethers, fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, end-capped polyglycol ethers, mixed ethers, hydroxy mixed ethers, and fatty acid polyglycol esters. Ethylene oxide / propylene oxide block polymers, fatty acid alkanolamides, and fatty acid polyglycol ethers are also suitable. Another important class of nonionic surfactants that can be used according to the invention are the polyol surfactants, and in particular the glycotidical surfactants, such as alkyl polyglycosides and fatty acid glucamides. Alkyl polyglycosides, and especially fatty alcohol alkoxylates (fatty alcohol polyglycol ethers), are particularly preferred.

[0058] Preferred fatty alcohol alkoxylates are unbranched or branched, saturated or unsaturated Cs-22 alcohols with a degree of alkoxylation up to 30, alkoxylated with ethylene oxide (EO) and / or propylene oxide (PO), preferably ethoxylated C 12-22 fatty alcohols with a degree of ethoxylation of less than 30, preferably 12 to 28, in particular 20 to 28, particularly preferably 25, for example C 16-18 fatty alcohol ethoxylates with 25 EO.

[0059] Alkyl polyglycosides are surfactants that can be obtained by reacting sugars and alcohols according to the relevant processes of preparative organic chemistry, resulting, depending on the method of preparation, in a mixture of monoalkylated, oligomeric, or polymeric sugars. Preferred alkyl polyglycosides are the alkyl polyglucosides, wherein the alcohol is particularly preferably a long-chain fatty alcohol or a mixture of long-chain fatty alcohols with branched or unbranched Cs to Cis alkyl chains, and the degree of oligomerization (DP) of the sugars is between 1 and 10, preferably 1 to 6, particularly 1.1 to 3, and most preferably 1.1 to 1.7, for example, C8-10-alkyl-1,5-glucoside (DP of 1.5).

[0060] Preferably, fatty alcohol ethoxylates are used in amounts of up to 20 wt%, particularly preferably 4 to 12 wt%, and particularly preferably 7 to 9 wt%. In addition, other nonionic surfactants, such as fatty acid monoalkanolamides and / or alkyl polyglycosides, may be present in amounts of up to 10 wt%.

[0061] In addition to the surfactant types mentioned so far, the mixture may also contain cationic surfactants and / or amphoteric or zwitterionic surfactants.

[0062] Suitable amphoteric surfactants are, for example, betaines of the formula (R iii< )(R iv< )(R v< )N +< CH 2 COO -< , in which R iii< represents an alkyl group with 8 to 25, preferably 10 to 21 carbon atoms, optionally interrupted by heteroatoms or heteroatom groups, and R iv< and R v< represent similar or different alkyl groups with 1 to 3 carbon atoms, in particular C 10 -C 18 -alkyl-dimethylcarboxymethyl betaine and C 11 -C 17 -alkylamidopropyl-dimethylcarboxymethyl betaine.

[0063] Suitable cation surfactants include, among others, the quaternary ammonium compounds of the formula (Rvi)(Rvii)(Rviii)(Rix)N<+X<-, in which Rvi to Rix represent four identical or different alkyl groups, in particular two long-chain and two short-chain, and X- represents an anion, in particular a halide ion, for example didecyldimethylammonium chloride, alkylbenzyldidecylammonium chloride, and mixtures thereof. Quaternary ammonium compounds with antimicrobial activity are preferred.

[0064] In various embodiments, it is preferred if, in addition to at least one perfume composition and at least one surfactant as defined above, a total of no more than 60 wt.% of further ingredients are included, preferably 0.01 to 60 wt.%, in particular 0.2 to 15 wt.%, in each case based on the total weight of the respective composition.

[0065] Particularly preferred are anionic surfactants such as sodium lauryl ether sulfates and non-ionic surfactants such as ethoxylated C16-C18 (fat) alcohols or ethoxylated C9-C11 (fat) alcohols. These are used in various embodiments, for example, in amounts of 0.1 to 60 wt.%, preferably 1 to 50 wt.%, based on the total weight of the composition.

[0066] To enhance cleaning performance against limescale and urine scale, the composition of the first layer and / or the second layer and / or a further optional layer can contain one or more acids and / or their salts. Preferably, the acids are produced from renewable raw materials. Therefore, suitable acids include, in particular, organic acids such as formic acid, acetic acid, citric acid, glycolic acid, lactic acid, succinic acid, adipic acid, malic acid, tartaric acid, and gluconic acid, as well as mixtures thereof. In addition, the inorganic acids hydrochloric acid, sulfuric acid, phosphoric acid, and nitric acid, or even sulfamic acid or mixtures thereof, can also be used. Particularly preferred are the acids and / or their salts selected from the group comprising citric acid, lactic acid, formic acid, their salts, and mixtures thereof. They are preferably used in amounts of 0.01 to 10 wt.%, and particularly preferably 0.2 to 5 wt.%.

[0067] In addition, inorganic salts may be present in the composition of one or more of the layers, preferably alkali or alkaline earth metal salts, in particular carbonates, sulfates, halides, or phosphates, as well as mixtures thereof. Sodium sulfate and / or sodium carbonate are particularly preferred. Sodium sulfate may be present in an amount of up to 60 wt.%, preferably 0.01 to 60 wt.%, particularly preferably 20 to 60 wt.%, and in particular 35 to 55 wt.%. Sodium carbonate and other salts may be present in an amount of up to 30 wt.%, preferably up to 10 wt.%, and particularly preferably up to 5 wt.%.

[0068] Furthermore, alkalis may be included. Preferably, bases from the group of alkali and alkaline earth metal hydroxides and carbonates, in particular sodium carbonate or sodium hydroxide, are used. However, ammonia and / or alkanolamines with up to 9 carbon atoms in the molecule can also be used, preferably ethanolamines, especially monoethanolamine.

[0069] Disinfection and sanitation represent a special form of cleaning. In various embodiments of the invention, the composition of one or more layers can therefore contain one or more antimicrobial agents, preferably in an amount of up to 40 wt.%, more preferably 0.01 to 25 wt.%, more preferably 0.1 to 5 wt.%, in particular 0.1 to 3.5 wt.%, and most preferably 0.5 to 3 wt.%, in each case based on the total weight of the respective composition.

[0070] Within the context of the invention, the terms disinfection, sanitation, antimicrobial effect, and antimicrobial agent have their customary meanings. While disinfection, in the narrower sense of medical practice, means the killing of—theoretically all—infectious agents, sanitation refers to the elimination of all germs—including saprophytic germs, which are normally harmless to humans—to the greatest extent possible. The degree of disinfection or sanitation depends on the antimicrobial effect of the agent used, which decreases with decreasing concentration of antimicrobial agent or increasing dilution of the agent.

[0071] Suitable according to the invention are, for example, antimicrobial agents from the groups of alcohols, aldehydes, antimicrobial acids or their salts, carboxylic acid esters, acid amides, phenols, phenol derivatives, diphenyls, diphenylalkanes, urea derivatives, oxygen and nitrogen acetals and formals, benzamidines, isothiazoles and their derivatives such as isothiazolines and isothiazolinones, phthalimide derivatives, pyridine derivatives, antimicrobial surfactants, guanidines, antimicrobial amphoteric compounds, quinolines, 1,2-dibromo-2,4-dicyanobutane, iodo-2-propynyl butylcarbamate, iodine, iodophores, active chlorine-releasing compounds and peroxides.Preferred antimicrobial agents are preferably selected from the group comprising ethanol, n-propanol, i-propanol, 1,3-butanediol, phenoxyethanol, 1,2-propylene glycol, glycerol, undecylenic acid, citric acid, lactic acid, benzoic acid, salicylic acid, thymol, 2-benzyl-4-chlorophenol, 2,2'-methylene-bis-(6-bromo-4-chlorophenol), 2,4,4'-trichloro-2'-hydroxydiphenyl ether, N-(4-chlorophenyl)-N-(3,4-dichlorophenyl)-urea, N,N'-(1,10-decandiyldi-1-pyridinyl-4-ylidene)-bis-(1-octanamine)-dihydrochloride, N,N'-Bis-(4-chlorophenyl)-3,12-diimino-2,4,11,13-tetraazatetradecanediimidamide, antimicrobial quaternary surfactants, guanidines, and sodium dichloroisocyanurate (DCI, 1,3-dichloro-5H-1,3,5-triazine-2,4,6-trione sodium salt). Preferred antimicrobial quaternary surfactants contain an ammonium, sulfonium, phosphonium, iodonium, or arsonium group.Furthermore, antimicrobial essential oils can also be used, which simultaneously provide fragrance to the cleaning agent. Particularly preferred antimicrobial agents are selected from the group comprising salicylic acid, quaternary surfactants, especially benzalkonium chloride, peroxo compounds, especially sodium percarbonate, phthalimidoperoxyhexanoic acid or hydrogen peroxide, alkali metal hypochlorite, trichloroisocyanuric acid, sodium dichloroisocyanurate, and mixtures thereof. Sodium dichloroisocyanurate is particularly preferred.

[0072] Preservatives may also be included. These can essentially be the same substances mentioned in connection with antimicrobial agents.

[0073] Chelating agents (INCI), also known as sequestrants, are ingredients that can complex and inactivate metal ions to prevent their adverse effects on the stability or appearance of the product, such as cloudiness. On the one hand, it is important to complex the calcium and magnesium ions associated with water hardness, which are incompatible with numerous other ingredients. On the other hand, the complexation of ions from heavy metals such as iron or copper slows down the oxidative degradation of the finished product. Furthermore, chelating agents enhance the cleaning effect.

[0074] Geeignet sind beispielsweise die folgenden gemäß INCI bezeichneten Komplexbildner, ohne darauf beschränkt zu sein: Aminotrimethylene Phosphonic Acid, Beta-Alanine Diacetic Acid, Calcium Disodium EDTA, Citric Acid, Cyclodextrin, Cyclohexanediamine Tetraacetic Acid, Diammonium Citrate, Diammonium EDTA, Diethylenetriamine Pentamethylene Phosphonic Acid, Dipotassium EDTA, Disodium Azacycloheptane Diphosphonate, Disodium EDTA, Disodium Pyrophosphate, EDTA, Etidronic Acid, Galactaric Acid, Gluconic Acid, Glucuronic Acid, HEDTA, Hydroxypropyl Cyclodextrin, Methyl Cyclodextrin, Pentapotassium Triphosphate, Pentasodium Aminotrimethylene Phosphonate, Pentasodium Ethylenediamine Tetramethylene Phosphonate, Pentasodium Pentetate, Pentasodium Triphosphate, Pentetic Acid, Phytic Acid, Potassium Citrate, Potassium EDTMP, Potassium Gluconate, Potassium Polyphosphate, Potassium Trisphosphonomethylamine Oxide, Ribonic Acid, Sodium Chitosan Methylene Phosphonate, Sodium Citrate,Sodium Diethylenetriamine Pentamethylene Phosphonate, Sodium Dihydroxyethylglycinate, Sodium EDTMP, Sodium Gluceptate, Sodium Gluconate, Sodium Glycereth-1 Polyphosphate, Sodium Hexametaphosphate, Sodium Metaphosphate, Sodium Metasilicate, Sodium Phytate, Sodium Polydimethylglycinophenolsulfonate, Sodium Trimetaphosphate, TEA-EDTA, TEA-Polyphosphate, Tetrahydroxyethyl Ethylenediamine, Tetrahydroxypropyl Ethylenediamine, Tetrapotassium Etidronate, Tetrapotassium Pyrophosphate, Tetrasodium EDTA, Tetrasodium Etidronate, Tetrasodium Pyrophosphate, Tripotassium EDTA, Trisodium Dicarboxymethyl Alaninate, Trisodium EDTA, Trisodium HEDTA, Trisodium NTA und Trisodium Phosphate.,

[0075] Other suitable ingredients, especially for cleaners or air fresheners such as toilet bowl fresheners, are polymers. These can, for example, reduce limescale buildup and the tendency for re-soiling (so-called soil repellent polymers). Preferred polymers are acrylic polymers, such as those commercially available from Rhodia under the trade name Mirapol.

[0076] The composition of the first layer, the composition of the second layer, and / or the composition of any further layer may contain aqueous and / or organic solvents. Water, dipropylene glycol, or paraffin are particularly preferred liquids.

[0077] The product may also contain one or more colorants (INCI colorants). Both water-soluble and oil-soluble colorants can be used, taking into account compatibility with other ingredients, such as bleaching agents, and ensuring that the colorant does not adversely affect the toilet bowl ceramic, even with prolonged exposure. Preferably, a water-soluble colorant is used to color the flush water. This colored flush water remains in sufficient concentration in the toilet bowl (the residual water remaining in the bowl) after the main flushing process to impart color. The colorants are preferably present in an amount of 0.0001 to 5% by weight, particularly 0.0005 to 0.05% by weight, and most preferably 0.001 to 0.01% by weight.

[0078] It is particularly preferred that the composition of the first layer and / or the composition of the second layer and / or a composition of an optional further layer, in addition to the perfume composition, comprises at least one dye.

[0079] By incorporating dye compositions into the perfume compositions, a color change of the multi-layer system can be created.

[0080] Furthermore, active ingredients can be used to prevent or reduce unpleasant odors, so-called malodor repellents. These are generally substances that adsorb, complex, oxidize, or form inclusion compounds with the volatile substances that cause the unpleasant odor, thus inactivating them (so-called deodorants), or they are fragrances that mask the unpleasant odor with their own scent and thus neutralize it (so-called odor improvers).

[0081] In the multilayer systems produced according to the invention, one or more layers may optionally contain water-soluble and / or water-insoluble builders. Water-soluble builders are preferred because they generally tend to leave less insoluble residues on hard surfaces. Common builders that may be present within the scope of the invention are low-molecular-weight polycarboxylic acids and their salts, homopolymeric and copolymeric polycarboxylic acids and their salts, citric acid and its salts, carbonates, phosphates, and silicates. Water-insoluble builders include zeolites, which can also be used, as well as mixtures of the aforementioned builder substances.

[0082] According to the invention, bleaching agents can also be used. Suitable bleaching agents include peroxo compounds, in particular peroxides, peracids, percarbonates, and / or perborates; sodium percarbonate, phthalimidoperoxyhexanoic acid, or hydrogen peroxide are particularly preferred. Alkali metal hypochlorites such as sodium hypochlorite, on the other hand, are less suitable for acidic cleaning agents due to the release of toxic chlorine gas vapors, but can be used in alkaline cleaning agents. Trichloroisocyanuric acid and, in particular, sodium dichloroisocyanurate are also suitable. In some cases, a bleach activator may also be necessary in addition to the bleaching agent.

[0083] Suitable corrosion inhibitors (INCI Corrosion Inhibitors) include, but are not limited to, the following substances named according to INCI: Cyclohexylamine, Diammonium Phosphate, Dilithium Oxalate, Dimethylamino Methylpropanol, Dipotassium Oxalate, Dipotassium Phosphate, Disodium Phosphate, Disodium Pyrophosphate, Disodium Tetrapropenyl Succinate, Hexoxyethyl Diethylammonium, Phosphate, Nitromethane, Potassium Silicate, Sodium Aluminate, Sodium Hexametaphosphate, Sodium Metasilicate, Sodium Molybdate, Sodium Nitrite, Sodium Oxalate, Sodium Silicate, Stearamidopropyl Dimethicone, Tetrapotassium Pyrophosphate, Tetrasodium Pyrophosphate, Triisopropanolamine.

[0084] The substances known as rinsing regulators primarily serve to control the consumption of the cleaning agent during use, ensuring that the intended service life is maintained. Suitable regulators include preferably solid long-chain fatty acids, such as stearic acid, but also salts of such fatty acids, fatty acid ethanolamides, such as coconut fatty acid monoethanolamide, or solid polyethylene glycols, such as those with molecular weights between 10,000 and 50,000.

[0085] Further suitable components that can be used in the multilayer system according to the invention, preferably in a cleaner or air freshener, in particular a toilet rim blocker, are enzymes, preferably proteases, lipases, amylases, hydrolases and / or cellulases. They can be added in any form established in the prior art. This includes solutions of the enzymes, advantageously as concentrated as possible, with low water content and / or containing stabilizers. Alternatively, the enzymes can be encapsulated, for example by spray drying or extrusion of the enzyme solution together with a polymer, preferably a natural one, or in the form of capsules, for example, those in which the enzymes are enclosed as if in a solidified gel or in those of the core-shell type, in which an enzyme-containing core is coated with a protective layer impermeable to water, air and / or chemicals.Additional active ingredients, such as stabilizers, emulsifiers, pigments, bleaching agents, or dyes, can be applied in superimposed layers. Advantageously, such granules are low-dust and, due to the coating, have a stable storage life, for example, through the application of polymeric film-forming agents.

[0086] Furthermore, enzyme stabilizers may be present in enzyme-containing systems or agents to protect an enzyme contained in a system or agent according to the invention from damage such as inactivation, denaturation or degradation, for example by physical influences, oxidation or proteolytic cleavage.Depending on the specific enzyme used, the following are particularly suitable as enzyme stabilizers: benzamidine hydrochloride, borax, boric acids, boronic acids or their salts or esters, especially derivatives with aromatic groups, such as substituted phenylboronic acids or their salts or esters; peptide aldehydes (oligopeptides with a reduced C-terminus), amino alcohols such as mono-, di-, triethanolamine and ethanol-propanolamine and their mixtures, aliphatic carboxylic acids up to C12, such as succinic acid, other dicarboxylic acids or salts of the aforementioned acids; end-capped fatty acid amido alkoxylates; lower aliphatic alcohols and especially polyols, for example, glycerol, ethylene glycol, propylene glycol or sorbitol; as well as reducing agents and antioxidants such as sodium sulfite and reducing sugars. Further suitable stabilizers are known from the prior art.Preferably, combinations of stabilizers are used, for example the combination of polyols, boric acid and / or borax, the combination of boric acid or borate, reducing salts and succinic acid or other dicarboxylic acids, or the combination of boric acid or borate with polyols or polyamino compounds and with reducing salts.

[0087] It is particularly preferred that the composition of the first layer and / or the composition of the second layer and / or the composition of a further layer, in addition to the at least one perfume composition, further comprises at least one further component, preferably two or more further components, wherein the components are preferably selected from the group consisting of surfactants, in particular sodium lauryl ether sulfate, ethoxylated C16-C18 (fat) alcohols and ethoxylated C9-C11 (fat) alcohols, humectants, for example propane-1,2,3-triol, dyes, emulsifying agents, preservatives, complexing agents, solvents, acids, in particular for limescale prophylaxis, polymers, further fragrances or mixtures thereof.

[0088] In a further aspect, the invention relates to a method for scenting the toilet, wherein a multi-layer system or an agent according to the invention is used in at least one process step. It is particularly preferred that the scent changes over time. This is achieved in particular by having one layer of the multi-layer system or agent be consumed over time, and then a second layer, which has a different scent, comes into contact with the flushing water and releases its scent into the surroundings.

[0089] The scenting of the toilet preferably also includes the scenting of the room in which the toilet is located. In particular, the processed fragrances are released into the ambient air, and it is preferred that the fragrances remain in the air for as long as possible so that they can be perceived.

[0090] In addition to scenting the toilet, the multi-layer system according to the invention can also preferably be used for cleaning and / or disinfecting the toilet by using suitable ingredients, as described above. Different active ingredients can be incorporated into different layers, which are released at different times depending on the degree of flushing.

[0091] When a toilet is mentioned in the context of this invention, a modern flush toilet is preferably meant.

[0092] Another aspect of the invention is a method for producing a multilayer system according to the invention, as described herein, wherein the composition of the first layer and / or the composition of the second layer is preferably melted at at least 50 °C, more preferably at least 60 °C, even more preferably at least 65 °C, even more preferably at least 70 °C and / or preferably at a maximum of 150 °C, more preferably at a maximum of 120 °C, even more preferably at a maximum of 100 °C, in particular at a maximum of 90 °C, for example at 50 to 150 °C, 60 to 100 °C or 70-90 °C, and subsequently cast in layers.

[0093] The compositions of the individual layers can, for example, be placed in an applicator that allows for portioning the multi-layer system. This enables the multi-layer system according to the invention to be stamped or sprayed onto the toilet bowl surface, for example. Another application method is filling the multi-layer system according to the invention into (plastic) containers, such as basket-like containers. These containers are usually shaped like hemispheres. The individual layers of the multi-layer system according to the invention must be filled alternately. This process could be repeated as often as desired to create, for example, two-, three-, or higher-layer systems. By cleverly formulating the perfume compositions in the different layers, a change in fragrance can be generated before, during, and after the flushing phase.Furthermore, it is conceivable that the multi-layer systems in the individual containers of the multi-chamber container differ in order to create a particularly complex fragrance or color experience or a special cleaning performance.

[0094] Finally, the invention relates to the use of the multi-layer system or the agent according to the invention for scenting and optionally for cleaning and / or disinfecting a toilet, in particular a flush toilet, wherein the scent impression preferably changes over time, as already described above.

[0095] In particularly preferred embodiments, both the fragrance and color impressions change over time. In addition to the perfume compositions of the individual layers of the multilayer system according to the invention, dyes or dye compositions are also incorporated into one, several, or all layers.

[0096] All facts, objects, and embodiments described for the multilayer system according to the invention are also applicable to the other subject matter of the invention. Therefore, explicit reference is made here to the disclosure at the relevant point, with the note that this disclosure also applies to the aforementioned means, uses, and methods according to the invention, and vice versa. Examples

[0097] A non-inventive multi-layer system comprises (a) a first layer comprising at least one perfume composition, wherein the perfume composition comprises (i) 0.01 wt% to 50 wt% of at least one fragrance with a vapor pressure of >0.0133 kPa at 25 °C and a ClogP ≤2.5; and (ii) less than 20 wt% of at least one fragrance with a vapor pressure of <0.000133 kPa at 25 °C and a ClogP ≥4.0; and (b) a second layer comprising at least one perfume composition, wherein the perfume composition comprises (i) 0.01 wt% to 20 wt% of at least one fragrance with a vapor pressure of >0.0133 kPa at 25 °C and a ClogP ≤2.5; and (ii) more than 30 wt.% of at least one fragrance ingredient having a vapor pressure of <0.000133 kPa at 25 °C and a ClogP ≥4.0; comprises.

[0098] This system offers the consumer a fragrance experience that changes over time. By incorporating various dye and perfume compositions into the first and / or second layer and / or further layers, diverse polysensory perception sequences can be created: Subtractive color mixing and separation of the layers, through transmission, can produce a color change of the product.

[0099] Different perfumery, e.g. a hygienic signature scent (aromatic, aldehydic) for the first two weeks, then a change to a refreshing, floral composition (floral, fougere), allows for a clear, olfactory definition.

[0100] This application contains images, which are briefly described below: Figure 1 shows a hemispherical plastic container comprising an exemplary multi-layer system, in particular a two-layer system. Figure 2shows an exemplary multi-chamber system consisting of individual hemispherical plastic containers and includes an exemplary multi-layer system, in particular a two-layer system. Figure 3 The figure shows the change in the scent impression and the color impression of a multi-layer system according to the invention over time, wherein in this exemplary representation the scent first makes a hygienic impression and then changes to a pleasant, for example floral, scent.

[0101] Similarly, the color of the product changes over time, for example from green (color impression when layering blue and yellow layers) to yellow (when the blue layer is used up).

Claims

1. A multilayer system comprising (a) a first layer consisting of a composition comprising at least one perfume composition, wherein the perfume composition comprises (i) 0.01% by weight to 30% by weight of at least one fragrance substance with a vapor pressure at 25°C of >0.0133 kPa and a ClogP ≤2.5; and (ii) less than 15% by weight of at least one odorant with a vapor pressure at 25°C of <0.000133 kPa and a ClogP 24.0; (b) a second layer consisting of a composition comprising at least one perfume composition, wherein the perfume composition comprises (i) 0.01 wt% to 20 wt% of at least one odorant having a vapor pressure at 25°C of >0.0133 kPa and a ClogP ≤2.5; and (ii) more than 55% by weight of at least one odorant with a vapor pressure at 25°C of <0.000133 kPa and a ClogP 24.0.

2. The multilayer system according to claim 1, wherein the at least one perfume composition of the first layer and / or the perfume composition of the second layer comprises at least one further fragrance with a vapor pressure at 25 °C of 0.0133 to 0.000133 kPa and optionally a ClogP of 2 to 4.

3. The multilayer system according to one of claims 1 or 2, wherein the at least one perfume composition is contained in the composition of the first layer or the composition of the second layer in an amount of 0.01 to 20 wt.%, preferably 0.1 to 10 wt.%, more preferably 1 to 5 wt.%, in particular 2 to 4 wt.%, based on the total weight of the respective composition.

4. The multilayer system according to one of claims 1 to 3, wherein the composition of the first layer and / or the composition of the second layer further comprises, in addition to the perfume composition, at least one further component, preferably selected from the group consisting of surfactants, in particular sodium lauryl ether sulfate, ethoxylated C16-C18 alcohols and ethoxylated C9-C11 alcohols, humectants, for example propane-1,2,3-triol, dyes, emulsifying aids, preservatives, complexing agents, acids, in particular for lime prevention, solvents, polymers, other fragrances or mixtures thereof, the composition of the first layer and / or the composition of the second layer preferably comprises at least one dye in addition to the perfume composition.

5. The multilayer system according to one of claims 1 to 4, wherein the multilayer system comprises at least one further layer, preferably a total of three layers or more, four- -layers or more, five layers or more, six layers or more, or seven layers or more.

6. The multilayer system according to any one of claims 1 to 5, wherein the first layer and / or the second layer is liquid or gel-like at room temperature.

7. An agent comprising a multilayer system according to any one of claims 1 to 6, wherein the agent is preferably a home care product, more preferably a cleaner or air freshener, even more preferably a toilet cleaner or toilet freshener, and in particular a liquid or gel-like toilet fragrance rinse.

8. A method for scenting and optionally cleaning and / or disinfecting the toilet, wherein at least one method step uses a multilayer system according to one of claims 1 to 6 or an agent according to claim 7, wherein the scent impression preferably changes over time.

9. A method for producing a multilayer system according to one of claims 1 to 6, wherein preferably the compositions of the first layer and / or the second layer are melted at at least 50 °C, preferably at least 60 °C, more preferably at least 65 °C, even more preferably at least 70 °C and / or preferably at a maximum of 150 °C, more preferably at a maximum of 120 °C, even more preferably at a maximum of 100 °C, in particular at a maximum of 90 °C, for example at 70-90 °C, and then cast in layers.

10. Use of the multilayer system according to one of claims 1 to 6 or the agent according to claim 7 for scenting and optionally for cleaning and / or disinfecting a toilet, wherein the scent impression preferably changes over time.

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