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] MULTI-LAYER SYSTEM COMPRISING COMPOSITIONS WITH SPECIAL PERFUME COMPOSITIONS

[0002] 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 comprising at least one specific perfume composition. Furthermore, the invention relates to an agent comprising the multilayer system according to the invention. The invention also relates to a method for perfuming 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 perfuming a toilet are aspects of the invention.

[0003] NECA (non-electrical continuous action) air fresheners, or liquid, gel, or solid active ingredient preparations for the toilet, are formulated with high perfume oil proportions to spread freshness in the room or to combat unpleasant odors. These air fresheners or toilet additives are usually formulated with a single perfume composition. Depending on the application, air fresheners or toilet additives, or their perfume compositions, are usually formulated to deliver the same intensity and the same fragrance impression for weeks after activation. Both NECAs and other technical systems are equipped to ensure that a complete “perfume composition” consisting of top, middle, and base notes is always released into the room and perceived. The FMCG (fast-moving consumer goods) marketFast-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 the habituation effect that occurs with classic room fragrances.

[0004] The individual components of a classically composed perfume evaporate at different speeds. The temporal progression in the perception of a perfume scent is referred to as the progression. This progression is divided into fragrance notes, which usually flow 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' a perfume conveys. The top note typically consists of intense, light, rapidly volatile fragrances with a maximum perception duration of several minutes. The heart note is the fragrance that is perceptible once the top notes have evaporated. The heart note of a perfume is responsible for the actual fragrance character of a perfume. The heart note consists of fragrances with a maximum perception duration of several hours. The base note is the fragrance that is perceptible last.It typically contains long-lasting, heavy fragrances that can linger for days.

[0005] Due to the high variances in the processing of ceramic materials, toilets exhibit a high degree of diversity in their flushing behavior. Nevertheless, toilet additives typically exhibit an olfactory delta, i.e., a perceptual lift in the intensity of the perfume, due to the flushing water flowing around or overflowing them. This is caused by the dissolution of the soap-like or gel-like active ingredient preparation, in which these toilet additives are typically formulated, and by turbulence and air movement generated by the flushing water in the toilet. These perfumes are traditionally formulated as is usual for NECA air fresheners. Fragrances are used that are released well to very well into the ambient air at room temperature.

[0006] It has now surprisingly been found that systems consisting of two or more layers, wherein preferably each layer contains a different perfume composition, preferably air fresheners or toiletry products, in particular liquid or gel toilet air fresheners, repeatedly evoke a new and / or changing fragrance experience over time. The individual layers are preferably liquid or gel. In particular, the release of flush water in a toilet and the consuming rinsing of the (gel) layers when using the toilet creates an olfactory delta, i.e. the perception of the intensity and the fragrance impression / fragrance progression achieved over the entire life cycle of the toiletry product changes once or several times over the time of use. In the context of this invention, this change is also referred to as a perception lift.

[0007] Thus, in a first aspect, the invention relates to a multi-layer system comprising

[0008] (a) a first layer comprising or consisting of a composition comprising at least one

[0009] Perfume composition, wherein the perfume composition

[0010] (i) at least one fragrance with a vapor pressure at 25 °C of >0.0133 kPa and a ClogP <2.5; and

[0011] (ii) at least one fragrance having a vapor pressure at 25°C of < 0.000133 kPa and a ClogP > 4.0;

[0012] (b) a second layer comprising or consisting of a composition comprising at least one

[0013] Perfume composition, wherein the perfume composition

[0014] (i) at least one fragrance with a vapor pressure at 25 °C of >0.0133 kPa and a ClogP <2.5; and

[0015] (ii) at least one fragrance having a vapor pressure at 25 °C of < 0.000133 kPa and a ClogP > 4.0;

[0016] In a particularly preferred embodiment, the multi-layer system comprises

[0017] (a) a first layer comprising or consisting of a composition comprising at least one perfume composition, wherein the perfume composition

[0018] (i) 0.01% to 30% by weight of at least one fragrance having a vapor pressure at 25°C of >0.0133 kPa and a ClogP <2.5; and

[0019] (ii) less than 15% by weight 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

[0020] (i) 0.01% to 20% by weight of at least one fragrance having a vapor pressure at 25°C of >0.0133 kPa at 25°C and a ClogP <2.5; and

[0021] (ii) more than 55% by weight of at least one fragrance having a vapor pressure at 25°C of <0.000133 kPa and a ClogP >4.0;

[0022] The first layer and / or the second layer of the multi-layer system are particularly preferably liquid or gel-like at room temperature (20°C and at standard pressure (1 bar)). In various embodiments, the first and second layers are directly adjacent, i.e. they border one another directly with at least one surface. Typically, the first layer lies 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 the components disperse upon contact with water. This property relates 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 also each further layer, are arranged such that they come into contact with the environment, and here in particular with water, only one after the other.This is typically achieved by stacking the layers one above the other in a container, so that only the top layer comes into contact with the environment, for example, the room air or rinse water. Only when the top layer has gradually dissolved, dispersed, or dissolved 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 superimposed layers can therefore create a different fragrance impression. This different fragrance impression is caused by the different perfume compositions contained in the respective layers.

[0023] In a further aspect, the invention relates to a product comprising the multi-layer system according to the invention. The multi-layer system can also be such a product. Examples of such products are toilet cleaners or toilet blocks, especially those in gel form.

[0024] A further aspect of the invention is a method for scenting a toilet, wherein the multilayer system according to the invention or the agent according to the invention is used in at least one method step. It is particularly preferred that the scent impression changes over time.

[0025] In a further aspect, the invention relates to a process for producing the multilayer system according to the invention. Preferably, the compositions of the first layer and / or the second layer are melted at at least 50°C and then cast into layered form.

[0026] In a final aspect, the invention relates to the use of the multi-layer system according to the invention or the agent according to the invention for scenting a toilet, wherein the scent impression preferably changes over time. These and other aspects, features, and advantages of the invention will become apparent to those skilled in the art from studying the following detailed description and claims. Any feature from one aspect of the invention can be used in any other aspect of the invention. Furthermore, it is to be understood that the examples contained herein are intended to describe and illustrate the invention, but not to restrict it, and in particular the invention is not limited to these examples.

[0027] All percentages are by weight unless otherwise stated. Numerical ranges expressed 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 various endpoints are also included.

[0028] Numerical values ​​stated without decimal places refer to the full specified value with one decimal place. For example, "99%" stands for "99.0%."

[0029] “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 to the absolute number of molecules. “At least one fragrance substance” thus means, for example, at least one type of fragrance substance, i.e., one type of fragrance substance or a mixture of several different fragrance substances can be meant. Together with weight information, the statement refers to all compounds of the specified type that are contained in the composition / mixture, i.e., the composition does not contain any further compounds of this type beyond the specified amount of the corresponding compounds.

[0030] According to the invention, the multi-layer system described in more detail below is characterized in that it comprises at least a first and a second layer, wherein

[0031] (a) the first layer comprises or consists of a composition comprising at least one perfume composition, wherein the perfume composition

[0032] (i) at least one fragrance with a vapor pressure at 25 °C of >0.0133 kPa and a ClogP <2.5; and

[0033] (ii) at least one fragrance having a vapor pressure at 25°C of < 0.000133 kPa and a ClogP > 4.0;

[0034] (b) the second layer comprises or consists of a composition comprising at least one perfume composition, wherein the perfume composition

[0035] (i) at least one fragrance with a vapor pressure at 25 °C of >0.0133 kPa and a ClogP <2.5; and

[0036] (ii) at least one fragrance with a vapor pressure at 25°C of <0.000133 kPa and a ClogP >4.0; In various embodiments, the perfume composition of the first layer and that of the second layer are different, preferably so different that they produce a distinctly different fragrance impression.

[0037] 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 ester, ether, aldehyde, ketone, alcohol and hydrocarbon type, as well as natural fragrance mixtures such as those obtainable from plant sources.

[0038] The smell 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 odors or to impart a desired scent to a non-odorous substance.

[0039] Typically, the structure of perfume compositions is described as classified below (see also the international patent application WO2016 / 200761 A2): Top note: Vapour pressure at 25°C: > 0.0133 kPa

[0040] Heart note: Vapor pressure at 25°C: 0.0133 - 0.000133kPa

[0041] Base note: Vapor pressure at 25°C: < 0.000133kPa.

[0042] 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.

[0043] In addition, it was found that the ClogP value of the odorants, which is a measure of the hydrophilicity of a compound, is also a decisive factor in scent perception, since depending on the ClogP value, certain odorants are rinsed off at different speeds, thus further enhancing the multisensory effect. For example, odorants with ClogP values ​​less than or equal to 2.5 are rinsed off more quickly and distributed better in the room than, for example, odorants with a ClogP of greater than or equal to 4. 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 a calculation, or lists with corresponding ClogP values, are known in the art and are readily available to the person skilled in the art. One suitable program is EPI-Suite 4.11 (KOWWIN v 1 .68).Unless otherwise stated, the values ​​mentioned herein were calculated using this program.

[0044] In preferred embodiments, the perfume compositions of the first layer and the second layer differ. The difference can be found, for example, in the fragrances used, or the same or similar fragrances are used, but they are used in different amounts in the perfume composition. However, it is also possible for the perfume compositions to contain both different fragrances and different concentrations of fragrances. It would also be conceivable for the compositions to contain the same base perfume composition, but for additional fragrances or fragrance enhancers to be added to one layer, creating a different fragrance experience.

[0045] In preferred embodiments,

[0046] (i) the at least one fragrance having a vapor pressure at 25°C of >0.0133 kPa and a ClogP <2.5 in an amount of 0.001 to 70 wt.%, preferably 0.05 to 60 wt.%, more preferably 0.01 to 50 wt.%, for example 0.01 to 30 wt.%, 0.1 to 20 wt.% or 1 to 40 wt.%, in the at least one perfume composition of the first layer; and / or

[0047] (ii) the at least one fragrance having a vapor pressure at 25°C of <0.000133 kPa and a ClogP >4.0 in an amount of less than 30 wt.%, preferably less than 25 wt.%, more preferably less than 20 wt.%, for example less than 15 wt.%, less than 10 wt.% or less than 5 wt.%, in the at least one perfume composition of the first layer; and / or

[0048] (iii) the at least one fragrance having a vapor pressure at 25 °C of >0.0133 kPa and a ClogP <2.5 in an amount of 0.001 to 40 wt.%, preferably 0.05 to 30 wt.%, more preferably 0.02 to 30 wt.%, even more preferably 0.01 to 20 wt.%, for example 0.01 to 10 wt.%, 0.1 to 15 wt.% or 1 to 20 wt.%, is contained in the at least one perfume composition of the second layer; and / or

[0049] (iv) the at least one fragrance having a vapor pressure at 25°C of <0.000133 kPa and a ClogP >4.0 in an amount of more than 30 wt.%, preferably more than 35 wt.%, more preferably more than 40 wt.%, even more preferably more than 50 wt.%, for example 30 to 50 wt.%, 35 to 60 wt.% or 32 to 55 wt.%, is contained in the at least one perfume composition of the second layer; wherein the amounts are in each case based on the total weight of the respective perfume composition.

[0050] A particularly preferred embodiment is a multi-layer system comprising

[0051] (a) a first layer comprising or consisting of a composition comprising at least one

[0052] Perfume composition, wherein the perfume composition

[0053] (i) 0.01% to 50% by weight of at least one fragrance having a vapor pressure at 25°C of >0.0133 kPa and a ClogP <2.5; and

[0054] (ii) less than 20% by weight of at least one fragrance having a vapor pressure at 25°C of <0.000133 kPa and a ClogP >4.0;

[0055] (b) a second layer comprising or consisting of a composition comprising at least one

[0056] Perfume composition, wherein the perfume composition

[0057] (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 30 wt% of at least one fragrance having a vapor pressure at 25°C of <0.000133 kPa and a ClogP >4.0;

[0058] 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. In various embodiments, the ClogP is <2.0, 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.In various embodiments, the ClogP is >4.5, for example >5.

[0059] 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.

[0060] “Liquid,” as used herein, includes liquids and gels as well as pasty compositions. It is preferred that the liquid compositions be flowable 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 second layer be liquid or gel-like. Preferably, both the first layer and the second layer are liquid or gel-like. Particularly preferably, all layers of the multilayer system are liquid or gel-like, i.e., in particular, they are all liquid or all gel-like, and they preferably have substantially the same viscosities and flow properties. However, the layers should preferably have a consistency that prevents mixing of the layers during production, storage, use, or application. Although not preferred, it is not excluded that at least one layer is solid at room temperature.

[0061] In various embodiments, the first layer in the multi-layer system is first poured into a container, and then the second layer is added on top. In other embodiments, the layers are arranged the other way around. Then, the composition for the second layer is first poured into a container, and then the composition for the first layer is added on top.

[0062] 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 further fragrance with a vapor pressure at 25°C of 0.0133 to 0.000133 kPa. Such a further fragrance can, 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 a further fragrance.

[0063] At least one fragrance of the multi-layer system according to the invention can be, for example, 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-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]acetaldehyd, 4-lsopropylbenzylaldehyd, 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-1 H-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- T rimethyl-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-,

[0064] 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-ene-2-carbaldehyde, 9-decenal, 3-methyl-5-phenyl-1-pentanal, methylnonylacetaldehyde, hexanal, and / or trans-2-hexenal. Mixtures of the above substances can also be used. In various embodiments, at least one fragrance substance of the multi-layer 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), tonalide (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, 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-on (und Isomere)), Methylcedrenylketon, Acetophenon, Methylacetophenon, para-Methoxyacetophenon, Methyl-beta-naphtylketon, Benzylaceton, Benzophenon, para-Hydroxyphenylbutanon, Sellerie- Keton(3-methyl-5-propyl-2-cyclohexenon), 6- lsopropyldecahydro-2-naphton, Dimethyloctenon, Frescomenthe (2-Butan-2-yl-cyclohexan-1-on), 4-(1- Ethoxyvinyl)-3,3,5,5-tetramethylcyclohexanon, Methylheptenon, 2-(2-(4-Methyl-3-cyclohexen-1 - yl)propyl)cyclopentanon, 1-(p-Menthen-6(2)yl)-1-propanon, 4-(4-Hydroxy-3-methoxyphenyl)-2-butanon, 2-Acetyl-3,3-dimethylnorbornan, 6,7-Dihydro-1 ,1 ,2,3,3-pentamethyl-4(5H)-indanon, 4-Damascol, Dulcinyl(4-(1 ,3-benzodioxol-5-yl)butan-2-on), Hexalon (1-(2,6,6-trimethyl-2-cyclohexene-1-yl)-1 ,6- heptadien-3-on), IsocyclemonE (2-Acetonaphthon-1 ,2,3,4,5,6,7,8-octahydro-2,3,8,8-tetramethyl), Methylnonylketon, Methylcyclocitron, Methyllavendelketon, Orivon (4-tert-Amyl-cyclohexanon), 4-tert- Butylcyclohexanon,Delphon (2-pentylcyclopentanone), 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 above substances can also be used.

[0065] In a further embodiment, at least one fragrance of the multi-layer 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.-butylcyclohexanol, 3,5,5-trimethylcyclohexanol, 3-hexanol, 3-methyl-5-phenylpentanol, 3-octanol, 3-phenylpropanol, 4-heptenol, 4-isopropylcyclohexanol, 4-tert.-Butycyclohexanol, 6,8-dimethyl-2-nona-nol, 6-nonen-1-ol, 9-decen-1-ol, a-methylbenzyl alcohol, a-terpineol, amyl salicylate, benzyl alcohol, benzyl salicylate, ß-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 these substances may also be used.

[0066] Ester-type fragrance compounds include benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate (DMBCA), phenylethyl acetate, benzyl acetate, ethyl methylphenylglycinate, allylcyclohexylpropionate, styrallylpropionate, benzyl salicylate, cyclohexyl salicylate, floramat, melusate, and jasmacyclate. Ethers include, for example, benzyl ethyl ether and ambroxan, and hydrocarbons primarily include terpenes such as limonene and pinene. However, mixtures of different fragrances are preferred, as they combine to create an appealing fragrance.

[0067] In a further embodiment, at least one fragrance of the multi-layer system according to the invention can be an essential oil, such as angelica root oil, anise oil, arnica blossom oil, basil oil, bay oil, champaca blossom oil, citrus oil, silver fir oil, silver fir cone oil, elemi oil, eucalyptus oil, fennel oil, spruce needle oil, galbanum oil, geranium oil, gingergrass 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 blossom oil, lime oil, mandarin oil, lemon balm oil, mint oil, musk seed oil, Clary Sage Oil, Myrrh Oil, Clove Oil, Neroli Oil, Niaouli Oil, Olibanum Oil, Orange Blossom Oil, Orange Peel Oil, Origanum Oil, Palmarosa Oil, Patchouli Oil, Peruvian Balsam Oil, Petitgrain Oil, Pepper Oil, Peppermint Oil, Pimento Oil, Pine Oil, Rose Oil, Rosemary Oil, Sage Oil, Sandalwood Oil, Celery Oil, Spike Oil,Star 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 and cypress oil as well as ambrettolide, ambroxan, alpha-amyl cinnamaldehyde, anethole, anisaldehyde, anise alcohol, anisole, anthranilic acid methyl ester, acetophenone, benzyl acetone, benzaldehyde, benzoic acid ethyl ester, benzophenone, benzyl alcohol, benzyl acetate, benzyl benzoate, benzyl formate, benzyl valerate, 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, heptynecarboxylic acid methyl ester, heptaldehyde, hydroquinone dimethyl ether, hydroxycinnamaldehyde, hydroxycinnamyl alcohol, indole, iron, isoeugenol, isoeugenol methyl ether, isosafrole, jasmone, camphor, carvacrol, carvone, p-cresol methyl ether, coumarin, p-methoxyacetophenone, methyl n-amyl ketone,

[0068] Methylanthranilic acid methyl ester, p-methylacetophenone, methyl chavicol, p-methylquinoline, methyl beta-naphthyl ketone, methyl n-nonyl acetaldehyde, 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, salicylic acid isoamyl ester, salicylic acid methyl ester, salicylic acid hexyl ester,

[0069] Cyclohexyl salicylate, santalol, sandelice, skatole, terpineol, thymen, thymol, troenan, gamma-undelactone, vanillin, veratrumaldehyde, cinnamaldehyde, cinnamyl alcohol, cinnamic acid, ethyl cinnamate, benzyl cinnamate, 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 above-mentioned substances may also be used.

[0070] 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.

[0071] D-limonene, for example, can be included as a perfume component. In a particularly preferred embodiment, the mixture contains long-lasting fragrances, in particular ethereal oils (also referred to as essential oils). Examples of such oils that can be used in the context of this invention include pine, citrus, jasmine, patchouli, rose, or ylang-ylang oil. 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, olibanum oil, galbanum oil, and labdanum oil, as well as orange blossom oil, neroliol, orange peel oil, and sandalwood oil. Other long-lasting fragrances, such as higher-boiling orSolid 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, can be used advantageously within the scope of the present invention.

[0072] In various embodiments, the at least two layers contain very different fragrances, creating a scent change from, for example, hygienic to floral. For example, once the first layer is consumed, the scent changes. This allows for a distinct olfactory formulation. This means that the consumer receives a product that allows for precise specification of the scent change and the desired appearance.

[0073] 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.

[0074] 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, even more preferably 0.1 to 1.5 cm, for example 1 cm.

[0075] In general, in addition to the thickness of the layer, the water solubility or dispersibility also determines the dissolution rate. The individual layers are consumed by dissolution or dispersion in the rinse water. Conventional products are formulated in such a way that, with a typical number of rinses, the product lasts for approximately four weeks before it is completely consumed, i.e., all layers are consumed.

[0076] According to the invention, the multilayer system comprises at least two layers. However, it can also comprise additional 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. However, multilayer systems with two layers (two-layer system), as described herein, or multilayer systems with three or four layers are particularly preferred.In such multi-layer systems, the first and second layers are as described herein; all further layers can be constructed similarly to the first or second layer and contain a perfume, optionally also another different perfume, but can alternatively also be perfume-free and then serve the purpose, for example, of separating the perfume-containing layers from one another and thereby ensuring the sharpest possible separation of the different fragrance impressions.

[0077] Preferably, the composition of the at least one further layer comprises at least one perfume composition, wherein the perfume composition

[0078] (i) at least one fragrance with a vapor pressure at 25 °C of >0.0133 kPa and a ClogP <2.5; and

[0079] (ii) at least one fragrance with a vapour pressure at 25 °C of < 0.000133 kPa and a ClogP > 4.0; and

[0080] (iii) optionally comprising a further fragrance having a vapour pressure at 25°C of from 0.0133 kPa to 0.000133 kPa;

[0081] The fragrances can be those described above and, furthermore, can preferably be used in amounts as described above for the first or second layer. Preferred 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.%, even more preferably 1 to 5 wt.%, in particular 2 to 4 wt.%, in each case based on the total weight of the layer.

[0082] It is preferred that each additional layer is also liquid or gel-like at room temperature.

[0083] A further aspect of the invention is an agent comprising a multilayer system according to the invention as described herein.

[0084] 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 for this purpose in a special holder.

[0085] Figure 1 shows a cross-section of a two-layer system 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 3 shows a side cross-section of a two-layer system in a holder and the state before and after rinsing off the upper layer, which exposes the underlying layer. Also shown is how rinsing off the upper layer causes a fragrance change.

[0086] According to the invention, it is particularly preferred if the compositions of the individual layers are gel-melted, i.e., they are liquefied, particularly by the application of heat, so that they have a gel-like consistency. The compositions are then preferably filled layer by layer into a container or, preferably, into a multi-chamber container. Furthermore, the compositions could be filled layer by layer into an applicator suitable for portioning the agent, particularly onto the toilet bowl, for example by stamping or spraying.

[0087] In addition to the described perfume compositions, the multilayer system or the agent according to the invention may contain other ingredients. Typical ingredients for air fresheners, toilet blocks, or toilet air fresheners are particularly preferred.

[0088] 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 multi-layer system according to the invention or of 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, rinse regulators, humectants, bleaching agents, builders, acids, bases, solvents, antimicrobial agents, polymers, salts, thickeners, preservatives, complexing agents, agents for reducing bad odors, perfume boosters, fillers, bleaching agents, corrosion inhibitors, rinse regulators, enzymes, microorganisms, active ingredients for biofilm removal, active ingredients for inhibiting limescale deposits, active ingredients for reducing dirt adhesion,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 layers, in addition to fragrances, are water and surfactants, especially nonionic and anionic surfactants. In various embodiments, these ingredients make up at least 70% by weight, preferably at least 80% by weight, particularly preferably at least 90% by weight of the respective layer.

[0089] In various embodiments of the invention, the different layers of the multilayer system are colored differently and visually distinguishable by using different dyes.

[0090] 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 of anionic surfactants, nonionic surfactants, amphoteric or zwitterionic surfactants, cationic surfactants, and mixtures thereof. Preferably, at least one anionic surfactant is included, particularly preferably at least one anionic and at least one nonionic surfactant.

[0091] The multi-layer system according to the invention, or at least one composition thereof, preferably contains the at least one surfactant in an amount of 10 to 80 wt.%, preferably 20 to 60 wt.%, particularly preferably 25 to 55 wt.%.

[0092] In the context of the present invention, fatty acids or fatty alcohols or their derivatives - unless stated otherwise - represent branched or unbranched carboxylic acids or alcohols or their derivatives having preferably 6 to 22 carbon atoms, in particular 8 to 20 carbon atoms, particularly preferably 10 to 18 carbon atoms, extremely preferably 12 to 16 carbon atoms, for example 12 to 14 carbon atoms. The former are particularly preferred for ecological reasons because of their plant-based nature as they are based on renewable raw materials, without, however, limiting the teaching of the invention to them. In particular, the oxo alcohols or oxo alcohols obtainable, for example, by the Roelen oxo synthesis are also suitable.their derivatives having preferably 7 to 19 carbon atoms, in particular 9 to 19 carbon atoms, particularly preferably 9 to 17 carbon atoms, extremely preferably 11 to 15 carbon atoms, for example 9 to 11, 12 to 15 or 13 to 15 carbon atoms, can be used accordingly.

[0093] Furthermore, the compositions may contain at least one alkylbenzenesulfonate and / or at least one olefinsulfonate. In addition, other surfactants may be included, in particular from the group of anionic and / or nonionic surfactants.

[0094] Other anionic surfactants that may be present in the multilayer system according to the invention are aliphatic sulfates such as fatty alcohol sulfates, fatty alcohol ether sulfates, dialkyl ether sulfates, monoglyceride sulfates, and aliphatic sulfonates such as alkanesulfonates, ether sulfonates, n-alkyl ether sulfonates, ester sulfonates, and lignin sulfonates. Also usable within the scope of the present invention are fatty acid cyanamides, sulfosuccinates (sulfosuccinic acid esters), in particular

[0095] Sulfosuccinic acid mono- and di-Cs-Cis-alkyl esters, sulfosuccinamates, sulfosuccinamides, fatty acid isethionates, acylaminoalkanesulfonates (fatty acid taurides), fatty acid sarcosinates, ethercarboxylic acids and alkyl (ether) phosphates as well as a-sulfofatty acid salts, acylglutamates, monoglyceride disulfates and alkyl ethers of glycerol disulfate.

[0096] Preferred 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 oxide, preferably ethylene oxide, with alcohols, preferably with longer-chain alcohols within the meaning of the present invention. Depending on the reaction conditions, n moles of ethylene oxide and one mole of alcohol generally form a complex mixture of addition products with varying degrees of ethoxylation. Another embodiment of the alkoxylation involves the use of mixtures of alkylene oxides, preferably a 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.

[0097] 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.

[0098] 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.

[0099] 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 and hydroxy mixed ethers, and fatty acid polyglycol esters. Ethylene oxide / propylene oxide block polymers, fatty acid alkanolamides, and fatty acid polyglycol ethers can also be used. Another important class of nonionic surfactants that can be used according to the invention are polyol surfactants, particularly glycosurfactants such as alkyl polyglycosides and fatty acid glucamides. Alkyl polyglycosides and, above all, fatty alcohol alkoxylates (fatty alcohol polyglycol ethers) are particularly preferred.

[0100] Preferred fatty alcohol alkoxylates are unbranched or branched, saturated or unsaturated Cs-22 alcohols alkoxylated with ethylene oxide (EO) and / or propylene oxide (PO) and having a degree of alkoxylation of up to 30, preferably ethoxylated Cs-22 fatty alcohols having a degree of ethoxylation of less than 30, preferably 12 to 28, in particular 20 to 28, particularly preferably 25, for example Cs-16 fatty alcohol ethoxylates with 25 EO.

[0101] Alkyl polyglycosides are surfactants that can be obtained by the reaction of sugars and alcohols according to the relevant processes of preparative organic chemistry, resulting in a mixture of monoalkylated, oligomeric, or polymeric sugars, depending on the type of preparation. Preferred alkyl polyglycosides are alkyl polyglucosides, where the alcohol is particularly preferably a long-chain fatty alcohol or a mixture of long-chain fatty alcohols with branched or unbranched Cs- to Cs-alkyl chains, and the degree of oligomerization (DP) of the sugars is between 1 and 10, preferably 1 to 6, in particular 1.1 to 3, extremely preferably 1.1 to 1.7, for example Cs-ω-alkyl-1,5-glucoside (DP of 1.5). Fatty alcohol ethoxylates are preferably used in amounts of up to 20% by weight, particularly preferably 4 to 12% by weight, particularly preferably 7 to 9% by weight.In addition, other non-ionic surfactants, such as fatty acid monoalkanolamides and / or alkyl polyglycosides, may be contained in amounts of up to 10% by weight.

[0102] In addition to the surfactant types mentioned above, the mixture may also contain cationic surfactants and / or amphoteric or zwitterionic surfactants.

[0103] Suitable amphoteric surfactants are, for example, betaines of the formula (R iii )(R iv )(R v )N + CH2COO _ , in which R'" is an alkyl radical optionally interrupted by heteroatoms or heteroatom groups having 8 to 25, preferably 10 to 21 carbon atoms and R iv and R v identical or different alkyl radicals having 1 to 3 carbon atoms, in particular Cw-Cis-alkyldimethylcarboxymethylbetaine and Cn-Ci7-alkylamidopropyldimethylcarboxymethylbetaine.

[0104] Suitable cationic surfactants include the quaternary ammonium compounds of the formula (R vi)(R vii )(R viii )(R ix )N + X , in the R vi to R ix represents four identical or different, in particular two long-chain and two short-chain, alkyl radicals, and X- represents an anion, in particular a halide ion, for example didecyldimethylammonium chloride, alkylbenzyldidecylammonium chloride, and mixtures thereof. Quaternary ammonium compounds with an antimicrobial effect are preferred.

[0105] 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 not more than 60% by weight of further ingredients is contained, preferably 0.01 to 60% by weight, in particular 0.2 to 15% by weight, in each case based on the total weight of the respective composition.

[0106] Particularly preferred are anionic surfactants such as sodium lauryl ether sulfates and nonionic surfactants such as ethoxylated C16-C18 (fatty) alcohols or ethoxylated C9-C11 (fatty) 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.

[0107] To enhance the cleaning performance against limescale and uric acid, 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. The acids are preferably produced from renewable raw materials. Particularly suitable acids are therefore 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 also amidosulfonic acid or mixtures thereof can also be used. The acids and / or their salts are particularly preferably 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.%, particularly preferably 0.2 to 5 wt.%.

[0108] 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. Particular preference is given to using sodium sulfate and / or sodium carbonate. 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.%, 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.%, particularly preferably up to 5 wt.%.

[0109] Alkalis may also be included. Bases preferably used are those from the group of alkali and alkaline earth metal hydroxides and carbonates, especially sodium carbonate or sodium hydroxide. However, ammonia and / or alkanolamines with up to 9 carbon atoms per molecule can also be used, preferably ethanolamines, especially monoethanolamine.

[0110] 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 active ingredients, preferably in an amount of up to 40% by weight, preferably 0.01 to 25% by weight, preferably 0.1 to 5% by weight, in particular 0.1 to 3.5% by weight, particularly preferably 0.5 to 3% by weight, in each case based on the total weight of the respective composition.

[0111] The terms disinfection, sanitation, antimicrobial effect, and antimicrobial agent have the usual technical meaning within the context of the teaching of the invention. While disinfection in the narrower sense of medical practice means the killing of – theoretically all – infectious germs, sanitation is understood to mean the elimination of all germs as far as possible, including saprophytic germs that are normally harmless to humans. The extent of disinfection or sanitation depends on the antimicrobial effect of the agent used, which decreases with decreasing antimicrobial agent content or increasing dilution of the agent used.

[0112] Suitable according to the invention are, for example, antimicrobial active ingredients 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 surface-active compounds, guanidines, antimicrobial amphoteric compounds, quinolines, 1,2-dibromo-2,4-dicyanobutane, iodo-2-propynyl butyl carbamate, 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, glycerin, 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-decanediyldi-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, antimicrobially active essential oils can also be used, which also provide a fragrance for the cleaning agent. However, 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.

[0113] Preservatives may also be included. These include, in particular, the substances listed under antimicrobial active ingredients.

[0114] Chelating agents (INCI: chelating agents), also known as sequestering agents, 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 that cause water hardness, which are incompatible with many ingredients. On the other hand, complexing the ions of heavy metals such as iron or copper delays the oxidative decomposition of the finished product. Furthermore, the complexing agents support the cleaning effect.

[0115] Suitable examples include, but are not limited to, the following complexing agents designated according to INCI:

[0116] 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 and Trisodium Phosphate.

[0117] Other suitable ingredients, especially for cleaners or air fresheners such as toilet air fresheners, are polymers. These can be used, for example, to reduce limescale formation and the tendency to re-soil (so-called soil repellent polymers). Preferred polymers are acrylic polymers, such as those commercially available from Rhodia under the trade name Mirapol.

[0118] The composition of the first layer, the composition of the second layer, and / or the composition of a possible further layer may contain aqueous and / or organic solvents. Preferred liquids include, in particular, water, dipropylene glycol, or paraffin.

[0119] One or more dyes (INCI colorants) may be included as additional ingredients. Both water-soluble and oil-soluble dyes can be used. However, compatibility with other ingredients, such as bleaching agents, must be taken into account and the dye used should not have a substantive effect on the toilet ceramic, even after prolonged contact. Preferably, it can be a water-soluble dye that colors the flush water. The flush water colored with this dye remains in the toilet sump, i.e. in the residual flush water remaining in the toilet bowl, in sufficient concentration to impart color to it after the actual flushing process. The dyes are preferably contained in an amount of 0.0001 to 5 wt.%, in particular 0.0005 to 0.05 wt.%, particularly preferably 0.001 to 0.01 wt.%.

[0120] 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 comprises at least one dye in addition to the perfume composition.

[0121] By incorporating dye compositions into the perfume compositions, a color change of the multi-layer system can be created.

[0122] 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). Alternatively, they are fragrances that mask the unpleasant odor with their own odor, thus neutralizing it (so-called odor enhancers).

[0123] The multilayer systems produced according to the invention may optionally contain water-soluble and / or water-insoluble builders in one or more layers. Water-soluble builders are preferred because they generally have less tendency to leave insoluble residues on hard surfaces. Common builders that may be present in the context 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 may also be used, as well as mixtures of the aforementioned builder substances.

[0124] According to the invention, bleaching agents can also be used. Suitable bleaching agents include peroxo compounds, in particular peroxides, peracids, percarbonates and / or perborates, particularly preferred are sodium percarbonate, phthalimidoperoxyhexanoic acid or

[0125] Hydrogen peroxide. 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 especially sodium dichloroisocyanurate are also suitable. In some cases, a bleach activator may also be required in addition to the bleaching agent.

[0126] 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.

[0127] The substances known as rinse regulators primarily serve to control the consumption of the detergent during use so that the intended service life is maintained. Suitable regulators are 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.

[0128] Further suitable components that can be used in the multi-layer system according to the invention, preferably a cleaner or air freshener, in particular a toilet air freshener, are enzymes, preferably proteases, lipases, amylases, hydrolases, and / or cellulases. They can be added in any form established according to the prior art. These include solutions of the enzymes, advantageously as concentrated as possible, low in water, and / or mixed with stabilizers. Alternatively, the enzymes can be encapsulated, for example by spray-drying or extrusion of the enzyme solution together with a, preferably natural, polymer, 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 water-, air-, and / or chemical-impermeable protective layer.Additional active ingredients, such as stabilizers, emulsifiers, pigments, bleaching agents, or dyes, can be applied in additional layers. Such granules are advantageously low in dust, for example, when polymeric film formers are applied, and the coating ensures long-term storage stability.

[0129] Furthermore, enzyme stabilizers may be present in enzyme-containing systems or agents in order to protect an enzyme contained in a system or agent according to the invention from damage such as inactivation, denaturation or degradation, for example due to physical influences, oxidation or proteolytic cleavage.Particularly suitable enzyme stabilizers, depending on the enzyme used, are: 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 propanolamine and mixtures thereof; aliphatic carboxylic acids up to C12, such as succinic acid, other dicarboxylic acids, or salts of the acids mentioned; end-capped fatty acid amide 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. Other 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.

[0130] 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 (fatty) alcohols and ethoxylated C9-C11-(fatty) alcohols, humectants, for example propane-1,2,3-triol, dyes, emulsifying aids, preservatives, complexing agents, solvents, acids, in particular for limescale prophylaxis, polymers, further fragrances or mixtures thereof.

[0131] In a further aspect, the invention relates to a method for scenting the toilet, wherein a multi-layer system according to the invention or a composition according to the invention is used in at least one method step. It is particularly preferred that the scent impression changes over time. This is achieved in particular by consuming one layer of the multi-layer system or composition over time, and then a second layer, which has a different scent, comes into contact with the flush water and releases its scent into the environment.

[0132] 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, with the preference being that the fragrances remain in the air for as long as possible so they can be perceived.

[0133] In addition to scenting the toilet, the multi-layer system according to the invention can also preferably be used to clean and / or disinfect the toilet by using suitable ingredients, as already described above. Different active ingredients can be incorporated into different layers, which are released at different times depending on the degree of flushing.

[0134] If a toilet is mentioned in the context of this invention, it preferably means a modern flush toilet.

[0135] A further aspect of the invention is a process for producing a multi-layer 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 is then layer-cast.

[0136] The compositions of the individual layers can, for example, be placed in an applicator that enables the multi-layer system to be portioned. This allows the multi-layer system according to the invention to be stamped or sprayed onto the toilet ceramic surface, for example. Another dosage format is to fill the multi-layer system according to the invention into (plastic) containers, for example 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 can be repeated as often as desired, for example to create two-, three-, or higher multi-layer systems. By cleverly formulating the perfume compositions in the different layers, a change of fragrance can be generated both before, during, and after the rinsing 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 specific cleaning performance. Finally, the invention relates to the use of the multi-layer system according to the invention or the agent according to the invention for fragrance and optionally for cleaning and / or disinfecting a toilet, in particular a flush toilet, wherein the fragrance impression preferably changes over time, as already described above.

[0137] In particularly preferred embodiments, both the fragrance impression and the color impression 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.

[0138] All facts, objects, and embodiments described for the multilayer system according to the invention are also applicable to the other subject matters of the invention. Therefore, explicit reference is made here to the disclosure at the corresponding point, with the note that this disclosure also applies to the above-mentioned agents, uses, and methods according to the invention, and vice versa.

[0139] Examples

[0140] An example multi-layer system includes

[0141] (a) a first layer comprising at least one perfume composition, wherein the perfume composition

[0142] (i) 0.01% to 50% by weight of at least one fragrance having a vapor pressure of >0.0133 kPa at 25 °C and a ClogP <2.5; and

[0143] (ii) less than 20% by weight of at least one fragrance having a vapor pressure of <0.000133 kPa at 25 °C and a ClogP >4.0; and

[0144] (b) a second layer comprising at least one perfume composition, wherein the perfume composition

[0145] (i) 0.01% to 20% by weight of at least one fragrance with a vapor pressure of >0.0133 kPa at 25 °C and a ClogP <2.5; and

[0146] (ii) more than 30% by weight of at least one fragrance having a vapor pressure of <0.000133 kPa at 25 °C and a ClogP >4.0;

[0147] This system offers the consumer a fragrance experience that changes over time.

[0148] By incorporating various dye and perfume compositions into the first and / or second layer and / or further layers, various polysensory perception sequences can be generated: Subtractive color mixing and demixing of the layers, through transmission, can produce a color change of the product.

[0149] By using different perfumes, e.g. a hygienic signature fragrance (aromatic, aldehydic) for the first two weeks, then changing to a refreshing, flowery composition (floral, fougere), a clear, olfactory formulation can be achieved.

[0150] This application contains figures which are briefly described below:

[0151] Figure 1 shows a hemispherical plastic container comprising an exemplary multi-layer system, in particular a two-layer system.

[0152] Figure 2 shows an exemplary multi-chamber system consisting of individual hemispherical plastic containers and comprising an exemplary multi-layer system, in particular a two-layer system.

[0153] Figure 3 shows the change in the fragrance impression and color impression of a multi-layer system according to the invention over time. In this exemplary illustration, the fragrance initially creates a hygienic impression and then changes to a pleasant, for example, floral scent. The color of the product also changes over time, for example, from green (color impression when blue and yellow layers are layered) to yellow (when the blue layer is used up).

Claims

Patent claims 1. Multi-layer system, encompassing (a) a first layer comprising or consisting of a composition which includes at least one Perfume composition includes, 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) comprises at least one fragrance ingredient with 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 which includes at least one Perfume composition includes, 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) comprises at least one fragrance ingredient having a vapor pressure at 25 °C of < 0.000133 kPa and a ClogP >4.

0.

2. The multilayer system according to claim 1, wherein (i) the at least one fragrance ingredient having a vapor pressure at 25 °C of >0.0133 kPa and a ClogP <2.5 in an amount of 0.001 to 70 wt.%, preferably 0.05 to 60 wt.%, more preferably 0.01 to 50 wt.%, in particular 0.01 to 30 wt.%, in which at least one perfume composition of the first layer is included; and / or (ii) the at least one fragrance ingredient having a vapor pressure at 25 °C of <0.000133 kPa and a ClogP >4.0 in an amount of less than 30 wt.%, preferably less than 25 wt.%, more preferably less than 20 wt.%, in particular less than 15 wt.%, in which at least one perfume composition of the first layer is included; and / or (iii) the at least one fragrance ingredient having a vapor pressure at 25 °C of >0.0133 kPa and a ClogP <2.5 in an amount of 0.001 to 40 wt.%, preferably 0.05 to 30 wt.%, more preferably 0.02 to 30 wt.%, and even more preferably 0.01 to 20 wt.%, in particular 0.01 to 15 wt.%, in which at least one perfume composition of the second layer is included; and / or (iv) the at least one fragrance ingredient having a vapor pressure at 25 °C of <0.000133 kPa and a ClogP >4.0 in an amount of more than 30 wt.%, preferably more than 35 wt.%, more preferably more than 40 wt.%, even more preferably more than 50 wt.%, in particular more than 55 wt.%, in which at least one perfume composition of the second layer is included; wherein the amounts are in each case based on the total weight of the respective perfume composition.

3. The multi-layer system according to claim 1 or 2, comprising (a) a first layer consisting of a composition comprising at least one perfume composition, wherein the perfume composition (i) 0.01 wt.% to 30 wt.% of at least one fragrance substance 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 ingredient having a vapor pressure at 25 °C of <0.000133 kPa and a ClogP >4.0; includes; (b) a second layer consisting of a composition comprising at least one perfume composition, wherein the perfume composition (i) 0.01 wt.% to 20 wt.% of at least one fragrance substance having a vapor pressure at 25 °C of >0.0133 kPa and a ClogP <2.5; and (ii) comprising 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.

4. The multilayer system according to one of claims 1 to 3, 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 ingredient having a vapor pressure at 25 °C of 0.0133 to 0.000133 kPa and optionally a ClogP of 2 to 4.

5. The multilayer system according to any one of claims 1 to 4, 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.

6. The multilayer system according to any one of claims 1 to 5, wherein the composition of the first layer and / or the composition of the second layer, in addition to the perfume composition, further comprises at least one additional 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 agents, preservatives, complexing agents, acids, in particular for limescale prophylaxis, solvents, polymers, further fragrances or mixtures thereof, particularly preferably comprising, in addition to the perfume composition, at least one dye.

7. The multilayer system according to any one of claims 1 to 6, 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.

8. The multilayer system according to any one of claims 1 to 7, wherein the first layer and / or the second layer is liquid or gel-like at room temperature.

9. A composition comprising a multi-layer system according to any one of claims 1 to 8, wherein the composition 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 toilet fragrance rinse.

10. A method for scenting and optionally cleaning and / or disinfecting the toilet, wherein in at least one method step a multi-layer system according to one of claims 1 to 8 or an agent according to claim 9 is used, wherein the scent impression preferably changes over time.

11. A method for producing a multilayer system according to any one of claims 1 to 8, wherein the compositions of the first layer and / or the second layer are preferably 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 are subsequently cast layer by layer.

12. Use of the multi-layer system according to one of claims 1 to 8 or of the agent according to claim 9 for scenting and optionally for cleaning and / or disinfecting a toilet, wherein the scent impression preferably changes over time.

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