EP2069468B1 - Perfume dispensing system - Google Patents

Description

The invention relates to a fragrance medium delivery system comprising a perfumed, polymer-containing shaped article which is provided in a removal container.

The invention further relates to the use of the fragrance medium dispensing system for dispensing fragrance and to a process for scenting aqueous systems.

The use of fragrances to create fragrances has been an important element of human culture for a long time. For example, fragrances were used very early for sacred or ritual purposes. An example of this is the burning of frankincense. As a rule, fragrances are intended to mask other, perceived as unpleasant odors or produce pleasant, attractive odors. The use of fragrances also often has the purpose of giving the impression of cleanliness.

Most washing and cleaning products also contain fragrances. These cover the original product smell and provide a pleasant smell.

EP 16 14 743 A1 describes a method for the prolonged scenting of textiles with water-soluble, perfume-containing films of polysaccharides or cellulose polymers.

As has been shown, the consumer is developing a need for ever-new fragrances, and accordingly, new fragranced products are continually being offered in the trade.

However, there is a certain shortcoming in the fact that the products offered on the market are very uniformly scented, as far as the intensity of the scent is concerned. The fragrance intensity is tailored to the needs of an average consumer. Accordingly, consumers who have a very pronounced or a reduced fragrance need to uniform product scenting. This particularly concerns those products, such as washing or cleaning agents, which are used in connection with aqueous systems.

Against this background, the object of the invention was to enable the consumer to individually perfume aqueous systems. This object is solved by the subject matter of the invention.

The subject matter of the invention is a fragrance medium delivery system comprising a perfumed, water-soluble or water-dispersible, shaped body which contains at least 20% by weight of polymer (s) and at least 10% by weight of fragrances,% by weight, based in each case on the entire shaped body, wherein the shaped body is provided in a dispensing container, and wherein the shaped body is a foamed sheet, and wherein the perfume contained in the shaped body is at least 5 wt .-% in encapsulated form.

A fragrance medium is a medium which carries fragrances, in the present case it is a perfumed shaped body. A Duftmediumabgsbesystem Is an object that allows the, preferably metered or portioned, delivery of the fragrance medium, so the perfumed molding to the consumer.

The polymer content of the molded article may, in a preferred embodiment, also be well above 20% by weight, e.g. at a value of at least 25% by weight. 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%. 65% by weight. 70 wt .-% or at least 75 wt .-% or even at least 80 wt .-%, wherein wt .-% based on the total molding is. Possible upper limits for the polymer portion of the molded article may e.g. at a maximum value of 95% by weight, 90% by weight, 85% by weight, 80% by weight, 75% by weight, 70% by weight, 65% by weight, 60% by weight. %. 55 wt .-%, 50 wt .-%, 45 wt .-%, 40 wt.%, 35 wt .-% or at most 30 wt .-% are.

The polymer content of the molded article may therefore be e.g. in the range of from 35% to 70% by weight, or e.g. Ranging from 40% to 80% by weight, etc.

According to a considerably preferred embodiment, the perfumed shaped body is a strip-shaped, sheet-shaped, disk-shaped, or web-shaped, preferably flexible, film.

A foil is a thin, flat material. As a rule, films are more or less flexible, their flexibility being dependent both on the thickness of the film web and on the type of raw material used. In the case of very stiff products, in general parlance, one often no longer speaks of films, but rather of plates. According to the invention, plates are also included. The thicknesses of the films may preferably be between about 1 and 500 microns. There are also thinner films possible, which are then called membranes. These too are encompassed by the invention. There are also thicker films with thicknesses> 500 microns possible. These too are encompassed by the invention.

Preferred film thicknesses are e.g. at values <400 μm, <300 μm, <200 μm or even smaller <100 μm. Thicknesses of e.g. <80 μm, <60 μm or <40 μm possible.

Possible minimum thicknesses may be, for example, values such as e.g. 2, 3, 4, 5, 6, 7, 8, 9 or 10 microns are. There are also minimum thicknesses of e.g. 15, 20, 25, 30, 35, 40, 45 or 50 microns possible, even values of at least 60, 70, 80, 90, 100, 150 or 200 microns are possible.

Accordingly, a film according to the invention may accordingly have, for example, a thickness of from 3 to <200 μm or, for example, from 20 to <80 μm, to name only two examples.

• (a) in der Länge vorzugsweise 1cm bis 30 cm, vorteilhafterweise 2cm bis 20 cm, in weiter vorteilhafter Weise 3 cm bis 15 cm, insbesondere 4 cm bis 10 cm,
• (b) in der Breite vorzugsweise 1 cm bis 25 cm, vortellhafterweise 2 cm bis 20 cm, in weiter vorteilhafter Weise 3 cm bis 15 cm, insbesondere 4 cm bis 10 cm.

The length-width dimensions of a preferred strip, sheet, disk or sheet film may be (independently of each other):

• (a) preferably 1 cm to 30 cm in length, advantageously 2 cm to 20 cm, more preferably 3 cm to 15 cm, in particular 4 cm to 10 cm,
• (b) preferably 1 cm to 25 cm in width, preferably 2 cm to 20 cm in width, more preferably 3 cm to 15 cm, in particular 4 cm to 10 cm.

The minimum length of the film can also be 5, 6, 7 or 8 cm. The minimum width of the film can also be 5, 6, 7 or 8 cm.

A film of the invention may have any shape, for example, square, rectangular, triangular, oval, circular. There are also special forms possible, such as heart shape, number form or letter form.

The films of the invention may be transparent or opaque. It can be e.g. to act solo or composite foils.

While so-called composite films, e.g. PA / PE films, multiple layers of different materials, e.g. a PA and a PE layer, solofilms consist only of a uniform film material, which of course may comprise a mixture of different substances, in particular a polymer mixture. Both solo and composite films are encompassed by the invention.

If films consist of two layers of the same material, they are called double films. A major reason for the production of double films may be the generation of larger film thicknesses. A variant here is the coextrusion of two layers of a thermoplastic as an alternative to a single thicker layer. Double foils are also included in the invention.

According to a preferred embodiment of the invention, the films according to the invention are multilayered.

The shaped articles according to the invention may comprise a single polymer or a blend of different polymers. In preferred cases, the shaped body comprises one or more materials from the group (optionally acetalized) polyvinyl alcohol (PVAL) and / or PVAL copolymers, polyvinylpyrrolidone, polyethylene oxide, polyethylene glycol, gelatin, cellulose and derivatives thereof; in particular MC, HEC, HPC, HPMC and / or CMC, and / or copolymers and mixtures thereof. Possibly. can the moldings known to the expert Softener to increase the flexibility of the material or other auxiliaries or additives mixed.

die in geringen Anteilen (ca. 2%) auch Struktureinheiten des Typs

enthalten.In the context of the present invention, polyvinyl alcohols are very particularly preferred as water-soluble polymers. "Polyvinyl alcohols" (abbreviated PVAL, occasionally PVOH) is the name for polymers of the general structure

in small proportions (about 2%) also structural units of the type

contain.

Commercially available polyvinyl alcohols, which are available as white-yellowish powders or granules with degrees of polymerization in the range of about 100 to 2500 (molar masses of about 4000 to 100,000 g / mol), have degrees of hydrolysis of 98-99 or 87-89 mol%. , so still contain a residual content of acetyl groups. The polyvinyl alcohols are characterized by the manufacturer by indicating the degree of polymerization of the starting polymer, the degree of hydrolysis, the saponification number or the solution viscosity.

Depending on the degree of hydrolysis, polyvinyl alcohols are soluble in water and a few highly polar organic solvents (formamide, dimethylformamide, dimethyl sulfoxide); They are not attacked by (chlorinated) hydrocarbons, esters, fats and oils. Polyvinyl alcohols are classified as toxicologically safe and are biologically at least partially degradable. The water solubility can be reduced by aftertreatment with aldehydes (acetalization), by complexation with Ni or Cu salts or by treatment with dichromates, boric acid or borax. Polyvinyl alcohol is largely impermeable to gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, but allows water vapor to pass through.

Moldings which are preferred in the context of the present invention are characterized in that they comprise polyvinyl alcohols and / or PVAL copolymers whose degree of hydrolysis is 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%.

Preference is given to using polyvinyl alcohols having a specific molecular weight range, preference being given to processes according to the invention in which the molded body comprises polyvinyl alcohols and / or PVAL copolymers whose molecular weight is in the range from 3,500 to 100,000 gmol ^-1 , preferably from 10,000 to 90,000 gmol ^-1 , more preferably from 12,000 to 80,000 gmol ^-1 and in particular from 13,000 to 70,000 gmol ^-1 .

The degree of polymerization of such preferred polyvinyl alcohols is between about 200 to about 2100, preferably between about 220 to about 1890, more preferably between about 240 to about 1680, and most preferably between about 260 to about 1500.

Shaped bodies preferred according to the invention are characterized in that the shaped body comprises polyvinyl alcohols and / or PVAL copolymers whose average degree of polymerization is between 80 and 700, preferably between 150 and 400, more preferably between 180 and 300 and / or their molecular weight ratio MW (50%). to MG (90%) is between 0.3 and 1, preferably between 0.4 and 0.8 and in particular between 0.45 and 0.6.

The polyvinyl alcohols described above are widely available commercially, for example under the trade name Mowiol ^® (Clariant). In the present invention, particularly suitable polyvinyl alcohols are, for example, Mowiol ^® 3-83, Mowiol ^® 4-88, Mowiol ^® 5-88 and Mowiol ^® 8-88.

Further polyvinyl alcohols which are particularly suitable as material for the moldings are shown in the following table: description Degree of hydrolysis [%] Molecular weight [kDa] Melting point [° C] Airvol ^® 205 88 15-27 230 Vinex ^® 2019 88 15-27 170 Vinex ^® 2144 88 44 - 65 205 Vinex ^® 1025 99 15-27 170 Vinex ^® 2025 88 25 - 45 192 Gohsefimer ^® 5407 30 - 28 23,600 100 Gohsefimer ^® LL02 41 - 51 17,700 100

Other suitable as a material for the shaped bodies are polyvinyl alcohols ^® ELVANOL 51-05, 52-22, 50-42, 85-82, 75-15, T-25, T-66, 90-50 (trademark of Du Pont), ALCOTEX ^® 72.5, 78, B72, F80 / 40, F88 / 4, F88 / 26, F88 / 40, F88 / 47 (trademark of Harlow Chemical Co.), Gohsenol ^® NK-05, A-300, AH-22, C -500, GH-20, GL-03, GM-14L, KA-20, KA-500, KH-20, KP-06, N-300, NH-26, NM11Q, KZ-06 (Trademark of Nippon Gohsei KK ). Also suitable are ERKOL types from Wacker.

die durch radikalische Polymerisation von 1-Vinylpyrrolidon nach Verfahren der Lösungs- oder Suspensionspolymerisation unter Einsatz von Radikalbildnern (Peroxide, Azo-Verbindungen) als Initiatoren hergestellt werden. Die ionische Polymerisation des Monomeren liefert nur Produkte mit niedrigen Molmassen. Handelsübliche Polyvinylpyrrolidone haben Molmassen im Bereich von ca. 2500-750000 g/mol, die über die Angabe der K-Werte charakterisiert werden und - K-Wertabhängig - Glasübergangstemperaturen von 130-175° besitzen. Sie werden als weiße, hygroskopische Pulver oder als wässrige Lösungen angeboten. Polyvinylpyrrolidone sind gut löslich in Wasser und einer Vielzahl von organischen Lösungsmitteln (Alkohole, Ketone, Eisessig, Chlorkohlenwasserstoffe, Phenole u.a.).A further preferred group of water-soluble polymers which may be present in the moldings according to the invention are the polyvinylpyrrolidones. These are marketed under the name Luviskol ^® (BASF). Polyvinylpyrrolidones [poly (1-vinyl-2-pyrrolidinones)], abbreviation PVP, are polymers of the general formula (I)

which are prepared by free-radical polymerization of 1-vinylpyrrolidone by the method of solution or suspension polymerization using free-radical initiators (peroxides, azo compounds) as initiators. The ionic polymerization of the monomer provides only low molecular weight products. Commercially available polyvinylpyrrolidones have molar masses in the range of about 2500-750000 g / mol, which are characterized by the specification of the K values and - depending on K value - have glass transition temperatures of 130-175 °. They are offered as white, hygroscopic powders or as aqueous solutions. Polyvinylpyrrolidones are readily soluble in water and a variety of organic solvents (alcohols, ketones, glacial acetic acid, chlorinated hydrocarbons, phenols, etc.).

Also suitable are copolymers of vinylpyrrolidone with other monomers, in particular vinylpyrrolidone / Vinylester copolymers, such as for example, under the trade name Luviskol ^® (BASF). Luviskol ^® VA 64 and Luviskol ^® VA 73, each vinylpyrrolidone / vinyl acetate copolymers, are particularly preferred non-ionic polymers.

als charakteristischem Grundbaustein der Makromoleküle. Von diesen haben die Vinylacetat-Polymere (R = CH₃) mit Polyvinylacetaten als mit Abstand wichtigsten Vertretern die größte technische Bedeutung.The vinyl ester polymers are vinyl ester-accessible polymers having the moiety of the formula (II)

as a characteristic building block of the macromolecules. Of these, the vinyl acetate polymers (R = CH ₃ ) with polyvinyl acetates as by far the most important representatives of the greatest technical importance.

The polymerization of the vinyl esters is carried out free-radically by different processes (solution polymerization, suspension polymerization, emulsion polymerization, bulk polymerization). Copolymers of vinyl acetate with vinylpyrrolidone contain monomer units of the formulas (I) and (II).

Further suitable water-soluble polymers are the polyethylene glycols (polyethylene oxides), which are referred to as PEG for short. PEG are polymers of ethylene glycol which are of the general formula (III)

H- (O-CH ₂ -CH ₂ ) _n -OH (III)

satisfy, where n can take values between 5 and> 100,000.

PEGs are prepared industrially by anionic ring-opening polymerization of ethylene oxide (oxirane), usually in the presence of small amounts of water. Depending on the reaction procedure, they have molar masses in the range of about 200-5,000,000 g / mol, corresponding to degrees of polymerization of about 5 to> 100,000.

The products with molecular weights <about 25 000 g / mol are liquid sore at room temperature are referred to as actual polyethylene glycols, abbreviated PEG. These short-chain PEGs can be used in particular other water-soluble polymers, e.g. Polyvinvlalkoholen or cellulose ethers are added as plasticizer. The polyethyleneglycols which can be used according to the invention and which are solid at room temperature are termed polyethylene oxides, abbreviated PEOX. High molecular weight polyethylene oxides have an extremely low concentration of reactive hydroxy end groups and therefore show only weak glycol properties.

Further suitable as a material for the molding according to the invention is also gelatin, which is preferably used together with other polymers. Gelatin is a polypeptide (molecular weight: about 15,000 to> 250,000 g / mol), which is obtained primarily by hydrolysis of the collagen contained in the skin and bones of animals under acidic or alkaline conditions. The amino acid composition of gelatin largely corresponds to that of the collagen from which it was obtained and varies depending on its prevalence. The use of gelatin as water-soluble coating material is extremely widespread, especially in pharmacy in the form of hard or soft gelatin capsules. In the form of films, gelatin generally has little use because of its high price compared to the polymers mentioned above.

• Celluloseether, wie Hydroxypropylcellulose, Hydroxyethylcellulose und Methylhydroxypropylcellulose, wie sie beispielsweise unter den Warenzeichen Culminal^® und Benecel^® (AQUALON) vertrieben werden.
  Celluloseether lassen sich durch die allgemeine Formel (IV) beschreiben,
  
  in der R für H oder einen Alkyl-, Alkenyl-, Alkinyl-, Aryl- oder Alkylarylrest steht. In bevorzugten Produkten steht mindestens ein R in Formel (III) für -CH₂CH₂CH₂-OH oder -CH₂CH₂-OH. Celluloseether werden technisch durch Veretherung von Alkalicellulose (z.B. mit Ethylenoxid) hergestellt. Celluloseether werden charakterisiert über den durchschnittlichen Substitutionsgrad DS bzw. den molaren Substitutionsgrad MS, die angeben, wieviele Hydroxy-Gruppen einer Anhydroglucose-Einheit der Cellulose mit dem Veretherungsreagens reagiert haben bzw. wie viel mol des Veretherungsreagens im Durchschnitt an eine Anhydroglucose-Einheit angelagert wurden. Hydroxyethylcellulosen sind ab einem DS von ca. 0,6 bzw. einem MS von ca. 1 wasserlöslich. Handelsübliche Hydroxyethyl- bzw. Hydroxypropylcellulosen haben Substitutionsgrade im Bereich von 0,85-1,35 (DS) bzw. 1,5-3 (MS). Hydroxyethyl- und -propylcellulosen werden als gelblichweiße, geruch- und geschmacklose Pulver in stark unterschiedlichen Polymerisationsgraden vermarktet. Hydroxyethyl- und -propylcellulosen sind in kaltem und heißem Wasser sowie in einigen (wasserhaltigen) organischen Lösungsmitteln löslich, in den meisten (wasserfreien) organischen Lösungsmitteln dagegen unlöslich; ihre wässrigen Lösungen sind relativ unempfindlich gegenüber Änderungen des pH-Werts oder Elektrolyt-Zusatz.

Further water-soluble polymers suitable according to the invention are described below:

• Cellulose ethers, such as hydroxypropylcellulose, hydroxyethylcellulose and methylhydroxypropylcellulose, as sold, for example, under the trademarks Culminal ^® and Benecel ^® (AQUALON).
  Cellulose ethers can be described by the general formula (IV)
  
  in which R is H or an alkyl, alkenyl, alkynyl, aryl or alkylaryl radical. In preferred products, at least one R in formula (III) is -CH ₂ CH ₂ CH ₂ -OH or -CH ₂ CH ₂ -OH. Cellulose ethers are produced industrially by etherification of alkali cellulose (eg with ethylene oxide). Cellulose ethers are characterized by the average degree of substitution DS or the molar degree of substitution MS, which indicate how many hydroxyl groups of an anhydroglucose unit of the cellulose reacted with the etherifying reagent or how many moles of the etherifying agent were attached on average to an anhydroglucose unit. Hydroxyethylcelluloses are water-soluble from a DS of about 0.6 or an MS of about 1. Commercially available hydroxyethyl or hydroxypropyl celluloses have degrees of substitution in the range of 0.85-1.35 (DS) and 1.5-3 (MS), respectively. Hydroxyethyl and propylcelluloses are marketed as yellowish-white, odorless and tasteless powders in widely varying degrees of polymerization. Hydroxyethyl and propylcelluloses are soluble in cold and hot water as well as in some (hydrous) organic solvents but insoluble in most (anhydrous) organic solvents; their aqueous solutions are relatively insensitive to changes in pH or electrolyte addition.

Preferred shaped bodies according to the invention are characterized in that they comprise hydroxypropylmethylcellulose (HPMC) which has a degree of substitution (average number of methoxy groups per anhydroglucose unit of the cellulose) of from 1.0 to 2.0, preferably from 1.4 to 1.9, and a molar substitution (average number of hydroxypropoxyl groups per anhydroglucose unit of cellulose) of from 0.1 to 0.3, preferably from 0.15 to 0.25.

Further polymers which are suitable according to the invention are water-soluble amphopolymers. Amphoteric polymers, ie polymers which contain both free amino groups and free -COOH or SO ₃ H groups in the molecule and are capable of forming internal salts, are zwitterionic polymers which contain quaternary ammonium groups in the molecule. COO ^- - or -SO ₃ ^- groups, and summarized those polymers containing -COOH or SO ₃ H groups and quaternary ammonium groups. An example of the present invention amphopolymer suitable is the acrylic resin commercially available as Amphomer ^® is a copolymer of tert-butylaminoethyl methacrylate, N- (1,1,3,3-tetramethylbutyl) -acrylamide and two or more monomers from the group of acrylic acid, Represents methacrylic acid and its simple esters. Likewise preferred amphopolymers are composed of unsaturated carboxylic acids (eg, acrylic and methacrylic acid), cationically derivatized unsaturated carboxylic acids (eg, acrylamidopropyltrimethylammonium chloride), and optionally further ionic or nonionogenic monomers together. Terpolymers of acrylic acid, methyl acrylate and methacrylamidopropyltrimonium as they are commercially available under the name Merquat ^® 2001 N, are inventively particularly preferred amphopolymers. Other suitable amphoteric polymers are for example sold under the names Amphomer ^® and Amphomer ^® LV-71 (DELFT NATIONAL) available octylacrylamide / methyl methacrylate / tert-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers.

• Vinylacetat/Crotonsäure-Copolymere, wie sie beispielsweise unter den Bezeichnungen Resyn^® (NATIONAL STARCH), Luviset^® (BASF) und Gafset^® (GAF) im Handel sind.
  Diese Polymere weisen neben Monomereinheiten der vorstehend genannten Formel (II) auch Monomereinheiten der allgemeinen Formel (V) auf:
  
          [-CH(CH₃)-CH(COOH)-]_n     (V)
  
  
• VinylpyrrolidonNinylacrylat-Copolymere, erhältlich beispielsweise unter dem Warenzeichen Luviflex^® (BASF). Ein bevorzugtes Polymer ist das unter der Bezeichnung Luviflex^® VBM-35 (BASF) erhältliche Vinylpyrrolidon/Acrylat-Terpolymere.
• Acrylsäure/Ethylacrylat/N-tert.Butylacrylamid-Terpolymere, die beispielsweise unter der Bezeichnung Ultrahold^® strong (BASF) vertrieben werden.
• Pfropfpolymere aus Vinylestern, Estern von Acrylsäure oder Methacrylsäure allein oder im Gemisch, copolymerisiert mit Crotonsäure, Acrylsäure oder Methacrylsäure mit Polyalkylenoxiden und/oder Polykalkylenglycolen.

Water-soluble anionic polymers suitable according to the invention include:

• Vinyl acetate / crotonic acid copolymers, such as those sold under the names Resyn ^® (National Starch), Luviset ^® (BASF) and Gafset ^® (GAF) are commercially available.
  These polymers also have monomer units of the formula (II) above
  
  [-CH (CH ₃ ) -CH (COOH) -] _n (V)
  
  
• Vinyl pyrrolidone copolymers, available, for example under the trade name Luviflex ^® (BASF). A preferred polymer is the VBM-35 (BASF) under the name Luviflex ^® available vinylpyrrolidone / acrylate terpolymers.
• Acrylic acid / ethyl acrylate / N-tert.butyl acrylamide terpolymers, for example, under the name Ultrahold ^® strong (BASF).
• Graft polymers of vinyl esters, esters of acrylic acid or methacrylic acid, alone or in admixture, copolymerized with crotonic acid, acrylic acid or methacrylic acid with polyalkylene oxides and / or polyalkylene glycols.

Such grafted polymers of vinyl esters, esters of acrylic acid or methacrylic acid alone or in admixture with other copolymerizable compounds on polyalkylene glycols are obtained by homogeneous-phase polymerization by reacting the polyalkylene glycols in the monomers of vinyl esters, esters of acrylic acid or methacrylic acid, in The presence of free radical initiator stirs.

Suitable vinyl esters are, for example, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate and as esters of acrylic acid or methacrylic acid those with aliphatic alcohols of low molecular weight, ie in particular ethanol, propanol, isopropanol, 1-butanol, 2-butanol, 2-methyl 1-propanol, 2-methyl-2-propanol, 1-pentanol, 2-pentanol, 3-pentanol, 2,2-dimethyl-1-propanol, 3-methyl-1-butanol; 3-methyl-2-butanol, 2-methyl-2-butanol, 2-methyl-1-butanol, 1-hexanol, are proven.

genügen, wobei n Werte zwischen 1 (Propylenglycol) und mehreren tausend annehmen kann. Technisch bedeutsam sind hier insbesondere Di-, Tri- und Tetrapropylenglycol, d.h. die Vertreter mit n=2, 3 und 4 in Formel (VI).Polypropylene glycols (abbreviated PPG) are polymers of propylene glycol which are of the general formula (VI)

satisfy, where n can assume values between 1 (propylene glycol) and several thousand. Of particular technical importance here are di-, tri- and tetrapropylene glycols, ie the representatives with n = 2, 3 and 4 in formula (VI).

• gepfropfte und vernetzte Copolymere aus der Copolymerisation von
  • i) mindesten einem Monomeren vom nicht-ionischen Typ,
  • ii) mindestens einem Monomeren vom ionischen Typ,
  • iii) von Polyethylenglycol und
  • iv) einem Vernetzer

In particular, the vinyl acetate copolymers grafted onto polyethylene glycols and the polymers of vinyl acetate and crotonic acid grafted onto polyethylene glycols can be used.

• grafted and crosslinked copolymers from the copolymerization of
  • i) at least one nonionic type monomer,
  • ii) at least one ionic-type monomer,
  • iii) of polyethylene glycol and
  • iv) a crosslinker

The polyethylene glycol used has a molecular weight between 200 and several million, preferably between 300 and 30,000.

The nonionic monomers may be of very different types and of these preferred are: vinyl acetate, vinyl stearate, vinyl laurate, vinyl propionate, allyl stearate, allylaurate, diethyl maleate, allyl acetate, methyl methacrylate, cetyl vinyl ether, stearyl vinyl ether and 1-hexene.

The non-ionic monomers may equally be of very different types, among which particularly preferably crotonic acid, allyloxyacetic acid, vinylacetic acid, maleic acid, acrylic acid and methacrylic acid are contained in the grafting polymers.

The crosslinkers used are preferably ethylene glycol dimethacrylate, diallyl phthalate, ortho-, meta- and para-divinylbenzene, tetraallyloxyethane and polyallyl sucrose having 2 to 5 allyl groups per molecule of saccharin.

1. i) 5 bis 85 Gew.-% mindesten eine Monomeren vom nicht-ionischen Typ,
2. ii) 3 bis 80 Gew.-% mindestens eines Monomeren vom ionischen Typ,
3. iii) 2 bis 50 Gew.-%, vorzugsweise 5 bis 30 Gew.-% Polyethylenglycol und
4. iv) 0,1 bis 8 Gew.-% eines Vernetzers, wobei der Prozentsatz des Vernetzers durch das Verhältnis der Gesamtgewichte von i), ii) und iii) ausgebildet ist.
   • durch Copolymerisation mindestens eines Monomeren jeder der drei folgenden Gruppen erhaltene Copolymere:
     1. i) Ester ungesättigter Alkohole und kurzkettiger gesättigter Carbonsäuren und/oder Ester kurzkettiger gesättigter Alkohole und ungesättigter Carbonsäuren,
     2. ii) ungesättigte Carbonsäuren,
     3. iii) Ester langkettiger Carbonsäuren und ungesättigter Alkohole und/oder Ester aus den Carbonsäuren der Gruppe ii) mit gesättigten oder ungesättigten, geradkettigen oder verzweigten C_8-18-Alkohols
     Unter kurzkettigen Carbonsäuren bzw. Alkoholen sind dabei solche mit 1 bis 8 Kohlenstoffatomen zu verstehen, wobei die Kohlenstoffketten dieser Verbindungen gegebenenfalls durch zweibindige Heterogruppen wie -O-, -NH-, -S_ unterbrochen sein können.
   • Terpolymere aus Crotonsäure, Vinylacetat und einem Allyl- oder Methallylester
     Diese Terpolymere enthalten Monomereinheiten der allgemeinen Formeln (II) und (IV) (siehe oben) sowie Monomereinheiten aus einem oder mehreren Allyl- oder Methallyestern der Formel (VII):
     

worin R³ für -H oder -CH₃, R² für -CH₃ oder -CH(CH₃)₂ und R¹ für -CH₃ oder einen gesättigten geradkettigen oder verzweigten C_1-6-Alkylrest steht und die Summe der Kohlenstoffatome in den Resten R¹ und R² vorzugsweise 7, 6, 5, 4, 3 oder 2 ist.The grafted and crosslinked copolymers described above are preferably formed from:

1. i) from 5 to 85% by weight of at least one nonionic type monomer,
2. ii) from 3 to 80% by weight of at least one ionic-type monomer,
3. iii) 2 to 50 wt .-%, preferably 5 to 30 wt .-% polyethylene glycol and
4. iv) 0.1 to 8 wt% of a crosslinker, wherein the percentage of crosslinker is formed by the ratio of the total weights of i), ii) and iii).
   • Copolymers obtained by copolymerization of at least one monomer of each of the following three groups:
     1. i) esters of unsaturated alcohols and short-chain saturated carboxylic acids and / or esters of short-chain saturated alcohols and unsaturated carboxylic acids,
     2. ii) unsaturated carboxylic acids,
     3. iii) esters of long-chain carboxylic acids and unsaturated alcohols and / or esters of the carboxylic acids of group ii) with saturated or unsaturated, straight-chain or branched C _8-18 -alcohols
     Short-chain carboxylic acids or alcohols are to be understood as meaning those having 1 to 8 carbon atoms, it being possible for the carbon chains of these compounds to be interrupted, if appropriate, by divalent hetero groups such as -O-, -NH-, -S--.
   • Terpolymers of crotonic acid, vinyl acetate and an allyl or methallyl ester
     These terpolymers comprise monomer units of the general formulas (II) and (IV) (see above) and monomer units of one or more allyl or methallyl esters of the formula (VII):
     

wherein R ^{3 is} -H or -CH ₃ , R ^{2 is} -CH ₃ or -CH (CH ₃ ) ₂ and R ^{1 is} -CH ₃ or a saturated straight or branched C _1-6 alkyl radical and the sum of the carbon atoms in the radicals R ¹ and R ^{2 is} preferably 7, 6, 5, 4, 3 or 2.

• Tetra- und Pentapolymere aus
  • i) Crotonsäure oder Allyloxyessigsäure
  • ii) Vinylacetat oder Vinylpropionat
  • iii) verzweigten Allyl- oder Methallylestern
  • iv)Vinylethern, Vinylesterrn oder geradkettigen Allyl- oder Methallylestern
• Crotonsäure-Copolymere mit einem oder mehreren Monomeren aus der Gruppe Ethylen, Vinylben zol, Vinymethylether, Acrylamid und deren wasserlöslicher Salze
• Terpolymere aus Vinylacetat, Crotonsäure und Vinylestern einer gesättigten aliphatischen verzweig ten Monocarbonsäure.

The abovementioned terpolymers preferably result from the copolymerization of 7 to 12% by weight of crotonic acid, 65 to 86% by weight, preferably 71 to 83% by weight of vinyl acetate and 8 to 20% by weight, preferably 10 to 17% by weight .-% allyl or Methallyletsre of the formula (VII).

• Tetra and pentapolymers from
  • i) crotonic acid or allyloxyacetic acid
  • ii) vinyl acetate or vinyl propionate
  • iii) branched allyl or methallyl esters
  • iv) vinyl ethers, Vinylesterrn or straight-chain allyl or methallyl esters
• Crotonic acid copolymers with one or more monomers from the group consisting of ethylene, vinylbenzene, vinyl methyl ether, acrylamide and their water-soluble salts
• Terpolymers of vinyl acetate, crotonic acid and vinyl esters of a saturated aliphatic branched th monocarboxylic acid.

Further polymers which can be used according to the invention are cationic polymers. Among the cationic polymers, the permanent cationic polymers are preferred. According to the invention, "permanently cationic" refers to those polymers which have a cationic group independently of the pH. These are usually polymers containing a quaternary nitrogen atom, for example in the form of an ammonium group.

• quaternisierte Callurose-Derivale, wie sie unter den Bezeichnungen Celquat^® und Polymer JR^® im Handel erhältlich sind, Die Verbindungen Celquat^® H 100, Celquat^® L 200 und Polymer JR^®400 sind bevorzugte quaternierte Cellulose-Derivate.
• Polyslloxane mit quaternären Gruppen, wie beispielsweise die im Handel erhältlichen Produkte Q2-7224 (Hersteller: Dow Corning; ein stabilisiertes Trimethylsilylamodimethicon), Dow Corning^® 929 Emulsion (enthaltend ein hydroxyl-amino-modifiziertes Silicon, das auch als Amodimethicone bezeichnet wird), SM-2059 (Hersteller: General Electric), SLM-55067 (Hersteller: Wacker) sowie Abil^®-Quat 3270 und 3272 (Hersteller: Th. Goldschmidt: diquaternäre Polydime- thylsiloxane, Quaternium-80),
• Kationische Guar-Derivate, wie insbesondere die unter den Handelsnamen Cosmedia^®)Guar und Jaguar^® vertriebenen Produkte.
• Polymere Dimethyldiallylammonlumsalze und deren Copolymere mit Estern und Amiden von Acrylsäure und Methacrylsäure. Die unter den Bezeichnungen Merquat^®100 (Poly(dimethyldiallylammoniumchlorid)) und Merquat^®550 (Dimethyldiallylammoniumchlorid-Acrylamid-Copolymer) im Handel erhältlichen Produkte sind Beispiele für solche kationischen Polymere.
• Copolymere des Vinylpyrrolidons mit quaternierten Derivaten des Dialkylaminoacrylats und - methacrylats, wie beispielsweise mit Diethylsulfat quaternierte Vinylpyrrolidon-Dimethylaminomethacrylat-Copolymere. Solche Verbindungen sind unter den Bezeichnungen Gafquat^®734 und Gafquat^®755 Im Handel erhältlich.
• vinylpyrrolidon-Methoimidazoliniumchlorid-Copolymere, wie sie unter der Bezeichnung Luviquat^® angeboten werden.
• quaternierter Polyvinylalkohol

sowie die unter den Bezeichnungen

• Polyquaternium 2,
• Polyquaternium 17,
• Polyquaternium 18 und
• Polyquaternium 27

bekannten Polymeren mit quartären Stickstoffatomen In der Polymerhauptkette. Die genannten Polymere sind dabei nach der so genannten INCI-Nomenklatur bezeichnet.Preferred cationic polymers are, for example

• quaternized Callurose-Derivale, as are obtainable under the names of Celquat ^® and Polymer JR ^® commercially, The compounds Celquat ^® H 100, Celquat L 200 and Polymer JR ^{® ®} 400 are preferred quaternized cellulose derivatives.
• Polyslloxanes with quaternary groups, such as the commercially available products Q2-7224 (manufactured by Dow Corning, a stabilized trimethylsilylamodimethicone), Dow ^Corning® 929 emulsion (containing a hydroxylamino-modified silicone, also referred to as amodimethicones), SM -2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil ^® quat 3270 and 3272 (manufacturer: Th Goldschmidt. diquaternary Polydime- thylsiloxane, quaternium-80)
• Cationic guar derivatives, in particular the products sold under the trade name Cosmedia ^®) and Guar Jaguar ^®.
• Polymers Dimethyldiallylammonlumsalze and their copolymers with esters and amides of acrylic acid and methacrylic acid. Under the names Merquat ^® 100 (Poly (dimethyldiallylammonium chloride)) and Merquat ^® 550 (dimethyldiallylammonium chloride-acrylamide copolymer) are examples of such cationic polymers.
• Copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoacrylate and - methacrylate, such as diethyl sulfate quaternized vinylpyrrolidone-dimethylaminomethacrylate copolymers. Such compounds are sold under the names Gafquat ^® 734 and Gafquat ^® 755 commercially.
• vinylpyrrolidone methoimidazolinium chloride copolymers, as offered under the name Luviquat.RTM ^®.
• quaternized polyvinyl alcohol

as well as those under the designations

• Polyquaternium 2,
• Polyquaternium 17,
• Polyquaternium 18 and
• Polyquaternium 27

known polymers with quaternary nitrogen atoms in the polymer main chain. The polymers mentioned are designated according to the so-called INCI nomenclature.

Cationic polymers preferred according to the invention are quaternized cellulose derivatives and polymeric dimethyldiallylammonium salts and their copolymers. Cationic cellulose derivatives, in particular the Händelsptodukt Polymer ^® JR 400, are very particularly preferred cationic polymers. The use of cationic polymers can help to further improve the scent effect of the film in use. In particular, the odor of a scented aqueous system can be further improved so that the fragrance lasts longer and is preferably more intense, with the same amount of fragrance used. Also the Aufziehverhalten the Fragrances on substrates treated in / with the perfumed aqueous system, such as textiles, can be improved by the use of cationic polymers, so that the fragrance of the substrate lasts longer and is preferably more intense.

The use of cationic polymers is particularly effective when preferably> 2 wt .-%, preferably> 4 wt .-%, in particular> 6 wt .-% of cationic polymers are contained in the molding, wt .-% based on the total molding , Upper limits may e.g. at 30, 20 or 10 wt .-% cationic polymer, based on the total molding.

In addition to the preferably water-soluble polymer or the water-dispersible polymer, the film paint material may contain further ingredients which in particular improve the processability of the starting materials for the film. In particular, plasticizers and release agents should be mentioned here. In addition, dyes and optical brighteners can be incorporated into the film to achieve aesthetic effects there.

Suitable release agents which may preferably be applied to the finished, dried films are e.g. Talc, starch or (physically, chemically and / or enzymatically) modified starch. Suitable chemical modifications are e.g. Crosslinking, acetylation, esterification, hydroxyethylation, hydroxypropylation, phosphorylation. The preferably hydrophobic release agent adheres in particular externally to the film.

By treating the films with a powdery release agent, possible adhesion of the films, e.g. as a result of storage or high humidity, be effectively prevented.

According to the invention, hydrophilic, high-boiling liquids can be used as the plasticizer, solids which may also be solid at room temperature being used as the solution. Dispersion or melt can be used. Particularly preferred plasticizers are selected from the group glycol, di-, tri-, tetra-, penta-, hexa-, hepta-, octa-, nona-, deca-, undeca-, dodecaethylene glycol, glycerol, neopentyl glycol, trimethylolpropane, pentaerythritol, mono -, di-, triglycerides, surfactants, in particular nonionic surfactants, and mixtures thereof. Plasticizers are preferably used in amounts of from 1 to 50% by weight, preferably from 2 to 40% by weight, in particular from 5 to 30% by weight. Upper limits may also be, for example, at 20 or 10% by weight of plasticizer, based on the total molding.

Surfactants, in particular nonionic surfactants, are also suitable as further plasticizers.

Further preferred substances to be used as plasticizers may be glycerol carbonate, propylene glycol and propylene carbonate.

As additional additives, which are preferably in solid form at room temperature, especially highly disperse silicas are suitable. Here, pyrogenic silicas such as the commercially available Aerosil ^® or precipitated silicas offer. Particularly preferred processes according to the invention are characterized in that as further additives one or more materials from the group (preferably finely divided) silica, dispersion powder, high molecular weight polyglycols, stearic acid and / or stearic acid salts, and / or from the group of inorganic salts such as sodium sulfate, calcium chloride and / or from the group of Inclusionbildner such as urea, cyclodextrin and / or from the group of superabsorbents such as (preferably crosslinked) polyacrylic acid and / or their salts such as Cabloc 5066 / CTF and mixtures thereof, is / are used.

Moldings preferred according to the invention may contain dyes. Suitable dyes preferably have a high storage stability and insensitivity to the other ingredients of the compositions and to light and no pronounced substantivity to the at least indirectly coming into contact with the dye-containing agents substrates such as textiles, glass, ceramics or plastic dishes, so as not to stain them.

When choosing the colorant it should be noted that the colorants have a high storage stability and insensitivity to light. At the same time, it should also be taken into account when choosing suitable colorants that colorants have different stabilities to oxidation. In general, water-insoluble colorants are more stable to oxidation than water-soluble colorants. Depending on the solubility and thus also on the sensitivity to oxidation, the concentration of the colorant in the moldings varies. In the case of readily water-soluble colorants, dyeing concentrations in the range of a few 10 ^-2 to 10 ^-3 % by weight, based on the total molding, are typically selected. In the preferred because of their brilliance, but less water-soluble On the other hand, for pigment dyestuffs, the suitable concentration of the dyestuff is typically about 10 ^-3 to 10 ^-4 % by weight, based on the total molding

Preference is given to those colorants which can be oxidatively destroyed in a washing process and mixtures thereof with suitable blue dyes, so-called blue toners. It has proven to be advantageous to use colorants which are soluble in water or at room temperature in liquid organic substances. Suitable are, for example, anionic colorants, e.g. anionic nitrosofibres.

Suitable optical brighteners, which may preferably be present in the molding according to the invention, are, for example, 1,3,5-triazinyl derivatives of 4,4'-diamino-2,2'-stilbenedisulfonic acid (flavonic acid), 4,4'-distyrylbiphenylene, Hymecromon (methylumbelliferone), coumarin, dihydroquinolinone, 1,3-diarylpyrazoline, naphthalimide, benzoxazole systems linked via CH = CH bonds, benzisoxazole and benzimidazole systems, and heterocyclic substituted pyrene derivatives.

According to a preferred embodiment of the invention, the films according to the invention are not a packaging material for liquids or solids, e.g. Washing or cleaning agents, so are no film material of detergent pouches or the like.

The films of the invention can be prepared by any known method, but the casting method is to be regarded as very advantageous.

Fulling via thermoplastic processing by calendering or extrusion is very preferred. In particular, coextrusion is preferred.

The blown film process and the flat film process according to the invention are very preferred processes for film production.

The production of blown films is known. For example, mixing of polymeric material, such as e.g. PVOH powder with additives and stabilizers in the solid state. This mixture is melted in the heated extruder. The fragrances required according to the invention may e.g. be added to the melt. This is followed by the blowing of the melt, the cooling and preferably the winding of the film.

Blown films are generally less expensive to produce than cast films, but the film thickness distribution can be slightly more slender and it may possibly lead to more air bubbles, but this can also be a desired effect. As a rule, blown films are something harder and have less recovery properties than cast films, whereas these can be soft, flexible, almost rubbery and can also have high Rückstellungsneigung.

When films are made from solutions of polymers, this is called the casting process. The polymer solutions can be prepared according to the invention by use of solvents, which is preferred, or by chemical conversion of insoluble macromolecules into soluble derivatives. The fragrances required according to the invention may e.g. be added to the polymer solution. There are several methods for converting the polymer solutions into films. When the polymer solution is precipitated in a bath, it is called wet-casting. For example, in cellophane production, a high-viscosity cellulose solution is forced through a slot die into a strong acid precipitation bath.

If the solvent evaporates and thereby the polymer is recovered as a film, so it is called dry casting, for the implementation of particular belt or drum casters can be used.

In the strip casting method (also called cast method or chill roll method), which is preferably used according to the invention, the polymer solution, which contains odoriferous substances according to the invention, is poured from a storage container preferably through a nozzle onto a generally endless, preferably highly polished, metal strip. The belt speeds depend strongly on the material used and on the desired film thickness. They can preferably be between 2 and 60 meters per minute. The film can be stripped off after evaporation of most of the solvents. For winding, it is preferably passed through a dryer with hot air or hot rollers. Resulting film thicknesses can be 15 to 300 microns in this process, for example. It is possible, and preferred, for the polymer solution to be forced over a filter prior to being cast onto the metal strip to retain any undissolved particles that might otherwise result in so-called speckling. It is likewise possible and preferred to at least partially free the polymer solution from air that is contained in a degassing container before it is poured onto the metal plate. The optional degassing is advantageously carried out before the addition of fragrance.

For the production of films such as PVOH films by the casting process, the PVOH powder / granules and plasticizers (eg PEG and / or glycerol) are dissolved in water eg in a batch tank. Subsequently, the solution is fed to a reservoir. The solution is then heated to, for example, about 80 ° C and then fed via a slot die to a rolled strip. In the drying process (air heating channel), the solution is expressed as a film. For example, perfume oils may be added to the PVOH mixture in the batch tank according to the invention.

Similar to the strip casting method is the Trommelgießverfahren. In this case, heated drums are used at the location of the metal strip, such as those with a diameter of 2-3 m and widths of about 2 m.

In the casting process, films are usually obtained which generally show uniform, uniform film thickness distribution and little air inclusions, although the process is expensive because of the energy-intensive drying. The cast process can produce thinner foils than the blown process. High levels of water can also be adjusted, e.g. 5-8 wt .-% water based on the entire film.

The cast method is preferably applied to those which are not meltable or decompose only with decomposition, e.g. Cellulose or polyimides. For the production of very thin films, the casting process is also preferably used.

Rolling or sintering processes are in principle also possible for film production, but only in exceptional cases makes sense, e.g. for the production of tetrafluoroethylene films and polyimide films.

It is also possible, for example, a method for producing a film, wherein first by dissolving or dispersing one or more polymers in a liquid carrier medium, a rollable preparation is prepared and this is then brought by means of rolling in the form of a film by means of a rolling device. In this case, simultaneously or subsequently, the liquid carrier medium can be evaporated.

A liquid carrier medium preferably comprises solvents or dispersants such as water, alcohols, ethers or hydrocarbons or mixtures of two or more of the substances mentioned, wherein the substances or mixtures of substances are liquid at room temperature (20 ° C.). Suitable alcohols are e.g. the monohydric or polyhydric alcohols having 1 to 5 carbon atoms, e.g. Ethanol, isopropanol, ethylene glycol, glycerol and propylene glycols.

In the rollable preparation, the content of the liquid carrier medium may be e.g. in the range of 20 to 90 wt .-% or 30 to 70 wt .-% are.

A suitable rollable formulation may e.g. semi-solid or dough-like consistency, or it may be a viscous liquid with which a suitable carrier is coated and the desired film thickness is produced by rolling with a rolling device.

The finished film is then removed from the carrier after drying. For example, from the group of silicone, metal, metallized polymers, polytetrafluoroethylene, polyether / polyamide block copolymers, polyurethanes, polyvinyl chloride, nylon, alkylene / styrene copolymers, polystyrene, polyester or other, redetachable materials can be selected suitable carrier materials. Suitable rolling devices are, for example, the known, with at least two equal or opposite rollers or rollers provided so-called forward roll or reverse roll coater, with a reverse roll method is preferred.

The resulting (by all possible methods) films can be further processed, for example, by vapor deposition, coating, printing or flocking. It is also possible that the perfuming of the film takes place only after the actual film production, e.g. by spraying, brushing or dipping the film into a perfume-containing preparation. However, it is more preferred if the perfuming of the film takes place in the course of the film production. A coupled process is also possible, in which perfuming takes place both in the course of film production and the finished film is then perfumed once again, e.g. by spraying.

The films according to the invention are foamed films. To obtain foamed films, gas bubbles of a suitable gas, e.g. Air included.

Such films with trapped gas bubbles are characterized by a particularly good feel. Furthermore, they can show improved water solubility.

Preferred foamed films have a density of <1 kg / m ³ .

There are various options for introducing the gas bubbles. Thus, e.g. a blowing or blowing agent can be used. It can e.g. foaming can be achieved by mechanical stirring of the still liquid or viscous carrier mass. It can e.g. to provoke a gas-producing chemical reaction. It can e.g. a volatile solvent may be used, which is evaporated at elevated temperatures. It can e.g. an introduction of a gas or a liquefied gas into the still viscous carrier mass.

However, it may be preferable to use blowing agents. These are substances that decompose on heating with evolution of gas, so that e.g. Nitrogen or carbon dioxide to be released.

Carbonates, bicarbonates, borohydrides, silicon oxyhydrides, etc. are examples of suitable inorganic blowing agents. However, it is also possible to use all organic blowing agents which are known to be used in the production of porous or bubble-containing plastics. Films according to the invention, such as preferably foamed films, can also be present in confetti form. Confetti form means that it is a variety of Foflenschnipseln or foil shreds. The term "confetti" is generally known for small, colorful scraps of paper. Confetti-shaped foils do not necessarily have to be as small as that well-known paper confetti, which is thrown in the air especially during carnival parades, but also at other celebrations, such as children's birthday parties or weddings. The confetti shape can be regular or irregular, it can be, for example, circular foil shreds, it can be, for example, bug-shaped foil snippets. Any conceivable shape is possible and obtainable, for example, by punching out the foil confetti from a larger mother foil. The use of films according to the invention in confetti form can be advantageous, for example, in hand-textile washing, if a certain amount of the films in confetti form is scattered in the textile treatment bath.

The removal container may be any container which is particularly suitable for at least partially enveloping and / or holding together a film-shaped molding.

The container may be made of e.g. be formed of a flexible, semi-rigid or dimensionally stable material.

A dimensionally stable container has the advantage, in particular to protect fragile film-shaped moldings from mechanical influences and to prevent corresponding damage.

In order to prevent swelling or unintentional activation of the film-shaped moldings, the container is preferably made water vapor-tight.

In order to prevent inadvertent emission of substances, such as fragrances, from the film-shaped moldings, the container is preferably odor-proof.

In a further preferred embodiment of the invention means for child-safe opening are provided on the container, to prevent inadvertent contact of children with the film-shaped moldings.

In particular, metering and removal aids for the film-shaped moldings are provided on the container according to the invention.

For a flexible container, it may be e.g. to act a packaging bag, such as a flat bag, sealed edge bag, bottom bag, double bag, bag or bag, e.g. a pouch made of a multilayer, sheet-like and flexible composite material, the pouch preferably having a tear-open aid, such as e.g. has a tear strip or Anreiflaussparung.

It is conceivable to arrange the roller-shaped moldings individually or in a plurality in a flexible container.

The film-shaped moldings packaged in one or more flexible containers may be intended for use in tape or sheet dispensers. Ribbon or sheet dispensers can also be used for unpacked film-shaped moldings.

The extraction container may also comprise or consist of a roll. The preferably strip-shaped, sheet-shaped, Schelbenförmige or web-shaped, flexible shaped body can therefore be wound on a roll, wherein the shaped body is preferably provided with separation points for portionwise removal. Such removal containers are known for example from the field of adhesive tape scooters. Adhesive tape scooters fall under the generic term of tape dispensers. All tape dispensers may be suitable as a removal container.

If the Entnahmebehältris thus comprises a roller, preferably a tape dispenser, wherein the shaped body is provided in particular with separation points for portion removal, so is a preferred embodiment.

For the production of pieces of tape also devices, so-called tape dispensers, are useful, with which the tape is unwound from a roll and passed over a cutting element. When the free end of the band has reached the desired length, it is cut off with the cutting element. In these devices, the length of the tape to be cut off is determined by the user by unwinding the tape in the desired length and then cutting it off. For cutting, it must lead the end of the tape over the cutting element, typically a saw-toothed cutting blade made of either metal or plastic, that this cutting can act on the tape. Such or similar tape dispensers can be advantageously used according to the invention.

Refillable tape dispensers are particularly preferred for repeatably receiving a tape roll.

Particularly suitable are e.g. also such tape dispensers as are known in the field of correction tape dispensers (film transfer rollers). If the removal container according to the invention is a film transfer roller, this is a preferred embodiment.

Also useful are containers for dispensing sheets or strips, so-called sheet dispensers. These are devices that contain a stack of sheets, strips or foils, etc., and include a dispensing aid for the sheets, strips or foils.

Preferably, this stack is arranged so that upon removal of the uppermost sheet, the underlying sheet is aligned so that it is then removed without difficulty. For example, In such devices with removal slot in the removal of the top sheet, the following sheet already tracked so far that it protrudes from the removal slot and can be easily removed afterwards.

For example, it is a block of films each having a layer of a flexible polymeric material which may be provided at a second end region with a coating of repositionable pressure-sensitive adhesive material, while remaining free of adhesive along a visually recognizable first end region in a stack with the adjacent ends of the sheets aligned and the first and second ends of successive sheets disposed adjacent one another. The stack may be disposed in a chamber which is partially bounded in the top wall by a slot through which the first end portion of the topmost sheet projects. By relative movement between the top wall and the topmost sheet, as the topmost sheet is withdrawn through the slot, alignment of the slot with subsequent portions of the sheet is achieved to its second end as these successive portions are withdrawn from the stack. Of the End portion of the underlying sheet is moved with the end portion of the uppermost sheet through the slot so as to leave the first end portion of the underlying sheet from the slit when the uppermost sheet is removed. Such or similar sheet dispensing systems are preferred according to the invention.

In a preferred embodiment, the fragrance medium delivery system of the present invention is configured to allow removal of at least 3, 4, 5, or more different perfume tablets. This may be, for example, a system comprising 3, 4 or 5 rolls of different perfume films. This can then also be described as a set of 3, 4 or 5 sets. The perfume tablets differ in their perfuming, so that the consumer can set the total perfume rating by the dosage of the individual perfume body. There are no limits to the creativity of the consumer. The different perfuming can advantageously be indicated by different colors.

The shaped bodies of a corresponding set configuration advantageously contain different fragrances, which can preferably be distinguished according to specific notes.

Another removal container are dosing dispensers for moldings. Such dosing dispensers usually consist of a housing with a storage chamber whose bottom is e.g. an outlet opening which opens into a guide for a slide with pressure plate and with return spring, wherein the slide has a channel located in its rest position below the outlet opening, the discharge opening is covered in the rest position by a cover.

Such dosing dispensers may contain perfumed shaped bodies, so that one can speak in such a case of a fragrance medium delivery system. The dimensions of corresponding metering dispensers are of course adapted to the dimensions of the molding in question. Such dosing dispensers may be preferred according to the invention.

• (a) mandelartigem Geruch, wie vorzugsweise Benzaldehyd, Pentanal, Heptenal, 6-Methylfurfural, Methylbutanal, Furfural und/oder Acetophenon oder
• (b) apfelartigem Geruch, wie vorzugsweise (S)-(+)-Ethyl-2-methylbutanoat, Diethylmalonat, Ethylbutyrat, Geranylbulyral, Geranylisopentanoat, Isobutylacetat, Linalylisopentanoat, (E)-β-Damascone, Heptyl-2-methylbutyrat, Methyl-3-methylbulanoat, 2-Hexenal-pentylmethylbutyrat, Ethylmethylbutyrate und/oder Methyl-2-Methylbutanoat oder
• (c) apfelschalenartigem Geruch, wie vorzugsweise Ethylhexanoat, Hexylbutanoat und/oder Hexylhexanoat oder
• (d) aprikosenartigem Geruch wie vorzugsweise γ-Undecalacton oder
• (e) bananenartigem Geruch, wie vorzugsweise Isobutylacetat, Isoamylacetat, Hexenylacelat und/oder Pentylbutanoat oder
• (f) bittermandelartigem Geruch wie vorzugsweise 4-Acetyltoluol oder
• (g) schwarze Johannisbeere-artigem Geruch wie vorzugsweise Mercaptomethylpentanon und/oder Methoxymethylbutanethiol oder
• (h) zitrusartigem Geruch wie vorzugsweise Linalylpentanoat, Heptanal, Linalylisopenlanoat dodecanal, Linalylformiat, α-p-Dimethylstyrol, p-Cymenol, Nonanal, β-Cubebene, (Z)-Limonenoxid, cis-6-Ethenyltetrahydro-2,2,6-trimethylpyren-3-ol, cis-pyranoidlinalcoloxid, Dihydrolinalool, 6(10)-Dihydromyrcenol, Dihydromyrcenol, β-Farnesen, (Z)-β-Farnesen, (Z)-Ocimen, (E)-Limonenoxid, Dihydroterpinylacetat, (+)-Limonen, (Epoxymethylbutyl)-methylfuran und/oder p-Cymen oder
• (i) kakaoartigem Geruch wie vorzugsweise Dimethylpyrazin, Butylmethylbutyrat und/oder Methylbutanal oder
• (j) kokusnußartigem Geruch, wie vorzugsweise γ-Octalacton, γ-Nonalacton, Methyllaurat, Tetradecanol, Methylnonanoat, (35,3aS,7aR)-3a,4,5,7a-tetrahydro-3,6-dimethylbenzofuran-2(3H)-on, 5-Butyldihydro-4-methyl-2(3H)-Furanon, Ethylundecanoat und/oder δ-Decalacton oder
• (k) sahneartigem Geruch wie vorzugsweise Diethylacetal, 3-Hydroxy-2-butanon, 2,3-Pentadion und/oder 4-Heptenal oder
• (l) blumenartigem Geruch wie vorzugsweise Benzylalcohol, Phenylessigsäure, Tridecanal, p-Anisylalcohol, Hexanol, (E,E)-Farnesylaceton, Methylgeranat, trans-Crotonaldehyd, Tetradecylaldehyd, Methylanthranilat, Linalooloxid, Epoxylinalool, Phytol, 10-epi-γ-Eudesmol, Neroloxid, Ethyldihydrocinnamat, γ-Dodecalacton, Hexadecanol, 4-Mercapto-4-methyl-2-pentanol, (Z)-Ocimene, Cetylalcohol, Nerolidol, Ethyl-(E)-cinnamat, Elemicin, Pinocarveol, α-Bisabolol, (2R,4R)-Tetrahydro-4-methyl-2-(2-methyl-1-propenyl)-2H-pyran, (E)-Isoelemicin, Methyl-2-methylpropanoat, Trimethylphenylbutenon, 2-Methylanisol, β-Farnesol, (E)-Isoeugenol, Nitro-phenylethan, Ethylvanillat, 6-Methoxyeugenol, Linalool, β-Ionon, Trimethylphenylbutenon, Ethylbenzoat, Phenylethylbenzoat, Isoeugenol und/oder Acetophenone oder
• (m) Frische-Geruch wie vorzugsweise Methylhexanoat, Undecanon, (Z)-limonenoxid, Benzylacetat, Ethylhydroxyhexanoat, Isopropylhexanoat, Pentadecanal, β-Elemene, α-Zingiberene, (E)-Limonenoxid, (E)-p-Mentha-2,8-dien-1-ol, Menthon, Piperiton, (E)-3-Hexenol und/oder Carveol oder
• (n) Frucht-Geruch wie verzugsweise Ethylphenylacetat, Geranylvalerat, γ-Heptalacton, Ethylpropionat, Diethylacetal, Geranylbutyrat, Ethylheptylat, Ethyloctanoat, Methylhexanoat, Dimethylheptenal, Pentanon, Ethyl-3-methylbutanoat, Geranylisovalerat, lobutylacetat, Ehoxypropanol, Mthyl-2-butenal, Methylnonanedion, Linalylacetat, Mthylgeranat, Lmonenoxid, Hdrocinnamicalcohol, Dethylsuccinat, Ehylhexanoat, Ehylmethylpyrazin, β-Cbebene, Nryletat, Ctronellylbutyrat, Heylacetat, Nonylacetat, Butylmethylbutyrat, Pentenal, Isopentyldimethylpyrazin, p-menth-1-en-9-ol, Hexadecanon, Octylacetat, γ-Dodecalacton, Epoxy-β-ionon, Ethyloctenoat, Ethylisohexanoat, Isobornylpropionat, Cedrenol, p-menth-1-en-9-yl acetat, Cadinadien, (Z)-3-Hexenylhexanoat, Ethylcyclohexanoat, 4-Methylthio-2-butanon, 3,5-Octadienon, Methylcyclohexancarboxylat, 2-pentylthiophen, α-Ocimene, Butandiol, Ethylvalerat, Pentanol, Isopiperiton, Butyloctanoat, Ethylvanillat, Methylbutanoat, 2-Mmethylbutylacetat, Propylhexanoat, Butylhexanoat, Isopropylbutanoat, Spathulenol, Butanol, 6-Dodecalacton, Methylquinoxalin, Sesquiphellandren, 2-Hexenol, Ethylbenzoate, Isopropylbenzoat, Ethyllactat und/oder Citronellylisobutyrat oder
• (o) Geranium-artigen Geruch, wie vorzugsweise Geraniol, (E,Z)-2,4-Nonadienal, Octadienon und/oder o-Xylen oder
• (p) weintraubenartigem Geruch wie vorzugsweise Ethyldecanoat und/oder Hexanon oder
• (q) grapefruitartigem Geruch wie vorzugsweise (+)-5,6-Dimethyl-8-isopropenylbicyclo[4.4.0]dec-1-en-3-on und/oder p-Menthenethiol oder
• (r) grasartigem Geruch wie vorzugsweise 2-Ethylpyridin, 2,6-Dimethylnaphthalen, Hexanal und/oder (Z)-3-Hexenol oder
• (s) grüner Note, vorzugsweise 2-Ethylhexanol, 6-Decenal, Dimethylheptenal, Hexanol, Heptanol, Methyl-2-butenal, Hexyloctanoate, Nonansäure, Undecanon, Methylgeranat, Isobornylformiate, Butanal, Octanal, Nonanal, Epoxy-2-decenal, cis-Linalool, Pyranoxid, Nonanol, alpha,γ-dimethylallylalcohol, (Z)-2-penten-1-ol, (Z)-3-hexenylbutanoat, Isobutylthiazol, (E)-2-nonenal, 2-dodecenal, (Z)-4-decenal, 2-octenal, 2-hepten-1-al, Bicyclogermacrene, 2-Octenal, α-Thujene, (Z)-β-Farnesene, (-)-γ-Elemene, 2,4-Octadienal, Fucoserraten, Hexenylacetat, Geranylaceton, Valencene, β-Eudesmol, 1-Hexenol, (E)-2-Undecenal, Artemisia keton, Viridiflorol, 2,6-Nonadienal, Trimethylphenylbutenon, 2,4-Nonadienal, Butylisothiocyanat, 2-Pentanol, Elemol, 2-Hexenal, 3-Hexenal, (+)-(E)-Limonen-oxid, cis-Isocitral, Dimethyloctadienal, Bornylformiat, Bornylisovalerat, Isobutyraldehyd, 2,4-Hexadienal, Trimethylphenylbutenon, Nonanon, (E)-2-Hexenal, (+)-cis-Rosenoxide, Menthone, Coumarin, (Epoxymethylbutyl)-methylfuran, 2-Hexenol, (E)-2-hexenol und/oder Carvylacetat oder
• (t) Grüner Tee-artigem Geruch, vorzugsweise (-)-Cubenol oder
• (u) kräuterartigem Geruch, vorzugsweise Octanon, Hexyloctanoat, Caryophyllenoxide, Methylbutenol, Safranal, Benzylbenzoat, Bornylbutyrat, Hexylacetat, β-Bisabolol, Piperitol, β-Selinene, α-Cubebene, p-Menth-1-en-9-ol, 1,5,9,9-Tetramethyl-12-oxabicyclododeca-4,7-dien, T-muurolol, (-)-Cubenol, Levomenol, Ocimene, α-Thujene, p-Menth-1-en-9-yl acetat, Dehydrocarveol, Artemisia alcohol, γ-Muurolene, Hydroxypentanon, (Z)-Ocimene, β-Elemene, δ-Cadinol, (E)-β-Ocimene, (Z)-Dihydrocarvone, α-Cadinol, Calamenen, (Z)-Piperitol. Lavandulol, β-Bourbonene, (Z)-3-Hexenyl-2-methylbutanoat, 4-(1-Methylethyl-benzenemethanol, Artemisia keton, Methyl-2-butenol, Heptanol, (E)-Dihydrocarvon, p-2-Menthen-1-ol, α-Curcumene, Spathulenol, Sesquiphellandren, Citronellylvalerat, Bornylisovalerat, 1,5-Octadien-3-ol, Methylbenzoat, 2,3,4,5-Tetrahydroanisol und/oder Hydroxycalamenen oder
• (v) honigartigem Geruch, vorzugsweise Ethylcinnamate, β-Phenethylacetat, Phenylessigsäure, Phenylethanal, Methylanthranilat, Zimtsäure, β-Damascenone, Ethyl-(E)-cinnamat, 2-Phenylethylalcohol, Citronellylvalerate, Phenylethylbenzoate und/oder Eugenol oder
• (w) Hyazinthen-artigem Geruch, vorzugsweise Hotrienol oder
• (x) jasminartigem Geruch, vorzugsweise Methyljasmonate, Methyldihydroepijasmonat und/oder Methylepijasmonat oder
• (y) lavendelartigem Geruch, vorzugsweise Linalylvalerate und/oder Linalool oder
• (z) zitronenartigem Geruch, vorzugsweise Neral, Octanal, δ-3-Carene, Limonen, Geranial, 4-mercapto-4-methyl-2-pentanol, Citral, 2,3-Dehydro-1,8-cineol und/oder α-Terpinen oder
• (aa) lilienartigem Geruch, vorzugsweise Dodecanal oder
• (bb) magnolienartigem Geruch, vorzugsweise Geranylaceton oder
• (cc) mandarinenartigem Geruch, vorzugsweise Undecanol oder
• (dd) melonenartigem Geruch, vorzugsweise Dimethylheptenal oder
• (ee) Minze-artigem Geruch, vorzugsweise Menthone, Ethylsalicylat, p-Anisaldehyd, 2,4,5,7a-tetra-hydro-3,6-dimethyl-benzofuran, Epoxy-p-menthene, Geranial, (Methylbutenyl)-methylfuran, Dihydrocarvylacetat, β-Cyclocitral, 1,8-Cineol, β-Phellandrene, Methylpentanon, (+)-Limonen, Dihydrocarveol (-)-Carvon, (E)-p-Mentha-2,8-dien-1-ol, Isopulegylacetat, Piperiton, 2,3-Dehydro-1,8-cineol, α-Terpineol, DL-carvon und/oder α-Phellandrene oder
• (ff) nußartigem Geruch, vorzugsweise 5-methyl-(E)-2-hepten-4-on, γ-Heptalacton, 2-Acetylpyrrol, 3-Octen-2-on, Dihydromethylcyclopentapyrazin, Acetylthiazol, 2-Octenal, 2,4-Heptadienal, 3-Octenon, Hydroxypentanon, Octanol, Dimethylpyrazin, Methylquinoxalin und/oder Acetylpyrrolin oder
• (gg) orangenartigem Geruch, vorzugsweise Methyloctanoat, Undecanon, Decylalcohol, Limonen und/oder 2-Decenal oder
• (hh) Orangenschalen-artigem Geruch, vorzugsweise Decanal und/oder β-Carene oder
• (ii) pfirsichartigem Geruch, vorzugsweise γ-Nonalacton, (Z)-6-Dodecene-γ-lacton, δ-Decalacton, R-δ-Decenolacton, Hexylhexanoat, 5-Octanolid, γ-Decalacton und/oder δ-Undecalacton oder
• (jj) Pfefferminze-artigem Geruch, vorzugsweise Methylsalicylat und/oder I-Menthol oder
• (kk) Kiefer-artigem Geruch, vorzugsweise α-p-Dimethylstyrol, β-Pinene, Bornylbenzoat, δ-Terpinen, Dihydroterpinylacetat und/oder α-Pinen oder
• (II) ananasartigem Geruch, vorzugsweise Propylbutyrat, Propylpropanoat und/oder Ethylacetat oder
• (mm)pflaumenartigem Geruch, vorzugsweise Benzylbutanoat, oder
• (nn) himbeerartigem Geruch, vorzugsweise β-Ionone oder
• (oo) Rose-artigem Geruch, vorzugsweise β-Phenethylacetat, 2-Ethylhexanol, Geranylvalerat, Geranylacetat, Citronellol, Geraniol, Geranylbutyrat, Geranylisovalerat, Citronellylbutyrat, Citronellylacetat, Isogeraniol, Tetrahydro-4-methyl-2-(2-methyl-1-propenyl)-2,5-cis-2H-pyran, Isogeraniol, 2-Phenylethylalcohol, Citronellylvalerat und/oder Citronellylisobutyrat, oder
• (pp) Grüne Minze-artigem Geruch, vorzugsweise Carvylacetate und/oder Carveol, oder
• (qq) erdbeerenartigem Geruch, vorzugsweise Hexylmethylbutyrat, Methylcinnamat, Pentenal, Methylcinnamate oder
• (rr) süßlichem Geruch, vorzugsweise Benzylalcohol, Ethylphenylacetat, Tridecanal, Nerol, Methylhexanoat, Linalylisovalerat, Undecanaldehyd, Caryophyllenoxid, Linalylacetat, Safranal, Uncineol, Phenylethanal, p-Anisaldehyd, Eudesmol, Ethylmethylpyrazin, Citronellylbutyrat, 4-Methyl-3-penten-2-on, Nonylacetat, 10-Epi-γ-eudesmol, β-Bisabolol, (Z)-6-Dodecen-γ-lacton, β-Famesene, 2-Dodecenal, γ-Dodecalacton, Epoxy-β-ionon, 2-Undecenal, Styrenglycol, Methylfuraneol, (-)-cis-Rosenoxid, (E)-β-Ocimene, Dimethylmethoxyfuranon, 1,8-Cineole, Ethylbenzaldehyd, 2-Pentylthiophen, α-Farnesene, Methionol, 7-Methoxycoumarin, (Z)-3-Hexenyl-2-methylbutanoat, o-Aminoacetophenon, Viridiflorol, Isopiperitone, β-Sinensal, Ethylvanillat, Methylbutanoat, p-Methoxystyrol, 6-Methoxyeugenol, 4-Hexanolid, δ-Dodecalacton, Sesquiphellandren, Diethylmalat, Linalylbutyrat, Guaiacol, Coumarin, Methylbenzoat, Isopropylbenzoat, Safrole, Durene, γ-Butyrolacton, Ethylisobutyrat und/oder Furfural oder
• (ss) Vanille-artigem Geruch, vorzugsweise Vanillin, Methylvanillat, Acetovanillon und/oder Ethylvanillat oder
• (tt) wassermelonenartigem Geruch, vorzugsweise 2,4-Nonadienal oder
• (uu) holzartigem Geruch, vorzugsweise α-Muurolene, Cadina-1,4-dien-3-ol, Isocaryophyllene, Eudesmol, α-Ionon, Bornylbutyrat, (E)-α-Bergamoten, Linalooloxid, Ethylpyrazin, 10-epi-γ-Eudesmol, Germacrene B, trans-Sabinenhydrat, Dihydrolinalool, Isodihydrocarveol, β-Famesene, β-Sesquiphellandren, δ-elemente, α-Calacorene, Epoxy-β-ionon, Germacrene D, Bicyclogermacrene, Alloaromadendrene, α-Thujene, oxo-β-Ionon, (-)-γ-Elemene. γ-Muurolene, Sabinene, α-Guaiene, α-Copaene, γ-Cadinene, Nerolidol, β-Eudesmol, α-Cadinol, δ-Cadinene, 4,5-Dimethoxy-6-(2-propenyl)-1,3-benzodioxol, [1ar-(1aalpha,4aalpha,7alpha,7abeta,7balpha)]-decahydro-1,1,7-trimethyl-4-methylene-1H-cycloprop[e]azulen, α-Gurjunen, Guaiol, α-Farnesene, γ-Selinene, 4-(1-Methylethyl)-benzenemethanol, Perillen, Elemol, α-Humulene, β-Caryophyllene und/oder β-Guaiene oder
• (vv) Mischungen aus vorgenannten

enthalten.The present invention provides those skilled in the art with considerable scope for scenting aqueous systems, thereby enabling them to produce aqueous systems with very individual, refined scents. For this purpose, the films according to the invention, according to a preferred embodiment, in particular fragrances with

• (a) almond-like odor, such as preferably benzaldehyde, pentanal, heptenal, 6-methylfurfural, methylbutanal, furfural and / or acetophenone or
• (b) apple-like odor, preferably (S) - (+) - ethyl-2-methylbutanoate, diethyl malonate, ethyl butyrate, geranylbulyral, geranylisopentanoate, isobutyl acetate, linalyl isopentanoate, (E) -β-damascone, heptyl-2-methyl butyrate, methyl 3-methylbulanoate, 2-hexenalpentylmethyl butyrate, ethylmethyl butyrate and / or methyl 2-methylbutanoate or
• (c) apple peel-like odor, such as preferably ethylhexanoate, hexylbutanoate and / or hexylhexanoate or
• (d) apricot-like odor, preferably γ-undecalactone, or
• (e) banana-like odor, such as preferably isobutyl acetate, isoamyl acetate, hexenyl acelate and / or pentyl butanoate or
• (f) bitter almond-like odor such as preferably 4-acetyltoluene or
• (g) blackcurrant-like odor, such as preferably mercaptomethylpentanone and / or methoxymethylbutanethiol or
• (c) citrus-like odor such as preferably linalyl pentanoate, heptanal, linalyl isopenlanoate dodecanal, linalyl formate, α-p-dimethylstyrene, p-cymenol, nonanal, β-cubebene, (Z) -liminene oxide, cis-6-ethenyl-tetrahydro-2,2,6- trimethylpyrene-3-ol, cis-pyranoidinalcoloxide, dihydrolinalool, 6 (10) -dihydromyrcenol, dihydromyrcenol, β-farnesene, (Z) -β-farnesene, (Z) -cimene, (E) -Limone oxide, Dihydroterpinylacetat, (+) - limonene, (Epoxymethylbutyl) -methylfuran and / or p-cymene or
• (i) cocoa like odor, preferably dimethylpyrazine, butylmethyl butyrate and / or methylbutanal or
• (j) coconut-like odor, preferably γ-octalactone, γ-nonalactone, methyl laurate, tetradecanol, methyl nonanoate, (35,3aS, 7aR) -3a, 4,5,7a-tetrahydro-3,6-dimethylbenzofuran-2 (3H) -on, 5-butyldihydro-4-methyl-2 (3H) -furanone, ethyl undecanoate and / or δ-decalactone or
• (k) creamy odor such as preferably diethyl acetal, 3-hydroxy-2-butanone, 2,3-pentadione and / or 4-heptenal, or
• (l) flower-like odor such as preferably benzyl alcohol, phenylacetic acid, tridecanal, p-anisyl alcohol, hexanol, (E, E) -farnesylacetone, methyl geranate, trans-crotonaldehyde, tetradecylaldehyde, methyl anthranilate, linalooloxide, epoxylinalool, phytol, 10-epi-γ-eudesmol , Nerol oxide, ethyldihydrocinnamate, γ-dodecalactone, hexadecanol, 4-mercapto-4-methyl-2-pentanol, (Z) -oximes, cetyl alcohol, nerolidol, ethyl (E) -cinnamate, elemicin, pinocarveol, α-bisabolol, ( 2R, 4R) -Tetrahydro-4-methyl-2- (2-methyl-1-propenyl) -2H-pyran, (E) -Isoelemicin, methyl 2-methylpropanoate, trimethylphenylbutenone, 2-methylanisole, β-farnesol, ( E) isoeugenol, nitro-phenylethane, ethyl vanillate, 6-methoxyeugenol, linalool, β-ionone, trimethylphenylbutenone, ethyl benzoate, phenylethyl benzoate, isoeugenol and / or acetophenones or
• (m) freshness odor, preferably methylhexanoate, undecanone, (Z) -limonoxide, benzylacetate, ethylhydroxyhexanoate, isopropylhexanoate, pentadecanal, β-elemene, α-zingiberene, (E) -liminic oxide, (E) -p-mentha-2, 8-dien-1-ol, menthone, piperone, (E) -3-hexenol and / or carveol or
• (n) Fruit odor, such as ethylphenylacetate, geranylvalerate, γ-heptalactone, ethylpropionate, diethylacetal, geranylbutyrate, ethylheptylate, ethyloctanoate, methylhexanoate, dimethylheptenal, pentanone, ethyl-3-methylbutanoate, geranylisovalerate, lobutylacetate, ethoxypropanol, methyl-2-butenal, Methylnonanedione, linalyl acetate, methyl geranate, lmone oxide, hdrocinnamiccohol, ethylsuccinate, ethylhexanoate, ethylmethylpyrazine, β-cbene, nylate, ctronellylbutyrate, heylacetate, nonylacetate, butylmethylbutyrate, pentenal, isopentyldimethylpyrazine, p-menth-1-en-9-ol, hexadecanone, octylacetate, γ-dodecalactone, epoxy β-ionone, ethyloctenoate, ethylisohexanoate, isobornyl propionate, cedrenol, p-menth-1-en-9-yl acetate, cadinadiene, (Z) -3-hexenylhexanoate, ethylcyclohexanoate, 4-methylthio-2-butanone , 3,5-octadienone, methylcyclohexanecarboxylate, 2-pentylthiophene, α-ocimene, butanediol, ethylvalerate, pentanol, isopiperiton, butyl octanoate, ethyl vanillate, methyl butanoate, 2-methylbutyl acetate, propyl hexanoate, Butyl hexanoate, isopropyl butanoate, spathulenol, butanol, 6-dodecalactone, methylquinoxaline, sesquiphenilene, 2-hexenol, ethyl benzoate, isopropyl benzoate, ethyl lactate and / or citronellyl isobutyrate or
• (o) Geranium-like odor, such as preferably geraniol, (E, Z) -2,4-nonadienal, octadienone and / or o-xylene or
• (p) grape-like odor such as preferably ethyl decanoate and / or hexanone or
• (q) grapefruit-like odor such as preferably (+) - 5,6-dimethyl-8-isopropenylbicyclo [4.4.0] dec-1-en-3-one and / or p-menthenethiol or
• (R) grassy odor such as preferably 2-ethylpyridine, 2,6-dimethylnaphthalene, hexanal and / or (Z) -3-hexenol or
• (s) green note, preferably 2-ethylhexanol, 6-decenal, dimethylheptenal, hexanol, heptanol, methyl-2-butenal, hexyloctanoates, nonanoic acid, undecanone, methyl geranate, isobornylformiate, butanal, octanal, nonanal, epoxy-2-decenal, cis -Linalool, pyranoxide, nonanol, alpha, γ-dimethylallylalcohol, (Z) -2-penten-1-ol, (Z) -3-hexenylbutanoate, isobutylthiazole, (E) -2-nonenal, 2-dodecenal, (Z) 4-decenal, 2-octenal, 2-hepten-1-al, bicyclo mermose, 2-octenal, α-thujene, (Z) -β-farnesene, (-) - γ-elemene, 2,4-octadienal, fucoserrate , Hexenylacetate, geranylacetone, valencene, β-eudesmol, 1-hexenol, (E) -2-undecenal, artemisia ketone, viridiflorol, 2,6-nonadienal, trimethylphenylbutenone, 2,4-nonadienal, butylisothiocyanate, 2-pentanol, elemole, 2-hexenal, 3-hexenal, (+) - (E) -lone oxide, cis-isocitral, dimethyloctadienal, bornyl formate, bornyl isovalerate, isobutyraldehyde, 2,4-hexadienal, trimethylphenylbutenone, nonanone, (E) -2-hexenal, (+) - cis-Rosenoxide, Menthone, Coumarin, (Epoxymethylbutyl) -methylfur on, 2-hexenol, (E) -2-hexenol and / or carvyl acetate or
• (t) Green Tea-like odor, preferably (-) - Cubenol or
• (u) herbaceous odor, preferably octanone, hexyloctanoate, caryophyllene oxides, methylbutenol, safranal, benzyl benzoate, bornyl butyrate, hexyl acetate, β-bisabolol, piperitol, β-selenene, α-cubebene, p-menth-1-en-9-ol, 1 , 5,9,9-tetramethyl-12-oxabicyclododeca-4,7-diene, T-muurolol, (-) - cubenol, levomenol, ocimene, α-thujene, p-menth-1-en-9-yl acetate, Dehydrocarveol, Artemisia alcohol, γ-Muurolene, hydroxypentanone, (Z) -Ocimene, β-elemene, δ-cadinol, (E) -β-Ocimene, (Z) -dihydrocarvone, α-cadinol, calamenene, (Z) -piperitol , Lavandulol, β-bourbonene, (Z) -3-hexenyl-2-methylbutanoate, 4- (1-methylethylbenzenemethanol, artemisia ketone, methyl-2-butenol, heptanol, (E) -dihydrocarvone, p-2-menthene 1-ol, α-Curcumene, Spathulenol, Sesquiphellandren, Citronellylvalerat, Bornylisovalerat, 1,5-octadien-3-ol, methyl benzoate, 2,3,4,5-tetrahydroanisole and / or Hydroxycalamenen or
• (v) honey-like odor, preferably ethyl cinnamate, β-phenethyl acetate, phenylacetic acid, phenylethanal, methyl anthranilate, cinnamic acid, β-damascenone, ethyl (E) -cinnamate, 2-phenylethylalcohol, citronellyl valerate, phenylethyl benzoate and / or eugenol or
• (w) Hyacinth-like odor, preferably Hotrienol or
• (x) jasmine-like odor, preferably methyl jasmonate, methyldihydroepijasmonate and / or methylepijasmonate or
• (y) lavender-like odor, preferably linalyl valerate and / or linalool or
• (z) lemon-like odor, preferably, neral, octanal, δ-3-carene, limonene, geranial, 4-mercapto-4-methyl-2-pentanol, citral, 2,3-dehydro-1,8-cineol and / or α -Terpines or
• (aa) lily-like odor, preferably dodecanal or
• (bb) magnolia-like odor, preferably geranylacetone or
• (cc) mandarin-like odor, preferably undecanol or
• (dd) melon-like odor, preferably dimethylheptenal or
• (ee) minty odor, preferably menthone, ethyl salicylate, p-anisaldehyde, 2,4,5,7a-tetra-hydro-3,6-dimethylbenzofuran, epoxy-p-menthene, geranial, (methylbutenyl) -methylfuran , Dihydrocarvyl acetate, β-cyclocitral, 1,8-cineole, β-phellandrene, methylpentanone, (+) - limonene, dihydrocarveol (-) - carvone, (E) -p-mentha-2,8-dien-1-ol, Isopulegyl acetate, piperitone, 2,3-dehydro-1,8-cineol, α-terpineol, DL-carvone and / or α-phellandrene or
• (ff) Nutty odor, preferably 5-methyl- (E) -2-hepten-4-one, γ-heptalactone, 2-acetylpyrrole, 3-octen-2-one, dihydromethylcyclopentapyrazine, acetylthiazole, 2-octenal, 2,4 Heptadienal, 3-octenone, hydroxypentanone, octanol, dimethylpyrazine, methylquinoxaline and / or acetylpyrroline or
• (gg) orange-like odor, preferably methyloctanoate, undecanone, decyl alcohol, limonene and / or 2-decenal or
• (hh) orange peel-like odor, preferably decanal and / or beta-carene or
• (ii) peach-like odor, preferably γ-nonalactone, (Z) -6-dodecene-γ-lactone, δ-decalactone, R-δ-decenolactone, hexylhexanoate, 5-octanolide, γ-decalactone and / or δ-undecalactone or
• (jj) peppermint-like odor, preferably methyl salicylate and / or I-menthol or
• (kk) pine-like odor, preferably α-p-dimethylstyrene, β-pinene, bornyl benzoate, δ-terpinene, dihydroterpinyl acetate and / or α-pinene or
• (II) pineapple-like odor, preferably propyl butyrate, propyl propanoate and / or ethyl acetate or
• (mm) plum-like odor, preferably benzyl butanoate, or
• (nn) raspberry-like odor, preferably β-ionone or
• (oo) Rose-like odor, preferably β-phenethyl acetate, 2-ethylhexanol, geranyl valerate, geranyl acetate, citronellol, geraniol, geranyl butyrate, geranyl isovalerate, citronellyl butyrate, citronellyl acetate, isogeraniol, tetrahydro-4-methyl-2- (2-methyl-1) propenyl) -2,5-cis-2H-pyran, isogeraniol, 2-phenylethyl alcohol, citronellyl valerate and / or citronellyl isobutyrate, or
• (pp) spearmint-like odor, preferably carvylacetate and / or carveol, or
• (qq) strawberry-like odor, preferably hexylmethyl butyrate, methyl cinnamate, pentenal, methyl cinnamate or
• (rr) sweet odor, preferably benzyl alcohol, ethyl phenylacetate, tridecanal, nerol, methylhexanoate, linalyl isovalerate, undecanedehyde, caryophyllene oxide, linalyl acetate, safranal, uncinol, phenylethanal, p-anisaldehyde, eudesmol, ethylmethylpyrazine, citronellylbutyrate, 4-methyl-3-pentene-2 -on, nonyl acetate, 10-epi-γ-eudesmol, β-bisabolol, (Z) -6-dodecene-γ-lactone, β-famesenes, 2-dodecenal, γ-dodecalactone, epoxy-β-ionone, 2-undecenal , Styrene glycol, methylfuraneol, (-) - cis-rose oxide, (E) -β-ocimene, dimethylmethoxyfuranone, 1,8-cineole, ethylbenzaldehyde, 2-pentylthiophene, α-farnesene, Methionol, 7-methoxycoumarin, (Z) -3-hexenyl-2-methylbutanoate, o-aminoacetophenone, viridiflorol, isopiperitones, β-sinensal, ethyl vanillate, methyl butanoate, p-methoxystyrene, 6-methoxyeugenol, 4-hexanolide, δ-dodecalactone, Sesquiphellandrene, diethyl malate, linalyl butyrate, guaiacol, coumarin, methyl benzoate, isopropyl benzoate, safroles, durene, γ-butyrolactone, ethyl isobutyrate and / or furfural or
• (ss) vanilla-like odor, preferably vanillin, methyl vanillate, acetovanillon and / or ethyl vanillate or
• (tt) watermelon-like odor, preferably 2,4-nonadienal or
• (uu) woody odor, preferably α-muurolene, cadina-1,4-dien-3-ol, isocaryophyllene, eudesmol, α-ionone, bornyl butyrate, (E) -α-bergamotene, linalooloxide, ethylpyrazine, 10-epi-γ Eudesmol, germacrene B, trans-sabine hydrate, dihydrolinalool, isodihydrocarveol, β-feamenes, β-sesquiphellandrene, δ-elements, α-calacorene, epoxy-β-ionone, germacrene D, bicyclogermacrene, alloaromadendrene, α-thujene, oxo-β Ionone, (-) - γ-elemene. γ-Muurolene, Sabinene, α-Guaiene, α-Copaene, γ-Cadinene, Nerolidol, β-Eudesmol, α-Cadinol, δ-Cadinene, 4,5-Dimethoxy-6- (2-propenyl) -1,3- benzodioxole, [1ar- (1aalpha, 4aalpha, 7alpha, 7abeta, 7balpha)] - decahydro-1,1,7-trimethyl-4-methylene-1H-cycloprop [e] azulen, α-gurjunen, guaiol, α-farnesene, γ-seleneins, 4- (1-methylethyl) -benzenemethanol, Perillen, Elemol, α-Humulenes, β-Caryophyllene and / or β-Guaiene or
• (vv) mixtures of the above

contain.

So the consumer can e.g. Create dishwashing water with a banana-like odor, bath water with a vanilla-like odor or, for example, window rinse water with a honey-like odor. He can also create completely new odor images by combining different moldings.

With appropriate applications, a so-called aromatherapeutischer added benefit for the consumer can be adjusted. For example, natural fragrances of essential oils can be used. Typical examples are chamomile, rosemary, thyme, jasmine, peppermint and sandalwood. The consumer can thus influence the subjective sense of well-being by selecting fragrances, and e.g. Psychosomatically concomitant complaints such as nervousness or stress accompany with the use of perfumed moldings. Also as an adjunctive remedy for colds or nervous gastrointestinal disorders appropriate moldings can be used to support the subjective well-being. However, this is not a therapeutic process in the true sense, but an odor-cosmetic process.

The set configuration already described is also suitable, for example, for designing a scent carousel.

Carousel configurations are known in particular from the field of spice carousel. These are usually rotatable structures, which comprise at least 4 or more, for example up to 12 individual, removable containers which are arranged in a round shape on a stand or a holding device. Such a perfume carousel with e.g. 12 containers, which comprise different fragrance tablets, may even be referred to as a so-called fragrance organ, with which the consumer can compose an individual fragrance.

According to a preferred embodiment, the molded article according to the invention contains at least 12% by weight of perfume, preferably at least 15% by weight of perfume, in particular at least 20% by weight of perfume, based on the total molding. Likewise, the molded article may also contain larger amounts of perfume, e.g. at least 25, 30, 35, 40, 45 or even at least 60% by weight of perfume. Useful upper limits of perfume may e.g. at 80 wt%, 75 wt%, 70 wt%, 65 wt%, 60 wt%, 55 wt%. 50 wt%, 45 wt%, 40 wt%, 35 wt%, 30 wt%. 25 wt .-%, 20 wt .-%, 15 wt .-% or 10 wt .-% are.

If the perfume contained at least 5, 10 or 15 wt .-% of fragrances having a boiling point above 250 ° C and a logP value of ≥ 3.0, so is a preferred embodiment. It has been found that moldings according to the invention which contain such minimum amounts of fragrances having a boiling point above 250 ° C. and a logP value of ≥ 3.0 have particularly advantageous scent properties. For example, a longer-lasting fragrance impression can be achieved when using the shaped bodies in aqueous systems. Likewise, the Aufziehverhalten the fragrances on substrates which are treated in / with the perfumed aqueous system, further improved, so that dia substrates, especially textiles longer and more intense smell.

The octanol / water partition coefficient of a perfume ingredient is the ratio between its equilibrium concentration in octanol and in water. Since the distribution coefficients of the perfume ingredients are often high, e.g. 1000 or higher, they are more conveniently given in the form of their base 10 logarithm, one speaks of the so-called log P value. Preferred fragrances of this invention have a logP of ≥ 3.0 or higher, e.g. From ≥ 3.1. preferably ≥ 3.2, in particular ≥ 3.3.

The logP value of numerous fragrances is documented; For example, the Pomona92 database, available from Daylight Chemical Information Systems, Inc., (Daylight CIS), Irvine, California, contains numerous logP values, along with citations to the original literature. However, the logP values are most conveniently calculated by the "CLOGP" program, which is also available from Daylight CIS. This program also lists the experimental logP values if they are available in the Pomona92 database. The "calculated logP" (ClogP value) is determined by the fragment approximation according to Harsch and Leo.

Table 1 below lists several fragrances that fulfill the criteria boiling point> 250 ° C and ClogP ≥ 3. Such fragrances which fulfill these criteria are also referred to as persistent fragrances in the further course. Table 1: Examples of persistent fragrances Perfume ingredients Approximately boiling point (° C) ClogP Boiling point> 250 ° C and ClogP ≥ 3.0 Allylcylclohexanpropionat 267 3,935 ambrettolide 300 6.261 amyl benzoate 262 3,417 Amylcinnamat 310 3,771 amyl cinnamic aldehyde 285 4,324 Amylzimtaldehyddimethylacetal 300 4,033 iso-amyl salicylate 277 4,601 aurantiol 450 4,216 benzophenone 306 3,120 benzyl 300 4,383 para-tert-butylcyclohexyl acetate +250 4,019 iso-butylquinoline 252 4,193 beta-caryophyllene 256 6,333 cardinene 275 7, 346 cedrol 291 4,530 cedryl acetate 303 5,436 Cedrylformiat +250 5,070 cinnamyl cinnamate 370 5,480 cyclohexyl 304 5,265 Cyclamenaldehyd 270 3,680 Dihydroisojasmonat +300 3,009 diphenylmethane 262 4,059 diphenyl 252 4,240 Dodecanlacton 258 4,359 iso E awesome +250 3,455 Ethylbrassylat 3321 4,554 ethyl methyl phenyl glycidate 260 3165 ethyl undecylenate 264 4,888 exaltolide 280 5.346 galaxolid +250 5,482 Geranylanthranilat 312 4,216 geranyl phenylacetate +250 5,233 hexadecanolide 294 6,805 hexenyl 271 4,716 hexyl cinnamic aldehyde 305 5,473 hexyl salicylate 290 5,260 alpha-Iron 250 3,820 Lilial (pt-bucinal) 258 3,858 Linalyl benzoate 263 5,233 2-methoxynaphthalene 274 3,235 Methyldihydrojasmon +300 4.843 gamma-n-methyl ions 252 4,309 Musk indanone +250 5,458 Musk ketone MP = 137 ° C 3,014 Musk Tibetin MP = 136 ° C 3,831 myristicin 276 3,200 Oxahexadecanolide-10 +300 4,336 Oxahexadecanolide-1 MP = 35 ° C 4,336 patchouli 285 4,530 Phantolide 288 5,977 phenylethyl benzoate 300 4,058 phenylethyl phenylacetate 325 3,767 Phenylheptanol 261 3,478 phenylhexanol 258 3,299 alpha-Santalol 301 3,800 Thibetolid 280 6,246 delta-undecalactone 290 3,830 gamma-undecalactone 297 4,140 Vetiverlyacetat 285 4,882 Yara-yara 274 3,235 (a) MP is the melting point; these ingredients have a boiling point higher than 250 ° C.

This table gives a sufficient number of non-limiting examples of persistent fragrances which are preferred for use in this invention. The shaped articles of the present invention preferably contain at least 3 different resistant fragrances, more preferably at least 4 different resistant fragrances, and even more preferably at least 5 different resistant fragrances.

According to a preferred embodiment of the invention, the shaped bodies preferably contain ≥20% by weight, ≥25% by weight, ≥30% by weight, ≥35% by weight, ≥40% by weight, ≥45% by weight. %, ≥50 wt%, ≥55 wt%, ≥60 wt%, ≥65 wt%, ≥75 wt%, ≥80 wt%, ≥85 wt% , ≥ 90 wt .-% or even ≥ 95 wt .-% of resistant fragrances, wt .-% based on the total amount of the fragrances contained in the molding.

In the perfume compartment, some non-odor or very low odor materials are used as perfume diluents or extenders. Nonlimiting examples of these materials are dipropylene glycol, diethyl phthalate, triethyl citrate, isopropyl myristate and benzyl benzoate. These materials are e.g. used to dilute and stabilize some other perfume ingredients. These materials are not included in the calculation of the total amount of fragrances contained in the molding.

Non-resistant fragrances in the context of this invention are those fragrances which have a boiling point of less than about 250 ° C or a ClogP of less than about 3.0, or both a boiling point of less than about 250 ° C and a ClogP of less than about 3.0. According to a preferred embodiment, non-resistant fragrances are preferably minimized in the shaped bodies of the present invention, ie the shaped bodies preferably contain ≦ 60% by weight, ≦ 55% by weight, ≦ 50% by weight, ≦ 45% by weight. , ≤ 40 wt%, ≤ 35 wt%, ≤ 30 wt%, ≤ 25 wt%, ≤ 20 wt%, ≤ 15 wt%, ≤ 10 wt%, ≤ 5 wt .-%, ≥ 3 Ges .-%, ≥ 2 wt .-% or even ≥ 1 wt .-% of non-resistant fragrances, wt .-% based on the total amount of fragrances contained in the molding.

However, it may be advantageous if non-resistant fragrances are used at least in small amounts, namely to improve the odor of the molded article as such. The shaped bodies of the present invention therefore preferably contain ≥1% by weight, preferably ≥5% by weight, more preferably ≥10% by weight, even more preferably ≥15% by weight, in particular even ≥20, ≥25 or even ≥ 30 wt .-%, of non-resistant fragrances, wt .-% based on the total amount of fragrances contained in the molding.

The perfume contained in the molding is at least 5% by weight in an encapsulated form. The proportion of the contained perfume in encapsulated form may be even greater, e.g. at values of at least 10, 15, 20, 25, 30, 35, 40 or 45 wt .-% are. Wt .-% refers to the total amount of the perfume contained in the molding.

Preferably, the encapsulated perfume particles are activated by moisture. Such perfume particles are known. They may be, for example, cyclodextrin / perfume inclusion complexes or perfume microcapsules, e.g. act with a polysaccharin binder. The encapsulation of the perfume minimizes premature volatilization of the fragrances even further. The verkapseit perfume is only then released. when the materials are moistened.

For example, the perfume capsules may have a diameter of 100 nm to e.g. 1 mm. It is also possible. To use perfume capsules that are larger than 1 mm in diameter

Preferred perfume microcapsules have e.g. a diameter of 0.5 .mu.m to 300 .mu.m, preferably 1 .mu.m to 200 .mu.m, in particular 2 .mu.m to 100 .mu.m. The Kapseidurchmesser is of course to vote on the film thickness. The maximum capsule diameter may e.g. even at values <90 μm, <80 μm, <70 μm, <60 μm, <50 μm or <40 μm.

Particularly useful methods of encapsulation include coacervation, liposome formation. Granulation. Coating, emulsification, atomization and spray cooling.

According to the present invention, the capsules can be incorporated into a preferably water-soluble film. The capsules are preferably immiscible with the film. Advantageously, the capsules are hydrophobic in nature to prevent their diffusion into the hydrophilic film. For example, the capsules may preferably be prepared in situ in the film as part of the film casting process.

The preferably hydrophobic ingredient for the capsules is especially selected from the group consisting of paraffin, wax, oil, vaseline, a hydrophobic polymer, and mixtures thereof.

In in-situ production, the e.g. hydrophobic continuous phase and then mixed with either an oil-soluble benefit agent (such as perfume) or a discontinuous phase or blender. The resulting solution or emulsion or dispersion is mixed with a solution of a water-soluble film in water (for example, ratio of film to water 1: 4). The mixture is preferably prepared at a relatively low temperature to protect sensitive benefit components, if present (eg, 30-45 ° C). The result is an emulsion in the water-soluble film. The emulsion is poured and e.g. sintered in an oven to form a film with capsules.

According to a preferred embodiment, the molding according to the invention contains perfume precursors, which preferably release fragrances by hydrolysis only in the presence of H ₂ O. The perfume precursors may advantageously be selected from β-aminoketone scavenger precursors, aldehyde- or ketone-releasing perfume precursors, alcohol-releasing perfume precursors, preferably silicic acid esters, and orthocarbonate and ortho ester perfume extenders.

Advantageously, the fragrance precursors are selected from acetals, ketals, orthoesters, orthocarbonates, and mixtures thereof.

worin R Wasserstoff, lineares C₁-C₈-Alkyl, verzweigles C₃-C₂₀-Alkyl, cyclisches C₃-C₂₀-Alkyl, verzweigtes cyclisches C₆-C₂₀-Alkyl, Ilneares C₆-C₂₀-Alkenyl, verzweigtes C₆-C₂₀-Alkenyl, cyclisches C₀-C₂₀Alkenyl, verzweigtes cyclisches C₆-C₂₀-Alkenyl, substituiertes oder unsubstituiertes C₆-C₂₀-Aryl und Mischungen hiervon bedeutet; R¹, R²² und R³ stehen unabhängig voneinander für lineares, verzweigtes oder substituiertes C₁-C₂₀-Alkyl, lineares, verzweigtes oder substituiertes C₂-C₂₀-Alkenyl, substituiertes oder unsubstituiertes, cyclisches C₃-C₂₀-Alkyl, substituiertes oder unsubstiuiertes C₈-C₂₀-Aryl, substituiertes oder unsubstituiertes C₂C₄₀-Alkylenoxy, substituiertes oder unsubstituiertes C₃-C₄₀-Alkylenoxyalkyl, substituiertes oder unsubstituiertes C₆-C₄₀-Alkylenaryl, substituiertes oder unsubstituiertes C₆-C₃₂-Aryloxy, substituiertes oder unsubstituiertes C₆-C₄₀-Alkylenoxyaryl, C₆-C₄₀-Oxyalkylenaryl und Mischungen hiervon.A particularly preferred fragrance precursor is of the formula

in which R is hydrogen, linear C ₁ -C ₈ -alkyl, branched C ₃ -C ₂₀ -alkyl, cyclic C ₃ -C ₂₀ -alkyl, branched cyclic C ₆ -C ₂₀ -alkyl, ilmenes C ₆ -C ₂₀ -alkenyl, branched C ₆ -C ₂₀ alkenyl, cyclic C ₀ -C ₂₀ alkenyl, branched cyclic C ₆ -C ₂₀ alkenyl, substituted or unsubstituted C ₆ -C ₂₀ aryl, and mixtures thereof; R ¹ , R ²² and R ³ independently of one another are linear, branched or substituted C ₁ -C ₂₀ -alkyl, linear, branched or substituted C ₂ -C ₂₀ -alkenyl, substituted or unsubstituted, cyclic C ₃ -C ₂₀ -alkyl , substituted or unsubstituted C ₈ -C ₂₀ -aryl, substituted or unsubstituted C ₂ C ₄₀ -alkyleneoxy, substituted or unsubstituted C ₃ -C ₄₀ -alkyleneoxyalkyl, substituted or unsubstituted C ₆ -C ₄₀ -alkylene-aryl, substituted or unsubstituted C ₆ -C ₃₂ -aryloxy, substituted or unsubstituted C ₆ -C ₄₀ -alkyleneoxyaryl, C ₆ -C ₄₀ - Oxyalkylenearyl and mixtures thereof.

enthalten,
worin R lineares C₁-C₂₀-Alkyl, verzweigtes C₃-C₂₀-Alkyl, cyclisches C₆-C₂₀-Alkyl, verzweigtes cyclisches C₆-C₂₀-Alkyl, lineares C₂-C₂₀-Alkenyl, verzweigtes C₃-C₂₀-Alkenyl, cyclisches C₆-C₂₀-Alkenyl, verzweigtes cyclisches C₆-C₂₀-Alkenyl, substituiertes oder unsubstituiertes C₆-C₂₀-Aryl und Mischungen hiervon ist; R¹ ist Wasserstoff oder R;
R² und R³ sind jeweils unabhängig voneinander gewählt aus der Gruppe, bestehend aus lineares C₁-C₂₀-Alkyl, verzweigtes C₃-C₂₀-Alkyl, cyclisches C₃-C₂₀-Alkyl, verzweigtes cyclisches C₆-C₂₀-Alkyl, lineares C₆-C₂₀-Alkenyl, verzweigtes C₆-C₂₀-Alkenyl, cyclisches C₆-C₂₀-Alkenyl, verzweigtes cyclisches C₆-C₂₀-Alkenyl, C₆-C₂₀-Aryl, substituiertes C₇-C₂₀-Aryl und Mischungen hiervon.According to a preferred embodiment, the fragrance precursor is an acetal or a ketal of the formula

contain,
in which R is linear C ₁ -C ₂₀ -alkyl, branched C ₃ -C ₂₀ -alkyl, cyclic C ₆ -C ₂₀ -alkyl, branched cyclic C ₆ -C ₂₀ -alkyl, linear C ₂ -C ₂₀ -alkenyl, branched C ₃ -C ₂₀ alkenyl, C ₆ -C ₂₀ cyclic alkenyl, branched cyclic C ₆ -C C ₆ -C ₂₀ alkenyl, substituted or unsubstituted ₂₀ aryl, and mixtures thereof; R ¹ is hydrogen or R;
R ² and R ³ are each independently selected from the group consisting of linear C ₁ -C ₂₀ alkyl, branched C ₃ -C ₂₀ alkyl, cyclic C ₃ -C ₂₀ alkyl, branched cyclic C ₆ -C ₂₀ Alkyl, linear C ₆ -C ₂₀ alkenyl, branched C ₆ -C ₂₀ alkenyl, cyclic C ₆ -C ₂₀ alkenyl, branched cyclic C ₆ -C ₂₀ alkenyl, C ₆ -C ₂₀ aryl, substituted C ₇ -C ₂₀ aryl and mixtures thereof.

worin R¹, R², R³ und R⁴ unabhängig voneinander lineares, verzweigtes oder substituiertes C₁-C₂₀-Alkyl, lineares, verzweigtes oder subsituiertes C₂-C₂₀-Alkenyl, substituiertes oder unsubstituiertes, cyclisches C₅-C₂₀-Alkyl, substituiertes oder unsubstituiertes C₆-C₂₀-Aryl, substituiertes oder unsubstituiertes C₂-C₄₀-Alkylenoxy, substituiertes oder unsubstituiertes C₃-C₄₀-Alkylenoxyalkyl, substituiertes oder unsubstituiertes C₆-C₄₀-Alkylenaryl, substituiertes oder unsubstituiertes C₆-C₃₂-Aryloxy, substituiertes oder unsubstituiertes C₆-C₄₀-Alkylenoxyaryl, C₆-C₄₀-Oxyalkylenaryl und Mischungen hiervon sind.According to a preferred embodiment, a fragrance precursor having the formula:

wherein R ¹ , R ² , R ³ and R ^{4 are} independently linear, branched or substituted C ₁ -C ₂₀ alkyl, linear, branched or substituted C ₂ -C ₂₀ alkenyl, substituted or unsubstituted, cyclic C ₅ -C ₂₀ -Alkyl, substituted or unsubstituted C ₆ -C ₂₀ -aryl, substituted or unsubstituted C ₂ -C ₄₀ -alkyleneoxy, substituted or unsubstituted C ₃ -C ₄₀ -alkyleneoxyalkyl, substituted or unsubstituted C ₆ -C ₄₀ -alkylene-aryl, substituted or unsubstituted C ₆ -C ₃₂ aryloxy, substituted or unsubstituted C ₆ -C ₄₀ alkyleneoxyaryl, C ₆ -C ₄₀ oxyalkylene aryl, and mixtures thereof.

The use of corresponding fragrance precursors leads to shaped articles having an outstanding odor behavior in aqueous systems, in particular as regards the length and duration of the resulting fragrance impression, also on treated substrates, in particular textile. Above all, the combination of perfume precursors with the above-mentioned persistent fragrances and / or cationic polymer leads to films with excellent odor behavior.

A shaped article according to the invention may preferably comprise fragrances selected from the group bergamot oil, tangerine oil, dimethyl anthranilate, dihydromyrcenol (2-methyl-6-methylene-2-octanol), Tetrahydrolinalool, isobomylacetate, ethyllinalool, limonene, orange oil, isobornylacetate, eucalyptus oil (globulus), aldehyde C 10, styrolylacetate, citronitrile ((Z, E) -methyl-5-phenyl-2-pentenitrile), undecavertol (4-methylbenzene) 3-decene-5-ol), styrolyl acetate, tartalide (acetyl hexamethyl tetralin). These fragrances can give a particularly good freshness impression, both as regards the molding itself and in its use in aqueous systems.

A molded article of the invention may preferably comprise fragrances selected from the group consisting of aldehyde C 14, decalactone gamma, cyclamen aldehyde, troenan (5-methyl-5-propyl-2- (1-methylbutyl) -1,3-dioxane), canthoxal (2 Methyl 3- (para-methoxy-phenyl) -propanal), citronellol, geraniol, musk, phenylethyl alcohol, phenatez (2-phenylethyl 2-methylpropanoate), phenylethyl isobutyrate, jasmelia (2H-pyran-4-ol, 3-butyltetrahydro-5- methyl acetate), hexyl cinnamic aldehyde (alpha), ylang, cyclohexyl salicylate, hexenyl salicylate (cis-3), Sandelice, guaiacolite, Iso E Super (7-acetyl, 1,2,3,4,5,6,7,8-octahydro -1,1,6,7-tetramethylnaphthalene), norlimbanol, ambroxan (3aR- (3aalpha, 5abeta, 9aalpha, 9bbeta)) - dodecahydro-3a, 6,6,9a-tetramethylnaphtho (2,1-b) furan Cinnamyl alcohol, cyclopentadecanolides, nirvanol ((S) - (+) - 5-ethyl-5-phenylhydantoin), Javanol (1-methyl-2 - ((1,2,2-trimethyl bicyclo (3.1.0) hex) 3-yl) methyl) cyclopropane methanol), habanolides (oxacyclohexadecene-2-ones), maltol, benzylacetone, coumarin, benzylsalicycl lat, melonal (2,6-dimethyl-5-heptenal), galbanum (oil), ethylvanillin, koavones (3-hepten-2-ones, 3,4,5,6,6-pentamethyl), methyl palmitate, methyl oleate and / or methyl myristate. These fragrances can give a particularly good care impression, both as regards the molding itself and when used in aqueous systems.

According to a preferred embodiment, the shaped body according to the invention is substantially free of constituents other than perfume and polymer material. Accordingly, a shaped article according to the invention is accordingly ≥65 wt%, ≥70 wt%, ≥75 wt%, ≥80 wt%, ≥85 wt%, ≥90 wt%, ≥ 95 wt .-% or even to ≥ 98 wt .-% of the components polymer and perfume.

Possible other constituents which may be present in the moldings according to the invention are advantageously selected from the group of surfactants, builders, bleaches, bleach activators, enzymes, electrolytes, non-aqueous solvents, pH adjusters, fluorescers, dyes, skincare agents, hydrotopes, softeners, foam inhibitors , Silicone oils, anti redeposition agents, optical brighteners, grayness inhibitors, anti-shrinkage agents, anti-crease agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, corrosion inhibitors, antistatic agents, ironing aids, repellents and impregnating agents, swelling and anti-slip agents and UV absorbers.

A further subject matter is a process for scenting or scent-enhancing an aqueous system, preferably a washing, cleaning or rinsing liquor, wherein at least one portion of the perfumed, water-soluble or water-dispersible, shaped body is removed from the scent medium delivery system according to the invention and these are removed from the aqueous system, in particular the wash liquor , admits. In the scenting in connection with the machine textile washing the molding according to the invention can be placed directly in the washing drum or in the Waschmitielschublade.

A further subject matter is a method for applying fragrances to textile goods in a washing machine by adding molded bodies according to the invention which have been taken from the fragrance medium dispensing system according to the invention, wherein the shaped bodies are added to the wet laundry in the washing or rinsing cycle of a machine washing process.

A further subject matter is a method for applying fragrances to textile material in an automatic laundry drier by addition of shaped bodies according to the invention which have been taken from the fragrance medium dispensing system according to the invention, wherein the shaped articles are added to the wet laundry to be dried in the drier.

A further subject of the present invention is the use of a shaped body removed from the fragrance medium delivery system according to the invention for scenting or Odor enhancement of an aqueous system, advantageously a textile washing liquor, a dishwashing wash liquor, bathing water or a cleaning liquid for cleaning hard surfaces, such as preferably floors or windows. Also the scenting of a toilet porcelain standard sink (so-called Sitzklo) is possible. To do this, place the molded body in the water of the siphon, where it then unfolds pleasant odors, for example, to cover already existing unpleasant odors.

Claims (8)

1. Fragrant medium dispensing system that includes a water-soluble or water-dispersible perfumed shaped article that comprises at least 20 wt.% polymer(s) as well as at least 10 wt.% odoriferous substances, each wt.% being based on the total shaped article, wherein the shaped article is supplied in a withdrawal receptacle, and wherein the shaped article is a foamed film and wherein the perfume comprised in the shaped article is present in at least 5 wt.% in encapsulated form.
2. System according to claim 1, characterized in that the withdrawal receptacle comprises a flexible or inflexible, advantageously reclosable receptacle, preferably a box, that surrounds the shaped article and is advantageously a storage reservoir with a dosing device, in particular a dosing dispenser.
3. System according to one of claims 1 or 2, characterized in that the withdrawal receptacle comprises a roll, on which a strip-shaped, a sheet-shaped, a disk-shaped or a web-shaped, flexible shaped article, is wound, wherein the shaped article is preferably provided with separation points for single portion withdrawal.
4. System according to one of claims 1-3, characterized in that the shaped article comprises at least 12 wt.% perfume, preferably at least 15 wt.% perfume, especially at least 20 wt.% perfume, based on the total shaped article.
5. System according to one of claims 1-4, characterized in that the comprised perfume consists of at least 5 wt.% of odoriferous substances having a boiling point above 250°C and a ClogP value of ≥ 3.0.
6. System according to one of claims 1-5, characterized in that the shaped article comprises precursors of odoriferous substances that preferable once in the presence of H₂O release odoriferous substances by hydrolysis.
7. Method for perfuming or reinforcing the fragrance of an aqueous system, preferably a laundry liquor, characterized in that at least a portion of the perfumed, preferably water-soluble or water-dispersible shaped article is taken out of the fragrant medium dispenser system according to one of claims 1-6 and added to the aqueous system, especially to the laundry liquor.
8. Use of a shaped article taken out of the fragrant medium dispensing system according to one of claims 1-6 for perfuming or reinforcing the fragrance of an aqueous system, advantageously a laundry liquor for textiles, a dishwasher liquor, bath water or a cleaning liquid for cleaning hard surfaces, such as preferably floors or windows.