EP1238053A1 - Moulded fragrance bodies and method for producing the same - Google Patents

Abstract

The invention relates to moulded fragrance bodies containing a) 65 to 95 wt. % support substance(s), 0 to 10 wt. % auxiliary substance(s) and 5 to 25 wt. % perfume, which are characterised in that a proportion of the support substances a) is selected from support substances that have an anionic, at least 2-dimensionally cross-linked partial structure and contain alkylammonium ions.

Description

 PERFUME MOLDED BODY AND METHOD FOR THE PRODUCTION THEREOF

The present invention relates to fragrance moldings, in particular fragrance pearls, which can be incorporated into detergents and cleaning agents and textile treatment and post-treatment agents and which have a fragrance-enhancing effect on the treated textiles. The invention further relates to detergents and cleaning agents which contain the moldings according to the invention and the use of certain substances for improving the absorption of fragrances on surfaces. The invention also relates to a production process for shaped fragrance articles.

In textile washing, treatment and post-treatment, it is common today to add small amounts of perfume to the detergents and post-treatment agents, which serve to give the washing or rinsing solution itself, but also the textile goods treated with the washing or rinsing solution, a pleasant fragrance to lend. In addition to color and appearance, the fragrance of detergents, cleaning agents and post-treatment agents is also an important aspect of the aesthetic product impression and an important point in the consumer decision for or against a specific product. For scenting, the perfume can either be incorporated directly into the agents or added to the washing or rinsing solution in an additional step. The first way specifies a certain product characteristic, while the second way, the consumer can individually decide on "his" fragrance from the different fragrance options on offer, comparable to choosing an eau de toilette or an aftershave.

Accordingly, fragrance moldings and processes for scenting washing and rinsing liquors are widely described in the prior art. For example, DE 41 33 862 (Henkel) discloses tablets which contain carrier materials, fragrances and, if appropriate, further ingredients customary in washing and cleaning agents, sorbitol and additionally 20 to 70% by weight of a carbonate and acid bubbling system being used as carrier material. These tablets, for example, the rinse and softener cycle The textile laundry can be added in a household washing machine, contain about 3 to 15, preferably 5 to 10 wt .-% fragrance. Due to the high disintegrant content of the tablets, they are sensitive to air humidity and must be stored appropriately protected.

DE 39 11 363 (Baron Freytag von Loringhoven) discloses a method for producing a washing or rinsing liquor enriched with fragrance and a fragrance addition agent used for this purpose. The addition agents, which are in the form of capsules or tablets, contain the fragrance together with an emulsifier in liquid form (capsules) or bound to fillers and carriers (tablets), sodium aluminum silicates or cyclodextrins being mentioned as carriers. The fragrance content of the capsules or tablets is at least 1 g, the volume of the compositions being over 1 cm ³ . Tablets or capsules with more than 2.5 g of fragrance and a volume of at least 5 cm ³ are preferred. During storage, such tablets or capsules must be provided with a gastight and watertight covering layer in order to protect the ingredients. Further details on the production and the physical properties of suitable tablets are not contained in this publication.

The international application WO 94/25563 (Henkel-Ecolab) describes a process for the production of washing and cleaning-active moldings using microwave technology, which works without high pressure pressing. The moldings produced in this way are distinguished by an extremely high dissolving speed or disintegration speed with simultaneous breaking strength, without the need for an explosive. At the same time, they are stable in storage and can be stored without additional precautions. In this way, it is also possible to produce moldings which have a perfume oil content, customary for detergents and cleaning agents, of between 1 and 3% by weight. Perfume oils are usually volatile and could therefore evaporate under the influence of microwave radiation. If higher proportions of volatile liquid substances are to be used, a two-component system consisting of one with the Component produced microwave technology and a component containing the sensitive liquid substances described.

Particulate additives for scenting washing liquors and for use in detergents and cleaning agents and processes for their preparation are described in international patent applications WO97 / 29176 and WO97 / 29177 (Procter & Gamble). According to the teaching of these documents, porous carrier materials (e.g. sucrose in a mixture with zeolite X) are mixed with perfume and finally coated with a coating material (carbohydrates) and brought to the desired particle size distribution.

The German patent application DE 197 35 783 (Henkel) describes high-dose perfume moldings which contain carrier material (s), 20 to 50% by weight of fragrance substances) and, if appropriate, other active substances and auxiliaries customary in detergents and cleaning agents, the moldings after subtracting the amount of fragrance, at least 50% by weight of its weight consists of fatty acids and fatty acid salts. These perfume moldings are suitable for scenting detergents and cleaning agents as well as for scenting textiles in a washing machine.

A method for applying fragrances to textile goods in a washing machine is described in DE 195 30 999 (Henkel). In this process, a fragrance-containing molded body, which is produced by irradiation with microwaves, is used in the rinse cycle of a washing machine. The production of the preferably spherical shaped bodies with diameters above 3 mm and bulk densities up to 1 100 g / 1 succeeds according to the teaching of this document in that a mixture of predominantly water-soluble carriers, hydrated substances, optional surfactants and perfume is filled into suitable shapes and sinters with the help of microwave radiation. The fragrance contents of the shaped bodies are between 8 and 40% by weight, starches, silicas, silicates and disilicates, phosphates, zeolites are found as carriers. Alkali salts of polycarboxylic acids. Oxidation products of polyglucosans and polyaspartic acids use. A prerequisite for the molded article production process described in this document is that the mixture, which is sintered to give molded articles with the aid of microwave radiation, is at least partially bound water is present, ie some of the starting materials are in hydrated form.

The proposed solutions either require additional barrier layers or enveloping layers to fix the perfume on the carrier, or are not equally suitable for scenting detergents and cleaning agents and for direct use as the sole fragrance, for example for the rinse aid in a washing machine. Patent application WO 99/21953 describes a process for the production of fragrance moldings and in particular fragrance pearls which contain up to 15% by weight of fragrance and yet do not have to be provided with a gastight and watertight covering layer or packaging during storage, to protect the ingredients or to prevent the loss of fragrance during storage. It is a process for the production of fragrance moldings, in particular fragrance pearls with bulk densities above 700 g / 1, a solid and essentially water-free premix consisting of a) 65 to 95% by weight of carrier (s), b) 0 up to 10% by weight of excipient (s) and c) 5 to 25% by weight of perfume are subjected to granulation or press agglomeration. The fragrance moldings produced in this way can be incorporated as a compound in conventional washing and cleaning agents, but can also be used directly for individual fragrance selection in the domestic washing process and give the treated textiles a scent-enhancing impression.

With these fragrance moldings, a significant improvement in the fragrance impression of detergents and cleaning agents and the surface treated with them can already be achieved. However, the yield of fragrance applied to the treated surface, in particular textile fibers, is still very low in relation to the amount of fragrance used. Therefore, there continues to be a need for improved production processes for such fragrance moldings which improve the absorption of the fragrances on surfaces and thus ensure a higher fragrance yield. German patent application 19941263.4 describes a manufacturing process for perfume moldings in which the premix contains 0.5 to 20% by weight of a substance which improves the absorption of the fragrance on surfaces. It is a process for the production of perfume moldings, in particular fragrance pearls, with bulk densities above 700 g / 1, a solid and essentially water-free premix consisting of a) 65 to 94.5% by weight of carrier substances), b ) 0 to 10% by weight of excipient (s) and c) 5 to 25% by weight of perfume are subjected to granulation or press agglomeration, characterized in that the premix contains 0.5 to 20% by weight of a substance which drawing up the fragrance on surfaces improves. The substances which improve the absorption of the fragrances are in particular one or more substances from the group of paraffins, quaternary ammonium compounds, soil-release polymers, in particular copolymeric polyesters and other polymers, such as in particular polyvinylpyrrolidone and block copolymers with blocks (-CH ₂ -CH -O) _n - with n> 2.

It has now been found that certain carriers are particularly suitable as elevator aids.

Accordingly, a first subject of the invention are shaped fragrance articles containing a) 65 to 95% by weight of carrier (s), 0 to 10% by weight of auxiliary (s) and 5 to 25% by weight of perfume, which are characterized in this way that a proportion of the carriers a) is selected from carriers which have an anionic, at least 2-dimensionally crosslinked partial structure and which contain alkylammonium ions.

In a preferred embodiment, the anionic, at least 2-dimensionally crosslinked partial structure is an inorganic, in particular a silicate, layer structure. In another, likewise preferred embodiment, the anionic, at least 2-dimensionally crosslinked partial structure is an organic polymer, in particular a derivative of a natural polymer, preferably a derivative of a polysaccharide. The inorganic layer structure is again preferred Embodiment around a modified silicate of the bentonite type, preferably of the montmorillonite type.

Bentonites are clays and rocks that contain smectites, especially montmorillonite, as the main minerals. In addition, they can contain mica, illite, cristobalite and zeolites as impurities. Montmorillonite gives the bentonites properties such as swellability (swelling clays), thixotropy and ion exchange capacity. The raw bentonites are either calcium bentonites (not swellable; inactivated bentonites, known in the UK as Fuller earths) or sodium bentonites (swellable; Wyoming bentonites). The properties of the bentonites can be modified; z. B. the swellability of raw bentonites by exchanging the Ca for Na ions (activated calcium bentonites), the specific surface by treating with inorganic acids (acid-activated bentonites) and the organophilicity by reacting sodium bentonites with quaternary ammonium Compounds (organophilic bentonites, also called bentones) increased. According to the invention, the latter organophilic bentonites are used, in which sodium ions have been exchanged for alkylammonium ions.

The mineral montmorillonite contained in these bentonites can be described by the empirical formula Al ₂ [(OH) ₂ / Si Oιo] ^• n H? O or Al ₂ O ₃ ^• 4 SiO ₂ ^• n H ₂ O. It is a clay mineral belonging to the dioctahedral (mica) smectites, which crystallizes monoclinic-pseudohexagonal. It forms a predominantly white, gray-white to yellowish, completely amorphous, slightly friable, swelling in water but not becoming plastic mass; Under the electron microscope, pseudohexagonal plates, stretched lamellae, stretched hexagonal or irregularly outlined leaflets as well as lamellar, moss-like or spherical aggregates can be seen.

Fig .: Montmorillonite layer grid in an idealized representation

The layer packs in the three-layer structure of montmorillonite (see Fig.) Can be reversibly incorporated by water (in 2-7 times the amount) and other substances such as. B. alcohols, glycols. Pyridine, α-picoline, ammonium compounds. Swell hydroxy aluminosilicate ions, etc.

The chemical formula given above is only approximate: since montmorillonite has a large ion exchange capacity, Al can be exchanged for Mg, Fe ²⁺ , Fe ³⁺ , Zn, Pb (e.g. from pollutants in waste water) Cr, also Cu , The resulting negative charge of the octahedral layers is caused by cations, esp. Na ⁺ (sodium montmorillonite) u. Ca ²⁺ (calcium montmorillonite; very little swellable) balanced in interlayer positions.

Montmorillonite occurs as a clay component especially in tropical soils. The swellable Na montmorillonite is the main constituent of sodium bentonite (so-called Wyoming type), which occurs primarily in Wyoming / USA; Ca-montmorillonite is the main clay mineral of the non-swelling calcium bentonites (cheto type; in the UK referred to as Fuller earths), e.g. B. in the area of Moosburg, Mainburg u. Landshut in Bavaria, Mississippi u. Texas / USA. Montmorillonites are also created by hydrothermal decomposition. igneous rocks. From the weathering of basic igneous rocks (e.g. basalts), montmorillonite can accumulate to buildable deposits.

The organophilization of montmorillonite or bentonites (exchange of the interlayer cations for quaternary alkylammonium ions) produces products that are preferred for dispersion in organic solvents and oils, fats. Ointments, paints and varnishes are used.

In the sense of the present invention, in a preferred embodiment, such organophilized montmorillonites or bentonites, which contain such montmorillonites, are used as carriers and elevator aids for fragrances.

These bentonites develop, when fragrance molded articles according to the invention are used in detergents, in addition to the effect as a lift aid for the fragrances, and also the known effects as ion exchangers or laundry softening additive.

In another, likewise preferred embodiment of the invention, crystalline phyllosilicates are used according to the invention. It is about

Phyllosilicates. in which starting from compounds of the formula M ₂ Si _x θ _{2 +} ryH ₂ θ. where M is a sodium and / or a hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20, cations have been exchanged for alkylammonium ions. Such organophilized layered silicates are commercially available, for example, under the trade name SKS "(from Clariant). Accordingly, it is preferred according to the invention if the carrier which contains alkylammonium ions is a layered silicate of the formula M ₂ Si _x θ ₂ χ ₊ ryH ₂ θ, where M is a sodium and / or a hydrogen and / or an alkylammonium ion, x is a number from 1, 9 to 4 and y is a number from 0 to 20. In a further preferred embodiment, organic polymers are used as carriers with anionic, at least 2-dimensionally cross-linked partial structure. It is conceivable here to use any anionic, partially crosslinked polymer, the cations of which are accessible to an ion exchange for alkylammonium ions. However, derivatives of natural polymers are preferably used. The use of polysaccharide derivatives is particularly preferred.

Essential steps in the derivatization of these polysaccharides are the generation of anionic groups in the molecule and the at least partial exchange of the counterions for alkylammonium ions.

Anionic functions can preferably be generated by oxidation. The oxidatively modified poly- or oligosaccharides which are preferably to be used according to the invention are compounds which are selected from the substance class of the oxidized starches or starch derivatives, in particular the thermally or enzymatically degraded starch derivatives. Starch, like glycogen or cellulose, belongs to the homoglycans. Starch consists of 3 different D-glucopyranose polymers. the amylose. the amylopectin and a so-called intermediate fraction, which is also referred to as abnormal amylopectin, as well as water (approx. 20%, depending on the variety and storage conditions), smaller amounts of protein, fats and phosphoric acid bound in ester form. The starch content of these components varies depending on the variety. Higher plants contain 0-40% amylose based on the dry matter. The intermediate fraction is structurally between the amylose and the amylopectin. In the case of analytical determination of the starch, the intermediate fraction is usually assigned to the amylopectin.

Amylose consists of predominantly linear α-1,4-glycosidically linked D-glucose. Diffusion amylose is the part of the amylose that is soluble in water at temperatures <100 ° C. Diffusion amylose is obtained at temperatures of 60-70 ° C. which is free of amylopectin. Starch with more than 70% amylose is called high amylose starch, e.g. B. marker pea starch (70% amylose) and Amylomais starch (> 50% amylose). The water and amylose content of starch is determined by NIR spectroscopy. The chains form double helices.

In addition to the α-1,4-linkages described for amylose, amylopectin also contains 4-6% α-1,6-linkages

amylopectin

The average distance between the branches is about 12 to 17 glucose units. The molar mass (M _R = 107-108) corresponds to approx. 105 glucose units, making amylopectin one of the largest biopolymers. The branches are distributed over the molecule in such a way that a tuft structure with relatively short side chains develops. Two of these side chains each form a double helix. Due to the many branching points, amylopectin is relatively readily soluble in water and. is better broken down enzymatically. As the amylopectin content increases, the crystallinity of a starch grain increases and the gelatinization energy increases. Starches that only contain amylopectin (from certain types of corn and potatoes) are called wax varieties. The appearance of the starch grains is typical of the respective parent plant. Amylose provides complexes in which organic or other molecules are embedded in the helical structure; with iodine it forms the blue-colored iodine-starch complex, the absorption maximum of which depends on the chain length of the amylose. Amylopectin forms a reddish brown complex with iodine. Amylose can from Amylopectin can be separated by adding n-butanol to a hot starch dispersion: When cooling, the amylose-n-butanol complex precipitates.

Starch is a reserve carbohydrate that is stored by many plants in the form of 1-200 mm starch grains in different parts of the plant, e.g. B. in tubers or roots [potatoes, Maranta (Arrowroot), cassava (tapioca). Batate], in cereal seeds (wheat, maize, rye, rice, barley, millet, oats, sorghum), in fruits (chestnuts, acorns, peas, beans and other legumes, bananas) and in the pulp (sago palm).

Starch is preferably obtained from vegetable raw materials from flour from corn, potatoes. Wheat, rice and Cassava (tapioca), the starch grains being mechanically removed from the cell structure by wet means after the adhesive has been removed; Corn is the most important starch plant worldwide.

Oxidation processes on starch or starch derivatives, in particular starch pyrolisates or enzymatic degradation products of starch, can in principle be carried out with any suitable oxidizing agent. Terminal aldehyde groups can be oxidized to acid functions and / or alcohol functions can be oxidized to aldehyde or acid functions. However, oxidatively modified starch derivatives used with preference essentially contain only alcohol and acid functions. The presence of aldehyde functions is undesirable in the starch derivatives preferred according to the invention. In principle, however, the oxidized starches also include the dialdehyde starches which are obtained in the treatment of starches with selectively acting oxidizing agents, such as periodic acid. However, these polymers tend to crosslink to form water-insoluble films. Their use in agents according to the invention is therefore less preferred and only possible in combination with very specific ingredients. These dialdehyde starches are further oxidized to dicarboxy starches, in which units of the following type

As a complexing group, such compounds can very well be present in the detergents according to the invention.

In a nutshell, a large number of oxidizing agents are used for the oxidation of polysaccharides, in particular polyglucosans composed exclusively of glucose. Examples include (air) oxygen, hydrogen peroxide, sodium hypochlorite or bromite, periodic acid or periodates, lead (IV) acetate, nitrogen dioxide and cerium (IV) salts. These oxidants react very differently with the anhydroglucose units. For example, periodates or lead (IV) acetate cause a C-C cleavage of the anhydroglucose rings; so-called 2,3-dialdehyde cellulose is obtained from cellulose and dialdehyde starch is obtained analogously from starch. It is also known that when nitrogen dioxide acts on cellulose, the oxidation of the primary alcohol group to the carboxyl group is the predominant reaction. The oxidizing agent, usually in equilibrium with dinitrogen tetroxide, can be used in gaseous or dissolved form in an inert organic solvent. Starting from the starch, too, largely selective oxidations of the primary alcohol group of the anhydroglucose units to the carboxyl group can be accomplished. The oxidation of starch with gaseous nitrogen dioxide or nitrogen dioxide dissolved in water or in various organic solvents is known from the US Pat. No. 2,472,590.

Under these conditions, the almost complete conversion of the primary alcohol groups of the polysaccharides into carboxyl groups can only be obtained after very long reaction times, which can in some cases take up to several days. In addition, high amounts of nitrogen dioxide are obtained in the known processes on polysaccharide to be oxidized. From international patent application WO 93/16110, a significant improvement in the production of such oxidation products of polysaccharides is known. The invention disclosed there is based on the knowledge that polycarboxylates can be obtained from polysaccharides in a simple process in high yields if the oxidation reaction with nitrogen dioxide / dinitrogen tetroxide is carried out in the presence of oxygen at elevated temperatures and preferably at elevated pressures. The formulation "nitrogen dioxide / dinitrogen tetroxide" stands for the equilibrium mixture of nitrogen dioxide and its dimer dinitrogen tetroxide present under the respective reaction conditions.

If the suspension and solvent-free oxidation described in this document is carried out using gaseous nitrogen dioxide / dinitrogen tetroxide, a polysaccharide which is selectively oxidized to C _{6 is obtained} in solid form. The sparingly water-soluble acid form is neutralized for use as an elevator aid in the sense of the present invention. This neutralization can be carried out with aqueous base. This procedure leads to aqueous solutions of the polycarboxylate. in which the cations are exchanged for alkylammonium ions.

A process for the production of solid polycarboxylic acid salts from polysaccharides by oxidation with gaseous nitrogen dioxide / dinitrogen tetroxide with conversion of at least part of the primary alcohol groups of the polysaccharides into carboxyl groups and at least partial neutralization of the carboxylic acid groups formed is suitable, which is characterized in that the solid polycarboxylic acid is mixed with a solid neutralizing agent mixed; this method is described in patent application DE-A-195 07 717.

The oxidation of the polysaccharide preceding the neutralization is preferably carried out as described in German patent application DE-A-44 26 443. This means that the reaction of the polysaccharide to be oxidized with nitrogen dioxide / dinitrogen tetroxide is only carried out for so long that the desired one Degree of oxidation, that is to say the degree of conversion of the primary alcohol groups into carboxyl groups, is achieved only to a maximum of 90%, preferably to 60% to 85% and in particular to 65% to 80%. The desired degree of oxidation is only fully achieved in the post-oxidation phase, that is to say when the nitrogen dioxide / dinitrogen tetroxide feed has ended and in comparison to the oxidation phase by at least 10 ° C., preferably 15 ° C. to 80 ° C. and in particular 20 ° C. to 50 ° C elevated temperature. Care should be taken to ensure that an increase in temperature does not exceed an upper limit of 160 ° C, since decomposition has been observed increasingly at higher temperatures.

The oxidation reaction to be terminated before complete conversion is preferably carried out at temperatures from 30 ° C. to 70 ° C., in particular from 40 ° C. to 60 ° C. Oxygen, alone or in a mixture with gas which is inert under the reaction conditions, can be present, the addition of which can take place once at the start of the reaction or several times, if desired continuously, during the reaction. In the last-mentioned reaction procedure, the oxidation reaction can, as is known, be controlled via oxygen metering as a function of temperature or pressure. The addition of oxygen is preferably controlled so that the reaction temperature remains in the range from 30 ° C. to 70 ° C.

Noble gases such as helium or argon and carbon dioxide, but in particular nitrogen, nitrogen monoxide and dinitrogen monoxide, but also any mixtures of such gases can be used as inert gases, ie gases which do not react under the respectively desired process conditions. The oxygen content in the gas mixture is preferably in the range from 1% by volume to 30% by volume, in particular from 3% by volume to 10% by volume. A preferred embodiment of the method according to the invention includes the supply of oxygen by injecting air.

A further embodiment of the oxidation process is characterized in that a pressure of less than 10 bar, in particular from 2 bar to 6 bar, at the desired reaction temperature in the reaction system before the start of the oxidation reaction Pressing on of said inert gas is set and then oxygen or a mixture of oxygen with said inert gas is pressed on several times, if desired continuously. The addition of nitrogen dioxide / dinitrogen tetroxide can take place before or after the addition of oxygen or the beginning of the addition of oxygen. It may be necessary to heat the reaction vessel to the desired reaction temperature after the initial injection of the inert gas. During the course of the oxidation reaction, which is expediently carried out with intensive mixing of the reactants, the reaction temperature can generally be maintained without the need for external heating solely by adding the amount of oxygen.

In the oxidation step, the oxidizing agent from the gas phase acts directly on the solid polysaccharide substrates, which are mixed as intensively as possible. Oxidation in a fluidized bed made of polysaccharide, the fluidizing agent of which is a gas containing nitrogen dioxide, is preferred. Such an oxidation process is described in German patent application DE-A-44 02 851. Fluid bed is to be understood - without being limited to this type of production - the phenomenon that can be observed when fine-grained bulk material stored on horizontal, perforated floors is flowed through from below by gases, referred to as fluidizing agents.

A particularly preferred class of oxidatively modified oligosaccharides are oxidized dextrin derivatives. Dextrins are, for example, oligomers or polymers of carbohydrates that can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary processes, for example acid-catalyzed or enzyme-catalyzed. They are preferably hydrolysis products with average molar masses in the range from 400 to 500,000 g / mol. A polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30, is preferred, DE being a customary measure of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100 , is. Both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher molar masses in the range from 2000 to 30000 g / mol can be used. A preferred dextrin is in British patent application 94 19 091. The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function. Such oxidized dextrins and processes for their preparation are known to the person skilled in the art from various patent applications.

An oxidized oligosaccharide according to German patent application DE-A-196 00 018 is also preferred. Glucose is the preferred monomer in this oligosaccharide to be used according to the invention after oxidative modification. The average degree of oligomerization, which can also take fractional numerical values as the quantity to be determined analytically, is preferably in the range from 2 to 20, in particular 2 to 10. The oligosaccharide which is preferably used as a builder or cobuilder is oxidative at its originally reducing end with the loss of a C- Atom has been modified. If the originally reducing end of the oligosaccharide was an anhydroglucose unit, there is an arabinonic acid unit after modification: (glucose) _n + ι -> (glucose) _n arabinonic acid.

This oxidative modification can be carried out, for example, with the aid of Fe, Cu, Ag, Co or Ni catalysts, as described in international patent application WO 92/18542, with the aid of Pd, Pt, Rh or Os catalysts , as described in European patent EP 0 232 202, or by means of a quinone / hydroquinone system in alkaline with the addition of oxygen and optionally aftertreatment with hydrogen peroxide. The oligosaccharide starting material which can be modified by means of such oxidation processes is preferably an oligosaccharide with a dextrose equivalent (DE) in the range from 20 to 50. So-called glucose syrups (DE 20-37) and the above-mentioned dextrins, both of which can be used in particular by partial hydrolysis of starch, which can be carried out by customary, for example acid- or enzyme-catalyzed, processes and which can be used as such or in high-polymer form, for example as starch, in the above-mentioned oxidation processes, if a corresponding one is used under the conditions of the oxidation Degradation of the polymer chain structure of the starch takes place. Preferably, the oligosaccharides modified in this way have the original reducing properties Instead of the group -CH (OH) -CHO end a group -COOH.

Regardless of whether inorganic or organic polymers are used as the anionic partial structure of the support, it is essential that at least some of the cations of these compounds consist of alkylammonium ions. This is expediently achieved by ion exchange of the cations present in the starting form, usually alkali and alkaline earth ions, for alkylammonium ions. The methods possible here are well known to the person skilled in the art and can be found in relevant textbooks.

According to the invention, alkylammonium ions are understood to mean all ions which obey the formula R 'R ² R ³ R ⁴ N ^T , the radicals being selected from H, C 1 -C ₅₀ -alkyl, alkenyl or hydroxyalkyl groups or functionalized Ci-Cso-alkyl groups. Up to 3 of the R'-R ⁴ radicals can be formed by hydrogen.

Suitable quaternary ammonium compounds are in particular also all customary surface-active substances, cationic surfactants having a textile-softening effect being clearly preferred.

Quaternary ammonium compounds are preferably used which correspond to one of the formulas I. II or III:

R '

R ^■ '' _- MNA ^{t +} '- (CH ₂ ) _n -TR ^/ (I)

(CH ₂ ) _n -TR ²

R ¹ R. 1 ¹ -Nτ (^ ⁺ ) '- (CH ₂ ) _n -CH-CH ₂ (II)

R ¹ TT

1 1 R ² R ²

R ¹

R ³ -N ^(+, - (CH ₂ ) _n -TR ² (III)

R ⁴

wherein each group R ^{1 is} independently selected from _-6 alkyl, alkenyl or hydroxyalkyl groups; each R group is independently selected from C _8-28 alkyl or alkenyl groups; R ³ = R ¹ or (CH ₂ ) _n -TR ² ; R ⁴ = R ¹ or R ² or (CH ₂ ) _n -TR ² ; T - -CH ₂ -, -O-CO- or -CO-O- and n is an integer from 0 to 5.

Furthermore, particularly for use in crystalline layer compounds, preference is given to those alkylammonium ions which only have a long, optionally substituted C ₅ . ₃₀ - alkyl group in which the other radicals by hydrogen or C | ₄ - alkyl residues are formed, but in certain crystal structures it may also be preferred to use alkyl ammonium ions which have two such long C ₃₀ alkyl residues.

Examples of such alkylammonium ions include stearyldimethylammonium and stearylbenzyldimethylammonium.

In particular, it is preferred if the carrier, which has an anionic, at least two-dimensionally crosslinked partial structure and contains alkylammonium ions, makes up at least 3% by weight, preferably at least 5 and in particular more than 7% by weight, of the fragrance molded body , It is also preferred if the Carrier is less than 80 wt .-%, preferably less than 70 and in particular less than 50 wt .-% of the fragrance molded body.

In addition to the carrier essential to the invention, the fragrance molded bodies according to the invention can also contain a further elevator aid, for example an elevator aid according to the older German patent application 19941263.4. These lift aids are one or more substances from the group of paraffins, quaternary ammonium compounds, soil release polymers. especially the copolymeric polyesters and other polymers, such as in particular polyvinylpyrrolidone and block copolymers with blocks (-CH ₂ -CH ₂ -O) _n - with n> 2.

Under paraffin, a solid or liquid mixture of purified, saturated aliphatic hydrocarbons, which is colorless, odorless and tasteless, dissolves easily in ether and chloroform, does not dissolve in water and 90% alcohol and does not fluoresce (ie, none contains aromatic compounds). Different paraffins can be used. Viscous paraffin (Paraffinum liquidum) is an oily liquid (D = 0.827-0.890, viscosity: 1 10-230 mPas). and thin liquid paraffin (Paraffinum perliquidum) is an oily liquid with a density of 0.810-0.875 and a viscosity of 25-80 mPas. Hard paraffin (Paraffinum solidum) is also known, which is a solid crystalline mass with a solidification temperature of 50-62 ° C. The liquid paraffin forms are often added to mineral oils in the technical field and are referred to as paraffin oil or white oil. Names such as soft paraffin are used for semi-solid paraffin qualities with melting points of 45-65 ° C, names such as petrolatum are used for those with a density of 0.820-0.880, a melting point of 38-60 ° C and a boiling point of> 300 ° C ; a well-known brand for the latter is petroleum jelly. Paraffin is water-repellent, can be melted together with fats, wax and walrus to form uniform masses, is non-toxic, non-reactive, fairly resistant to sulfuric acid. Bromine and cold nitric acid and, unlike fats and fatty oils, does not go rancid (ie it cannot be stranded); in contrast to this, it is sometimes incorrectly referred to as "mineral fat". Paraffin is usually produced from residues from petroleum distillation, from bituminous shale, Peat coal and the products of lignite smelting, synthetically by medium pressure synthesis from CO and H ₂ using catalysts after a modified Fischer-Tropsch synthesis. Hard paraffin is separated by cooling, de-oiled and bleached from the porridge, which is usually called paraffin-Gatsch and is obtained during the oil distillation. liquid paraffin is obtained by distillation. Some paraffin fractions are also traded as micro wax, ceresin, petrolatum and waxes in terms of their manufacture and intended use. According to the invention, all forms of paraffin listed here can be used, it being possible to use certain paraffins with regard to processing processes. In particular, the liquid, preferably the viscous, qualities can have advantages during processing. If the scented pearls are produced using high pressures or temperatures, however, it may also be preferred to use hard paraffin, which, however, is liquid under the processing conditions when the scented pearls are stored.

All customary surface-active substances are suitable as quaternary ammonium compounds, with cationic surfactants having a textile-softening effect, which have already been described above, being clearly preferred.

Soil-release polymers are those polymers that have a dirt-removing ability. The term “soil repellent” polymers is also found in the literature for such polymers. It is usually polyester. which contain dicarboxylic acid units and alkylene glycol units and / or polyalkylene glycol units.

For example, German Offenlegungsschrift DT 16 17 141 describes a washing process using polyethylene terephthalate-polyoxyethylene glycol copolymers. German laid-open specification DT 22 00 91 1 relates to detergents which contain nonionic surfactant and a copolymer of polyoxyethylene glycol and polyethylene terephthalate. In the German patent application DT 22 53 063 acidic textile finishing agents are mentioned, which are a copolymer of a dibasic carboxylic acid and an alkylene or cycloalkylene polyglycol and optionally an alkylene or Contain cycloalkylene glycol. Polymers made from ethylene terephthalate and polyethylene oxide terephthalate, in which the polyethylene glycol units have molecular weights from 750 to 5000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate is 50:50 to 90:10, and their use in detergents is described in the German patent DE 28 57 292 described. Polymers with a molecular weight of 15,000 to 50,000 made of ethylene terephthalate and polyethylene oxide terephthalate, the polyethylene glycol units having molecular weights of 1000 to 10,000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate being 2: 1 to 6: 1, can be according to the German published patent application DE 33 24 258 can be used in detergents. European patent EP 066 944 relates to textile treatment agents which are a copolyester made from ethylene glycol. Contain polyethylene glycol, aromatic dicarboxylic acid and sulfonated aromatic dicarboxylic acid in certain molar ratios. From European patent EP 0 185 427, methyl- or ethyl group-end-capped polyesters with ethylene and or propylene terephthalate and polyethylene oxide terephthalate units and detergents containing such a soil release polymer are known. European patent EP 0 241 984 relates to a polyester which, in addition to oxyethylene groups and terephthalic acid units, also contains substituted ethylene units and glycerol units. From the European patent EP 0 241 985 polyesters are known which contain, in addition to oxyethylene groups and terephthalic acid units, 1,2-propylene, 1,2-butylene and / or 3-methoxy-1,2-propylene groups and glycerol units and with Ci-bis C ₄ alkyl groups are end group capped. The European patent EP 0 253 567 relates to soil release polymers with a molecular weight of 900 to 9000 made of ethylene terephthalate and polyethylene oxide terephthalate, the polyethylene glycol units having molecular weights of 300 to 3000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate 0.6 to Is 0.95. European patent application EP 0 272 033 discloses polyesters with poly-propylene terephthalate and polyoxyethylene terephthalate units which are at least partly capped by C -alkyl or acyl radicals. European patent EP 0 274 907 describes sulfoethyl end group-capped terephthalate-containing soil release polyesters. In European patent application EP 0 357 280, sulfonation of unsaturated end groups describes soil-release polyesters with terephthalate, alkylene glycol and poly-C ₂ - ₄ glycol units manufactured. International patent application WO 95/32232 relates to dirt-releasing polyesters of the general formula

X- (O- (CHR-) _a ) _b [O-OC-Ph-CO- (O- (CHR-) _o ) p] _y OY (I)

in which a is a number from 2 to 8, b is a number from 1 to 300, o is a number from 2 to 8, p is a number from 1 to 300 and y is a number from 1 to 500,

Ph is an o-, m- or p-phenylene radical which can carry 1 to 4 substituents selected from alkyl radicals having 1 to 22 carbon atoms, sulfonic acid groups, carboxyl groups and mixtures thereof,

R is selected from hydrogen, an alkyl radical having 1 to 22 carbon atoms and mixtures thereof, and

X and

Y independently of one another from hydrogen, alkyl and aryl monocarboxylic acid residues with 5 to 32 C atoms, hydroxymonocarboxylic acid residues with 2 to 22 C atoms and a degree of oligomerization from 1 to 100 and dicarboxylic acid half-ester residues. whose second carboxylic acid group is esterified with an alcohol A- (OCHZCH ₂ ) _- OH, in which A is an alkyl or alkenyl radical with 8 to 22 C atoms, Z is hydrogen or an alkyl radical with 1 to 2 C atoms and d is a number means from 1 to 40, with the proviso that X and Y are not simultaneously hydrogen when R is hydrogen or an alkyl radical having 1 carbon atom, a and / or o 2 and b and / or p 1. Soil repellent active ingredients for materials made of cotton are known from international patent application WO 97/31085, which must have several functional units: a first unit, which may be cationic, for example, is capable of adsorption onto the cotton surface by electrostatic interaction, and one the second unit, which is made hydrophobic, is responsible for the remaining of the active substance at the water / cotton interface. Although the active ingredients disclosed there are not exclusively polymers in the sense of chemical Defmition of this term, they should also be counted among the dirt-releasing polymers in the context of the present application because of their corresponding function.

In the sense of DE 19941263.4, however, not only such preferred polyesters, but all polymers with soil release properties are considered to be soil release polymers.

In the chemical sense, polyvinylpyrrolidone is [poly (1-vinyl-2-pyrrolidinone, a polymer of the general formula:

Polyvinylpyrrolidones are produced by radical polymerization of 1-vinylpyrrolidone by the process of substance, solution or suspension polymerization using radical formers (peroxides, azo compounds) as initiators. The ionic polymerization of the monomer only provides products with low molecular weights.

Commercial polyvinylpyrrolidones have molar masses in the range of approximately 2500-750,000 g / mol. which are characterized by the specification of the K values.

Other polymers which are suitable as elevator aids are those block copolymers which contain blocks (-CH ₂ -CH ₂ -O) _n - with n> 2. That is, polyoxyethylene units. It can be both the polyesters already described above and modified polyethylene glycols.

The compounds to be used as additional elevator aid according to the invention lead, when used according to the invention, to a further improvement in the fragrance impression which the fragrance molded articles leave on the laundry. In addition to the carriers essential to the invention, with anionic, at least 2-dimensionally cross-linked substructures, the fragrance molded bodies preferably also contain other carriers. These are generally substances which are suitable for introducing the fragrances, which are usually liquid, into solid granules or shaped bodies.

Preferred carriers are detergent ingredients, which are selected, for example, from the group of surfactants, surfactant compounds, di- and polysaccharides, silicates, zeolites, carbonates, sulfates and citrates. In a likewise preferred embodiment, the shaped bodies contain such carriers in amounts of 30 to 80% by weight, preferably 40 to 75% by weight, in each case based on the weight of the shaped body.

All surfactants or surfactant compounds that are solid at temperatures up to 40 ° C. can be used as surfactant carriers. In the context of the present invention, the term “surfactant compound” is understood to mean a surfactant-containing preparation which, in addition to customary carrier materials and auxiliaries, contains at least 20% by weight of an anionic, cationic or nonionic surfactant, based on the surfactant compound. The carriers customary in surfactant compounds can preferably the same as the abovementioned carriers which are used according to the invention, but other than the abovementioned carriers can also be present as carriers in the surfactant compounds.

One or more anionic surfactant compounds or anionic surfactants, in particular soaps, are preferably used as carrier materials in amounts of 65 to 94.5% by weight, preferably 70 to 90% by weight, in each case based on the weight of the resulting molded article. Examples of anionic surfactant compounds are alkylbenzenesulfonate (ABS) compounds on silicate or zeolite supports with ABS contents of, for example, 10, 15, 20 or 30% by weight, fatty alcohol sulfate (FAS) compounds on silicate, zeolite or sodium sulfate - Sluggish with active substance contents of, for example, 50-70, 80 or 90% by weight and compounds containing anionic surfactants based on sodium carbonate / sodium silicate with anionic surfactant contents above 40% by weight. The pure anionic surfactants can also be used as carriers in the context of the present invention, provided they are solid and their use is not prohibited because of possible hygroscopicity. Soaps in particular are preferred as purely anionic surfactants, since on the one hand they can remain solid up to high temperatures and on the other hand they do not cause any problems with regard to undesired water absorption. All of the salts of fatty acids are used as soaps in the carrier materials for the shaped bodies according to the invention. While in principle, for example, aluminum, alkaline earth and alkali metal salts of the fatty acids can be used, moldings are preferred in which the alkali metal and, in turn, the sodium salts of the fatty acids are preferably contained. All acids obtained from vegetable or animal oils and fats are suitable as fatty acids, the salts of which can be used as carrier material. The fatty acids can be saturated or mono- to polyunsaturated. Of course, not only "pure" fatty acids can be used, but also the technical fatty acid mixtures obtained from the splitting of fats and oils, for example palm kernel, coconut, peanut or rape oil or beef tallow, these mixtures again being clearly preferred from an economic point of view are.

For example, individual species or mixtures of the salts of the following acids can be used in the carrier materials for the high-dose perfume shaped bodies according to the invention: caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid. Palmitic acid, stearic acid. Octadecano-12-ol-acid, arachic acid, behenic acid, lignoceric acid, cerotinic acid, melissic acid, 10-undecenoic acid, petroselinic acid, petroselaidic acid, oleic acid, elaidic acid, ricinoleic acid, linolaidic acid, α- and ß-eläosterainic acid. Gadoleic acid erucic acid. Brassidic. Of course, the salts of fatty acids with an odd number of carbon atoms can also be used, for example the salts of undecanoic acid, tridecanoic acid, pentadecanoic acid, heptadecanoic acid, nonadecanoic acid. Heneicosanoic acid, tricosanoic acid, pentacosanoic acid, heptacosanoic acid. One or more substances from the group of the sodium salts of saturated or unsaturated C _8-24 fatty acids, preferably of saturated or unsaturated, are particularly preferred as carrier (s) and in particular of saturated or unsaturated C ₆ fatty acids, in amounts of 75 to 94.5 wt .-%, preferably from 80 to 90 wt .-%, each based on the weight of the molded body. Other suitable carriers are, for example, di- and polysaccharides, and a wide range of substances can be used, from sucrose and maltose to oligosaccharides to the "classic" polysaccharides such as cellulose and starch and their derivatives. The substances from these subgroups are again those Strengths particularly preferred.

The carriers normally used in detergents and cleaning agents, such as silicates and zeolites, are also suitable as carriers in the context of the present invention. The finely crystalline, synthetic zeolite containing bound water used is preferably zeolite A and / or P. The zeolite P, zeolite MAP is for example Doucil A24 ^® (commercially available from Crosfield) was used. Also suitable however are zeolite X and mixtures of A, X and / or P, for example, a co-crystallizate of zeolites A and X, the VEGOBOND ^® AX (commercial product of Condea Augusta SpA). The zeolite can be used as a spray-dried powder or as an undried stabilized suspension that is still moist from its manufacture. In the event that the zeolite is used as a suspension, it may contain small additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C ₂ -C ₈ fatty alcohols with 2 to 5 ethylene oxide groups , Ci ₂ -C | ₄ -fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols. Suitable zeolites have an average particle size of less than 10 μm (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water. In preferred embodiments, zeolites are contained in the moldings in amounts of 10 to 94.5% by weight, it being particularly preferred if zeolites are contained in amounts of 20 to 70, in particular 30 to 60% by weight.

Suitable carriers are also layered sodium silicates of the general formula NaMSi _x O _2x + ι ^' yH ₂ O. where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4. Such crystalline layered silicates are described, for example, in the European patent application EP-A-0 164 514. Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicate Na ₂ Si ₂ θ ₅ 'y H ₂ O are preferred.

The preferred builder substances and thus the preferred carriers also include amorphous sodium silicates with a modulus Na ₂ O: SiO ₂ of 1: 2 to 1: 3.3, preferably of 1: 2 to 1: 2.8 and in particular of 1: 2 to 1: 2.6, which are delayed release and have secondary washing properties. The delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compaction / compression or by overdrying. In the context of this invention, the term "amoφh" is also understood to mean "roentgenamoφh". This means that the silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle. However, it can very well lead to particularly good builder properties if the silicate particles deliver washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be integrated in such a way that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray silicates, which also have a delay in dissolution compared to conventional water glasses, are described, for example, in German patent application DE-A-44 00 024. Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray silicates.

Suitable carrier materials are furthermore sheet silicates of natural and synthetic origin. Their usability is not limited to a special composition or structural formula. However, smectites, in particular bentonites, are preferred here.

Suitable layered silicates, which belong to the group of water-swellable smectites, are, for example, montmorrilonite, hector or saponite. In addition, Stall grid of the layered silicates according to the above formulas small amounts of iron can be installed. Due to their ion-exchanging properties, the layered silicates can also contain hydrogen, alkali, alkaline earth ions, in particular Na ⁺ and Ca ²⁺ . The amount of water of hydration is usually in the range of 8 to 20% by weight and depends on the swelling condition or the type of processing. Layered silicates which are largely free of calcium ions and strongly coloring iron ions due to an alkali treatment are preferably used.

Usable organic carriers are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid. Sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided that such use is not objectionable for ecological reasons, and mixtures of these. Preferred salts are the salts of polycarboxylic acids such as citric acid. Adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.

The acids themselves can also be used. In addition to their property as a carrier substance, the acids typically also have the property of an acidifying component and thus also serve to establish a lower and milder pH of detergents or cleaning agents. Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof can be mentioned in particular. If they are used in the premix according to the invention and are not subsequently added, these acids are preferably used in anhydrous form.

In principle, any combination of the substances listed here can be used as a carrier. It is particularly preferred if combinations are used which can be referred to as basic detergents, ie have the compositions which are customary in detergents. Optionally, the shaped body may contain auxiliary substances which improve the cohesion of the carrier particles with the perfume.

Suitable auxiliaries are those from the group of polyethylene glycols

Fatty alcohol ethoxylates and fatty acid alkoxylates, which are used in preferred processes in amounts of 0 to 10% by weight, preferably 2 to 9% by weight and in particular 5 to 7

% By weight, based in each case on the weight of the resulting molded body, are used.

The optional fatty acid alkoxylates can be generalized

Describe Formula I:

R -COO- (CH ₂ -CH-O) _k -H (I),

R '

in which R ^{1 is} selected from C - | ₇ -Alkyl- or -alkenyl, R ² = -H or -CH ₃ and k = 2 to 10. Suitable fatty alcohol alkoxylates satisfy the formula II:

R ³ -O- (CH ₂ -CH-O), - H (II),

R ⁴

is selected in which R ³ is selected from C _8- ι ₈ alkyl or alkenyl, ^R4 = -H or -CH ₃ and 1 = 2 to

10th

In both cases, the corresponding auxiliaries can be ethoxylated or

Easily produce propoxylation of fatty acids or fatty alcohols in a manner known per se, technical mixtures of the individual species being preferred for economic reasons. Other suitable auxiliaries are polyethylene glycols (short: PEG), which can be described by the general formula III:

H- (O-CH ₂ -CH ₂ ) _n -OH (III),

in which the degree of polymerization n can vary from about 5 to> 100,000, corresponding to molecular weights from 200 to 5,000,000 gmof. The products with molar masses below 25,000 gmol ^" are referred to as the actual polyethylene glycols, while higher molecular weight products are often referred to in the literature as polyethylene oxides (abbreviated to: PEOX). The polyethylene glycols which are preferably used can have a linear or branched structure, linear polyethylene glycols being particularly preferred ,

The particularly preferred polyethylene glycols include those with relative molecular weights between 2000 and 12000, advantageously around 4000, polyethylene glycols with relative molecular weights below 3500 and above 5000, in particular in combination with polyethylene glycols with a relative molecular weight of around 4000, and such combinations advantageously to more than 50 wt .-%, based on the total amount of polyethylene glycols. Have polyethylene glycols with a molecular weight between 3500 and 5000. However, polyethylene glycols which are in the liquid state at room temperature and a pressure of 1 bar can also be used as binders; here we are mainly talking about polyethylene glycol with a molecular weight of 200, 400 and 600.

The moldings contain auxiliaries of this type in amounts of from 0 to 10% by weight, preferably from 2 to 9% by weight and in particular from 5 to 7% by weight. each based on the weight of the molded body.

As perfume oils or fragrances, individual fragrance compounds, for example the synthetic products of the ester, ether, Aldehydes, ketones, alcohols and hydrocarbons can be used. Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate (DMBCA), phenylethyl acetate, benzyl acetate, ethylmethylphenylglycinate,

Allyl cyclohexyl propionate, styrallyl propionate, benzyl salicylate, cyclohexyl salicylate, floramate, melusate and jasmine cyclate. The ethers include, for example, benzyl ethyl ether and ambroxan, the aldehydes e.g. the linear alkanals with 8 - 18 C atoms, citral. Citronellal. Citronellyloxy-acetaldehyde, cyclamenaldehyde, Lilial and Bourgeonal, to the ketones e.g. the Jonone, cc-isomethylionon and methyl-cedryl ketone, to the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and Teφineol, to the hydrocarbons belong mainly the Teφene like limonene and pinene. However, preference is given to using mixtures of different fragrances which together produce an appealing fragrance.

Such perfume oils can also contain natural fragrance mixtures as are available from plant sources, e.g. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil.

The general description of the perfumes which can be used (see above) generally represented the different substance classes of fragrances. In order to be perceptible, a fragrance must be volatile, the molar mass also playing an important role in addition to the nature of the functional groups and the structure of the chemical compound , Most odoriferous substances have molecular weights of up to about 200 daltons, while molecular weights of 300 daltons and more are an exception. Due to the different volatility of odoriferous substances, the smell of a perfume or fragrance composed of several odoriferous substances changes during evaporation, whereby the odor impressions are classified as "top note", "heart or middle note" (middle note or body) and "base note" (end note or dry out). Since the smell is largely based on the intensity of the smell, the head of a perfume or fragrance is not solely made up of volatile compounds, while the base note consists largely of less volatile, ie non-stick fragrances. When composing perfumes, more volatile fragrances can be bound to certain fixatives, for example, which prevents them from evaporating too quickly. In the subsequent classification of the fragrances into “more volatile” or “adhesive” fragrances, nothing is said about the odor impression and whether the corresponding fragrance is perceived as a top or heart note.

Tenacious odoriferous substances which are usable in the context of the present invention are, for example, essential oils such as angelica root oil, anise oil, arnica blossom oil, basil oil, bay oil, bergamot oil, Champacablütenöl, silver fir oil, noble fir cone oil, elemi oil, eucalyptus oil, fennel oil, pine needle oil, galbanum oil, geranium oil, ginger grass oil. Guaiac wood oil, gurjun balsam oil, helichrysum oil, ho oil, ginger oil, iris oil, kajeput oil, calamus oil, chamomile oil, camphor oil, kanaga oil, cardamom oil. Cassia oil, pine needle oil, Kopaϊvabalsamöl, coriander oil, spearmint oil, caraway oil, cumin oil, lavender oil, lemongrass oil, lime oil, mandarin oil, lemon balm oil, musk grain oil, myrrh oil. Clove oil. Neroli. Niaouli. Olibanum oil, orange oil. Origanum oil, palmarosa oil, patchouli oil, Peru balsam oil. Petitgrain oil, pepper oil, peppermint oil. Allspice oil, pine oil. Rose oil. Rosemary oil. Sandalwood oil, celery oil, spik oil. Anise. Teφentinöl. Thuja oil. Thyme oil, verbena oil, vetiver oil, juniper berry oil, wormwood oil. Wintergreen oil, ylang-ylang oil, hyssop oil, cinnamon oil, cinnamon leaf oil, lemon oil, lemon oil and cypress oil.

However, the higher-boiling or solid fragrances of natural or synthetic origin can also be used in the context of the present invention as adhesive fragrances or fragrance mixtures, that is to say fragrances. These compounds include the compounds mentioned below and mixtures of these: ambrettolide. α- amyl cinnamaldehyde, anethole, anisaldehyde, anis alcohol, anisole,

Anthranilic acid methyl ester, acetophenone, benzylacetone, benzaldehyde,

Ethyl benzoate, benzophenone, benzyl alcohol, benzyl acetate, benzo benzoate, Benzyl formate, benzyl valerianate, bomeol, bomylacetate, α-bromostyrene, n-decylaldehyde, n-dodecylaldehyde, eugenol, eugenol methyl ether, eucalyptol, famesol, fenchone. Fenchylacetate, geranyl acetate, geranyl formate, heliotropin,

Heptincarboxylic acid methyl ester, heptaldehyde, hydroquinone dimethyl ether,

Hydroxycinnamaldehyde, Hydroxyzimtalkohol, Indol, Iron, Isoeugenol,

Isoeugenol methyl ether, isosafrol, jasmon, camphor, karvakrol, carvone, p-cresol methyl ether, coumarin, p-methoxyacetophenone, methyl-n-amyl ketone, methyl anthranilic acid methyl ester, p-methylacetophenone, methyl chavikol, p-methyl quinaphone, methyl n-methyl-ketoline, methyl-n-methyl-ketoline nonylacetaldehyde, methyl-n-nonyl ketone, muscon, ß-naphthol ethyl ether, ß-naphthol methyl ether, nerol, n-nonyl aldehyde, nonyl alcohol, n-octyl aldehyde. p-Oxy-acetophenone, pentadecanolide, ß-phenylethyl alcohol, phenylacetaldehyde dimethyacetal, phenylacetic acid, pulegon, safrol, salicylic acid isoamyl ester, salicylic acid methyl ester, salicylic acid hexyl ester, salicylic acid cyclohexyl ester. Santalol. Skatol, Teφineol, Thymen, Thymol, γ-undelactone, Vanilin, Veratrumaldehyde, Cinnamaldehyde, Zimatalkohol, Cinnamic acid, Cinnamic acid ethyl ester, Cinnamic acid benzyl ester.

The more volatile fragrances include, in particular, the lower-boiling fragrances of natural or synthetic origin, which can be used alone or in mixtures. Examples of more volatile fragrances are alkyl isothiocyanates (alkyl mustard), butanedione, limonene, linalool, linaylacetate and propionate, menthol, menthone, methyl-n-heptenone, phellandrene, phenylacetaldehyde, teφinylacetate. Citral. Citronellal.

In addition to the constituents mentioned, the shaped bodies according to the invention can contain further ingredients in minor amounts of 1 to 10% by weight, preferably 1 to 5% by weight and in particular 1 to 2% by weight, based in each case on the shaped bodies , These substances can be used to dye the fragrance pearls or to give them technical advantages. However, detergent ingredients can also be added, the usual incorporation of which entails process engineering disadvantages. So are usually low Amounts of substances used such as optical brighteners, phosphonates, color transfer inhibitors, etc. are subsequently added. By introducing these substances, fragrance molded bodies, in particular fragrance pearls, are produced which contain further active substances and can thus be incorporated as a fragrance and active compound in detergents and cleaning agents. In addition, an additional process step is saved in the production of detergents and cleaning agents.

Preferred perfume moldings are suitable for incorporation into modern detergent preparations with a high bulk density. Therefore, these shaped bodies preferably have a bulk density above 600 g / 1, in particular above 700 g / 1. It is further preferred that the shaped bodies have an average particle size distribution from the range from 0.3 to 5.0 mm, preferably from the range from 0.5 to 3.0 mm.

Another object of the present invention is a process for the production of fragrance shaped bodies, in particular fragrance pearls, in which a solid and essentially water-free premix of a) 20 to 92 wt .-% detergent base granules, b) 0 to 10 wt .-% % Of excipient (s), c) 5 to 25% by weight of perfume and d) 3 to 60% by weight of carrier which has an anionic, at least 2-dimensionally crosslinked partial structure and contains alkylammonium ions, is subjected to granulation or press agglomeration becomes.

In the context of this invention, “essentially water-free” is understood to mean a state in which the content of liquid water, ie water not present in the form of hydrated water and / or constitutional water, is below 2% by weight, preferably below 1% by weight. and in particular even less than 0.5% by weight, based in each case on the premix. Accordingly, water can essentially only be in chemically and / or physically bound form or as a constituent of the raw materials or compounds present as a solid, but not as Liquid, solution or dispersion can be introduced into the process for producing the premix. Advantageously, the premix has a total water content of not more than 15% by weight, so this water is not chemically and / or physically bound but not in liquid free form, and it is particularly preferred that the content of not zeolite and or water bound to silicates in the solid premix is not more than 10% by weight and in particular not more than 7% by weight.

The ingredients to be used in the process, such as carrier substances, auxiliaries and in particular fragrances, have already been described in detail above. It is particularly preferred if the detergent base granules used according to the invention contain one or more substances from the group of surfactants, surfactant compounds, di- and polysaccharides, silicates, zeolites, carbonates, sulfates and citrates in quantities, and the base granules in quantities of 30 to 80 wt .-%, preferably from 40 to 75 wt .-%, each based on the weight of the resulting molded body, is used.

Furthermore, one or more substances from the group of the polyethylene glycols, the fatty alcohol alkoxylates and the fatty acid alkoxylates are preferably used as auxiliary (s) in the process according to the invention in amounts of 1 to 10% by weight, preferably 2 to 9% by weight and in particular of 5 to 7 wt .-%, each based on the weight of the molded body used. In particular, it is preferred if one or more substances from the group of polyethylene glycols with molecular weights between 2 and 15 kgmol ^"1 , preferably between 4 and 10 kgmol ^{" 1} , in amounts of 0 to 10% by weight, as auxiliary (s), preferably from 2 to 9% by weight and in particular from 5 to 7% by weight, based in each case on the weight of the molded body formed.

In the process according to the invention, the essentially water-free premix is subjected to granulation or press agglomeration after the individual constituents have been combined. During the granulation, the premix is compressed and homogenized by the rotating mixing tools and into perfume shaped bodies. especially scented pearls, granulated. The granulation of the essentially water-free premix provides fragrance pearls with a wider range of coms (coarse and fine fractions), which is why the process variant of press agglomeration is preferred over granulation.

In the process of press agglomeration, the premix is compressed and plasticized under pressure and under the action of shear forces, homogenized in the process and then discharged from the apparatus in a shaping manner. The most technically significant press agglomeration processes are extrusion, roller compaction, pelleting and tableting. In the context of the present invention, preferred press agglomeration processes are extrusion, roller compaction and pelletization.

In a preferred embodiment of the invention, the premix is preferably fed continuously to a planetary roller detector or a 2-shaft extruder or 2-screw extruder with co-rotating or counter-rotating screw guidance, the housing and the extruder pelletizing head of which can be heated to the predetermined extrusion temperature. Under the shear action of the extruder screws, the premix is compressed, plastified under pressure, which is preferably at least 25 bar, but at extremely high throughputs depending on the apparatus used. extruded in the form of fine strands through the perforated die plate in the extruder head and finally the extrudate is preferably reduced to approximately spherical to cylindrical granules by means of a rotating knock-off knife. The hole diameter of the perforated nozzle plate and the strand cut length are matched to the selected granulate dimension. In this embodiment, the production of granules of an essentially uniformly predeterminable particle size succeeds, and in particular the absolute particle sizes can be adapted to the intended use. In general, particle diameters up to at most 0.8 cm are preferred. Important embodiments provide for the production of uniform granules in the millimeter range, for example in the range from 0.5 to 5 mm and in particular in the range from approximately 0.8 to 3 mm. In an important embodiment, the length / diameter ratio of the chipped primary granules lies in Range from about 1: 1 to about 3: 1. Furthermore, it is preferred to feed the still plastic primary granulate to a further shaping processing step; edges present on the crude extrudate are rounded off so that ultimately spherical to approximately spherical extrudate grains can be obtained. If desired, small amounts of dry powder, for example zeolite powder such as zeolite NaA powder, can also be used in this step. This shape can be done in standard rounding machines. Care should be taken to ensure that only small amounts of fine grain are produced in this stage. Drying of the resulting extrudates is not necessary in the context of the present invention, since the process according to the invention is essentially water-free, that is to say without the addition of free, non-bound water.

Alternatively, extrusions / pressings can also be carried out in low-pressure extruders, in the Kahl press or in the extruder.

Just as in the extrusion process, it is also preferred in the other production processes to feed the resulting primary granules / compactates to a further shaping processing step, in particular to round them, so that ultimately spherical to approximately spherical (pearl-shaped) grains can be obtained.

The fact that the process according to the invention is carried out essentially in an anhydrous manner - ie with the exception of water contents (“impurities”) of the solid raw materials used in an anhydrous manner — provides an ecologically valuable process, since not only energy is saved but a waiving of a subsequent drying step emissions such as those which occur predominantly with conventional types of drying can also be avoided.Furthermore, the fact that subsequent drying steps are dispensed with enables the fragrances to be incorporated into the premix and thus the fragrance moldings according to the invention, in particular fragrance pearls, to be produced. In a further preferred embodiment of the present invention, the method according to the invention is carried out by means of roller compaction. Here, the fragrance-containing solid and essentially water-free premix is metered in between two smooth rollers or with depressions of a defined shape and rolled out between the two rollers under pressure to form a leaf-shaped compact, the so-called Schülpe. The rollers exert a high line pressure on the premix and can be additionally heated or cooled as required. When using smooth rollers, you get smooth, unstructured wristbands. while by using structured rollers, correspondingly structured slugs can be produced, in which, for example, certain shapes of the later fragrance molded bodies can be specified. The sliver belt is subsequently broken up into smaller pieces by a knocking-off and comminution process and can be processed into granules in this way, which can be further tempered, in particular in an approximately spherical shape, by further known surface treatment processes.

In a further preferred embodiment of the present invention, the method according to the invention is carried out by means of pelleting. Here, the fragrance-containing solid and essentially water-free premix is applied to a perforated surface and pressed through the holes by means of a pressure-producing body with plasticization. In conventional embodiments of pellet presses, the premix is compressed under plastic pressure, plasticized, pressed through a perforated surface by means of a rotating roller in the form of fine strands and finally comminuted into granules using a knock-off device. The most varied configurations of the pressure roller and perforated die are conceivable here. For example, flat perforated plates are used as well as concave or convex ring matrices through which the material is pressed using one or more pressure rollers. The press rolls can also be conical in the plate devices, in the ring-shaped devices dies and press roll (s) can have the same or opposite direction of rotation. An apparatus suitable for carrying out the method according to the invention is described, for example, in the German patent application DE 38 16 842 (Schlüter GmbH). The ring die press disclosed in this document consists of a rotating ring die interspersed with press channels and at least one press roller which is operatively connected to its inner surface and which presses the material supplied to the die space through the press channels into a material discharge. Here, the ring die and the press roller can be driven in the same direction, which means that a reduced shear stress and thus a lower temperature increase in the premix can be achieved. Of course, it is also possible to work with heatable or coolable rollers in the pelletizing in order to set a desired temperature of the premix.

Another press agglomeration process that can be used according to the invention is tableting. Because of the size of the molded article produced, it may be useful for tableting to add conventional disintegration aids, for example cellulose and its derivatives or crosslinked PVP, in addition to the binder, which facilitates the disintegration of the compacts in the wash liquor.

The perfume moldings produced according to the invention can additionally be sprayed with perfume afterwards. The conventional fragrance variant, i.e. dimming and spraying with perfume can be carried out on the fragrance molded articles produced according to the invention.

Advantageously, at least 30% by weight, preferably at least 40% by weight and in particular at least 50% by weight, of the total perfume contained in the molded body is introduced into the compositions in the inventive process, i.e. incorporated into the granules or press agglomerates, while the remaining 70% by weight, preferably 60% by weight and in particular 50% by weight of the total perfume contained in the agent is sprayed onto the granules or press agglomerates, which may optionally have been surface-treated or applied differently.

By dividing the total perfume content of the agents into perfume, which is contained in the granules or press agglomerates and perfume, which is on the granules or Press agglomerates adheres, a variety of product characteristics can be realized, which are only possible through the inventive method. For example, it is conceivable and possible to divide the total perfume content of the compositions into two portions x and y, the proportion x consisting of non-stick, ie less volatile, and the proportion y consisting of more volatile perfume oils.

It is now possible to produce detergents or cleaning agents in which the proportion of the perfume which is introduced into the detergents via the granules or press agglomerates is composed mainly of adhering odoriferous substances. In this way, adherent odoriferous substances, which are intended to scent the treated articles, in particular textiles, can be "held" in the product and thus have their effect mainly on the treated laundry. In contrast, the more volatile fragrance substances contribute to a more intensive fragrance of the agents themselves In this way it is also possible to produce detergents and cleaning agents which have an odor which differs from the smell of the treated articles, and there are hardly any limits to the creativity of perfumers, because of the choice of fragrances on the one hand and about the choice of the method of incorporation into the means, on the other hand, there are almost limitless possibilities for scenting the means and, via the means, the objects treated with them.

The principle described above can of course also be reversed by incoφorating the more volatile fragrances into the granules or press agglomerates and spraying the less volatile, adherent fragrances onto the compositions. In this way, the loss of the more volatile fragrances from the packaging during storage and transport is minimized, while the fragrance characteristics of the agents are determined by the more adhesive perfumes. The elevator aids contained in the fragrance molded bodies then ensure that the fragrance components are evenly applied to the laundry.

In a further embodiment, the present invention relates to detergents or cleaning agents, the fragrance shaped bodies according to the invention or fragrance shaped bodies produced according to the invention, in particular fragrance pearls, in amounts of more than 0.5 % By weight, preferably more than 1% by weight and in particular more than 2% by weight, based in each case on the detergent or cleaning agent.

This perfume shaped body. fragrance pearls in particular can be incorporated into conventional detergents and cleaning agents and are then used for scenting these agents in accordance with the abovementioned use. However, it is also possible to offer the fragrance shaped bodies, in particular fragrance pearls, separately as part of a “modular system”, in which the consumer acquires a fragrance-free basic detergent and can add various fragrance shaped bodies, in particular fragrance pearls, all the more so to be able to choose from a wide variety of fragrances based on the type of laundry treated.

In all of these embodiments, the fragrance shaped bodies according to the invention are ultimately used for scenting surfaces, in particular fibers, and in a very particularly preferred embodiment for scenting textile fibers. Another object of the invention is therefore the use of carrier materials which have an anionic, at least 2-dimensionally crosslinked partial structure and which contain alkylammonium ions, to improve the fragrance impression and leave the fragrances on surfaces.

Examples:

By mixing the recipe components mentioned below in a Lödige mixer, free-flowing premixes were produced which were compacted and plasticized in an extinguisher.

Table 1: Composition of the premixes or fragrance pearls

Tixogel VZ: cationized with stearylbenzyldimethylammonium

bentonite; Commercial product from Süd-Chemie

Tixogel VP: bentonite canonized with distearyldimethylammonium;

Commercial product from Süd-Chemie

Optigel CL: bentonite; Commercial product from Süd-Chemie Wessalith P: zeolite NaA; Commercial product from Degussa-Huls Repelotex SRP 4: terephthalic acid-ethylene glycol-polyethylene glycol ester;

Commercial product from Rhodia

PEG: polyethylene glycol

Composition of the spray granules (surfactant compounds produced by spray drying): 26.2% by weight Na-C ₉ .π-alkylbenzenesulfonate, 4.0% by weight Sodium carbonate, 55.6% by weight zeolite 4A, 0.7% by weight salts from solution, 13.0% by weight water and 0.5% by weight sodium hydroxide.

After leaving the mixer, the free-flowing premixes had a bulk density of approximately 400 g / l and were placed in a twin-screw extruder from Lihotzky and plasticized and extruded under pressure.

The plasticized premixes left the extender at a pressure of 85 bar through a perforated plate with outlet bores of 1.4 mm in diameter. The extruded strands were chopped to a length / diameter ratio of approx. 1 with a rotating chopper and rounded in a Marumerizer ^® . After the fine parts (<0.4 mm) and the coarse parts (> 2.0 mm) had been sieved, the extrudates had the bulk densities listed in Table 1.

The fragrance beads E1 to E3 produced according to the invention were mixed with perfume-free extrudates to form detergents and tested in a pair comparison with detergents produced analogously, which contained fragrance pearls without the canonized bentonites (VI or V2). The perfume oil content in the respective recipes was kept constant.

The composition of the perfume oil used in the individual fragrance pearls is given in Table 2. The fragrance of the product and treated textiles (cotton) was assessed as a subjective vegetable impression by several perfumers. The numerical values in the evaluation table (Table 3) indicate the number of perfumers who perceived the respective fragrance as better in a pair comparison.

Table 2: Composition of the perfume oil [% by weight]:

Table 3: Fragrance impression (preference of favor, number of perfumers)

While the bentonite-containing scented pearl (V2) in the pair comparison was significantly worse than the zeolite-based scented pearl (VI), the scented pearls E1 - E3 in comparison with the zeolite-based scented pearl (VI) showed a significant improvement, particularly on the laundry Dufteindmcks.

Claims

claims:

1. Perfume molded body containing a) 65 to 95 wt .-% carrier (e), b) 0 to 10 wt .-% excipient (e) and c) 5 to 25 wt .-% perfume, characterized in that a The proportion of carriers a) is selected from carriers which have an anionic, at least 2-dimensionally crosslinked partial structure and which contain alkylammonium ions.

2. Perfume molded body according to Anspmch 1, characterized in that the anionic, at least 2-dimensionally cross-linked substructure is an inorganic, in particular a silicate, layer structure.

3. Perfume molded body according to Anspmch 1, characterized in that the anionic, at least 2-dimensionally cross-linked partial structure is an organic polymer, in particular a derivative of a natural polymer, preferably a derivative of a polysaccharide.

4. fragrance molded body according to claim 1 or 2, characterized in that it is in the carrier which contains alkylammonium ions, a layered silicate of the formula M ₂ Si _x θ _{2X +} ryH ₂ θ, where M for a sodium and / or is a hydrogen and / or an alkylammonium ion, x is a number from 1, 9 to 4 and y is a number from 0 to 20.

5. fragrance molded body according to Anspmch 1 or 2, characterized in that it is in the carrier, which contains alkylammonium ions, is a modified silicate of the bentonite type, preferably of the montmorillonite type.

6. Perfume molded body according to one of claims 1 to 5, characterized in that the carrier, which has an anionic, at least 2-dimensionally crosslinked partial structure and contains alkylammonium ions, at least 3 wt .-%, preferably at least 5 and in particular more accounts for 7% by weight of the fragrance molded article.

7. fragrance molded body according to one of claims 1 to 6, characterized in that the carrier, which has an anionic, at least 2-dimensionally crosslinked partial structure and contains alkylammonium ions, less than 80 wt .-%, preferably less than 70 and makes up in particular less than 50% by weight of the fragrance shaped body.

8. Perfume molded article according to one of claims 1 to 7, characterized in that the molded article has a bulk density above 600 g / 1, preferably above 700 g / 1 and an average particle size distribution in the range from 0.3 to 5.0 mm, preferably from the range of 0.5 to 3.0 mm.

9. fragrance-shaped body according to one of claims 1 to 8, characterized in that the shaped body in addition to the above-mentioned ingredients also contain a substance which improves the absorption of the fragrance on surfaces, which is one or more substances from the group of Paraffins, the quaternary ammonium compounds, the soil-release polymers, in particular the copolymeric polyesters and other polymers, such as in particular polyvinylpyrrolidone and block copolymers with blocks (-CH ₂ -CH ₂ -O) _n - with n> 2.

10. Perfume molded body according to one of claims 1 to 9, characterized in that the molded body as a component of the carrier material a) one or more substances from the group of surfactants, surfactant compounds, di- and polysaccharides, silicates, zeolites, carbonates, sulfates and contains citrates, and this component is present in amounts of 30 to 80% by weight, preferably 40 to 75% by weight, in each case based on the weight of the molded body.

11. Process for the production of fragrance shaped bodies, in particular fragrance pearls, wherein a solid and essentially water-free premix of a) 20 to 92% by weight of detergent base granules, b) 0 to 10% by weight of auxiliary (s), c ) 5 to 25% by weight of perfume and d) 3 to 60% by weight of carrier which has an anionic, at least 2-dimensionally crosslinked partial structure and contains alkylammonium ions, is subjected to granulation or press agglomeration.

12. The method according to Anspmch 1 1, characterized in that the solid and essentially water-free premix is subjected to a press agglomeration, preferably an extinction, a roller compacting or a pelletizing.

13. The method according to any one of claims 1 1 or 12, characterized in that the premix has a total water content of not more than 15 wt .-%, which water is not in free form and preferably the content of not zeolite and / or silicate-bound water is not more than 10% by weight and in particular not more than 7% by weight.

14. The method according to any one of claims 1 1 to 13, characterized in that the detergent base granules contain one or more substances from the group of surfactants, surfactant compounds, di- and polysaccharides, silicates, zeolites, carbonates, sulfates and citrates in quantities, and the base granules are used in amounts of 30 to 80% by weight, preferably 40 to 75% by weight, in each case based on the weight of the resulting molded article.

15. The method according to any one of claims 11 to 14, characterized in that as auxiliary (s) one or more substances from the group of polyethylene glycols, the fatty alcohol alkoxylates and the fatty acid alkoxylates in amounts of 1 to 10% by weight, preferably from 2 to 9% by weight and in particular from 5 to 7% by weight, each based on the weight of the resulting molded body.

16. The method according to any one of claims 11 to 15, characterized in that one or more substances from the group of polyethylene glycols with molecular weights between 2 and 15 kgmol ^"1 , preferably between 4 and 10 kgmol ^{* 1} , in amounts as auxiliary (s) from 0 to 10% by weight, preferably from 2 to 9% by weight and in particular from 5 to 7% by weight, in each case based on the weight of the molded body formed.

17. washing or cleaning agent containing fragrance molded article according to one of claims 1 to 10 or fragrance molded article, which were produced by a process according to claims 1 1 to 16, in amounts of more than 0.5 wt .-% , preferably more than 1 wt .-% and in particular more than 2 wt .-%, each based on the detergent or cleaning agent.

18. Use of carrier materials which have an anionic, at least two-dimensionally crosslinked partial structure and which contain alkylammonium ions, to improve the fragrance impression, leave the fragrances on surfaces.