CA2306300A1 - Perfume bags - Google Patents

Abstract

Perfume beads which contain at least 1 % by weight of perfume oil and which otherwise consist essentially of ingredients of detergents are eminently suitable for use in perfume bags for perfuming dry laundry.
Beads larger than 2.3 mm in diameter are particularly suitable. One advantage of these beads is that they can be used as detergents after their perfuming effect has faded.

Description

Perfume Bags Field of the Invention This invention relates to perfume bags which are suitable for perfuming dry laundry.
Background of the Invention The subject of perfuming laundry has already been investigated and researched for some time. The laundry is normally perfumed during the washing process or in the dryer either by the detergent used or by corresponding auxiliaries or special perfume additives. Even when the perfuming of laundry is carried out with special additives which are intended to guarantee a lasting perfume adhering to the laundry, the perfume still fades continuously during storage of the dry laundry. In general, hardly any perfume at all is noticeable only one week after washing. Accordingly, there is a need to perfume dry laundry in such a way that the impression of freshly washed laundry is maintained even in the event of prolonged storage.
It would be logical to use a device for this purpose which, in an airing cupboard for example, would give off perfume to the laundry stored therein.
Fabric bags filled with dried plant parts, for example lavender stems, which give off perfumes are frequently used for this purpose. Bags such as these are commercially obtainable. However, commercially obtainable bags generally do not contain parts of plants, but instead perfumes which have been applied to suitable supports/carriers.
DE-OS 26 22 70T for example describes a perfume bag containing a nonwoven carrier impregnated with a perfume emulsion. In DE-OS 26 03 823, the perfumes are applied to an absorbent carrier made, for example, of a textile material, paper, felt or foam. This carrier is surrounded by a plastic film which thus forms a perfume pad. These perfume pads are particularly suitable for perfuming laundry in dryers although they can also be used for perfuming rooms if the pads are placed on a heat source. It is crucial that the pads are heated because only then does the film allow sufficient perfume through.
Perfume preparations of the type in question are only suitable for perfuming spaces and have to be disposed of as waste as soon as they stop releasing perfume.
It has now been found that perfume preparations containing detergent ingredients can be used for perfuming dry laundry. After they have stopped releasing perfume, these preparations may be used for washing laundry. Accordingly, there is hardly any waste where such perfume bags are used.
Summary of the Invention In a first embodiment, therefore, the present invention relates to perfume bags for perfuming dry laundry which are characterized in that they contain perfume beads which contain at least 1% by weight of perfume oil and which consist essentially of detergent ingredients.
In a second embodiment, the present invention relates to perfume beads which are suitable for use in perfume bags and which are charac-terized in that they contain at least 1 % by weight of perfume oil, consist essentially of detergent ingredients and have a mean particle size of more than 1.5 mm.
These embodiments of the invention are described in more detail in the following.
Detailed Description of the Invention The envelope of the perfume bag, i.e. the actual bag, consists of a perfume-permeable material, the pore diameter of the envelope material being below 0.5 mm. The envelope material may be a woven or nonwoven material, i.e. for example a woven material of natural or synthetic fibers, for example of cellulose, wool, silk, linen, jute, sisal, polyamide, polyester, polyacrylonitrile, polyvinyl derivatives, polyolefins or rayon, or a blended fabric of these fibers. Other suitable envelope materials are foams of viscose or synthetic polymers, more particularly polyurethane. The envelope material may also be a flexible film formed with slits or pores.
Suitable film materials are, for example, polyolefins, more particularly poly-ethylene and polypropylene, polyesters, polyamides and cellulose esters.
Films such as these may be transparent or impermeable to light and, in particular, may be color-printed. Preferred perfume bags have a device which enables the bags to be easily fastened to a suspension point, such as a hook, a screw or nail, but more particularly to a clothes hanger.
Irrespective of the type of envelope used, it is crucial that the envelope material have pores to guarantee its permeability to perfume. Basically, however, these pores are smaller than 0.5 mm and preferably even smaller than 3 mm because the perfume beads themselves could drop through larger pores under mechanical load.
The perfume beads themselves have a mean particle size of more than 1.5 mm, their particle sizes preferably being in the range from 2 to 10 mm and more preferably in the range from 2.3 to 5 mm. On the one hand, there is an upper limit to the particle size because the surface through which the perfume is released becomes increasingly smaller with increasing particle size. On the other hand, the perfume beads are also intended to dissolve sufficiently quickly during their ultimate use as a detergent. A lower limit is imposed firstly by the need to have particles which are distinctly larger than the pores of the envelope material and secondly by the sensitive impression which the consumer receives on handling the perfume bags.
The shape of the perfume beads is also crucial to the sensitive impression. In one preferred embodiment, these beads - as their name suggests - are spherical. However, the "beads" in the context of the present invention are not confined to a spherical shape but instead may assume any shape. The possible shapes are dependent solely on the process used to produce the "perfume beads", extrusion in particular allowing a wide variety of shapes. If complicated shapes, such as stars or figures, are used for the beads, it can be of advantage to place these "beads" in transparent perfume bags. In addition, in transparent perfume bags such as these, the perfume beads are preferably colored.
To enable the beads to be handled in the perfume bags, the beads must be dust-free and substantially abrasion-resistant. For this reason, too, the beads are preferably substantially spherical in shape. To test abrasion behavior, a sample of the perfume beads is sieved on a sieve of suitable mesh width, the residue is weighed and is then sieved for 5 minutes on an analytical sieve together with metal balls. In preferred embodiments of the beads according to the invention, the abrasion is less than 2% by weight. If the perfume beads are substantially spherical in shape, abrasion is preferably even less than 1 % by weight and more preferably even less than 0.5% by weight. The required perfume impression of the beads can last a few days or even several months.
According to the invention, the perfume impression of the bags filled with perfume beads remains substantially constantly noticeable for at least one month and preferably for even six months. The period for which the perfume impression remains noticeable depends on the one hand on the process used to produce the perfume beads and, on the other hand, on the perfume oils used.
The perfume beads contain at least 1 % by weight of perfume oil.
Preferred perfume beads contain 3 to 30% by weight of perfume oil, perfume beads containing 5 to 20% by weight of perfume oil being particularly preferred.
The perfume oils or perfumes used may be individual perfume compounds, for example synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type. Examples of perfume compounds of the ester type are benzyl acetate, phenoxyethyl isobutyrate, p-tert.butyl cyclohexyl acetate, linalyl acetate, dimethyl benzyl carbinyl acetate (DMBCA), phenyl ethyl acetate, benzyl acetate, ethyl methyl phenyl glycinate, allyl cyclohexyl propionate, styrallyl propionate, benzyl salicylate, cyclohexyl salicylate, floramate, melusate and jasmecyclate. The ethers include, for example, benzyl ethyl ether and Ambroxan; the aldehydes include, for example, linear alkanals containing 8 to 18 carbon atoms, citral, 5 citronellal, citronellyloxy acetaldehyde, cyclamen aldehyde, lilial and bourgeonal; the ketones include, for example, ionones, a-isomethyl ionone and methyl cedryl ketone; the alcohols include anethol, citronellol, eugenol, geraniol, linalool, phenyl ethyl alcohol and terpineol while the hydrocarbons include, above all, terpenes, such as limonene and pinene. However, mixtures of different perfumes which together produce an attractive perfume note are preferably used.
Perfume oils such as these may also contain natural perfume mixtures obtainable from vegetable sources, for example pine, citrus, jasmine, patchouli, rose or ylang-ylang oil. Also suitable are clary oil camomile oil, clove oil, melissa oil, mint oil, cinnamon leaf oil, lime blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil and orange blossom oil, neroli oil, orange peel oil and sandalwood oil.
In order to be noticeable, a perfume has to be volatile, its molecular weight being an important factor along with the nature of the functional groups and the structure of the chemical compound. Thus, most perfumes have molecular weights of up to about 200 dalton, molecular weights of 300 dalton and higher being more the exception. In view of the differences in volatility of perfumes, the odor of a perfume or fragrance composed of several perfumes changes during the evaporation process, the odor impressions being divided into the top note, the middle note or body and the end note or dry out. Since odor perception is also based to a large extent on odor intensity, the top note of a perfume or fragrance does not consist solely of readily volatile compounds whereas the end note or dry out consists largely of less volatile, i.e. firmly adhering, perfumes. In the composition of perfumes, more readily volatile perfumes may be fixed, for i example, to certain "fixatives", which prevents them from vaporizing too rapidly. The above-described embodiment of the present invention, in which the more readily volatile perfumes or fragrances are incorporated in the press agglomerate, is one such method of fixing a perfume.
Accordingly, in the following classification of perfumes as "readily volatile"
and "firmly adhering" perfumes, nothing is said about the odor impression or about whether the corresponding perfume is perceived as a top note or middle note.
Firmly adhering perfumes suitable for use in accordance with the present invention are, for example, the essential oils, such as angelica root oil, aniseed oil, arnica flowers oil, basil oil, bay oil, bergamot oil, champax blossom oil, silver fir oil, silver fir cone oil, elemi oil, eucalyptus oil, fennel oil, pine needle oil, galbanum oil, geranium oil, ginger grass oil, guaiac wood oil, Indian wood oil, helichrysum oil, ho oil, ginger oil, iris oil, cajeput oil, sweet flag oil, camomile oil, camphor oil, canaga oil, cardamom oil, cassia oil, Scotch fir oil, copaiba balsam oil, coriander oil, spearmint oil, caraway oil, cumin oil, lavender oil, lemon grass oil, limette oil, mandarin oil, melissa oil, amber seed oil, myrrh oil, clove oil, neroli oil, niaouli oil, olibanum oil, orange oil, origanum oil, palmarosa oil, patchouli oil, Peru balsam oil, petit grain oil, pepper oil, peppermint oil, pimento oil, pine oil, rose oil, rosemary oil, sandalwood oil, celery seed oil, lavender spike. oil, Japanese anise oil, turpentine oil, thuja oil, thyme oil, verbena oil, vetiver oil, juniper berry oil, wormwood oil, wintergreen oil, ylang-ylang oil, ysop oil, cinnamon oil, cinnamon leaf oil, citronella oil, citrus oil and cypress oil.
However, relatively high-boiling or solid perfumes of natural or synthetic origin may also be used in accordance with the invention as firmly adhering perfumes or perfume mixtures. These compounds include those mentioned in the following and mixtures thereof: ambrettolide, a-amyl cinnamaldehyde, anethole, anisaldehyde, anisalcohol, anisole, methyl anthranilate, acetophenone, benzyl acetone, benzaldehyde, ethyl benzoate, benzophenone, benzyl alcohol, benzyl acetate, benzyl benzoate, benzyl formate, benzyl valerate, borneol, bornyl acetate, a-bromostyrene, n-decyl aldehyde, n-dodecyl aldehyde, eugenol, eugenol methyl ether, eucalyptol, farnesol, fenchone, fenchyl acetate, geranyl acetate, geranyl formate, heliotropin, methyl heptyne carboxylate, heptaldehyde, hydroquinone dimethyl ether, hydroxycinnamaldehyde, hydroxycinnamyl alcohol, indole, irone, isoeugenol, isoeugenol methyl ether, isosafrol, jasmone, camphor, carvacrol, carvone, p-cresol methyl ether, coumarin, p-methoxyacetophenone, methyl-n-amyl ketone, methyl anthranilic acid methyl ester, p-methyl acetophenone, methyl chavicol, p-methyl quinoline, methyl-~i-naphthyl ketone, methyl-n-nonyl acetaldehyde, methyl-n-nonyl ketone, muskone, ~3-naphthol ethyl ether, ~i-naphthol methyl ether, nerol, nitrobenzene, n-nonyl aldehyde, nonyl alcohol, n-octyl aldehyde, p-oxyacetophenone, pentadecanolide, ~i-phenyl ethyl alcohol, phenyl acetaldehyde dimethyl acetal, phenyl acetic acid, pulegone, safrol, isoamyl salicylate, methyl salicylate, hexyl salicylate, cyclohexyl salicylate, santalol, scatol, terpineol, thymene, thymol, y-undecalactone, vanillin, veratrum aldehyde, cinnamaldehyde, cinnamyl alcohol, cinnamic acid, ethyl cinnamate, benzyl cinnamate.
The more readily volatile perfumes include, in particular, the relatively low-boiling perfumes of natural or synthetic origin which may be used either individually or in the form of mixtures. Examples of more readily volatile perfumes are alkyl isothiocyanates (alkyl mustard oils), butanedione, limonene, linalool, linalyl acetate and propionate, menthol, menthone, methyl-n-heptenone, phellandrene, phenyl acetaldehyde, terpinyl acetate, citral, citronellal.
Besides the perfumes, the perfume beads contain typical detergent ingredients as essential constituents. These detergent ingredients have the crucial function of guaranteeing the function of the perfume beads as a detergent when the perfume impression fades and of acting in the washing process. In addition, however, these substances are also essential as carriers for the perfume oils.
Preferred carrier materials are selected from the group of surfactants, surfactant compounds, di- and polysaccharides and builders and are used in quantities of up to 99% by weight, preferably in quantities of 65 to 97% by weight and more preferably in quantities of 70 to 90% by weight, based on the weight of the shaped body formed.
Any surfactants or surfactant compounds solid at temperatures of up to 40°C may be used as surface-active carrier materials. In the context of the present invention, a "surfactant compound" is understood to be a surfactant-containing preparation which, besides typical carrier materials and auxiliaries, contains at least 20% by weight of an anionic, cationic or nonionic surfactant, based on the surfactant compound. The carrier materials typically used in surfactant compounds may advantageously be identical with the above-mentioned carrier materials used in the process according to the invention, although other carrier materials than those mentioned above may also be present as carriers in the surfactant compounds.
In preferred processes, one or more anionic surfactant compounds or anionic surfactants, more particularly soaps, is/are used as carrier materials in quantities of 65 to 99% by weight and preferably 70 to 90% by weight, based on the weight of the shaped body formed. Examples of anionic surfactant compounds are alkyl benzenesulfonate (ABS) compounds on silicate or zeolite carriers with ABS contents of, for example, 10, 15, 20 or 30% by weight, fatty alcohol sulfate (FAS) compounds on silicate, zeolite or sodium sulfate carriers with active substance contents of, for example, 50 to 70, 80 or 90% by weight and anionic-surfactant-containing compounds based on sodium carbonate/sodium silicate with anionic surfactant contents above 40% by weight. Pure anionic surfactants may also be used as carriers in accordance with the present invention providing they are solid and non-hygroscopic. Soaps are particularly preferred as pure anionic surfactant carriers because, on the one hand, they remain solid up to high temperatures and, on the other hand, do not present any problems through the unwanted absorption of water. Any salts of fatty acids are used as soaps in the carrier materials for the shaped bodies according to the invention. Whereas, in principle, aluminium, alkaline earth metal and alkali metal salts of the fatty acids, for example, may be used, preferred shaped bodies are those in which the alkali metal salts and preferably the sodium salts of the fatty acids are present.
Suitable fatty acids, of which the salts may be used as carrier material, are any acids obtained from vegetable or animal oils and fats. The fatty acids may be saturated or mono- to poly-unsaturated. It is of course possible to use not only "pure" fatty acids, but also the technical fatty acid mixtures obtained in the hydrolysis of fats and oils, for example palm kernel oil, coconut oil, peanut oil or rapeseed oil or bovine tallow, these mixtures being distinctly preferred from the economic point of view.
Thus, individual species or mixtures of salts of the following acids, for example, may be used in the carrier materials: caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, octadecan-12-oleic acid, arachic acid, behenic acid, lignoceric acid, cerotic acid, melissic acid, 10-undecenoic acid, petroselic acid, petroselaidic acid, oleic acid, elaidic acid, ricinoleic acid, linolaidic acid, a- and ~i-elaeostearic acid, gadoleic acid, erucic acid, brassidic acid. The salts of the fatty acids with an odd number of carbon atoms, for example the salts of undecanoic acid, tridecanoic acid, pentadecanoic acid, heptadecanoic acid, nonodecanoic acid, heneicosanoic acid, tricosanoic acid, pentacosanoic acid, heptacosanoic acid, may of course also be used.
In particularly preferred perfume beads, one or more substances from the group of sodium salts of saturated or unsaturated C8_24 fatty acids, preferably saturated or unsaturated C~2_~8 fatty acids and, more preferably, saturated or unsaturated C16 fatty acids is/are used as carrier materials) in quantities of 65 to 99% by weight and preferably in quantities of 70 to 90%
by weight, based on the weight of the shaped body formed.
Other suitable carrier materials are, for example, di- and 5 polysaccharides, a broad range of substances from sucrose and maltose through oligosaccharides to the "traditional" polysaccharides, such as cellulose and starch and derivatives thereof, being suitable. Among the substances belonging to these sub-groups, the starches are particularly preferred.

10 The carriers typically used in detergents, such as silicates and zeolites, are also suitable as carriers for the purposes of the invention. The finely crystalline, synthetic zeolite containing bound water used is preferably zeolite A, X and/or P. Zeolite MAP~ (a Crosfield product), for example, is used as zeolite P. However, zeolite Y and mixtures of A, X, Y
andlor P are also suitable. A mixture of zeolites A and X is marketed, for example, as Vegobond~AX (by Condea Augusta S.p.A.). The zeolite may be used in the form of a spray-dried powder or even in the form of an undried stabilized suspension still moist from its production. Where the zeolite is used in the form of a suspension, the suspension may contain small additions of nonionic surfactants as stabilizers, for example 1 to 3%
by weight, based on zeolite, of ethoxylated C~2_~s fatty alcohols containing 2 to 5 ethylene oxide groups, C~2-,Q fatty alcohols containing 4 to 5 ethylene oxide groups or ethoxylated isotridecanols. Suitable zeolites have a mean particle size of less than 10 ~m (volume distribution, as measured by the Coulter Counter Method) and contain preferably 18 to 22% by weight and more preferably 20 to 22% by weight of bound water.
Other suitable carriers are layer-form sodium silicates corresponding to the general formula NaMSiXO~+~AyH20, where M is sodium or hydrogen, x is a number of 1.9 to 4 and y is a number of 0 to 20, preferred values for x being 2, 3 or 4. Crystalline layer silicates such as these are described, for example, in European patent application EP-A-0 164 514.
Preferred crystalline layer silicates corresponding to the above formula are those in which M is sodium and x assumes the value 2 or 3. Both Vii- and 8-sodium disilicates Na2Si205AyH20 are particularly preferred.
Other preferred builders are amorphous sodium silicates with a modulus (Na20:Si02 ratio) of 1:2 to 1:3.3, preferably 1:2 to 1:2.8 and more preferably 1:2 to 1:2.6 which dissolve with delay and exhibit multiple wash cycle properties. The delay in dissolution in relation to conventional amorphous sodium silicates can have been obtained in various ways, for example by surface treatment, compounding, compacting or by overdrying.
In the context of the invention, the term "amorphous" is also understood to encompass GX-ray amorphous". In other words, the silicates do not produce any of the sharp X-ray reflexes typical of crystalline substances in X-ray diffraction experiments, but at best one or more maxima of the scattered X-radiation which have a width of several degrees of the diffraction angle. Particularly good builder properties may even be achieved where the silicate particles produce crooked or even sharp diffraction maxima in electron diffraction experiments. This may be interpreted to mean that the products have microcrystalline regions between 10 and a few hundred nm in size, values of up to at most 50 nm and, more particularly, up to at most 20 nm being preferred. So-called X-ray amorphous silicates such as these, which also dissolve with delay in relation to conventional waterglasses, are described for example in German patent application DE-A-44 00 024. Compacted amorphous sili-Gates, compounded amorphous silicates and overdried X-ray-amorphous silicates are particularly preferred.
Other suitable carrier materials are layer silicates of natural and synthetic origin. Such layer silicates are known, for example, from patent applications DE-B-23 34 899, EP A- 0 026 529 and DE-A-35 26 405. Their suitability is not confined to a particular composition or structural formula.

However, smectites, especially bentonites, are preferred.
Suitable layer silicates which belong to the group of water-swellable smectites are, for example, montmorillonite, hectorite or saponite. In addition, small quantities of iron may be incorporated in the crystal lattice of the layer silicates in accordance with the above formulae. By virtue of their ion-exchanging properties, the layer silicates may additionally contain hydrogen, alkali metal, alkaline earth metal ions, more particularly Na+ and Ca++. The water of hydration content is generally between 8 and 20% by weight, depending on the degree of swelling and the processing technique.
Useful layer silicates are known, for example, from US-A-3,966,629, EP-A-0 026 529 and EP-A-0 028 432. Layer silicates substantially freed from calcium ions and strongly coloring iron ions by an alkali treatment are preferably used.
Useful organic carriers are, for example, polycarboxylic acids usable 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), providing their use is not ecologically unsafe, and mixtures thereof. Preferred salts are the salts of the polycarboxylic acids, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof.
The acids per se may also be used. Besides their efectiveness as a carrier, the acids also typically have the property of an acidifying component and, hence, also serve to establish a relatively low and mild pH
value in detergents. Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and mixtures thereof are particularly mentioned in this regard.
These acids are preferably used in water-free form in the perfume beads according to the invention.
If the perfume beads are used for washing, they may be used on their own as detergents. However, the perfume beads preferably replace only part of the detergent used. In one preferred embodiment, up to 50%

by weight of the detergent used is formed by the perfume beads and, in one particularly preferred embodiment, 10 to 30% by weight of the detergent is replaced by perfume beads.
The present invention also relates to a process for the production of perfume beads suitable for use in perfume bags which is characterized in that a solid and substantially water-free premix of 1 to 30% by weight perfume oil, 65 to 99% by weight carriers and 0 to 10% by weight auxiliaries is subjected to granulation or press agglomeration, the granulation or press agglomeration being carried out in such a way that the resulting perfume beads have a mean particle size of more than 1.5 mm.
The procedure adopted in this regard may largely correspond to the disclosure of earlier German patent application DE 197 46 780.6. How-ever, it is essential that the process according to the present invention be carried out in such a way that the resulting perfume beads have a mean particle size of more than 1.5 mm, preferably in the range from 2 to 10 mm and more preferably in the range from 2.3 to 5 mm.
In the context of the present invention, the expression "substantially water-free" is understood to apply to a state in which the content of liquid water, i.e. water which is not present as water of hydration and/or water of constitution, is below 2% by weight, preferably below 1 % by weight and, more preferably, even below 0.5% by weight, based on the premix.
Accordingly, water can only be introduced into the process for producing the premix in chemically andlor physically bound form or as a constituent of the raw materials or compounds present as solids, but not as a liquid, solution or dispersion. The premix advantageously has a total water content of not more than 15% by weight, i.e. the water is present in chemically andlor physically bound form and not in liquid, free form. In a particularly preferred embodiment, the content of water not bound to zeolite andlor to silicates in the solid premix is no more than 10% by weight and preferably no more than 7% by weight.

After the individual constituents have been combined, the substantially water-free premix is subjected to granulation or press agglomeration. In granulation, the premix is compacted and homogenized by the rotating mixing tools and granulated to form perfume shaped bodies, more particularly perfume beads. The granulation of the substantially water-free premix gives perfume beads with a broader particle size distribution (coarse and fine fractions) so that the press agglomeration variant is preferred to the granulation variant.
In the press agglomeration process, the premix is compacted and plasticized under pressure and under the effect of shear forces, homogenized and then discharged from the machines via a formingl shaping stage. Technically the most important press agglomeration processes are extrusion, roller compacting, pelleting and tabletting.
Preferred press agglomeration processes for the purposes of the present invention are extrusion, roller compacting and pelleting.
The function of the carrier materials is to absorb the generally liquid components of the perfume without the particles sticking to one another. A
homogeneously plasticized mixture in which the perfume is incorporated in the carrier in fine distribution is only obtained by the action of the mixing tools during the granulation step or the relatively strong shear forces in the press agglomeration step and optionally through the addition of an auxiliary or auxiliaries. This procedure has clear advantages over the conventional application of perfume to porous carrier materials, as will be explained in more detail hereinafter.
One or more substances from the group of surfactants, surfactant compounds, di- and polysaccharides, silicates, zeolites, carbonates, sulfates and citrates is/are preferably used as carrier materials) in the process in quantities of up to 99% by weight, preferably in quantities of 65 to 97% by weight and more preferably in quantities of 70 to 90% by weight, based on the weight of the shaped body formed. In one particularly preferred embodiment, one or more anionic surfactant compounds or anionic surfactants, more particularly soaps, is/are used as carrier materials) in quantities of 65 to 99% by weight and preferably in quantities of 70 to 90% by weight, based on the weight of the shaped body formed.
5 In a likewise preferred process, one or more substances from the group of sodium salts of saturated or unsaturated C8_24 fatty acids, preferably saturated or unsaturated C~Z_,8 fatty acids and more preferably saturated or unsaturated C~6 fatty acids islare used as carrier materials) in quantities of 65 to 99% by weight and preferably in quantities of 70 to 90% by weight 10 based on the weight of the shaped body formed.
The premix may optionally contain auxiliaries which improve the cohesion of the carrier particles mixed with the perfume and which, under the granulation or press agglomeration conditions, envelop the solid particles and bond them to one another in such a way that the final end 15 products are made up almost exactly of these numerous small individual particles that are held together by the auxiliary which acts as a preferably thin dividing wall between the individual particles.
These auxiliaries on the one hand facilitate the plasticization of the premix under the granulation or press agglomeration conditions and, on the other hand, develop disintegration-promoting properties during the dissolution of the perfume beads without the beads sticking to one another in transit, when used in the perfume bags for perfuming dry laundry or during storage.
Suitable auxiliaries are those from the group of polyethylene glycols, fatty alcohol ethoxylates and fatty acid alkoxylates which, in preferred processes, are used in quantities of 0 to 10% by weight, preferably in quantities of 2 to 9% by weight and more preferably in quantities of 5 to 7%
by weight, based on the weight of the shaped body formed.
The fatty acid alkoxylates optionally used may be described by general formula (I):

R'-COO-( i H2-CH-O)k-H (I) in which R' is selected from C~_» alkyl or alkenyl, R2 = -H or -CH3 and k = 2 to 10. Suitable fatty alcohol alkoxylates correspond to formula (II):
R3-O-(CH2- i H-O),-H (II) in which R3 is selected from C8_~8 alkyl or alkenyl, R4 = -H or -CH3 and I = 2 to 10. In both cases, the corresponding auxiliaries may readily be produced in known manner by ethoxylation or propoxylation of fatty acids or fatty alcohols, technical mixtures of the individual species being preferred for economic reasons.
Other suitable auxiliaries are polyethylene glycols (PEGs) which may be described by general formula (III):
H-(O-CH2-CH2)"-OH (I I I) in which the degree of polymerization n can vary from about 5 to >100,000, corresponding to molecular weights of 200 to 5,000,000 g/mol'. The products with molecular weights below 25,000 glmol' are actual polyethylene glycols whereas relatively high molecular weight products are often referred to in the literature as polyethylene oxides (PEOXs). The polyethylene glycols preferably used may have a linear or branched structure, linear polyethylene glycols being particularly preferred.
Particularly preferred polyethylene glycols include those with relative molecular weights of 2000 to 12,000 and advantageously around 4000, polyethylene glycols with relative molecular weights below 3500 and above 5000 being usable in particular in combination with polyethylene glycols having a relative molecular weight of around 4000 and more than 50% by weight of these combinations, based on the total quantity of polyethylene glycols, advantageously containing polyethylene glycols having a relative molecular weight of 3500 to 5000. However, other suitable binders are polyethylene glycols which, basically, are present as liquids at room temperature/1 bar pressure, above all polyethylene glycol with a relative molecular weight of 200, 400 and 600.
According to the invention, a preferred process is characterized in that one or more substances from the group of polyethylene glycols with molecular weights of 2 to 15 kgmol-' and preferably in the range from 4 to 10 kgmol-' is/are used as auxiliaries in quantities of 0 to 10% by weight, preferably 2 to 9% by weight and more preferably 5 to 7% by weight, based on the weight of the shaped body formed.
After the individual constituents have been combined, the substantially water-free premix is subjected to granulation or press agglomeration. In granulation, the premix is compacted and homogenized by the rotating mixing tools and granulated to form perfume shaped bodies, more particularly perfume beads. The granulation of the substantially water-free premix gives perfume beads with a broader particle size distribution (coarse and fine fractions) so that the press agglomeration variant is preferred to the granulation variant.
In the press agglomeration process, the premix is compacted and plasticized under pressure and under the effect of shear forces, homogenized and then discharged from the machines via a formingl shaping stage. Technically the most important press agglomeration processes are extrusion, roller compacting, pelleting and tabletting.
Preferred press agglomeration processes for the purposes of the present invention are extrusion, roller compacting and pelleting.

In one preferred embodiment of the invention, the premix is delivered, preferably continuously, to a planetary roll extruder or to a twin-screw extruder with co-rotating or contra-rotating screws, of which the barrel and the extrusion/granulation head can be heated to the prede-termined extrusion temperature. Under the shearing effect of the extruder screws, the premix is compacted under a pressure of preferably at least 25 bar or - with extremely high throughputs - even lower, depending on the apparatus used, plasticized, extruded in the form of fine strands through the multiple-bore extrusion die in the extruder head and, finally, size-reduced by means of a rotating cutting blade, preferably into substantially spherical or cylindrical granules. The bore diameter of the multiple-bore extrusion die and the length to which the strands are cut are adapted to the selected granule size. In this embodiment, granules are produced in a substantially uniformly predeterminable particle size, the absolute particle sizes being adaptable to the particular application envisaged. In general, particle diameters of 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 more particularly in the range from about 0.8 to 3 mm. In one important embodiment, the length-to-diameter ratio of the primary granules is in the range from about 1:1 to about 3:1. In another preferred embodiment, the still plastic primary granules are subjected to another shaping process step in which edges present on the crude extrudate are rounded off so that, ultimately, spherical or substantially spherical extrudate granules can be obtained. If desired, small quantities of drying powder, for example zeolite powder, such as zeolite NaA powder, may be used in this step. This shaping step may be carried out in commercially available spheronizers. It is important in this regard to ensure that only small quantities of fines are formed in this stage. According to the present invention, however, there is no need for drying because the process according to the invention is carried out in the substantial absence of water, i.e. without the addition of free non-bound water.
Alternatively, extrusionlcompression steps may also be carried out in low-pressure extruders, in a Kahl press or in a so-called Bextruder.
As in the extrusion process, it is also preferred in the other production processes to subject the primary granules/compactates formed to another shaping process step, more particularly spheronizing, so that, ultimately, spherical or substantially spherical (bead-like) granules can be obtained.
By virtue of the fact that the process according to the invention is carried out in the substantial absence of water, i.e. except for the water present as "impurity" in the solid raw materials used, an ecologically valuable process is also provided because elimination of the need for a subsequent drying step not only saves energy, emissions which occur predominantly in conventional drying techniques can also be avoided. In addition, the absence of subsequent drying steps enables the perfumes to be incorporated in the premix and thus provides for the production of the perfume shaped bodies, more particularly perfume beads, according to the invention.
In another preferred embodiment of the present invention, the process according to the invention is carried out by roller compacting. In this variant, the perfume-containing, solid and substantially water-free premix is introduced between two rollers - either smooth or provided with depressions of defined shape - and rolled under pressure between the two rollers to form a sheet-like compactate. The rollers exert a high linear pressure on the premix and may be additionally heated or cooled as required. Where smooth rollers are used, smooth untextured compactate sheets are obtained. By contrast, where textured rollers are used, correspondingly textured compactates, in which for example certain shapes can be imposed in advance on the subsequent perfume shaped bodies, can be produced. The sheet-like compactate is then broken up into smaller pieces by a chopping and size-reducing process and can thus be processed to granules which can be further refined and, more particularly, converted into a substantially spherical shape by further surface treatment 5 processes known per se.
In another preferred embodiment of the present invention, the process according to the invention is carried out by pelleting. In this process, the perfume-containing, solid and substantially water-free premix is applied to a perforated surface and is forced through the perforations 10 and at the same time plasticized by a pressure roller. In conventional pellet presses, the premix is compacted under pressure, plasticized, forced through a perforated surface in the form of fine strands by means of a rotating roller and, finally, is size-reduced to granules by a cutting unit.
The pressure roller and the perforated die may assume many different forms.
15 For example, flat perforated plates are used, as are concave or convex ring dies through which the material is pressed by one or more pressure rollers.
In perforated-plate presses, the pressure rollers may also be conical in shape. In ring die presses, the dies and pressure rollers may rotate in the same direction or in opposite directions. A press suitable for carrying out 20 the process according to the invention is described, for example, in DE-OS
38 16 842 (Schliiter GmbH). The ring die press disclosed in this document consists of a rotating ring die permeated by pressure bores and at least one pressure roller operatively connected to the inner surface thereof which presses the material delivered to the die space through the pressure bores into a discharge unit. The ring die and pressure roller are designed to be driven in the same direction which reduces the shear load applied to the premix and hence the increase in temperature which it undergoes.
However, the pelleting process may of course also be carried out with heatable or coolable rollers to enable the premix to be adjusted to a required temperature.

Another press agglomeration process which may be used in accordance with the invention is tabletting. In view of the size of the shaped bodies produced, it may be appropriate in the tabletting variant to add conventional disintegration aids, for example cellulose and cellulose derivatives or crosslinked PVP, in addition to the binder described above to facilitate the disintegration of the shaped bodies in the wash liquor.
The perfume beads produced in accordance with the invention may be additionally sprayed with perfume in a subsequent step. The conventional perfuming variant, i.e. powdering and spraying with perfume, can also be carried out with the perFume beads produced in accordance with the invention.
Advantageously, at least 30% by weight, preferably at least 40% by weight and more preferably at least 50% by weight of the total perfume present in the perfume shaped bodies produced in accordance with the invention are introduced into the detergent by the production process according to the invention, i.e. incorporated in the granules or press agglomerates, while the remaining 70% by weight, preferably 60% by weight and more preferably 50% by weight of the total perfume present may be sprayed onto or otherwise applied to the granules or press agglomerates which may optionally be surface-treated.
By dividing the total perfume content of the detergents into perfume present in the granules or press agglomerates and perfume adhering to the granules or press agglomerates, it is possible to achieve a number of product features which are only possible through the process according to the invention. For example, the total perfume content of the beads can be divided into two portions x and y, portion x consisting of firmly adhering perfume oils, i.e. less volatile perfume oils, and portion y consisting of more volatile perfume oils.
Now, it is possible to produce perfume beads where the percentage of perfume introduced into the detergent through the granules or press agglomerates is mainly made up of firmly adhering perfumes. In this way, firmly adhering perfumes are "retained" in the product and thus develop their effect primarily in the washing process. By contrast, the more readily volatile perfumes contribute towards more intensive perfuming of the perfume bags and the dry laundry treated with them. The principle described above can of course also be reversed by incorporating the more readily volatile perfumes in the granules or press agglomerates and spraying the less volatile firmly adhering perfumes onto the beads. In this way, the loss of the more readily volatile perfumes in storage and in transit is minimized while the perfume characteristic of the beads is determined by the more firmly adhering perfumes.
In addition to the above-mentioned constituents of the substantially water-free premix, other ingredients may be introduced into the process according to the invention in small quantities of 1 to 10% by weight, preferably 1 to 5% by weight and more preferably 1 to 2% by weight, based on the premix. These substances may be used to color the perfume beads or to provide them with certain performance properties. However, it is also possible to add detergent ingredients of which the incorporation is normally attended by process-related disadvantages. Thus, substances normally used in small quantities, such as optical brighteners, phosphonates, dye transfer inhibitors, etc., may be added.
Specific embodiments of the invention are described in the following examples which are not to be construed as limiting.
Examples A free-flowing premix was prepared by mixing the formulation ingredients listed below in a Lodige mixer and was then compacted and plasticized in an extruder.

Table 1:
Perfume beads premix (composition in % by weight) DUP DUP DUP DUP DUP DUP

Na salt of a fatty 85.7 88.0 88.0 - -acid (80% paIm/20% coconut) C,v,8 fatty alcohol - - - - - 5.0 sulfate Zeolite A 20.0 Zeolite X - - - 10.0 - -Na silicate, modulus- - - - 10.0 -2.4 PEG 4000 4.8 - 4.0 7.0 7.0 5.0 Spray-dried granules- - - 73.0 - -Spray-dried granules- - - - 73.0 -Spray-dried granules- - - - - 60.3 Perfume oil 9.5 12.0 8.0 10.0 10.0 9.7 Composition of the spray-dried granules (surfactant compounds produced by spray drying) Spray-dried granules 1:
26.17% by weight Na C~~3 alkyl benzenesulfonate 4.00% by weight sodium carbonate 55.63% by weight zeolite 4A
0.70% by weight salts from solution 13.00% by weight water 0.50% by weight sodium hydroxide Spray-dried granules 2:
30.00% by weight Na C9_~3 alkyl benzenesulfonate 4.25% by weight sodium carbonate 53.73% by weight sodium silicate, modulus 2.4 0.85% by weight salts from solution 11.17% by weight water Spray-dried granules 3:
23.0% by weight Na C9_~3 alkyl benzenesulfonate 1.3% by weight C»~$ fatty alcohol + 5 EO
46.4% by weight zeolite 4A
8.0% by weight acrylic acidlmaleic acid copolymer, Na salt 1.6% by weight 1-hydroxyethane-1,1-diphosphonic acid (HEDP) 3.8% by weight sodium sulfate 0.5% by weight sodium hydroxide 0.5% by weight optical brightener 1.6% by weight salts from solution 13.3% by weight water After leaving the mixer, the free-flowing premix had a bulk density of about 400 gll and was introduced into a Lihotzky twin-screw extruder in which it was plasticized and extruded under pressure.
The plasticized premix left the extruder through a multiple-bore die with a bore diameter of 2.5 mm. The extruded strands were cut to a length-to-diameter ratio of about 1 by a rotating blade and rounded in a Marumerizer~. After the fine particles (< 1.6 mm) and the coarse particles (> 3.2 mm) had been removed by sieving, the extrudates had the physical properties set out in Table 2.
Table 2:
Physical properties of the perfume beads DUP DUP DUP DUP DUP DUP

Bulk density [gl']760 750 770 720 790 750 Granule diameter 2.6 2.3 2.4 2.6 2.5 2.6 [mm]

Abrasion resistance< 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 [loss % by weight]

To determine abrasion resistance, 200 g of the perfume beads were sieved for 2 minutes at an amplitude of 2 mm on an analytical sieving machine (Retsch AS 200) with a 0.8 mm mesh sieve. 100 g of the residue were then sieved for 5 minutes at an amplitude of 2 mm on the AS 200 together with 10 ceramic balls (diameter 12 mm, weight 8 g). The difference between the residue after this abrasion sieving and the 100 g used is determined as the sieving weight loss. The results in Table 2 represent the average values of double determinations.
The composition of the perfume oils used in the individual perfume beads is shown in Table 3.
Table 3:
Composition of the perfume oils [% by weight]
Perfume oil perfume 1; flowery, ozony perfume Ethylene brassylate 180 ISO E Super 135 Hedione 130 Cyclohexyl salicylate 100 Lilial gp Sihydro-[i-ionone 60 Troenan 60 Phenyl ethyl alcohol 45 Geraniol 40 Citronellol 40 Linalool 37 Helional 34 Eugenol pure 10 Canthoyal g Calone 7 Cyclovertal g Dimetol 5 Methyl anthranilate 10% in DPG 5 Decalactone Gamma 4 Phenyl acetic acid 3 Damascenonene 10% in DPG 3 Neroli Phase Oil 3 Cyclogalbanate 2 ~ Indole 1 Isoeugenol methyl ether 1 Ambroxan 1 Perfume oil fragrance 2; fresh, rosy perfume Hexyl cinnamaldehyde (Alpha) 170 Lilial 170 Ethyl linalool 152 Citronellol 106 Ethylene brassylate g0 Benzyl acetate 41 Cyclohexyl salicylate 40 Citronellyl acetate 40 Acetoacetic ester 34 Geraniol 30 Phenyl ethyl alcohol 2g Geranium oil Bourbon 20 Linalool 14 Isoraldein 70 10 Indoflor Ethyl vanillin 10% in DPG 5 Rose oxide R 10% in DPG 5 Muguet-aldehyde 100% 5 Styrolyl acetate 5 Cumin aldehyde 10% in DPG 5 Calone 10% in DPG 5 Phenyl acetal aldehyde dimenthyl acetal 5 Cyclovertal 10% in DPG 5 Petitgrain oil Paraguay Ethyl phenyl acetate 4 Hexenyl acetate 3 Hexenol (Beta Gamma) 3 Hydratropaaldehyde Dim. Acetal 2 Phenyl ethyl phenyl acetate 1 Cyclogalbanate 1 ~ Ambroxan 1 9 cm x 9 cm bags of polyester fabric were filled with 10 g of the perfume beads according to the invention.
The perfuming of treated fabrics (cotton) was evaluated by perfumists as a subjective perfume impression. To this end, the perfume bags were hung up in the airing cupboard where the dry laundry was stored or were directly placed in the pile of laundry. Comparison tests were carried out with laundry which had been perfumed while damp with a fabric softener (Vernel~, Henkel KGaA) containing the same perfume and which had also been stored in an airing cupboard after drying. The figures in the evaluation table (Table 4) represent the intensity (Int.) on a scale of 1 to 5 where 5 corresponds to a very strong perfume and 1 means that no perfume was noticeable. The individual liking was expressed on a scale of 1 to 7 where 1 was awarded for an unfavorable impression and 7 for a very strong liking. The values shown represent average values over the seven perfumists involved in the perfume evaluation process.
Table 4:
Evaluation of the perfume impression by perfumists: intensity (Int.): 1 (no perfume) - 5 (very strong perfume); liking (Ikg.): 1 (very weak) - 7 (very strong) Perfume evaluationFresh After After After davs days weeks Variant' Int.Lkg Int. Lkg. Int. Lkg. Int. Lkg.

Fabric softener 4-5 5 3-4 4 1-2 4 1 --perfume 1 DUP 6 - perfume 4-5 5 4-5 5 4-5 5 3 5 hanging in the "airing cupboard DUP 6 - perfume 5 5 5 5 5 5 3-4 5 in laundry pile Fabric softener 4-5 4 3-4 3-4 2 3-4 1 --perfume 2 DUP 6 - perfume 4-5 4 4-5 4 4 4 3-4 4 hanging in the "airing cupboard DUP 6 - perfume 5 4 5 4 4-5 4 4 4 in laundry pile The laundry perfumed while damp and the laundry perfumed when dry were comparable in regard both to intensity and to liking both when fresh and after 3 days. After only 1 week, however, the perfume intensity of the laundry perfumed while damp faded dramatically. After 6 weeks the perfume impression of the laundry perfumed with perfume bags was still intensive and was found to be pleasant whereas perfume was no longer noticeable on the laundry treated with fabric softener.
After 6 weeks in the perfume bag, DUP 6 was used for washing laundry. 30% of the heavy-duty detergent used (Spee~, Henkel KGaA) was replaced by the perfume beads. The washing results obtained in all these tests were good. Both single-cycle and multiple-cycle wash performance were comparable to tests where the heavy duty detergent was used on its own.

Claims (56)

1. Perfume bags for perfuming dry laundry containing at least 1% by weight of perfume oil and consisting essentially of detergent ingredients.

2. Perfume bags as claimed in claim 1, wherein the envelope of the bag consists of a perfume-permeable material, the pore diameter of the envelope material being smaller than 0.5 mm.

3. Perfume bags as claimed in claim 1 or 2, wherein the perfume beads have a mean particle size of more than 1.5 mm.

4. Perfume bags as claimed in claim 3, wherein the perfume beads have a mean particle size in the range of from 2 to 10 mm.

5. Perfume bags as claimed in claim 4, wherein the perfume beads have a mean particle size in the range of from 2.3 to 5 mm.

6. Perfume bags as claimed in any of claims 1 to 5, wherein the perfume beads contain 3 to 30% by weight of perfume oil.

7. Perfume bags as claimed in claim 6, wherein the perfume beads contain 5 to 20% by weight of perfume oil.

8. Perfume bags as claimed in any of claims 1 to 7, wherein the perfume beads contain one or more substances selected from the group consisting of surfactants, surfactant compounds, di- and polysaccharides, silicates, zeolites, carbonates, sulfates and citrates as carrier materials) in quantities of up to 99% by weight based on the weight of the shaped body formed.

9. Perfume bags as claimed in claim 8, wherein the perfume beads contain one or more of the carrier material(s) in quantities of 65 to 97% by weight.

10. Perfume bags as claimed in claim 9, wherein the perfume beads contain one or more of the carrier material(s) in quantities of 70 to 90% by weight.

11. Perfume bags as claimed in any of claims 1 to 10, wherein the perfume beads contain one or more anionic surfactant compounds or anionic surfactants as carrier(s) in quantities of 65 to 99% by weight based on the weight of the shaped body formed.

12. Perfume bags as claimed in claim 11, wherein the perfume beads contain one or more anionic surfactant compounds or anionic surfactants as carrier(s) in quantities of 70 to 90% by weight.

13. Perfume bags as claimed in claim 11 or 12, wherein the anionic surfactants are soaps.

14. Perfume bags as claimed in any of claims 1 to 13, wherein the perfume beads contain one or more substances selected from the group consisting of sodium salts of saturated or unsaturated C8-24 fatty acids as carrier material(s) in quantities of 65 to 99% by weight based on the weight of the shaped body formed.

15. Perfume bags as claimed in claim 14, wherein the perfume beads contain one or more substances selected from the group consisting of sodium salts of saturated or unsaturated C12-18 fatty acids as carrier material(s).

16. Perfume bags as claimed in claim 15, wherein the perfume beads contain one or more substances selected from the group consisting of sodium salts of saturated or unsaturated C16 fatty acids as carrier material(s).

17. Perfume bags as claimed in any of claims 14 to 16, wherein the perfume beads contain said carrier materials) in quantities of 70 to 90% by weight.

18. Perfume beads suitable for use in perfume bags containing at least 1% by weight of perfume oil, consisting essentially of detergent ingredients and having a mean particle size of more than 1.5 mm.

19. Perfume beads as claimed in claim 18, wherein the mean particle size is in the range of from 2 to 10 mm.

20. Perfume beads as claimed in claim 19, wherein the mean particle size is in the range of from 2.3 to 5 mm.

21. Perfume beads as claimed in claims 18 to 20, wherein the perfume beads contain 3 to 30% by weight of perfume oil.

22. Perfume beads as claimed in claim 21, wherein the perfume beads contain 5 to 20% by weight of perfume oil.

23. Perfume beads as claimed in any of claims 18 to 22, wherein the perfume beads contain one or more substances selected from the group consisting of surfactants, surfactant compounds, di- and polysaccharides, silicates, zeolites, carbonates, sulfates and citrates as carrier material(s) in quantities of up to 99% by weight based on the weight of the shaped body formed.

24. Perfume beads as claimed in claim 23, containing said carrier material(s) in quantities of 65 to 95% by weight.

25. Perfume beads as claimed in claim 24, containing said carrier material(s) in quantities of 70 to 90% by weight.

26. Perfume beads as claimed in any of claims 18 to 25, containing one or more anionic surfactant compounds or anionic surfactants as carrier(s) in quantities of 65 to 99% by weight based on the weight of the shaped body formed.

27. Perfume beads as claimed in claim 26, containing said carrier(s) in quantities of 70 to 90% by weight.

28. Perfume beads as claimed in claim 26 or 27, wherein said anionic surfactants are soaps.

29. Perfume beads as claimed in any of claims 18 to 28, containing one or more substances selected from the group consisting of sodium salts of saturated or unsaturated C8-24 fatty acids as carrier material(s) in quantities of 65 to 99% by weight based on the weight of the shaped body formed.

30. Perfume beads as claimed in claim 29, containing one or more substances selected from the group consisting of sodium salts of saturated or unsaturated C12-18 fatty acids as carrier material(s).

31. Perfume beads as claimed in claim 30, containing one or more

32 substances selected from the group consisting of sodium salts of saturated or unsaturated C16 fatty acids as carrier material(s).
32. Perfume beads as claimed in any one of claims 29 to 31, containing one or more of said carrier material(s) in quantities of 70 to 90% by weight.

33. A process for the production of perfume beads suitable for use in perfume bags, wherein a solid and substantially water-free premix of 1 to 30% by weight perfume oil, 65 to 99% by weight carriers and 0 to 10% by weight auxiliaries is subjected to granulation or press agglomeration, the granulation or press agglomeration being carried out in such a way that the resulting perfume beads have a mean particle size of more than 1.5 mm.

34. A process as claimed in claim 33, wherein the solid and substantially water-free premix is subjected to press agglomeration.

35. A process as claimed in claim 34, wherein the press agglomeration is accomplished by extrusion, roller compacting or pelleting.

36. A process as claimed in any of claims 33 to 35, wherein the premix has a total water content of not more than 15% by weight, this water not being present in free form and the content of water not bound to zeolite and/or to silicates being no more than 10% by weight.

37. A process as claimed in claim 36, wherein the content of water not bound to zeolite and/or to silicates being no more than 7% by weight.

38. A process as claimed in any of claims 33 to 37, wherein one or more substances from the group of surfactants, surfactant compounds, di- and polysaccharides, silicates, zeolites, carbonates, sulfates and citrates is/are used as carrier material(s) in quantities of up to 99% by weight based on the weight of the shaped body formed.

39. A process as claimed in claim 38, wherein said carrier material(s) are used in quantities of 65 to 95% by weight.

40. A process as claimed in claim 39, wherein said carrier material(s) are used in quantities of 70 to 90% by weight.

41. A process as claimed in any of claims 33 to 40, wherein one or more anionic surfactant compounds or anionic surfactants are present as carriers) in quantities of 65 to 99% by weight based on the weight of the shaped body formed.

42. A process as claimed in claim 41, wherein said carrier(s) are present in quantities of 70 to 90% by weight.

43. A process as claimed in any of claims 41 to 42, wherein said anionic surfactants are soaps.

44. A process as claimed in any of claims 33 to 43, wherein one or more substances from the group of sodium salts of saturated or unsaturated C8-24 fatty acids is/are used as carrier material(s) in quantities of 65 to 99% by weight based on the weight of the shaped body formed.

45. A process as claimed in claim 44, wherein one or more substances from the group of sodium salts of saturated or unsaturated C12-18 fatty acids are used as carrier material(s).

46. A process as claimed in claim 45, wherein one or more substances from the group of sodium salts of saturated or unsaturated C16 fatty acids are used as carrier material(s).

47. A process as claimed in any of claims 44 to 46, wherein said carrier material(s) are used in quantities of 70 to 90% by weight.

48. A process as claimed in any of claims 33 to 47, wherein one or more substances selected from the group consisting of polyethylene glycols, fatty alcohol alkoxylates and fatty acid alkoxylates is/are used as auxiliary(ies) in quantities of 1 to 10% by weight based on the weight of the shaped body formed.

49. A process as claimed in claim 48, wherein said auxiliaries are used in quantities of 2 to 9% by weight.

50. A process as claimed in claim 49, wherein said auxiliaries are used in quantities of 5 to 7% by weight.

51. A process as claimed in any of claims 33 to 50, wherein one or more substances from the group of polyethylene glycols with molecular weights of 2 to 15 kgmol-1 is/are used as auxiliaries in quantities of 0 to 10% by weight based on the weight of the shaped body formed.

52. A process as claimed in claim 51, wherein one or more substances from the group of polyethylene glycols with molecular weights of 4 to 10 kgmol-1 is/are used as auxiliaries.

53. A process as claimed in claims 51 or 52, wherein said auxiliaries are used in quantities of 2 to 9% by weight.

54. A process as claimed in any of claims 51 to 53, wherein said auxiliaries are used in quantities of 5 to 7% by weight.

55. The use of perfume beads in perfume bags for perfuming dry laundry.

56. The use of perfume beads as claimed in claim 55, wherein the perfume beads have a diameter of more than 2.3 mm and contain more than 5% by weight of perfume oil.