WO2000063485A1 - Perfumed sachet - Google Patents

Abstract

The invention relates to perfumed pearls that contain at least 1 wt.- % perfumed oil and that otherwise essentially comprise the ingredients of detergents. These perfumed pearls are especially suitable for use in perfumed sachets, for perfuming dry laundry. Pearls that have a diameter of greater than 2.3 mm are especially suitable. The inventive pearls are characterized in that they can be used as detergents once their perfume effects have worn off.

Description

 "Scented sachet"

The subject of the present application are sachets of fragrance which are suitable for scenting dry laundry.

The scenting of laundry is a topic that has been studied for a long time. The laundry is usually scented during the washing process or in the tumble dryer by the detergents or corresponding aids or special fragrance additives. Even if this scenting is carried out with special additives, which are intended to ensure a permanent, adhering scent to the laundry, this scent will continuously decrease during storage of the dry laundry. As a rule, scent is barely noticeable a week after washing. There is therefore a need for scenting the dry laundry, which maintains the impression of freshly washed laundry even when stored for a long time.

It is obvious to use a device for this purpose, which, for example, emits fragrance in the wardrobe to the stored laundry. For this purpose, fabric bags are often used, which are filled with dried plant parts, for example lavender stems, which release fragrances. Such sachets are also commercially available. However, commercially available bags usually do not contain any parts of the plant, but fragrances that have been applied to suitable carriers.

German Offenlegungsschrift DT 2622707, for example, describes a fragrance bag which contains a fleece carrier impregnated with a fragrance emulsion. Also in DT 26 03 823, the fragrances are applied to an absorbent carrier, which can consist, for example, of textile materials, paper, felt or foam. This carrier is wrapped in a plastic film, which forms a fragrance cushion. These scented pillows are particularly suitable for scenting laundry in the dryer, but for example also for scenting rooms when the pillows are placed on a heater. It is essential here that the pillows are heated, since only then does the film allow enough fragrance to pass through.

Such fragrance preparations are only suitable for scenting the environment and must be disposed of as waste as soon as the fragrance release subsides.

It has now been found that it is possible to use fragrance preparations which contain detergent ingredients to scent dry laundry. These preparations can then be used to wash textiles after the release of the fragrance. As a result, there is almost no waste when using such fragrance bags.

Accordingly, a first subject of the invention are fragrance bags for scenting dry laundry, which are characterized in that they contain fragrance pearls which contain at least 1% by weight of perfume oil and consist essentially of detergent ingredients.

A second object of the invention are fragrance pearls which are suitable for use in fragrance bags and are characterized in that they contain at least 1% by weight of perfume oil, consist essentially of detergent ingredients and have an average particle size of more than 1.5 mm.

These objects of the invention are explained in more detail below:

The envelope of the fragrance sachet, i.e. the actual sachet, consists of a fragrance-permeable material, the pore diameter of the envelope material being less than 0.5 mm. The wrapping material can be woven or non-woven material. So, for example, a fabric made of natural or synthetic fibers, for example made of cellulose, wool, silk, linen, jute, sisal, polyamide, polyester, polyacrylonitrile, polyvinyl derivatives, polyolefins or rayon, or mixed fabrics made from these fibers. Foams made of viscose or synthetic polymers, in particular polyurethanes, are also suitable. Furthermore, the wrapping material can also be flexible foils that have slits or pores. Suitable film materials are, for example, polyolefins, in particular polyethylene and polypropylene, polyesters, polyamides and cellulose esters. Such films can be transparent or opaque, in particular printed in color. Preferred scented sachets have a device which makes it possible to attach the sachets in a simple manner to a hanging device, such as a hook, a screw or a nail, but in particular also to a clothes hanger or the clothes rail. Regardless of the type of wrapping material used, it is essential that the wrapping material has pores in order to ensure fragrance permeability. However, these pores are generally smaller than 0.5 mm, preferably even smaller than 0.3 mm, since larger pores could also cause the fragrance pearls to fall out under mechanical stress.

The scented pearls themselves have an average particle size of more than 1.5 mm, the particle size preferably being in the range 2 to 10 mm, particularly preferably in the range 2.3 to 5 mm. On the one hand, the upper limit of the particle size is limited, since with increasing particle size the surface over which the fragrance is emitted becomes proportionately smaller. On the other hand, the scented pearls should also dissolve sufficiently quickly when used as a detergent. The lower limit results on the one hand from the need to have particles that are significantly larger than the pore openings of the wrapping material and on the other hand from the sensitive impression that the consumer receives when touching the scented sachets.

The shape of the fragrance pearls is also essential for the sensitive impression. In a preferred embodiment, as the name suggests, these beads are spherical. However, the "pearls" in the sense of the present invention are not limited to the spherical shape, rather they can have any shape. The possible forms depend only on the manufacturing process of the "fragrance pearls", whereby especially the extrusion allows a wide variety of shapes. If complex shapes such as stars or figures are realized, it may be preferable to use these "pearls" in transparent fragrance bags. In such transparent fragrance bags it is further preferred if the fragrance pearls are colored.

So that the pearls can be handled in the fragrance bags, it is essential that they are dust-free and largely resistant to abrasion. For this reason too, it is preferred if the beads have an approximately spherical shape. To test the abrasion behavior, a sample of the fragrance pearls is sieved on a sieve of suitable mesh size, the residue is weighed and then sieved on an analytical sieve together with metal balls for 5 minutes. In preferred embodiments of the beads according to the invention, the abrasion is less than 2% by weight. If the beads are approximately spherical, the abrasion is preferably even less than 1% by weight, in particular even less than 0.5% by weight. The desired fragrance impression of the pearls can last a few days or even several months. It is preferred according to the invention if the scent impression of the sachets filled with scented pearls remains approximately constant for at least one month, preferably even 6 weeks. The duration over which the scent impression remains perceptible depends on the one hand on the manufacturing process of the fragrance pearls and on the other hand on the perfume oils used.

The fragrance pearls contain at least 1% by weight of perfume oil. Preferred fragrance pearls contain 3 to 30% by weight of perfume oil, with fragrance pearls containing 5 to 20% by weight of perfume oil being particularly preferred. Individual fragrance compounds, for example the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type, can be used as perfume oils or fragrances. Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbyl acetate (DMBCA), phenylethyl acetate, benzyl acetate, ethylmethylphenylglycinate, allylcyclohexylpropylate, methyllateylalylateylamylylpylate, methyllateylamylylpylate, methyllateylamylateylamylylpylate, methylallylate, methyllateylamylatepylate, stylamylatepylate, methylalylatepylate, stylamylateylateylamylylpylate, methylalylateylate, methylateylateolate, styl melate, The ethers include, for example, benzylethyl ether and ambroxan, the aldehydes, for example, the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, lilial and bourgeonal, the ketones, for example, the jonones, oc-isomethylionone and methyl -cedryl ketone, to the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons mainly include terpenes such as 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.

In order to be perceivable, a fragrance must be volatile, whereby in addition to the nature of the functional groups and the structure of the chemical compound, the molar mass also plays an important role. 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, the odor impressions being described in "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 top note of a perfume or fragrance does not consist solely of volatile compounds, while the base note largely consists of less volatile In the composition of perfumes, more volatile fragrances can be bound, for example, to certain fixatives, which prevents them from evaporating too quickly.The embodiment of the present invention described above, in which the more volatile fragrances or fragrances are incorporated into the press agglomerate be incorporated is such a method for fragrance fixation. 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.

Adhesive odoriferous substances which can be used in the context of the present invention are, for example, the essential oils such as angelica root oil, anise oil, arnica flower oil, basil oil, bay oil, bergamot oil, champagne flower oil, noble fir oil, noble pine cone oil, Elemi oil, eucalyptus oil, fennel oil, pine spruce 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, cardamom oil, cardamom oil, cardamom oil, cardamom oil, cardamom oil , Caraway oil, cumin oil, lavender oil, lemongrass oil, lime oil, mandarin oil, lemon balm oil, musk seed oil, myrrh oil, clove oil, neroliol, niaouli oil, olibanum oil, orange oil, origanum oil, palmarosa oil, patchouli oil, Peru oil, pepper oil, pepper oil, pine oil, petitgrain oil, petitgrain oil , Rosemary oil, sandalwood oil, celery oil, spik oil, star anise oil, turpentine oil, thuja oil, thyme oil, verbena oil, vetiver oil, juniper berry oil, wormwood oil, wintergreen oil, ylang-ylang oil, hyssop oil, cinnamon oil, cinnamon leaf oil, lemon oil and lemon oil, lemon oil, lemon oil and lemon oil, lemon oil, lemon oil and lemon 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 .alpha.-amylcinnamaldehyde, anethole, anisaldehyde, anise alcohol, anisole, anthranilic acid methyl ester, acetophenone, benzylacetone, benzaldehyde, benzoic acid ethyl ester, benzophenone, benzyl alcohol, benzyl acetate, benzyl benzyl benzate, benzyl formate benzyl benzyl benzate, benzyl formate benzyl benzyl benzyl benzyl benzyl benzyl benzyl benzyl benzyl benzyl benzyl benzyl benzyl benzyl benzyl benzyl benzyl benzyl benzyl benzyl benzyl benzyl benzyl benzyl benzyl benzyl benzyl benzyl benzate , Bornyl acetate, α-bromostyrene, n-decylaldehyde, n-dodecylaldehyde, eugenol, eugenol methyl ether, eucalyptol, farnesol, fenchone, fenchylacetate, geranyl acetate, geranyl formate, heliotropine, heptincarboxylic acid methyl ester, heptaldehyde, hydroquinone dimethyl ether dimethyl ether, hydroquinone dimethyl ether, hydroquinone dimethyl ether, , Isoeugenolmethylether, Isosafrol, Jasmon, Kampfer, Karvakrol, Karvon, p- Cresolmethylether, Coumarin, p-Methoxyacetophenon, Methyl-n-amylketone, Methylanthranilsäuremethylester, p-Methylacetophenon, Methylchavikol, p-Methylquinon, Methyl-methyl-naphtholinol, Methyl-n-Methyl-methyl-naphthol -nonylacetaldehyde, methyl-n-nonylketone, muskon, -Naphtholethylether, ß-Naphtholmethylether, Nerol, Nitrobenzol, n- Nonylaldehyde, Nonylaohol, n-Octylaldehyd, p-Oxy-Acetophenon, Pentadekanolid, ß- Phenylethylakohol, Phenylacetaldehyd-Dimethyacetal, Phenylessigsäure acid, Salicylyl acidic acid, Salicylyl acidic acid, Salicylyl acidic acid, Salicylyl acidic acid, Puliconyl acidic acid, Puliconyl acidic acid, Puliconyl acidic acid, Salicyl acidic acid, Salicylyl acidic acid, Puliconyl acid acid, , Santalol, Skatol, Terpineol, 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 alkyisothiocyanates (alkyl mustards), butanedione, limonene, linalool, linaylacetate and propionate, menthol, menthone, methyl-n-heptenone, phellandrene, phenylacetaldehyde, terpinylacetate, citral, citronellal.

In addition to the fragrance substances, the fragrance pearls contain typical detergent ingredients as essential components. These detergent ingredients have the essential funion to ensure the function of the fragrance pearls as the detergent diminishes as they act and act in the washing process. In addition, these substances are also essential as carrier substances for the perfume oils.

Preferred carriers are selected from the group of surfactants, surfactant compounds, di- and polysaccharides and builder substances and are used in amounts of up to 99% by weight, preferably between 65 and 97% by weight, in particular from 70 to 90% by weight. each based on the weight of the molded body used.

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 in the process according to the invention, but other than the abovementioned carriers can also be present as carriers in the surfactant compounds.

In preferred embodiments, one or more anionic surfactant compounds or anionic surfactants, in particular soaps, are used as carrier materials in amounts of 65 to 99% by weight, preferably 70 to 90% by weight, in each case based on the weight of the shaped body formed. 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 carriers with active substance contents of, for example, 50-70, 80 or 90% by weight as well as 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 anio-surfactant carriers, 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 salts of fatty acids are used as soaps in the carrier materials for the moldings 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: caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, octadecan-12-ol-acid, arachic acid, behenic acid, lignoceric acid, cerotic acid, meissic 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 acid. 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.

In particularly preferred fragrance pearls, one or more substances from the group of the sodium salts of saturated or unsaturated C 1 -C 8 -fatty acids, preferably of saturated or unsaturated C _12, are used as the carrier substance (s). ₁₈ fatty acids and in particular saturated or unsaturated Ci6 fatty acids, in amounts of 65 to 99 wt .-%, preferably from 70 to 90 wt .-%, each based on the weight of the resulting molded body.

Other suitable carriers are, for example, di- and poiysaccharides, 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 the strengths are 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 and bound water-containing zeolite used is preferably zeolite A, X and / or P. As zeolite P, for example, zeolite MAP ^(R) (commercial product from Crosfield) is used. However, zeolite Y and mixtures of A, X, Y and / or P are Such a mixture of zeolite A and zeolite X is, for example, under the designation AX VEGOBOND ^® (Messrs. Condea Augusta SpA) commercially. 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, this small addition of nonionic surfactants as Stabilizers contain, for example 1 to 3% by weight, based on zeolite, of ethoxylated Ci2-C-i8 fatty alcohols with 2 to 5 ethylene oxide groups, C - ^ - C- 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.

Suitable carriers are also layered sodium silicates of the general formula NaMSi _x Ö ₂ χ ₊ 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 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 disilicates Na ₂ Si ₂ O ₅ y l-feO are preferred.

The preferred builder substances also include amorphous sodium silicates with a modulus Na ₂ O: SiO ₂ from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2, 6, which are delayed release and have secondary washing properties. The dissolution delay compared to conventional amorphous sodium silicates can be done in various ways, for example by surface treatment, compounding,

Compacting / compaction or caused by overdrying. In the context of this invention, the term “amorphous” is also understood to mean “X-ray amorphous”. 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 interpreted as meaning 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 amorphous 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. Compressed / compacted are particularly preferred amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates.

Suitable carrier materials are furthermore sheet silicates of natural and synthetic origin. Layered silicates of this type are known, for example, from patent applications DE-B-23 34 899, EP-A-0 026 529 and DE-A-35 26 405. 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, hectorite or saponite. In addition, small amounts of iron can be incorporated into the crystal lattice of the layered silicates according to the above formulas. Furthermore, due to their ion-exchanging properties, the layered silicates can 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. Useful sheet silicates are known, for example, from US-A-3,966,629, EP-A-0 026 529 and EP-A-0 028 432. Layered silicates are preferably used which are largely free of calcium ions and strongly coloring iron ions due to an alkali treatment.

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. These acids are preferably used in the fragrance pearls without water.

If the fragrance pearls are used for washing, the fragrance pearls can be used alone as a detergent. However, it is preferred if the scented pearls replace only part of the detergent used. In particular, it is preferred if up to 50% by weight of the detergent used is formed by the fragrance beads, it being particularly preferred if 10 to 30% by weight of the detergent is replaced by fragrance beads.

Another object of the invention is a process for the production of fragrance pearls, which are suitable for use in fragrance bags, which is characterized in that a solid and essentially water-free premix of 1 to 30 wt .-% perfume oil, 65 to 99 wt .-% % Of carriers and 0 to 10% by weight of auxiliaries are subjected to granulation or press agglomeration, the granulation or press agglomeration being carried out in such a way that the resulting fragrance beads have an average particle size of more than 1.5 mm.

It can largely work according to the disclosure of the older German patent application DE 19746780.6. Essential in the

Process control, however, is that the process according to the present invention is carried out such that the resulting fragrance pearls have an average particle size of more than 1.5 mm, preferably in the range from 2 to 10 mm and particularly preferably in the range from 2.3 to 5 mm.

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 chemically and / or physically bound form or as a component of the raw materials or compounds present as a solid, but not as a liquid, solution or dispersion in 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 essentially water-free premix is subjected to granulation or press agglomeration after the individual components have been combined. During the granulation, the premix is compressed and homogenized by the rotating mixing tools and granulated into a fragrance form, in particular fragrance pearls. The granulation of the essentially water-free premix provides fragrance pearls with a broader range of particles (coarse and fine fractions), which is why the process variant of press agglomeration is preferred to 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.

The carriers have the task of absorbing the mostly liquid components of the perfume without the particles sticking together. Only through the action of the mixing tools during the granulation or higher shear forces during the pessagglomeration is a homogeneous plasticized mixture obtained, possibly with the addition of auxiliary material (s), in which the perfume is finely distributed in the Carrier is incorporated. This procedure has clear advantages over the conventional application of perfume to porous carriers, as will be described in more detail later. The carriers to be used in the process have already been described above.

In the process, one or more substances from the group of the surfactants, surfactant compounds, di- and polysaccharides, silicates, zeolites, carbonates, sulfates and citrates are preferably used in the process in amounts of up to 99% by weight, preferably from 65 to 97% by weight, in particular from 70 to 90% by weight, in each case based on the weight of the shaped body formed. In particular, it is preferred if one or more anionic surfactant compounds or anionic surfactants, in particular soaps, are used as the carrier (s) in amounts of 65 to 99% by weight, preferably 70 to 90% by weight, in each case based on the weight of the molded body formed , are used. In a likewise preferred process, one or more substances from the group of the sodium salts of saturated or unsaturated C ₈ are used as the carrier (s). ₂₄ fatty acids, preferably of saturated or unsaturated C ₂ . ₁₈ fatty acids, and in particular saturated or unsaturated C ₁₆ fatty acids, in amounts of 65 to 99% by weight, preferably 70 to 90% by weight, in each case based on the weight of the molding formed.

If appropriate, the premix can contain auxiliaries which improve the cohesion of the carrier particles which have been mixed with the perfume and, under the process conditions of granulation or press agglomeration, enclose the solid particles in such a way by the auxiliaries and then bond them to one another in such a way that the finished products are almost exactly from them Many small individual particles are built up, which are held together by the auxiliary substances, which take on the function of a preferably thin partition between these individual particles.

On the one hand, these auxiliaries facilitate the plasticization of the premix under the process conditions of granulation or press agglomeration, on the other hand they develop disintegration-promoting properties when the fragrance pearls dissolve, without glue the moldings together during transport, use in the fragrance sachets for scenting dry laundry or storage.

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 shaped body formed, can be used.

The optional fatty acid alkoxylates can be generalized

Describe Formula I:

R ¹ -COO- (CH ₂ -CH-O) _k -H (I),

in which R ^{1 is} selected from C ₇ . ₁ -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

in which R ^{3 is} selected from C ₈ -ι ₈ alkyl or alkenyl, R ⁴ = -H or -CH ₃ and I = 2 to 10. In both cases, the corresponding auxiliaries can be obtained by ethoxylation or propoxylation of fatty acids or Easily produce 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 IM:

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 gmol ^" . The products with molecular weights below 25,000 gmol ^{* 1} are referred to as the actual polyethylene glycols, while higher molecular weight products are often referred to in the literature as polyethylene oxides (in short: PEOX). The polyethylene glycols 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% by weight, based on the total amount of the polyethylene glycols, have polyethylene glycols with a relative 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 relative molecular mass of 200, 400 and 600.

In the context of the present invention, a method is preferred in which one or more substances from the group of polyethylene glycols with molecular weights between 2 and 15 kgmol ^"1 , preferably between 4 and 10 k gmol ^{" 1} , in amounts of 0 to 10 wt .-%, preferably from 2 to 9 wt .-% and in particular from 5 to 7 wt .-%, each based on the weight of the resulting molded body, are used.

The essentially water-free premix is subjected to granulation or press agglomeration after the individual components have been combined. During the granulation, the premix is compressed and homogenized by the rotating mixing tools and granulated into fragrance pearls, in particular fragrance pearls. The granulation of the essentially water-free premix provides fragrance pearls with a broader range of particles (coarse and fine fractions), which is why the process variant of press agglomeration is preferred to 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 extruder or a 2-screw extruder or 2-screw extruder with co-rotating or counter-rotating screw guide, 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, plasticized, extruded in the form of fine strands through the perforated die plate in the extruder head and finally, under pressure, which is preferably at least 25 bar, but can also be lower at extremely high throughputs depending on the apparatus used the extrudate is preferably reduced to approximately spherical to cylindrical granules by means of a rotating 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 chopped-off primary granules is in the 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. It is important to ensure that at this stage only small amounts of fine grain are created. 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, unbound 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.

Because the method of the invention is essentially anhydrous - i.e. with the exception of water contents ("impurities") of the solid raw materials used, water-free, an ecologically valuable process is provided, since the omission of a subsequent drying step not only saves energy, but also emissions, which occur predominantly with conventional types of drying, In addition, the fact that subsequent drying steps are dispensed with enables the fragrances to be incorporated into the premix and thus the fragrance pearls 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 recesses of a defined shape and rolled out under pressure between the two rollers to form a sheet-like 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, smooth, unstructured sliver belts are obtained, while by using structured rollers, correspondingly structured slugs can be produced in which, for example certain forms of the later fragrance pearls can be specified. The sliver belt is subsequently broken into smaller pieces by a knocking-off and crushing 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 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 German laid-open specification DE 38 16 842 (Schlüter GmbH). The ring die press disclosed in this document consists of a rotating ring die penetrated by 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, ring die and press roller can be driven in the same direction, which results in a reduced shear stress and thus a lower temperature increase in the

Premix is feasible. 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 articles produced, it may be useful for tableting to add customary disintegration aids, for example cellulose and its derivatives or crosslinked PVP, in addition to the binder, which facilitate the disintegration of the compacts in the wash liquor.

The fragrance beads produced according to the invention can additionally be sprayed with perfume afterwards. The conventional fragrance variant, i.e. powdering and spraying with perfume can be carried out on the scented pearls according to the invention.

In the case of the scented pearls produced according to the invention, 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 shaped body is advantageously introduced into the compositions via the production process according to the invention, 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 adheres to the granules or press agglomerates, a variety of product characteristics can be realized, which are only possible by the inventive method. For example, it is conceivable and possible to divide the total perfume content of the pearls 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. Fragrance pearls can now be produced in which the proportion of the perfume which is introduced into the compositions via the granules or press agglomerates is composed mainly of adhesive fragrances. In this way, sticky fragrances can be "held" in the product and thus have their effect mainly in the washing process. In contrast, the more volatile fragrances contribute to a more intensive fragrance of the sachets and the dry laundry treated with them. Of course, the principle described above can also be reversed by incorporating the more volatile fragrances into the granules or press agglomerates and spraying the less volatile, adherent fragrances onto the beads, thus minimizing the loss of the more volatile fragrances during storage and transport, while reducing the fragrance characteristics of the beads from the more adhesive perfumes is determined.

In addition to the above-mentioned constituents of the essentially water-free premix, further ingredients can be obtained in minor amounts from 1 to 10% by weight, preferably 1 to 5% by weight and in particular 1 to 2% by weight, in each case on the premix. 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. For example, substances such as optical brighteners, phosphonates, color transfer inhibitors, etc. can be added.

Examples

A free-flowing premix was produced by mixing the formulation constituents mentioned below in a Lödige mixer, which was compressed and plasticized in an extruder.

Table 1: Fragrance pearl premix (composition in% by weight)

Composition of the spray granules (surfactant compounds produced by spray drying)

Spray granules 1: 26.17% by weight Na-Cg- _13- alkylbenzenesulfonate 4.00% by weight sodium carbonate 55.63% by weight zeolite A 0.70% by weight salts from solution 13.00% by weight % Water 0.50% by weight sodium hydroxide

Spray granules 2: 30.00% by weight Na-C ₉ . _13- Alkylbenzenesulfonate 4.25% by weight sodium carbonate 53.73% by weight sodium silicate, module 2.4 0.85% by weight salts from solution 11, 17% by weight water

Spray granules 3: 23.0% by weight of Na-C ₉ -i ₃ -alkylbenzenesulfonate

1, 3 wt .-% Cι ₆ .ιs fatty alcohol + 5 EO

46.4% by weight of zeolite A

8.0% by weight acrylic acid-maleic 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 of optical brighteners

1.6% by weight salts from solution

13.3 wt% water

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

The plasticized premix left the extruder through a perforated plate with outlet bores of 2.5 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 (<1.6 mm) and the coarse parts (> 3.2 mm) had been sieved, the extrudates had the physical properties listed in Table 2.

Table 2: Physical properties of the fragrance pearls

Zur Bestimmung der Abriebfestigkeit wurden 200 g der Duftperlen 2 Minuten bei einer Amplitute von 2 mm auf einer analytischen Siebmaschine (AS 200; Fa. Retsch) mit einem Sieb, das 0,8 mm Maschenweite besaß, gesiebt. 100 g des Rückstands wurden anschließend zusammen mit 10 Keramikkugeln (Durchmesser 12 mm; Gewicht 8 g) 5 Minuten bei einer Amplitute von 2 mm auf der AS 200 gesiebt. Als Gewichtsverlust beim Sieben, wird die Differenz des Rückstandes nach diesem Abrasionssieben zu den eingesetzten 100 g bestimmt. Die Ergebnisse in Tablle 2 sind dabei Mittelwerte, die sich aus Doppelbestimmungen ergeben.

To determine the abrasion resistance, 200 g of the fragrance pearls were sieved for 2 minutes at an amplitude of 2 mm on an analytical sieving machine (AS 200; Retsch) with a sieve which had a mesh width of 0.8 mm. 100 g of the residue were then sieved together with 10 ceramic balls (diameter 12 mm; weight 8 g) for 5 minutes at an amplitude of 2 mm on the AS 200. As a weight loss during sieving, the difference between the residue after this abrasion sieving and the 100 g used is determined. The results in Table 2 are mean values that result from duplicate determinations.

The composition of the perfume oils used in the individual fragrance pearls is given in Table 3.

Table 3: Composition of the perfume oils [% by weight]:

In each case, 10 g of the fragrance beads according to the invention were filled into bags (9 cm × 9 cm) made of polyester fabric.

The fragrance of treated textiles (cotton) was assessed as a subjective smell impression by perfumers. For this purpose, the scented sachets were hung in the wardrobe in which the dry laundry was kept, or placed directly in the laundry pile. Comparative tests were carried out to wash, with a fabric softener (Vernel ^®;. Henkel) containing the same fragrance, moist scented was and was also stored in the closet after drying. The numerical values in the evaluation table (Table 4) indicate the intensity (int.) On a scale of 1-5, 5 corresponding to a very strong fragrance and 1 meaning that no fragrance was perceptible. The individual favor was expressed on a scale from 1 to 7, whereby 1 was given for an unpleasant impression and 7 for very good favor. The values given are mean values for the seven perfumers who were involved in the fragrance assessment.

Table 4: Evaluation of the fragrance impression by perfumers: Intensity (lnt.): 1 (no fragrance) - 5 (very strong fragrance); Liked: 1 (very bad) - 7 (very good)

Fresh and after 3 days, the moist-scented laundry and the dry-scented laundry performed comparably in terms of both intensity and pleasure. After just one week, however, the intensity of the fragrance in the moist-scented laundry decreased significantly. After 6 weeks, the fragrance impression of the laundry scented with scented sachets was still intense and was felt to be pleasant, while no scent was perceptible on the laundry treated with fabric softener. After 6 weeks in the sachet, DUP 6 was used to wash textiles. Here, 30 wt .-% was the universal detergent used (Spee ^®;. Henkel) is replaced by the perfume beads. The wash results in these experiments were consistently good. Both the primary and secondary washing behavior were comparable to tests in which the universal detergent was used alone.

Claims

Patent claims 1. Scented sachets, for scenting dry laundry, characterized in that the sachets contain fragrance pearls which contain at least 1% by weight of perfume oil and consist essentially of detergent ingredients. 2. Fragrance sachet according to claim 1, characterized in that the envelope of the sachet consists of a fragrance-permeable material, the pore diameter of the envelope material being less than 0.5 mm. 3. Fragrance sachet according to one of claims 1 or 2, characterized in that the scented pearls have an average particle size of more than 1.5 mm, the particle size preferably in the range from 2 to 10 mm, particularly preferably in the range from 2.3 to 5 mm. 4. fragrance sachet according to one of claims 1 to 3, characterized in that the fragrance pearls contain 3 to 30 wt .-%, preferably 5 to 20 wt .-% perfume oil. 5. fragrance sachet according to one of claims 1 to 4, characterized in that the fragrance beads as carrier (s) one or more substances from the group of surfactants, surfactant compounds, di- and polysaccharides, silicates, zeolites, carbonates, sulfates and citrates in quantities up to 99% by weight, preferably from 65 to 97% by weight, in particular from 70 to 90% by weight, in each case based on the weight of the shaped body formed. 6. fragrance sachet according to one of claims 1 to 5, characterized in that the scented pearls as carrier (s) one or more anionic surfactant compounds or anionic surfactants, especially soaps, in amounts of 65 to 99 wt .-%, preferably from 70 to 90 wt. -%, each based on the weight of the resulting molded article. 7. fragrance sachet according to one of claims 1 to 6, characterized in that the fragrance beads as carrier (s) one or more substances from the group of Sodium salts of saturated or unsaturated C ₈ . ₂ fatty acids, preferably of saturated or unsaturated C ₂ . ₁₈ fatty acids and in particular saturated or unsaturated C ₁₆ fatty acids, in amounts of 65 to 99 wt .-%, preferably from 70 to 90 wt .-%, each based on the weight of the molded article. 8. fragrance pearls which are suitable for use in fragrance bags, characterized in that they contain at least 1% by weight of perfume oil, consist essentially of detergent ingredients and have an average particle size of more than 1.5 mm. 9. fragrance pearls according to claim 8, characterized in that the average particle size is in the range 2 to 10 mm, preferably in the range 2.3 to 5 mm. 10. fragrance pearls according to one of claims 8 or 9, characterized in that the fragrance pearls contain 3 to 30 wt .-%, preferably 5 to 20 wt .-% perfume oil. 11. fragrance beads according to one of claims 8 to 10, characterized in that the fragrance beads as carrier (s) one or more substances from the group of surfactants, surfactant compounds, di- and polysaccharides, silicates, zeolites, carbonates, sulfates and citrates in quantities up to 99% by weight, preferably from 65 to 95% by weight, in particular from 70 to 90% by weight, in each case based on the weight of the molding formed. 12. Fragrance beads according to one of claims 8 to 11, characterized in that the fragrance beads as carrier (s) one or more anionic surfactant compounds or anionic surfactants, in particular soaps, in amounts of 65 to 99 wt .-%, preferably from 70 to 90 wt. -%, each based on the weight of the resulting molded article. 13. scented pearls according to one of claims 8 to 12, characterized in that the scented pearls as carrier (s) one or more substances from the group of sodium salts of saturated or unsaturated C _{8th 24} fatty acids, preferably of saturated or unsaturated C ₁₂ . ₁₈ fatty acids and especially saturated or unsaturated C ₆ fatty acids, in amounts of 65 to 99 wt .-%, preferably from 70 to 90 wt .-%, each based on the weight of the resulting molded body. 14. A process for the production of fragrance pearls which are suitable for use in scented sachets, characterized in that a solid and essentially water-free premix of 1 to 30% by weight of perfume oil, 65 to 99% by weight of carriers and 0 to 10% by weight .-% auxiliaries are subjected to granulation or press agglomeration, the granulation or press agglomeration being carried out in such a way that the resulting fragrance beads have an average particle size of more than 1.5 mm. 15. The method according to claim 14, characterized in that the solid and substantially water-free premix is subjected to a press agglomeration, preferably an extrusion, a roller compacting or a pelletizing. 16. The method according to any one of claims 14 or 15, 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. 17. The method according to any one of claims 14 to 16, characterized in that the carrier (s) one or more substances from the group of surfactants, surfactant compounds, di- and polysaccharides, silicates, zeolites, carbonates, sulfates and citrates in amounts up to 99% by weight, preferably from 65 to 95% by weight, in particular from 70 to 90% by weight, in each case based on the weight of the shaped body formed. 18. The method according to any one of claims 14 to 17, characterized in that one or more anionic surfactant compounds or anionic surfactants, in particular soaps, in amounts of 65 to 99 wt .-%, preferably from 70 to 90 wt .-% as the carrier (s) , in each case based on the weight of the molded body that is used. 19. A method according to any one of claims 14 to 18, characterized in that as a carrier (e) one or more substances from the group of the sodium salts of saturated or unsaturated C _8-24 fatty acids, preferably -ι of saturated or unsaturated C _{12 8} Fatty acids and in particular saturated or unsaturated C ₁₆ fatty acids, in amounts of 65 to 99% by weight, preferably 70 to 90% by weight, in each case based on the weight of the molded body formed. 20. The method according to any one of claims 14 to 19, characterized in that as auxiliary (s) one or more substances from the group of polyethylene glycols, fatty alcohol alkoxylates and fatty acid alkoxylates in amounts of 1 to 10 wt .-%, 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 article formed. 21. The method according to any one of claims 14 to 20, characterized in that as auxiliary (s) 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 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 shaped body formed. 22. Use of scented pearls in scented sachets for scenting dry laundry. 23. Use of fragrance pearls according to claim 22, wherein the fragrance pearls have a diameter greater than 2.3 mm and contain more than 5% by weight of perfume oil.