WO2001016280A2

WO2001016280A2 - Method for producing scented beads

Info

Publication number: WO2001016280A2
Application number: PCT/EP2000/008173
Authority: WO
Inventors: Kathleen Paatz; Wolfgang Lahn
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 1999-08-31
Filing date: 2000-08-22
Publication date: 2001-03-08
Also published as: WO2001016280A3; CA2317168A1; DE19941263A1; AU7411600A

Abstract

The invention relates to a method for producing scented shaped bodies, in particular, scented pearls with bulk densities greater than 700 g/l. According to said method, a solid and substantially anhydrous premix consisting of a) 65 to 94.5 wt. % carrier agent(s), b) 0 to 10 wt. % auxiliary agent(s) and c) 5 to 25 wt. % perfume is subjected to granulation or compacted agglomeration. The method is characterised in that the premix contains 0.5-20 wt. % of a substance which improves the absorption of the scent onto surfaces. The invention also relates to detergents and cleansing agents which contain the shaped bodies produced by said method and to a method for adding scent to textiles in a washing machine.

Description

"Process for the production of fragrance pearls"

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

In textile washing, treatment and post-treatment, it is common today to add small amounts of perfume to the detergents and post-treatment agents, which serve to give the washing or rinsing solution itself, but also the textile goods treated with the washing or rinsing solution, a pleasant fragrance to lend. In addition to color and appearance, the fragrance of detergents, cleaning agents and post-treatment agents is also an important aspect of the aesthetic product impression and an important point in the consumer decision for or against a specific product. For scenting, the perfume can either be incorporated directly into the agents or added to the washing or rinsing solution in an additional step. The first way specifies a certain product characteristic, while the second way, the consumer can individually decide on "his" fragrance from the different fragrance options on offer, comparable to choosing an eau de toilette or an aftershave. Accordingly, fragrance moldings and processes for scenting washing and rinsing liquors are widely described in the prior art. For example, DE 41 33 862 (Henkel) discloses tablets which contain carrier materials, fragrances and, if appropriate, further ingredients customary in detergents and cleaning agents, sorbitol and additionally 20 to 70% by weight of a carbonate and acid bubbling system being used as carrier material , These tablets, which can be added, for example, to the rinsing and fabric softening cycle in a household washing machine, contain about 3 to 15, preferably 5 to 10,% by weight of fragrance. Due to the high disintegrant content of the tablets, they are sensitive to air humidity and must be stored appropriately protected.

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

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

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

The older German patent application 197 35 783.0 (Henkel) describes high-dose fragrance moldings which contain carrier material (s), 20 to 50% by weight of fragrance (s) and, if appropriate, further active ingredients and auxiliaries customary in washing and cleaning agents, the Moldings after deduction of the amount of fragrance consist of at least 50% by weight of their weight of fatty acids and fatty acid salts. These perfume moldings are suitable for scenting detergents and cleaning agents as well as for scenting textiles in a washing machine.

A method for applying fragrances to textile goods in a washing machine is described in DE 195 30 999 (Henkel). In this process, a fragrance-containing molded body, which is produced by irradiation with microwaves, is used in the rinse cycle of a washing machine. According to the teaching of this document, the production of the preferably spherical shaped bodies with diameters above 3 mm and bulk weights of up to 1100 g / 1 is achieved by filling a mixture of predominantly water-soluble carriers, hydrated substances, optional surfactants and perfume into suitable shapes and with With the help of microwave radiation sinters. The fragrance contents of the shaped bodies are between 8 and 40% by weight, starches, silicas, silicates and disilicates, phosphates, zeolites, alkali salts of polycarboxylic acids, oxidation products of polyglucosans and polyaspartic acids are used as carriers. One of the essential requirements of this document The molding process described is that at least partially bound water is present in the mixture which is sintered to shaped bodies with the aid of microwave radiation, ie some of the starting materials are in hydrated form.

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

With these fragrance moldings, a significant improvement in the fragrance impression of detergents and cleaning agents and the surface treated with them can already be achieved. However, the yield of fragrance applied to the treated surface, in particular textile fibers, is still very low in relation to the amount of fragrance used. Therefore, there continues to be a need for improved production processes for such fragrance moldings which improve the absorption of the fragrances on surfaces and thus ensure a higher fragrance yield. It has now been found that this requirement is met by a production process in which the premix contains 0.5 to 20% by weight of a substance which improves the absorption of the fragrance on surfaces.

A first subject of the invention is accordingly a process for the production of perfume moldings, in particular fragrance pearls, with bulk densities above 700 g / l, a solid and essentially water-free premix consisting of a) 65 to 94.5% by weight of carrier ( en), b) 0 to 10% by weight of excipient (s) and c) 5 to 25% by weight of perfume are subjected to granulation or press agglomeration, characterized in that the premix is 0.5 to 20% by weight of a Contains substance that improves the absorption of the fragrance on surfaces.

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

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 press agglomeration is a homogeneous plasticized mixture obtained, if necessary through the addition of auxiliary substance (s), in which the perfume is incorporated into the carrier in finely divided form. This procedure has compared to conventional application from perfume to porous carriers, clear advantages, as will be described in more detail later.

Preferred carriers are selected from the group of surfactants, surfactant compounds, di- and polysaccharides, silicates, zeolites, carbonates, sulfates and citrates and are used in amounts between 65 and 94.5% by weight, preferably 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 processes, one or more anionic surfactant compounds or anionic surfactants, in particular soaps, are used as carrier materials in amounts of 65 to 94.5% by weight, preferably 70 to 90% by weight, in each case based on the weight of the molded body formed. Examples of anionic surfactant compounds are alkylbenzenesulfonate (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, 50-70, 80 or 90% by weight and compounds containing anionic surfactants based on sodium carbonate / sodium silicate with anionic surfactant contents above 40% by weight. The pure anionic surfactants can also be used as carriers in the context of the present invention, provided they are solid and their use is not prohibited because of possible hygroscopicity. Soaps in particular are preferred as purely anionic surfactants, since on the one hand they can remain solid up to high temperatures and on the other hand they do not cause any problems with regard to undesired water absorption. All 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 for the high-dose perfume moldings according to the invention: 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, melissic acid, 10-undecenoic acid, petroselinic acid, petroselaidic acid, oleic acid, elaidic acid, ricinoleic acid, linolaidic acid, α- and ß-elaosteric 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 methods, as the carrier substance (s) one or more substances from the group of the sodium salts of saturated or unsaturated C _{_8-24} fatty acids, preferably from saturated or unsaturated C. ₁ ₁₈ fatty acids and in particular of saturated or unsaturated C ₆ fatty acids, in amounts of 75 to 94.5 wt .-%, preferably from 80 to 90 wt .-%, each based on the weight of the molded article used.

Other suitable carriers are, for example, di- and polysaccharides, and a wide range of substances can be used, from sucrose and maltose to oligosaccharides to the "classic" polysaccharides such as cellulose and starch and their derivatives. The substances from these subgroups are again those Strengths particularly preferred. The carriers normally used in detergents and cleaning agents, such as silicates and zeolites, are also suitable as carriers in the context of the present invention. The finely crystalline, synthetic zeolite containing bound water used is preferably zeolite A and / or P. The zeolite P, zeolite MAP is for example Doucil A24 ^® (commercially available from Crosfield) was used. Also suitable however are zeolite X and mixtures of A, X and P or, for example, a co-crystallizate of zeolites A and X, the VEGOBOND ^® AX (commercial product of Condea Augusta SpA). The zeolite can be used as a spray-dried powder or as an undried stabilized suspension that is still moist from its manufacture. In the event that the zeolite is used as a suspension, it can contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C ₁ -C ₈ fatty alcohols with 2 to 5 ethylene oxide groups , C ₁₂ -C ₁₄ fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols. Suitable zeolites have an average particle size of less than 10 μm (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water. In preferred embodiments, zeolites are contained in the premix in amounts of 10 to 94.5% by weight, it being particularly preferred if zeolites are contained in amounts of 20 to 70, in particular 30 to 60% by weight.

Suitable carriers are also layered sodium silicates of the general formula NaMSi _x O _{2x +} ι 'yH 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 O ₅ 'y H ₂ O are preferred.

The preferred builder substances also include amorphous sodium silicates with a modulus Na ₂ O: SiO 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. Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.

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. If they are used in the premix according to the invention and are not subsequently added, these acids are preferably used in anhydrous form.

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 moldings dissolve, without the moldings sticking together during transport or storage.

Suitable auxiliaries are those from the group of polyethylene glycols, fatty alcohol ethoxylates and fatty acid alkoxylates, which are used in quantities in preferred processes from 0 to 10% by weight, 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 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),

R ¹

in which R ^{1 is} selected from C -π-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 _8-18 alkyl or alkenyl, R ⁴ = -H or -CH ₃ and 1 = 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 III:

H- (O-CH ₂ -CH ₂ ) _n -OH (III),

in which the degree of polymerization n can vary from about 5 to> 100,000, corresponding to molecular weights from 200 to 5,000,000 gmol ^"1. The products with molecular weights below 25,000 gmol ^" ¹ are referred to as the actual polyethylene glycols, while higher molecular weight products in the Literature is often referred to as polyethylene oxides (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 especially in combination with polyethylene glycols with a relative molecular weight around 4000 can be used 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 process 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 kgmol ^{* 1} , in amounts of 0 to 10 wt. %, 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.

In the process according to the invention, 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 benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethyl benzyl (DMBCA), phenylethyl acetate, benzyl acetate, Ethylmethylphenylglycinat, Allylcyclohexyl- propionate, Styrallylpropionat, benzyl salicylate, cyclohexyl salicylate, floramat, Melusat and Jasmecyclat. 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, to the Hydrocarbons mainly belong to the terpenes like limonene and pinene. However, preference is given to using mixtures of different fragrances which together produce an appealing fragrance.

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

The substances which improve the absorption of the fragrance on the surface are preferably substances which improve the absorption of the fragrance on surfaces, one or more substances from the group of paraffins, quaternary ammonium compounds, soil release Polymers, in particular the copolymeric polyester and other polymers, such as in particular polyvinylpyrrolidone and block copolymers with blocks (-CH ₂ -CH ₂ -O) “- with n> 2.

Under paraffin, a solid or liquid mixture of purified, saturated aliphatic hydrocarbons, which is colorless, odorless and tasteless, dissolves easily in ether and chloroform, does not dissolve in water and 90% alcohol and does not fluoresce (i.e. that contains no aromatic compounds). Different paraffins can be used. Viscose paraffin (Paraffinum liquidum) is an oily liquid (D = 0.827-0.890, viscosity: 110-230 mPas), and thin paraffin (Paraffinum perliquidum) is an oily liquid with a density of 0.810-0.875 and a viscosity of 25-80 mPas. Hard paraffin (Paraffinum solidum) is also known, which is a solid crystalline mass with a solidification temperature of 50-62 ° C. The liquid paraffin forms are often added to mineral oils in the technical field and are referred to as paraffin oil or white oil. Names like soft paraffin are used for semi-solid paraffin qualities with melting points of 45-65 ° C, names like petrolatum are used for those with a density of 0.820-0.880, a melting point of 38-60 ° C and a boiling point of> 300 ° C ; a well-known brand for the latter is petroleum jelly. Paraffin is water-repellent, with fats, wax and walrus too uniform masses meltable, non-toxic, inert, fairly resistant to sulfuric acid, bromine and cold nitric acid and, unlike fats and fatty oils, does not become rancid (ie it is unsaponifiable); in contrast to this, it is sometimes incorrectly referred to as "mineral fat". Paraffin is usually produced from residues from petroleum distillation, from bituminous shale, peat coal and the products of lignite smelting, synthetically by means of medium-pressure synthesis from CO and H using catalysts after a A modified Fischer-Tropsch synthesis: Hard paraffin is separated by cooling, de-oiled and bleached from the porridge, mostly called paraffin gatsch, which is obtained in this process and during petroleum distillation. Liquid paraffin is obtained by distillation - from the production and the intended use Some paraffin fractions are also traded here as micro waxes, ceresin, petrolatum and waxes. According to the invention, all forms of paraffin listed here can be used, although it may be preferred to use certain paraffins with regard to processing processes The viscous qualities have advantages in processing. If the scented pearls are produced using high pressures or temperatures, however, it may also be preferred if hard paraffins are used which, however, are liquid under the processing conditions when the scented pearls are stored.

Suitable quaternary ammonium compounds for the process according to the invention are all customary surface-active substances, cationic surfactants having a textile-softening effect being clearly preferred.

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

R ¹

R'-N ⁽⁺⁾ - (CH ₂ ) _n -TR ² (I)

(CH ₂ ) _n -TR ² R ¹

R'-N ⁽⁺⁾ - (CH ₂ ) _n -CH-CH ₂ (II)

R ¹ TT

R ² R ²

R ¹

R ³ -N ⁽⁺⁾ - (CH ₂ ) _n -TR ² (III)

R ⁴

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

For the purposes of the present invention, soil release polymers are those polymers which have a dirt-removing ability. In the literature, the term "soil repellenf polymers" is also used for such polymers. These are usually polyesters which contain dicarboxylic acid units and alkylene glycol units and / or polyalkylene glycol units.

For example, German Offenlegungsschrift DT 16 17 141 describes a washing process using polyethylene terephthalate-polyoxyethylene glycol copolymers. German laid-open specification DT 22 00 911 relates to detergents which contain nonionic surfactant and a copolymer of polyoxyethylene glycol and polyethylene terephthalate. In the German patent application DT 22 53 063 acidic textile finishing agents are mentioned, which are a copolymer of a dibasic carboxylic acid and an alkylene or Contain cycloalkylene polyglycol and optionally an alkylene or cycloalkylene glycol. Polymers made from ethylene terephthalate and polyethylene oxide terephthalate. in which the polyethylene glycol units have molecular weights of 750 to 5000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate is 50:50 to 90:10, and their use in detergents is described in German patent DE 28 57 292. Polymers with a molecular weight of 15,000 to 50,000 made of ethylene terephthalate and polyethylene oxide terephthalate, the polyethylene glycol units having molecular weights of 1000 to 10,000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate being 2: 1 to 6: 1, can be according to the German published patent application DE 33 24 258 can be used in detergents. European patent EP 066 944 relates to textile treatment agents which contain a copolyester of ethylene glycol, polyethylene glycol, aromatic dicarboxylic acid and sulfonated aromatic dicarboxylic acid in certain molar ratios. European or European patent EP 0 185 427 discloses methyl or ethyl end-capped polyesters with ethylene and / or propylene terephthalate and polyethylene oxide terephthalate units and detergents which contain such a soil release polymer. European patent EP 0 241 984 relates to a polyester which, in addition to oxyethylene groups and terephthalic acid units, also contains substituted ethylene units and glycerol units. Polyesters are known from European patent EP 0 241 985 which, in addition to oxyethylene groups and terephthalic acid units, contain 1, 2-propylene, 1,2-butylene and / or 3-methoxy-1,2-propylene groups and glycerol units and are combined with Ci - C ₄ -alkyl groups are end group-capped. European patent EP 0 253 567 relates to soil release polymers with a molecular weight of 900 to 9000 made of ethylene terephthalate and polyethylene oxide terephthalate, the polyethylene glycol units having molecular weights of 300 to 3000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate 0.6 is up to 0.95. From European patent application EP 0 272 033, polyesters with poly-propylene terephthalate and polyoxyethylene terephthalate units which are end group-capped by C -alkyl or acyl radicals are known. European patent EP 0 274 907 describes sulfoethyl end group-capped terephthalate-containing soil release polyesters. In European patent application EP 0 357 280, sulfonation of unsaturated end groups produces soil-release polyesters with terephthalate, alkylene glycol and poly-C _2-4 glycol units. The International patent application WO 95/32232 relates to dirt-releasing polyesters of the general formula

X- (O- (CHR-) _a ) _b [O-OC-Ph-CO- (O- (CHR-) ₀ ) p] _y OY (I)

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

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

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

X and

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

For the purposes of this invention, however, not only such preferred polyesters, but also all polymers with soil release properties are considered as soil release polymers.

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

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

Commercial polyvinylpyrrolidones have molar masses in the range from approx. 2500-750,000 g / mol, which are characterized by specifying the K values.

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

The compounds to be used according to the invention as an elevator aid, when used in accordance with the invention, lead to an improvement in the fragrance impression which the fragrance molded articles leave on the laundry. Conversely, this means that fragrance moldings produced according to the invention achieve an equally good fragrance impression with less perfume as conventional fragrance moldings. Saving perfume oil in particular means a great cost advantage, since perfume oils are one of the most expensive ingredients in detergents and cleaning agents. In the process according to the invention, the essentially water-free premix is subjected to granulation or press agglomeration after the individual constituents have been combined. During the granulation, the premix is compacted and homogenized by the rotating mixing tools and granulated to form fragrance moldings, 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 press agglomeration process, the premix is compressed and plasticized under pressure and under the action of shear forces. homogenized and then discharged form-giving from the apparatus. 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 guidance, the housing and the extruder pelletizing head of which are heated to the predetermined extrusion temperature can. 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 see 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 about 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. Care should be taken to ensure that only small amounts of fine grain are produced in this stage. Drying of the resulting extrudates is not necessary in the context of the present invention, since the process according to the invention is essentially water-free, that is to say without the addition of free, non-bound water.

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

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

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

In a further preferred embodiment of the present invention, the method according to the invention is carried out by means of pelleting. Here, the fragrance-containing, solid and essentially water-free premix is applied to a perforated surface and pressed through the holes by means of a pressure-producing body with plasticization. In conventional embodiments of pellet presses, the premix is compressed under 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 one disclosed in this document Ring die press consists of a rotating ring die, through which press channels pass, and at least one press roller which is operatively connected to the inner surface thereof and which presses the material supplied to the die space through the press channels into a material discharge. Here, the ring die and the press roller can be driven in the same direction, which means that a reduced shear stress and thus a lower temperature increase in the premix can be achieved. Of course, it is also possible to work with heatable or coolable rollers in the pelletizing in order to set a desired temperature of the premix.

Another press agglomeration process that can be used according to the invention is tableting. Because of the size of the molded 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 perfume moldings produced according to the invention can additionally be subsequently sprayed with perfume. The conventional fragrance variant, i.e. powdering and spraying with perfume can be carried out on the fragrance moldings produced according to the invention.

Advantageously, in the fragrance moldings 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 molded body is 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 composition is sprayed onto the granules or press agglomerates, which may or may not 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 conceivable and possible to divide the total perfume content of the agents into two portions x and y, the portion x consisting of non-stick, ie less volatile and the portion y consisting of more volatile perfume oils.

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

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

The general description of the perfumes which can be used (see above) generally represented the different substance classes of fragrances. In order to be perceptible, a fragrance must be volatile, the molar mass also playing an important role in addition to the nature of the functional groups and the structure of the chemical compound , Most fragrances have molecular weights up to about 200 daltons, while molecular weights of 300 daltons and above are more of 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 as "top note" (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, i 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.

Tenacious odoriferous substances which are usable in the context of the present invention are, for example, the essential oils such as angelica root oil, anise oil, arnica blossom oil, basil oil, bay oil, bergamot oil, Champacablütenöl, silver fir oil, noble fir cone oil, elemi oil, eucalyptus oil, fennel oil, pine needle oil, galbanum oil, geranium oil, ginger grass oil, guaiac wood oil, gurjun balsam oil, Helichrysumöl, Ho oil, ginger oil, iris oil, cajeput oil, calamus oil, camomile oil, camphor oil, Kanagaöl, cardamom oil, cassia oil, pine needle oil, Kopaϊvabalsamöl, coriander oil, spearmint oil, caraway oil, Kuminöl, lavender oil, lemongrass oil, lime oil, mandarin oil, melissa oil, Musk grain oil, myrrh oil, clove oil, neroli oil, niaouli oil, olibanum oil, orange oil, origanum oil, palmarosa oil, patchouli oil, Peru balsam oil, petitgrain oil, pepper oil, peppermint oil, allspice oil, pine oil, rose oil, rosemary oil, sandalwood oil, spelled oil, celery oil, celery oil, celery oil, celery oil, celery oil Thyme oil, verbe na oil, vetiver oil, juniper berry oil, wormwood oil, wintergreen oil, ylang-ylang oil, hyssop oil, cinnamon oil, cinnamon leaf oil, lemon oil, lemon oil and cypress oil.

However, the higher-boiling or solid odoriferous substances of natural or synthetic origin can also be used as adhesive odoriferous substances or Fragrance mixtures, i.e. fragrances, are used. These compounds include the compounds mentioned below and mixtures of these: ambrettolide, α-amylcinnamaldehyde, anethole, anisaldehyde, anisalcohol, anisole, anthranilic acid methyl ester, acetophenone, benzylacetone, benzaldehyde, ethyl benzoate, benzophenone, benzyl alcohol, benzyl acetate, benzyl benzyl benzate, benzyl acetate benzate. Bomeol, bornyl acetate, α-bromostyrene, n-decylaldehyde, n-dodecylaldehyde, eugenol, eugenol methyl ether, eucalyptol, famesol, fenchone, fenchyl acetate, geranyl acetate, geranyl formate, heliotropine, heptincarboxylic acid, methyl ester, heptaldehyde dimethyl, hydroxymethyl alcoholdimethylaldehyde, hydrochloride aldehyde, hydrochloride aldehyde dimethyl ether, hydrochloride aldehyde dimethyl ether, hydrochloride dehydroethyl ether, hydrochloride dehydroethyl ether, hydrochloride dehydroethyl alcohol dehydroethyl ether Isoeugenol, isoeugenol methyl ether, isosafrol, jasmon, camphor, karvakrol, karvon, p-cresol methyl ether, coumarin, p-methoxyacetophenone, methyl-n-amyl ketone,

Methylanthranilic acid methyl ester, p-methylacetophenone, methylchavicol, p-methylquinoline, methyl-ß-naphthyl ketone, methyl-n-nonylacetaldehyde, methyl-n-nonyl ketone, muskon, ß-naphthol ethyl ether, ß-naphthol methyl ether, nerol, n-nonyl aldehyde Octylaldehyde, p-oxy-acetophenone, pentadecanolide, ß-phenylethyl alcohol, phenylacetaldehyde dimethyacetal, phenylacetic acid, pulegon, safrol, salicylic acid isoamyl ester, salicylic acid methyl ester, salicylic acid hexyl ester,

Salicylic acid cyclohexyl ester, Santalol, Skatol, Teφineol, Thymen, Thymol, γ-undelactone, Vanilin, Veratrumaldehyde, Cinnamaldehyde, Zimatalkohol, Cinnamic acid, Cinnamic acid ethyl ester, Cinnamic acid benzyl ester.

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

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 are usually used in small quantities. Phosphonates. Color transfer inhibitors etc. subsequently mixed. By introducing these substances into the process according to the invention, fragrance moldings, in particular fragrance pearls, are produced which contain further active substances and can thus be incorporated as a fragrance and active compound in washing and cleaning agents. In addition, an additional process step is saved in the production of detergents and cleaning agents.

In further embodiments, the present invention provides for the use of fragrance moldings, in particular fragrance pearls, with bulk densities above 700 g / l; produced by the process according to the invention by granulation or press agglomeration of a solid and essentially water-free premix from a) 65 to 94.5% by weight of excipient (s), b) 0 to 10% by weight of excipient (s), c) 5 up to 25% by weight of perfume, and d) 0.5 to 20% by weight of a substance which improves the absorption of the fragrance on surfaces for the scenting of detergents and cleaning agents.

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

The fragrance moldings produced in accordance with the invention, in particular fragrance pearls, can be incorporated into customary detergents and cleaning agents and are then used for scenting these agents in accordance with the use mentioned above. However, it is also possible to offer the fragrance shaped bodies, in particular fragrance pearls, separately as part of a “modular system” in which the consumer acquires a fragrance-free basic detergent and various fragrance shaped bodies, especially fragrance pearls, can be mixed in order to be able to choose from a wide variety of fragrances depending on the type of laundry being treated.

In all of these embodiments, the fragrance shaped bodies are ultimately used for scenting surfaces, in particular fibers, and in a very particularly preferred embodiment for scenting textile fibers. Another object of the invention is therefore the use of substances which improve the absorption of fragrances on surfaces, to improve the impression of fragrance on laundry, when using fragrance moldings, in particular fragrance pearls, with bulk densities above 700 g / 1, by granulation or press agglomeration are produced from a solid and essentially water-free premix containing a) 65 to 94.5% by weight of carrier (s), b) 0 to 10% by weight of auxiliaries and c) 5 to 25% by weight of perfume , Particularly suitable for this use are the substances described above from the group of paraffins, quaternary ammonium compounds, soil-release polymers, in particular copolymeric polyesters and other polymers, such as in particular polyvinylpyrrolidone and block copolymers with blocks (-CH -CH -O) _n - with n> 2.

Another preferred embodiment of the present invention is a method for applying fragrances to textile goods in a washing machine by adding fragrance-containing molded articles, in particular fragrant pearls, in the rinse cycle, whereby molded articles with bulk densities above 700 g / 1; prepared by the process according to the invention by granulation or press agglomeration of a solid and essentially water-free premix consisting of a) 65 to 94.5% by weight of excipient (s), b) 0 to 10% by weight of excipient (s) and c) 5 up to 25% by weight of perfume, d) 0.5 to 20% by weight of a substance which improves the absorption of the fragrance on surfaces are added to the washing or rinsing cycle of a machine washing process for wet washing. Examples:

By mixing the formulation components mentioned below in a Lödige mixer, free-flowing premixes were produced which were compressed and plasticized in an extruder.

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

Dehyquart AU 57 / AU 48: N-methyl-N, N- bis (acyloxyethyl) -N-

(2-hydroxylethyl) ammonium methosulfate;

Commercial products from Henkel

Repelotex SRP 4: terephthalic acid-ethylene glycol-polyethylene glycol ester;

Commercial product from Rhodia Sokalan HP 22: modified polyalkylene glycol; Commercial product of the company

BASF PEG: polyethylene glycol

Composition of the spray-dried granules (prepared by spray-drying surfactant compounds): 26.2 wt .-% Na-C _9- ι ₃ alkyl benzene sulfonate, 4.0 wt .-% Sodium carbonate, 55.6% by weight zeolite 4A, 0.7% by weight salts from solution. 13.0% by weight of water and 0.5% by weight of sodium hydroxide.

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

The plasticized premixes left the extruder at a pressure of 85 bar through a perforated plate with exit bores of 0.5 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 (<0.4 mm) and the coarse parts (> 2.0 mm) had been sieved, the extrudates had the bulk densities listed in Table 1.

The scented pearls E1 to E8 produced according to the invention were mixed with perfume-free extrudates to form detergents and compared with extrudates with a similar composition, in which the perfume oils in question were sprayed onto the extruded and rounded particles, which were powdered with finely divided zeolite, in a conventional manner (V2) or with detergents produced analogously, which contained fragrance pearls without elevator aid (VI). The perfume oil content in the respective recipes was kept constant.

The composition of the perfume oil used in the individual fragrance pearls is given in Table 2. The fragrance of the product and of treated textiles (cotton) was assessed as a subjective smell impression by several perfumers. The numerical values in the evaluation table (Table 3) each enter the sequence of the intensity felt by the perfumers. A higher numerical value means a weaker fragrance impression. Table 2: Composition of the perfume oil [% by weight]:

Table 3: Fragrance enhancement (intensity preference, averaged over the number of perfumers)

Preference of intensity

Product wet laundry dry laundry

El 2 3 1

E2 1 1 2

E3 3 2 4

E4 4 4 3

V2 5 5 5

VI 3 3

E5 1 1 1

E6 2 2 2

VI 2 3 3

E7 1 1 2

E8 3 2 1

In a first series of experiments, examples E1 to E4 according to the invention were compared with comparative example V2. The fragrance impression of the comparative examples was felt to be the weakest both in the fragrance pearls themselves and on the damp laundry and in the dry laundry. All examples according to the invention performed better. In a second series of tests, fragrance pearls without elevator aid (VI) were compared with Examples E5 and E6 according to the invention. Here, too, the examples according to the invention performed consistently better in fragrance impression than the fragrance pearls without elevator aid. The third series of tests also showed that the examples according to the invention smell the laundry much more than is possible with the scented pearls without the aid of an elevator. Accordingly, the examples show that when using fragrance pearls according to the invention, the fragrance impression is improved with a constant amount of perfume oil.

Claims

claims:

1. A process for the production of fragrance moldings, in particular fragrance pearls, with bulk densities above 700 g / 1, a solid and essentially water-free premix consisting of a) 65 to 94.5% by weight of carrier (s), b) 0 up to 10% by weight of excipient (s) and c) 5 to 25% by weight of perfume is subjected to granulation or press agglomeration, characterized in that the premix contains 0.5 to 20% by weight of a substance which is absorbed of the fragrance on surfaces improved.

2. The method according to claim 1, 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.

3. The method according to any one of claims 1 or 2, characterized in that it improves the substance that improves the absorption of the fragrance on surfaces by one or more substances from the group of paraffins, quaternary ammonium compounds, soil release Polymers, in particular the copolymeric polyester and further polymers, such as in particular polyvinylpyrrolidone and block copolymers with blocks (-CH ₂ -CH ₂ -O) _n - with n> 2.

4. The method according to any one of claims 1 to 3, 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.

5. The method according to any one of claims 1 to 4, characterized in that one or more substances from the group of surfactants as the carrier (s), Surfactant compounds, di- and polysaccharides. Silicates, zeolites, carbonates. Sulfates and citrates are used in amounts of 65 to 94.5% by weight, preferably 70 to 90% by weight, based in each case on the weight of the molded body formed.

6. The method according to any one of claims 1 to 5, characterized in that one or more anionic surfactant compounds or anionic surfactants, in particular soaps, in amounts of 75 to 94.5 wt .-% as the carrier (s). preferably from 80 to 90% by weight, in each case based on the weight of the molded body which is used.

7. The method according to any one of claims 1 to 6, characterized in that one or more substances from the group of the sodium salts of saturated or unsaturated C _8-24 fatty acids, preferably of saturated or unsaturated C ₁₂ as the carrier (s). ₁₈ fatty acids and in particular saturated or unsaturated C ₁₆ fatty acids, in amounts of 75 to 94.5% by weight, preferably 80 to 90% by weight, in each case based on the weight of the molded body formed.

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

9. The method according to any one of claims 1 to 8, 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 molded body formed.

10. Use of fragrance shaped bodies, in particular fragrance pearls with bulk densities above 700 g / 1, produced by granulation or press agglomeration of a solid and essentially water-free premix from a) 65 to 94.5% by weight of carrier (s), b) 0 to 10% by weight of excipient (s), c) 5 to 25% by weight of perfume, and d) 0.5 to 20% by weight of a substance which improves the absorption of the fragrance on surfaces for the scenting of washing - and cleaning agents.

11. washing or cleaning agent containing fragrance moldings, in particular fragrance pearls, produced according to one of claims 1 to 9, in amounts of more than 0.5% by weight, preferably more than 1% by weight and in particular more than 2 % By weight, based in each case on the detergent or cleaning agent.

12. Use of substances which improve the absorption of fragrances on surfaces to improve the fragrance impression of the fragrance shaped body, in particular fragrance pearls, with bulk densities above 700 g / l, which are obtained by granulation or press agglomeration from a solid and essentially water-free premix which a) 65 to 94.5% by weight of excipient (s), b) 0 to 10% by weight of excipient (s), c) containing 5 to 25% by weight of perfume, were made, left on laundry.

13. Use of one or more substances from the group of the paraffins, the quaternary ammonium compounds, the soil-release polymers, in particular the copolymeric polyesters and other polymers, such as in particular polyvinylpyrrolidone and block copolymers with blocks (-CH ₂ -CH ₂ -O) _n - with n> 2 according to claim 12.

14. Use of quaternary ammonium compounds according to formulas I. II or III:

R ¹

R'-N ⁽⁺⁾ - (CH ₂ ) _n -TR ² (I)

(CH ₂ ) _n -TR ²

R ¹

R ¹ -N ⁽⁺⁾ - (CH ₂ ) _n -CH-CH ₂ (II)

R ¹ TT

R ² R ²

R ¹

R ³ -N ⁽⁺⁾ - (CH ₂ ) _n -TR ² (III)

R ⁴

wherein each group R ^{1 is} independently selected from Cι _-6 - alkyl, alkenyl or hydroxyalkyl groups; each group R ^{2 is} independently selected from C _8-28 alkyl or alkenyl groups; R ³ = R ¹ or (CH ₂ ) _n -TR ² ; R ⁴ = R ¹ or R ² or (CH ₂ ) _n -TR ² ; T = -CH ₂ -, -O-CO- or -CO-O- and n is an integer from 0 to 5, according to approach 12.

15. A method for applying fragrances to textile goods in a washing machine by adding fragrance shaped bodies in the rinse cycle, characterized in that that perfume molded body, in particular fragrance pearls, with bulk densities above 700 g / 1, produced according to one of claims 1 to 9 by granulation or press agglomeration of a solid and essentially water-free premix of a) 65 to 94.5 wt .-% carrier (s ), b) 0 to 10% by weight of excipient (s) and c) 5 to 25% by weight of perfume, d) 0.5 to 20% by weight of a substance which improves the absorption of the fragrance on surfaces, be put into the washing or rinsing cycle of a machine washing process for wet washing.