DE19953503A1 - Process for the production of fragrance pearls - Google Patents

Abstract

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

Description

The present invention relates to perfume moldings, in particular fragrance pearls, which in Detergents and cleaning agents as well as textile treatment and post-treatment agents can be incorporated and the one on the treated textiles effect fragrance enhancing. The invention further relates to washing and Detergents containing the moldings according to the invention and the use certain substances to improve the absorption of fragrances on surfaces. The invention also relates to a production process for fragrance = shaped bodies.

It is common today for textile washing, treatment and post-treatment Mix small amounts of perfume into detergents and post-treatment agents serve the washing or rinsing solution itself, but also with the washing or Rinse-treated textile goods to give a pleasant fragrance. The fragrance of Detergents, cleaning agents and post-treatment agents are still in addition to color and Appearance is an important aspect of the aesthetic product impression and an important point when making a consumer decision for or against a specific product. For scenting the perfume can either be incorporated directly into the agents or in one additional step of the washing or rinsing solution can be supplied. The first way lays one certain product characteristics, the second way the consumer can Decide different offered fragrance variants individually about "his" fragrance, comparable to the choice of an eau de toilette or an aftershave.

Perfume moldings and processes for scenting washing and rinsing liquors are accordingly broadly described in the prior art. So DE 41 33 862 discloses  (Henkel) tablets, the carrier materials, fragrances and possibly other in Detergents and cleaning agents contain the usual ingredients, being the carrier material Sorbitol and an additional 20 to 70% by weight of a carbonate and acid bubbling system be used. These tablets, for example, the rinse and softener cycle can be added to the textile laundry in a household washing machine 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 ³ are preferred. During storage, such tablets or capsules must be provided with a gastight and watertight covering layer in order to protect the ingredients. Further details on the production and the physical properties of suitable tablets are not contained in this publication.

International application WO94 / 25563 (Henkel-Ecolab) describes a method for the production of washing and cleaning active moldings using the Microwave technology that works without high pressure pressing. That way molded articles are characterized by an extremely high dissolving speed or Decay rate with simultaneous breaking strength, without using an explosive necessary is. At the same time, they are stable in storage and can be used without additional precautions be kept. Moldings can also be produced in this way a typical perfume oil content for detergents and cleaning agents between 1 and 3% by weight. Perfume oils are usually volatile and could therefore already be evaporate under the influence of microwave radiation. Should have higher proportions of light  volatile liquid substances are used, therefore becomes a two-component system, consisting of a component manufactured with microwave technology and a component containing the sensitive liquid substances.

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

The German patent application DE 197 35 783 (Henkel) describes high-dose fragrance Shaped body, the carrier material (ien), 20 to 50 wt .-% fragrance (s) and optionally contain further active ingredients and auxiliaries customary in detergents and cleaning agents, where the moldings after deduction of the amount of fragrance to at least 50 wt .-% of their weight consist of fatty acids and fatty acid salts. These perfume moldings are suitable both for scenting detergents and cleaning agents and for scenting Textiles in a washing machine.

A process for applying fragrances to textiles in a washing machine is described in DE 195 30 999 (Henkel). In this procedure, a fragrance-containing molded body, which is produced by irradiation with microwaves, in Rinse aid used in a washing machine. The manufacture of the preferably spherical shaped bodies with diameters above 3 mm and bulk densities According to the teaching of this document, up to 1100 g / l can be achieved by mixing a mixture predominantly water-soluble carriers, hydrated substances, optional surfactants and fills perfume into suitable shapes and sinters with the help of microwave radiation. The Perfume contents of the shaped bodies are between 8 and 40% by weight as carriers find starches, silicas, silicates and disilicates, phosphates, zeolites, alkali salts of Polycarboxylic acids, oxidation products of polyglucosans and polyaspartic acids Use. One of the essential requirements of this document Shaped body manufacturing process described is that in the mixture that with the help of  Microwave radiation is sintered into shaped bodies, at least partially bound Water is present, d. H. some of the starting materials are in hydrated form.

The proposed solutions either require additional blocking or Sheath layers to fix the perfume on the carrier or are not alike for scenting detergents and cleaning agents and for direct use as a single product Fragrance, suitable for example for the rinse aid in a washing machine. In the Patent application WO 99/21953 describes a method for producing fragrance Shaped bodies and in particular fragrance pearls described, up to 15 wt .-% fragrance included and still not with a gastight and watertight during storage Wrapping layer or packaging must be provided to contain the ingredients protect or prevent the loss of fragrance during storage. It is about a process for the production of fragrance moldings, in particular fragrance pearls with bulk weights above 700 g / l, being a firm and essentially anhydrous premix of a) 65 to 95% by weight of carrier (s), b) 0 to 10% by weight Excipient (s) and c) 5 to 25% by weight of perfume from a granulation or press agglomeration is subjected. The fragrance moldings thus produced can be used as a compound in Usual washing and cleaning agents can be incorporated, but can also be used directly individual fragrance selection can be used in the domestic washing process and cause a fragrance-enhancing impression on the treated textiles.

With these fragrance moldings, a significant improvement in the Fragrance of detergents and cleaning agents as well as the surface treated with them to reach. However, the yield of fragrance is still on the treated one Surface, in particular textile fibers, is applied in relation to the used Very little fragrance. Therefore, there is still a need for improved ones Manufacturing process for such perfume moldings, which the fragrances are absorbed Improve surfaces and thus ensure a higher fragrance yield.

German patent application 199 41 263.4 describes a manufacturing process for perfume moldings in which the premix contains 0.5 to 20% by weight of a substance which improves the absorption of the fragrance on surfaces. It is a process for the production of fragrance 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 (s) , b) 0 to 10% by weight of excipient (s) and c) 5 to 25% by weight of perfume are subjected to granulation or press agglomeration, characterized in that the premix contains 0.5-20% by weight of a substance , which improves the absorption of the fragrance on surfaces. The substances which improve the absorption of the fragrances are in particular one or more substances from the group of paraffins, quaternary ammonium compounds, soil-release polymers, in particular copolymeric polyesters and other polymers, such as in particular polyvinylpyrrolidone and block copolymers with blocks (-CH ₂ -CH ₂ -O) _n - with n <2.

It has now been found that certain carriers are particularly useful as lift aids own.

Accordingly, a first subject of the invention is shaped perfume bodies containing a) 65 to 95 wt .-% carrier (s), 0 to 10 wt .-% excipient (s) and 5 to 25% by weight of perfume, which are characterized in that a proportion of the carrier substances a) is selected from carriers that crosslink an anionic, at least two-dimensional Have partial structure and contain the alkylammonium ions.

In a preferred embodiment, the anionic at least 2-dimensionally cross-linked substructure around an inorganic, in particular one silicate layer structure. In another, also preferred embodiment is the anionic, at least 2-dimensionally cross-linked substructure an organic polymer, in particular a derivative of a natural polymer, preferably a derivative of a polysaccharide. With the inorganic layer structure in another preferred embodiment, it is a modified one Bentonite-type silicate, preferably montmorillonite-type.

Bentonites are clays and rocks that smectites, above all Montmorillonite, as main minerals. They can also have mica, illite, Contain cristobalite and zeolites as impurities. Montmorillonite gives the  Bentonite properties such as swellability (swelling clays), thixotropy and Ion exchange capacity. The raw bentonites are either calcium bentonites (not swellable; inactivated bentonites, known in the UK as Fuller earths) or Sodium bentonite (swellable; Wyoming bentonite). The properties of bentonites can be modified; e.g. B. the swellability of raw bentonites Exchange of the Ca for Na ions (activated calcium bentonite), the specific one Surface by treatment with inorganic acids (acid activated bentonite) and organophilia by reacting sodium bentonite with quaternary ammonium Compounds (organophilic bentonites, also called bentones) increased. According to the invention the latter, organophilic bentonites are used, in which sodium ions were exchanged for alkylammonium ions.

The mineral montmorillonite contained in these bentonites can be described by the empirical formula Al ₂ [(OH) ₂ / Si ₄ O ₁₀ ] .nH ₂ O or Al ₂ O ₃ -4SiO ₂ .nH ₂ O. It is a clay mineral belonging to the dioctahedral (mica) smectites, which crystallizes monoclinic-pseudohexagonal. It forms a predominantly white, gray-white to yellowish, completely amorphous, slightly friable, swelling in water but not becoming plastic mass; Under the electron microscope, pseudohexagonal plates, stretched lamellae, stretched hexagonal or irregularly outlined leaflets as well as lamellar, moss-like or spherical aggregates can be seen.

Illustration: Montmorillonite layer grid in an idealized representation

The layer packs in the three-layer structure of montmorillonite (see illustration) can be used reversible storage of water (in 2-7 times the amount) and other substances such as e.g. B. alcohols, glycols, pyridine, α-picoline, ammonium compounds, hydroxy Swell aluminosilicate ions, etc.

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

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

By organophilizing montmorillonite or bentonites (exchange of Interlayer cations against quaternary alkylammonium ions) result in products that preferably for dispersion in organic solvents and oils, fats, ointments, Paints and varnishes are used.

For the purposes of the present invention, in a preferred embodiment such organophilized montmorillonites or bentonites, such montmorillonites included, used as a carrier and elevator aid for fragrances.

These bentonites unfold when the fragrance molded article according to the invention is in Detergents are used, in addition to acting as a lift aid for the fragrances also the known effects as ion exchangers or the laundry softening Additive.

In another, likewise preferred embodiment of the invention, crystalline phyllosilicates are used according to the invention. These are layered silicates in which, starting from compounds of the formula M ₂ Si _x O _{2x + 1} .yH ₂ O, where M is a sodium and / or a hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20, cations have been exchanged for alkylammonium ions. Such organophilized layered silicates are commercially available, for example, under the trade name SKS® (from Clariant). Accordingly, it is preferred according to the invention if the carrier which contains alkylammonium ions is a layered silicate of the formula M ₂ Si _x O2 _{x + 1} .yH ₂ O, where M is a sodium and / or a hydrogen and / or an alkylammonium ion, x is a number from 1.9 to 4 and y is a number from 0 to 20.

In a further preferred embodiment, as carriers with anionic, at least 2-dimensionally cross-linked partial structure organic polymers used. Conceivable here is the use of any anionic, partially cross-linked polymers, their cations  an ion exchange for alkyl ammonium ions are accessible. Preferably However, derivatives of natural polymers are used. The is particularly preferred Use of polysaccharide derivatives.

The main steps in the derivatization of these polysaccharides are production anionic groupings in the molecule and the at least partial exchange of the Counterions against alkylammonium ions.

Anionic functions can preferably be generated by oxidation. Both according to the invention preferably to be used oxidatively modified poly or Oligosaccharides are compounds that belong to the substance class of oxidized starches or starch derivatives, especially those thermally or enzymatically degraded starch derivatives are selected. Starch belongs just like glycogen or Cellulose to the homoglycans. Starch consists of 3 different D-glucopyranose Polymers, the amylose, the amylopectin and a so-called intermediate fraction, the also referred to as abnormal amylopectin, as well as water (approx. 20%, depending on the variety and storage conditions), smaller amounts of protein, fats and ester-bound Phosphoric acid. The starch content of these components varies depending on the variety. Higher plants contain 0-40% amylose based on the dry matter. The The intermediate fraction is structurally between the amylose and the amylopectin. At The intermediate fraction is usually the amylopectin for analytical determination of the starch attributed.

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

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

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

Starch is a reserve carbohydrate used by many plants in the form of 1-200 mm large starch grains are stored in different parts of plants, e.g. B. in tubers or roots [potatoes, maranta (arrowroot), cassava (tapioca), batate], in cereals Seeds (wheat, corn, rye, rice, barley, millet, oats, sorghum) in the fruit  (Chestnuts, acorns, peas, beans and other legumes, bananas) and in the pulp (Sago palm).

Starch is preferably obtained from vegetable raw materials from flour of corn, potatoes, wheat, rice and the like. Cassava (tapioca), with the starch grains after Removal of the adhesive mechanically detached from the cell structure by wet means become; Corn is the most important starch plant worldwide.

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

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

To summarize roughly: A large number of oxidizing agents is for the oxidation of Polysaccharides, especially those made exclusively from glucose Polyglucosans in use. Examples include (air) oxygen, Hydrogen peroxide, sodium hypochlorite or bromite, periodic acid or periodates, lead (IV) acetate, nitrogen dioxide and cerium (IV) salts. This Oxidizing agents react very differently with the anhydroglucose units. So be For example, periodates or lead (IV) acetate act as a C-C cleavage of the anhydro glucose rings; the so-called 2,3-dialdehyde cellulose and analog are obtained from cellulose from starch dialdehyde starch. It is also known that when exposed to nitrogen dioxide on cellulose the oxidation of the primary alcohol group to the carboxyl group reaction is by far the predominant one. The oxidant, usually in equilibrium present with nitrous oxide, can be gaseous or dissolved in an inert organic solvents are used. You can also start from the strength correspondingly largely selective oxidations of the primary alcohol group of the anhydro Create glucose units to the carboxyl group. So is from the US Patent US 2,472,590 the oxidation of starch with gaseous or in water or nitrogen dioxide dissolved in various organic solvents known.

Under these conditions, the almost complete conversion of the primary alcohol groups of the polysaccharides in carboxyl groups only after a very long time Response times, which may be up to several days. Moreover high amounts of nitrogen dioxide, based on oxidizing polysaccharide, needed. From the international patent application WO 93/16110 is a significant improvement in the production of such Oxidation products of polysaccharides known. The invention disclosed there is based on recognizing that polycarboxylates from polysaccharides in a simple Processes can be obtained in high yields if the oxidation reaction with stick Dioxide / nitrous oxide in the presence of oxygen at elevated temperatures and is preferably carried out at elevated pressures. The wording "Nitrogen dioxide / nitrous oxide" stands for that under the respective reaction conditions existing equilibrium mixture of nitrogen dioxide and its Dimeric nitrous oxide.  

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

A method for producing solid polycarboxylic acid salts from is suitable Polysaccharides by oxidation with gaseous nitrogen dioxide / nitrous oxide converting at least a portion of the primary alcohol groups of the Polysaccharides in carboxyl groups and at least partial neutralization of the first Henden carboxylic acid groups, which is characterized in that the solid Polycarboxylic acid mixed with a solid neutralizing agent; this procedure is in patent application DE-A-195 07 717.

The oxidation of the polysaccharide preceding the neutralization preferably carried out as in the German patent application DE-A-44 26 443 described. This means that the reaction of the polysaccharide to be oxidized with Performs nitrogen dioxide / nitrous oxide only so long that the desired Degree of oxidation, that is, the degree of conversion of the primary alcohol groups into Carboxyl groups, only at most 90%, preferably from 60% to 85% and in particular 65% to 80% of which is achieved. The complete achievement of the desired The degree of oxidation takes place only in the post-oxidation phase, that is to say when the phase has ended Nitrogen dioxide / nitrous oxide supply and compared to the oxidation phase at least 10 ° C, preferably 15 ° C to 80 ° C and in particular 20 ° C to 50 ° C elevated temperature. It is important to ensure that by increasing the temperature an upper limit of 160 ° C is not exceeded if possible, since at higher Temperatures of increasing decomposition were observed.  

The oxidation reaction to be stopped before full conversion is reached preferably at temperatures from 30 ° C. to 70 ° C., in particular from 40 ° C. to 60 ° C. carried out. Oxygen, alone or in a mixture with the Reaction conditions inert gas, be present, the addition of which once Start of the reaction or several times, if desired continuously, during the reaction can be done. If the latter is carried out, the oxidation reaction As is known, who controls temperature or pressure-dependent oxygen metering the. Preferably, the addition of oxygen is controlled so that the reaction temperature in the Range from 30 ° C to 70 ° C remains.

As inert, that is, not under the process conditions desired in each case reacting gases can include noble gases such as helium or argon and carbon dioxide, but especially nitrogen, nitrogen monoxide and nitrous oxide, but also any mixtures of such gases can be used. The oxygen content in the The gas mixture is preferably in the range from 1% by volume to 30% by volume, in particular from 3% by volume to 10% by volume. A preferred embodiment of the The inventive method includes the supply of oxygen by the Auf squeeze air.

Another embodiment of the oxidation process is characterized in that a pressure of less than 10 bar in the reaction system before the start of the oxidation reaction, in particular from 2 bar to 6 bar, at the desired reaction temperature Pressing an inert gas mentioned is set and then oxygen or a mixture of oxygen with said inert gas, several times, if desired continuously, is pressed on. The addition of nitrogen dioxide / nitrous oxide can be before or after the addition of oxygen or the start of Oxygen is added. It may be necessary to add the reaction vessel after initially injecting the inert gas to the desired reaction temperature to heat up. During the course of the oxidation reaction, which is convenient under intensive mixing of the reactants takes place, the reaction temperature in usually kept without external heating solely by the amount of oxygen added become.  

In the oxidation step, the oxidizing agent passes from the gas phase directly onto the solid polysaccharide substrates mixed as intensively as possible for exposure. Oxidation in a fluidized bed made of polysaccharide, the vortex of which is preferred medium is a gas containing nitrogen dioxide. Such an oxidation process is in the German patent application DE-A-44 02 851 described. Under the fluidized bed should - without being limited to this type of production - understood the appearance that can be observed when stored fine on horizontal, perforated floors granular bulk material is flowed through from below by gases, known as eddies.

A particularly preferred class of oxidatively modified oligosaccharides are oxidized Dextrin derivatives. Dextrins are, for example, oligomers or polymers of Carbohydrates that can be obtained by partial hydrolysis of starches. The Hydrolysis can be carried out by customary, for example acid or enzyme-catalyzed, processes be performed. They are preferably hydrolysis products with medium Molar masses in the range from 400 to 500000 g / mol. There is a polysaccharide with one Dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30 preferred, where DE is a common measure of the reducing effect of a polysaccharide in Compared to dextrose, which has a DE of 100. Both are usable Maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher ones Molar masses in the range from 2000 to 30000 g / mol. A preferred dextrin is in the British patent application 94 19 091 described. In the oxidized derivatives such ger dextrins are their reaction products with oxidizing agents, which are capable of at least one alcohol function of the saccharide ring to the carboxylic acid function to oxidize. Such oxidized dextrins and methods of their manufacture are known to the person skilled in the art from various patent applications.

An oxidized oligosaccharide according to German patent application DE-A-196 00 018 is also preferred. Glucose is the preferred monomer in this oligosaccharide to be used according to the invention after oxidative modification. The average degree of oligomerization, which can also take fractional numerical values as the quantity to be determined analytically, is preferably in the range from 2 to 20, in particular 2 to 10. The oligosaccharide which is preferably used as a builder or cobuilder is oxidative at its originally reducing end with the loss of a C- Atom has been modified. If the originally reducing end of the oligosaccharide was an anhydroglucose unit, there is an arabinonic acid unit after modification:
(Glucose) _{n + 1} → (glucose) _n arabinonic acid.

This oxidative modification can, for example, with the help of Fe, Cu, Ag, Co or Ni catalysts, as described in international patent application WO 92/18542, with the help of Pd, Pt, Rh or Os catalysts, as in the European patent EP 0 232 202, or using a quinone / hydroquinone system in Alka mix with the addition of oxygen and optionally aftertreatment with hydrogen peroxide. The one that can be modified by means of such an oxidation process Oligosaccharide starting material is preferably an oligosaccharide with a dextrose equivalent (DE) in the range from 20 to 50. Particularly useful so-called glucose syrups (DE 20-37) and the above-mentioned dextrins, both of which partial hydrolysis of starch by conventional, for example acid or enzyme based procedures can be carried out, are accessible and as such or in higher polymer form, for example as starch in the above-mentioned oxidation processes can be used if under the conditions of oxidation a ent speaking degradation of the polymer chain structure of the starch takes place. Preferably point the oligosaccharides modified in this way take place at the originally reducing end the group -CH (OH) -CHO a group -COOH.

Regardless of whether inorganic or organic polymers as an anionic substructure of the carrier, it is essential that at least some of the cations of these compounds, consists of alkylammonium ions. Conveniently achieved one does this by ion exchange of the cations present in the starting form, usually alkali and alkaline earth ions, against alkylammonium ions. This one possible methods are well known to the person skilled in the art and can be relevant Textbooks are taken.

According to the invention, alkylammonium ions are understood to mean all ions which obey the formula R ¹ R ² R ³ R ⁴ N ⁺ , the radicals being selected from H, Cl-C ₅₀ alkyl, alkenyl or hydroxyalkyl groups or functionalized C ₁ -C ₅₀ alkyl groups. Up to 3 of the R ¹ -R ⁴ radicals can be formed by hydrogen.

Quaternary ammonium compounds include in particular all the usual ones surface-active substances into consideration, with cationic surfactants with fabric softening Effect are clearly preferred.

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

wherein each R ^{1 group is} independently selected from C _1-6 alkyl, alkenyl or hydroxyalkyl groups; each R ^{2 group is} independently selected from C _8-28 alkyl or alkenyl groups; R ³ = R ¹ or (CH ₂ ) _n -TR ² ; R ⁴ = R ¹ or R ² or (CH ₂ ) _n TR ² ; T = -CH ₂ -, -O-CO- or -CO-O- and n is an integer from 0 to 5.

Furthermore, particularly for use in crystalline layer compounds, preference is given to those alkylammonium ions which have only one long, optionally substituted C _5-30 alkyl group in which the other radicals are formed by hydrogen or C _1-4 alkyl radicals. In certain crystal structures, however, the use of alkylammonium ions which have two such long C _5-30 alkyl radicals may also be preferred.

Examples of such alkylammonium ions are, in particular, stearyldimethyl to name ammonium and stearylbenzyldimethylammonium.

In particular, it is preferred if the carrier, which is an anionic, at least 2- has dimensionally cross-linked partial structure and contains alkylammonium ions, at least 3% by weight, preferably at least 5 and in particular more than 7% by weight of the fragrance molded body. It is also preferred if the Vehicle less than 80 wt .-%, preferably less than 70 and in particular accounts for less than 50% by weight of the fragrance molding.

In addition to the carrier essential to the invention, the fragrance molded articles according to the invention can also contain a further elevator aid, for example an elevator aid according to the older German patent application 199 41 263.4. These lift aids are one or more substances from the group of paraffins, quaternary ammonium compounds, soil release polymers, especially copolymeric polyesters and other polymers, such as especially polyvinylpyrrolidone and block copolymers with blocks (-CH ₂ -CH ₂ -O) _n - with n <2.

Paraffin is a solid or liquid mixture of purified, saturated aliphatic hydrocarbons, which is colorless, odorless and tasteless, easily dissolves in ether and chloroform, does not dissolve in water and 90% alcohol and does not fluoresce (that is, no aromatic Contains connections). Different paraffins can be used. Thick paraffin (Paraffinum liduidum) is an oily liquid (D = 0.827-0.890, viscosity: 110-230 mPa.s), and thin paraffin (Paraffinum perliquidum) is an oily liquid with a density of 0.810-0.875 and a viscosity of 25 -80 mPa.s. 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. For semi-solid paraffin qualities with melting points of 45-65 ° C, names like soft paraffin 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, names like petrolatum are used ; a well-known brand for the latter is petroleum jelly. Paraffin is water-repellent, can be melted together with fats, wax and whale into uniform masses, is 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 these, it is sometimes incorrectly referred to as "mineral fat". Paraffin is usually produced from residues from petroleum distillation, from bituminous shale, peat coals and the products of lignite smelting, synthetically by medium pressure synthesis from CO and H ₂ using catalysts using a modified Fischer-Tropsch synthesis. Hard paraffin is separated by cooling, de-oiled and bleached from the porridge, which is usually called paraffin-Gatsch and is obtained during the oil distillation. liquid paraffin is obtained by distillation. Some paraffin fractions are also traded as micro waxes, ceresin, petrolatum and waxes in terms of their manufacture and intended use. According to the invention, all forms of paraffin listed here can be used, it being possible to use certain paraffins with regard to processing processes. In particular, the liquid, preferably the viscous, qualities can have advantages during processing. If the scented pearls are produced using high pressures or temperatures, however, it may also be preferred if hard paraffin is used which, however, is solid under the processing conditions when the scented pearls are stored.

All common surface-active substances come as quaternary ammonium compounds into consideration, cationic surfactants with a fabric softening effect that are already further have been described above, are clearly preferred.

Soil-release polymers refer to those polymers that have a Have dirt-removing ability. Such polymers are also found in the literature the term "soil repellent" polymers. It is usually about Polyester, the dicarboxylic acid units and alkylene glycol units and / or Contain 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. German laid-open specification DT 22 53 063 mentions acidic textile finishing agents which contain a copolymer of a dibasic carboxylic acid and an alkylene or 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 50:50 to 90:10 be, and their use in detergents is in the 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. From the European patent EP 0 241 985 polyesters are known which contain, in addition to oxyethylene groups and terephthalic acid units, 1,2-propylene, 1,2-butylene and / or 3-methoxy-1,2-propylene groups and glycerol units and with C ₁ - to 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 terephthalate, the polyethylene glycol units having molecular weights of 300 to 3000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate 0.1. 6 to 0.95. European patent application EP 0 272 033 discloses polyesters with poly-propylene terephthalate and polyoxyethylene terephthalate units which are end-capped at least partially by C _1-4 -alkyl or acyl radicals. European patent EP 0 274 907 describes sulfoethyl end group-capped tere phthalate-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. International patent application WO 95/32232 relates to dirt-releasing polyesters of the general formula

X- (O- (CHR-) _a ) _b [O-OC-Ph-C0- (O- (CHR-) _o ) _p ] _y OY (I)

in the
a is a number from 2 to 8,
b is a number from 1 to 300,
o a number from 2 to 8,
p is a number from 1 to 300 and
y represents 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 aryhnonocarboxylic 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 as well as 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 having 8 to 22 carbon atoms, Z is hydrogen or an alkyl radical having 1 to 2 carbon 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 carbon 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 may be cationic, for example, is capable of adsorption onto the cotton surface by electrostatic interaction, and one the second unit, which is made hydrophobic, is responsible for the remaining of the active substance at the water / cotton interface. Although the active substances disclosed there are not exclusively polymers in the sense of the chemical definition of this term, they should also be counted among the dirt-releasing polymers in the context of the present application because of their corresponding function.

Within the meaning of DE 199 41 263.4, however, not only such preferred polyesters apply, but all polymers with soil release properties as soil-release polymers.

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

Polyvinylpyrrolidones are produced by radical polymerization of 1- Vinyl pyrrolidone by bulk, 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 molecular weights in the range of approx. 2500-750 000 g / mol, which are characterized by the specification of the K values.

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

The connections to be used according to the invention as additional elevator aid in the use according to the invention for a further improvement in the fragrance impression, which the fragrance moldings leave on the laundry.

In addition to the carriers essential to the invention, with anionic, at least two-dimensional cross-linked substructures preferably contain the fragrance molded articles Carrier. These are generally substances that are suitable for the Fragrances, which are usually liquid, in solid granules or moldings bring in.

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

All surfactants solid at temperatures up to 40 ° C. can be used as surfactant carriers or surfactant compounds are used. Within the scope of the present invention the term "surfactant compound" is understood to mean a surfactant-containing preparation which, in addition to usual carrier materials and auxiliaries at least 20% by weight of an anionic, contains cationic or nonionic surfactant, based on the surfactant compound. The Carriers customary in surfactant compounds can preferably be identical to the aforementioned carriers that are used according to the invention, but it can  also other than the above-mentioned carriers as carriers in the surfactant compounds be included.

One or more anionic surfactant compounds or anionic surfactants are preferred, especially soaps, in amounts of 65 to 94.5% by weight, preferably 70 to 90 % By weight, in each case based on the weight of the shaped body formed, as Carrier materials used. Examples of anionic surfactant compounds are included Alkylbenzenesulfonate (ABS) compounds on silicate or zeolite substrates with ABS Contained for example 10, 15, 20 or 30 wt .-%, 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 in the context of the present invention Carriers are used, provided they are solid and not because of their use any hygroscopicity is prohibited. Soaps in particular are considered pure Anionic surfactants are preferred because on the one hand they are solid up to high temperatures can remain and on the other hand no problems regarding an unwanted Cause water absorption. As soaps found in the backing materials for the Shaped bodies according to the invention use all salts of fatty acids. While in principle, for example, aluminum, alkaline earth and alkali metal salts of fatty acids Shaped articles are preferred in which the alkali metal and from these in turn preferably contain the sodium salts of the fatty acids. As fatty acids, whose salts can be used as a carrier material, are all from vegetable or acids derived from animal oils and fats. The fatty acids can be saturated or mono- to polyunsaturated. Of course, not only "Pure" fatty acids are used, but also those in the breakdown of fats and Oils, for example palm kernel, coconut, peanut or turnip oil or beef tallow, technical fatty acid mixtures obtained, these mixtures of economic View are clearly preferred.

So can be in the carrier materials for the high-dose according to the invention Fragrance moldings, for example, individual species or mixtures of the salts below Use acids: 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 β- Eläosterainic acid, gadoleic acid, erucic acid, brassidic acid. Of course, too the salts of the fatty acids with an odd number of carbon atoms can 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.

Particularly preferred as carrier (s) are 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 _12-18 fatty acids and in particular of saturated or unsaturated C _1-6 - 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 shaped body.

Other suitable carriers are, for example, di- and polysaccharides Sucrose and maltose to oligosaccharides to the "classic" Polysaccharides such as cellulose and starch and their derivatives offer a wide range Fabrics can be used. Among the substances from this subgroup 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 and / or P. As zeolite P, for example, zeolite MAP z. B. Doucil A24® (commercial product from Crosfield). However, zeolite X and mixtures of A, X and / or P, for example a co-crystallizate from zeolites A and X, the Vegobond® AX (commercial product from Condea Augusta S. p. A.) are also suitable. The zeolite can be used as a spray-dried powder or as an undried stabilized suspension that is still moist from its production. In the event that the zeolite is used as a suspension, it may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C ₁₂ -C ₁₈ 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 in amounts from 10 to 94.5% by weight contain the moldings, it being particularly preferred if zeolites in Amounts of 20 to 70, in particular 30 to 60 wt .-% are included.

Suitable carriers are also layered sodium silicates of the general formula NaMSi _x O _{2x + 1} .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 .yH ₂ O are preferred.

The preferred builder substances and thus the preferred carriers also include amorphous sodium silicates with a modulus Na ₂ O: SiO ₂ of 1: 2 to 1: 3.3, preferably of 1: 2 to 1: 2.8 and in particular of 1: 2 to 1: 2.6, which are delayed release and have secondary washing properties. The delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compaction or 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 blurred 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 60 024. Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.

Suitable carrier materials are furthermore layered silicates natural and synthetic Origin. Their usability is not based on a special composition or Structural formula limited. 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. 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, those in the form of their sodium salts usable polycarboxylic acids, such as citric acid, adipic acid, succinic acid, Glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, and Mixtures of these. Preferred salts are the salts of polycarboxylic acids such as Citro Nenoic acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and Mi created from these.

The acids themselves can also be used. The acids have besides theirs Property as a carrier typically also the property of a Acidifying component and thus also serve to set a lower and milder pH of detergents or cleaning agents. In particular, here are Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any To call mixtures of these. These acids are preferred when used in premix according to the invention is used and is not subsequently added, used anhydrous.  

In principle, any combination of the substances listed here can be used as a carrier be used. It is particularly preferred if combinations are used that can be called basic detergents, d. H. the compositions have, as are common in detergents.

If necessary, the moldings can contain auxiliary substances which ensure cohesion improve the carrier particles with the perfume.

Suitable auxiliaries are those from the group of polyethylene glycols Fatty alcohol ethoxylates and fatty acid alkoxylates used in preferred processes in quantities from 0 to 10% by weight, preferably from 2 to 9% by weight and in particular from 5 to 7 wt .-%, each based on the weight of the molded body used become.

The optional fatty acid alkoxylates can be described by the general formula I:

in which R ^{1 is} selected from C _7-17 alkyl or alkenyl, R ² = -H or -CH ₃ and k = 2 to 10. Suitable fatty alcohol alkoxylates satisfy the formula II:

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 molar masses from 200 to 5,000,000 gmol ^-1 . The products with molar masses 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 which are preferably used can have a linear or branched structure, linear polyethylene glycols in particular being preferred.

The particularly preferred polyethylene glycols include those with relative moles cooling masses between 2000 and 12000, advantageously around 4000, polyethylene glycol kole with relative molecular weights below 3500 and above 5000 especially in Combination with polyethylene glycols with a molecular weight around 4000 can be used and such combinations advantageously to more than 50 % By weight, based on the total amount of polyethylene glycols, with polyethylene glycols have a relative molecular mass between 3500 and 5000. Can as a binder however, polyethylene glycols are also used, which in themselves at room temperature and a pressure of 1 bar in the liquid state; here is mostly from Polyethylene glycol with a relative molecular weight of 200, 400 and 600.

The moldings contain such auxiliaries in amounts of 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.

Individual perfume oils or fragrances can be used in the moldings Fragrance compounds, e.g. B. the synthetic products of the ester, ether, Aldehydes, ketones, alcohols and hydrocarbons can be used. Fragrance compounds of the ester type are e.g. B. benzyl acetate, phenoxyethyl  isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate (DMBCA), phenylethyl acetate, benzyl acetate, ethyl methylphenylglycinate, allylcyclohexyl propionate, styrallyl propionate, benzyl salicylate, cyclohexyl salicylate, floramate, melusate and Jasmine Cyclate. The ethers include, for example, benzyl ethyl ether and ambroxan the aldehydes e.g. B. the linear alkanals with 8-18 C atoms, citral, citronellal, Citronellyloxy-acetaldehyde, cyclamenaldehyde, Lilial and Bourgeonal, to the ketones e.g. B. the Jonone, ∝-isomethyl ionone and methyl cedryl ketone, to the alcohols anethole, Citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol Hydrocarbons mainly belong to the terpenes like limonene and pinene. However, mixtures of different odoriferous substances are preferably used create an appealing fragrance together.

Such perfume oils can also contain natural fragrance mixtures such as those from plant sources are accessible, e.g. B. pine, citrus, jasmine, patchouly, rose or Ylang-ylang oil. Also suitable are muscatel sage oil, chamomile oil, clove oil, Melissa oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, Olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, Orange peel oil and sandalwood oil.

The general description of the perfumes that can be used (see above) generally provided the different substance classes of odoriferous substances. To be perceptible, a fragrance be volatile, in addition to the nature of the functional groups and the Structure of the chemical compound also the molecular weight plays an important role. So 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 changes the smell several perfumes or perfume compound during the Vaporizing, with the odor impressions in "top note", "heart or Middle note "(middle note or body) and" base note "(end note or dry out) divided. Since the smell is largely based on the smell intensity, the top note of a perfume or fragrance does not consist solely of volatile Compounds, while the base note is largely made up of less volatile, i.e. H.  non-stick fragrances. When composing perfumes can be easier volatile fragrances, for example, are bound to certain fixatives, thereby too fast evaporation is prevented. In the following classification of Fragrances in "more volatile" or "sticky" fragrances is so over Odor impression and whether the corresponding fragrance as a top or heart note is perceived, nothing is said.

Adhesive fragrances that 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, champaca flower oil, noble fir oil, noble pine cone oil, Elemi oil, eucalyptus oil, fennel oil, spruce needle oil, galbanum oil, geranium oil, ginger grass oil, Guaiac wood oil, gurjun balsam oil, helichrysum oil, ho oil, ginger oil, iris oil, kajeput oil, Calamus oil, chamomile oil, camphor oil, kanaga oil, cardamom oil, cassia oil, pine needle oil, Kopaïva balsam oil, coriander oil, spearmint oil, caraway oil, cumin oil, lavender oil, Lemongrass oil, lime oil, mandarin oil, lemon balm oil, musk seed 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, 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, lemon oil and cypress oil.

But also the higher-boiling or solid fragrances, natural or synthetic Origin can be used in the context of the present invention as adhesive odoriferous substances or Fragrance mixtures, i.e. fragrances, are used. These connections include the following compounds and mixtures of these: ambrettolide, α- Amyl cinnamaldehyde, anethole, anisaldehyde, anis alcohol, anisole, anthranilic acid methyl ester, Acetophenone, benzylacetone, benzaldehyde, ethyl benzoate, benzophenone, Benzyl alcohol, benzyl acetate, benzyl benzoate, benzyl formate, benzyl valerianate, borneol, Bornyl acetate, α-bromostyrene, n-decylaldehyde, n-dodecylaldehyde, eugenol, Eugenol methyl ether, eucalyptol, farnesol, fenchone, fenchyl acetate, geranyl acetate, Geranyl formate, heliotropin, heptin carboxylic acid methyl ester, heptaldehyde, hydroquinone Dimethyl ether, hydroxycinnamaldehyde, hydroxycinnamyl alcohol, indole, iron, isoeugenol, Isoeugenol methyl ether, isosafrol, jasmon, camphor, karvakrol, karvon, p-  Cresol methyl ether, cumann, p-methoxyacetophenone, methyl-n-amyl ketone, Methylanthranilic acid methyl ester, p-methylacetophenone, methylchavilcol, p- Methylquinoline, methyl-β-naphthyl ketone, methyl-n-nonylacetaldehyde, methyl-n nonyl ketone, muskon, β-naphthol ethyl ether, β-naphthol methyl ether, nerol, n- Nonyl aldehyde, nonyl alcohol, n-octyl aldehyde, p-oxy-acetophenone, pentadehanolide, β- Phenylethyl alcohol, phenylacetaldehyde dimethyacetal, phenylacetic acid, pulegon, safrol, Salicylic acid isoamyl ester, salicylic acid methyl ester, salicylic acid hexyl ester, Cyclohexyl salicylic acid, Santalol, Skatol, Terpineol, Thymen, Thymol, γ-undelactone, Vanilin, veratrum aldehyde, cinnamaldehyde, cimate alcohol, cinnamic acid, ethyl cinnamate, Benzyl cinnamate.

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

In the moldings according to the invention, in addition to those mentioned Ingredients other ingredients in minor amounts from 1 to 10 wt .-%, preferably 1 to 5 wt .-% and in particular 1 to 2 wt .-%, each based on the Shaped bodies may be included. These substances can serve to stain the fragrance pearls or to give them application-related advantages. But it can also Detergent ingredients are added, their usual incorporation brings procedural disadvantages. So are usually low Amounts of substances used such as optical brighteners, phosphonates, Color transfer inhibitors etc. subsequently mixed. By bringing this in Fabrics are made of perfume moldings, in particular fragrance pearls, the others Active substances contained and so as a fragrance and active compound in washing and Detergents can be introduced. In addition, in this way the Production of detergents and cleaning agents an additional process step saved.  

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

Another object of the present invention is a method for producing Fragrance moldings, in particular fragrance pearls, in which a solid and essentially anhydrous premix of a) 20 to 92% by weight of detergent base granules, b) 0 to 10 % By weight of excipient (s), c) 5 to 25% by weight of perfume and d) 3 to 60% by weight of carrier, which has an anionic, at least 2-dimensionally cross-linked partial structure and Contains alkylammonium ions, subjected to granulation or press agglomeration becomes.

In the context of this invention, a condition is "substantially water-free" understand, in which the content of liquid, i.e. H. not in the form of water of hydration and / or Constitutional water 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 part of the raw materials present as a solid or Compounds, but not as a liquid, solution or dispersion in the process for Preparation of the premix can be introduced. This advantageously indicates Premix a total water content of not more than 15 wt .-%, wherein this water is not in liquid, free form, but chemically and / or physically is bound, and it is particularly preferred that the content of non-zeolite and / or water bound to silicates in the solid premix not more than 10% by weight % and in particular not more than 7% by weight.

The ingredients to be used in the process, such as carrier substances, auxiliaries and fragrances in particular have already been described in detail above. In particular, it is preferred if the detergent used according to the invention  Basic granulate one or more substances from the group of surfactants, surfactant compounds, di- and contains polysaccharides, silicates, zeolites, carbonates, sulfates and citrates in quantities, and the base granules in amounts of 30 to 80% by weight, preferably 40 to 75 % By weight, based in each case on the weight of the shaped body formed, is used.

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

The essentially water-free premix is used in the process according to the invention after combining the individual components of a granulation or Subjected to press agglomeration. During the granulation, the premix is replaced by the rotating mixing tools compacted and homogenized and to perfume Shaped bodies, especially fragrance pearls, granulated. The granulation of the essentially water-free premix provides fragrance pearls with a broader range of grains (Coarse and fine fractions), which is why the process variant of press agglomeration compared granulation is preferred.

In the press agglomeration process, the premix is under pressure and under The action of shear forces compresses and plastifies, thereby homogenizing and then discharged form-giving from the apparatus. The most technically significant Press agglomeration processes are extrusion, roller compaction, Pelleting and tableting. Preferred in the context of the present invention Press agglomeration processes are extrusion, roller compaction and Pelleting.  

In a preferred embodiment of the invention, the premix is preferred continuously a planetary roller extruder or a 2-shaft extruder or 2- Screw extruder with co-rotating or counter-rotating screw guide is supplied leads, its housing and its extruder pelletizing head to the predetermined extrusion temperature can be heated. Under the shear of the extruder screws the premix is under pressure, which is preferably at least 25 bar, at extreme high throughputs depending on the apparatus used but also below can lie, compressed, plasticized, in the form of fine strands through the perforated nozzle plate in the -Extruder head extruded and finally the extrudate using a rotating tee knife preferably to approximately spherical to cylindrical granules downsized. The hole diameter of the perforated nozzle plate and the strand cut length are matched to the selected granule size. In this embodiment it works the production of granules of an essentially uniformly predictable Particle size, the absolute particle sizes being the intended one Purpose can be adapted. Generally, particle diameters are up to at most 0.8 cm 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. The length / diameter The ratio of the primary granules cut off is an important one Embodiment in the range from about 1: 1 to about 3: 1. It is further preferred that plastic primary granules a further shaping processing step feed; edges present on the crude extrudate are rounded off, so that ultimately spherical to approximately spherical extrudate grains can be obtained. If Small amounts of dry powder, for example, may be desired in this stage Zeolite powder such as zeolite NaA powder can also be used. This shape can be in commercially available rounding machines. It is important to ensure that at this stage only small amounts of fine grain content arise. A drying of the resulting extrudates is unnecessary in the context of the present invention, since the method according to the invention essentially anhydrous, i.e. without the addition of free, unbound water he follows.

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

As in the extrusion process, it is also in the other manufacturing processes prefers the resulting primary granules / compactate another form Ver to carry out work step, in particular to round off, so that ultimately spherical to approximately spherical (pearl-shaped) grains can be obtained.

Because the process according to the invention is essentially anhydrous - that is, H. with off Taking water contents ("impurities") of the solid raw materials used is carried out, an ecologically valuable process is provided because not only saving energy by not using a subsequent drying step but also emissions, as they predominantly with conventional types of drying occur, can be avoided. In addition, the waiver of Subsequent drying steps include the incorporation of the fragrances into the premix and thus the production of the fragrance molded articles according to the invention, in particular Scented pearls.

In a further preferred embodiment of the present invention, the 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 targeted between two smooth rollers or with recesses of a defined shape metered in and between the two rollers under pressure to form a sheet Kompaktat, the so-called Schülpe, rolled out. The rollers practice on the premix a high line pressure and can be additionally heated or cooled as required become. When using smooth rollers, you get smooth, unstructured Cuffs, while using structured rollers accordingly structured slugs can be created, in which, for example, certain shapes the later perfume molded body can be specified. The wristband will subsequently by a knocking and crushing process into smaller pieces broken and can in this way be processed into granules by further surface treatment processes known per se are further compensated, in particular can be brought into an approximately spherical shape.  

In a further preferred embodiment of the present invention, the Process according to the invention carried out by means of pelleting. Here is the fragrance-containing solid and essentially water-free premix on a perforated Surface applied and by means of a pressure-producing body with plasticization the holes pressed. In usual embodiments of pellet presses, this is Premix compressed under pressure, plasticized, by means of a rotating roller in the form fine strands pressed through a perforated surface and finally with a Chopping device crushed into granules. Here are the most varied Configurations of the pressure roller and perforated die are conceivable. So find it for example flat perforated plates as well as concave or convex plates Ring matrices through which the material is held by means of one or more pressure rollers is pressed through. The press rolls can also be conical in the plate machines in the ring-shaped devices, dies and press roller (s) can run in the same direction or have opposite sense of rotation. One for performing the invention Apparatus suitable for the process is described, for example, in the German patent application DE 38 16 842 (Schlüter GmbH). The one disclosed in this document The ring die press consists of a rotating one with press channels Ring die and at least one with its inner surface in operative connection Press roll, which the material supplied to the die space through the press channels into one Material discharge presses. The ring die and press roller can be driven in the same direction, whereby a reduced shear stress and thus a lower temperature increase of the Premix is feasible. Of course, it can also be used for pelleting heatable or coolable rollers are worked to a desired temperature of the Adjust premix.

Another press agglomeration process which can be used according to the invention is the tableting. Due to the size of the molded body it can be Tableting may be useful, in addition to the binder, customary disintegration aids, for example to add cellulose and its derivatives or cross-linked PVP, which the Ease disintegration of the compacts in the wash liquor.  

The fragrance molded articles produced according to the invention can additionally be sprayed with perfume afterwards. The conventional fragrance variant, i.e. H. powdering and spraying with perfume can be done according to the invention perform perfume moldings produced.

The fragrance moldings produced according to the invention are advantageously used 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 via the Manufacturing methods according to the invention introduced into the agent, d. H. into the granules or Press agglomerates incorporated, while the remaining 70% by weight, preferably 60% by weight % and in particular 50% by weight of the total perfume contained on the Granules or press agglomerates, which can optionally be surface-treated, sprayed or applied in another way.

By dividing the total perfume content of the agent into perfume, which in the Granules or press agglomerates is contained and perfume, which on the granules or Press agglomerates adheres, a variety of product characteristics can be realized, which are only possible through the inventive method. For example conceivable and possible, the total perfume content of the funds in two portions x and y to divide, the proportion x consisting of adherent, d. H. less volatile and the portion y from there is more volatile perfume oils.

Washing or cleaning agents can now be produced in which the proportion of the perfume, which is introduced into the agents via the granules or press agglomerates, mainly is composed of strong odoriferous substances. In this way, adherent Fragrances that are intended to scent the treated objects, especially textiles, in Product "held" and its effect mainly on the unfold treated laundry. In contrast, the more volatile fragrances contribute an intensified scenting of the agents. In this way it is also possible To produce detergents and cleaning agents that have a smell as a means that differs from the smell of the treated objects. The creativity of perfumers there are hardly any limits, because on the one hand and on the choice of fragrances On the other hand, the choice of the method of incorporation into the funds is almost limitless  Possibilities exist, the means and, via the means, those treated with them Scent objects.

The principle described above can of course also be reversed by the more volatile fragrances are incorporated into the granules or press agglomerates and the more volatile, adherent fragrances are sprayed onto the agent. To this The loss of the more volatile fragrances from the packaging will help Storage and transportation are minimized, while the fragrance characteristics of the agents differ more adhesive perfumes is determined. The contained in the fragrance moldings Elevator aids then ensure that the laundry is evenly wound on the laundry Fragrance components is achieved.

In a further embodiment, the present invention relates to washing or Detergents, the perfume molded articles according to the invention or according to the invention Manufactured perfume moldings, in particular fragrance pearls, in quantities of more than 0.5 % By weight, preferably more than 1% by weight and in particular more than 2% by weight, in each case based on the detergent or cleaning agent.

These perfume moldings, in particular fragrance pearls, can be used in conventional washing and Detergents are incorporated and then serve according to the above Use for scenting these funds. But it is also possible to use the invention Manufactured perfume moldings, in particular fragrance pearls, separately as part of a Offer "modular" system in which the consumer has a fragrance-free Acquires basic detergent and various perfume moldings, in particular Fragrance pearls, can be mixed, depending on the type of laundry treated under the to be able to select a wide variety of fragrances.

In all of these embodiments, the perfume molded articles according to the invention are ultimately for scenting surfaces, especially fibers, and in a very special way preferred embodiment used for scenting textile fibers. Therefore is a Another object of the invention, the use of carrier materials, the one Have anionic, at least 2-dimensionally cross-linked partial structure and the  Alkylammonium ions contain the fragrances to improve the fragrance impression Leave surfaces.

Examples

By mixing the recipe components mentioned below in a Lödige Mixers were made into free-flowing premixes that were compressed in an extruder and were plasticized.

Table 1

Composition of the premixes or fragrance pearls

Composition of the spray granules (surfactant compounds produced by spray drying): 26.2% by weight Na-C _9-13 alkylbenzenesulfonate, 4.0% by weight sodium carbonate, 55.6% by weight zeolite 4A, 0.7% by weight. % Salts from solution, 13.0% by weight water and 0.5% by weight sodium hydroxide.

The free-flowing premixes showed after leaving the mixer Bulk density of about 400 g / l and was in a twin-screw extruder from Lihotzky given and plasticized and extruded under pressure.

The plasticized premixes left the extruder at a pressure of 85 bar a perforated plate with exit holes of 1.4 mm in diameter. The extruded Strands were cut to a length / diameter with a rotating chopper Cut off ratio of approx. 1 and rounded in a Marumerizer®. After this Sieving the fine parts (<0.4 mm) and the coarse parts (<2.0 mm) showed the extrudates the bulk weights listed in Table 1.

The fragrance beads E1 to E3 produced according to the invention were perfume-free Extrudates mixed into detergents and with detergents produced analogously, which Fragrance pearls without the cationized bentonite contained (V1 or V2), in a pair comparison tested. The perfume oil content in the respective recipes was kept constant.

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

Table 2

Perfume oil composition [% by weight]

Table 3

Fragrance impression (preference of favor, number of perfumers)

While the bentonite-containing fragrance pearl (V2) is significantly worse in a pair comparison section as the zeolite-based fragrance pearl (V1), showed the invention Fragrance pearls E1-E3 in pair comparison with the zeolite-based fragrance pearl (V1) in particular on the laundry a significant improvement in the fragrance impression.

Claims (18)

1. Containing perfume moldings

• a) 65 to 95% by weight of carrier (s),
• b) 0 to 10 wt .-% excipient (s) and
• c) 5 to 25% by weight of perfume,

characterized in that a proportion of the carriers a) is selected from carriers which have an anionic, at least 2-dimensionally crosslinked partial structure and which contain alkylammonium ions. 2. Perfume molded article according to claim 1, characterized in that it is the anionic, at least 2-dimensionally cross-linked substructure by one inorganic, in particular a silicate layer structure. 3. Perfume molded article according to claim 1, characterized in that it is the anionic, at least 2-dimensionally cross-linked substructure organic polymer, in particular a derivative of a natural polymer, preferably a derivative of a polysaccharide. 4. Perfume molded article according to claim 1 or 2, characterized in that it is in the carrier which contains alkylammonium ions, a layered silicate of the formula M ₂ Si _x O _{2x + 1} .yH ₂ O, where M is a sodium - and / or a hydrogen and / or an alkylammonium ion, x is a number from 1.9 to 4 and y is a number from 0 to 20. 5. Perfume molded article according to claim 1 or 2, characterized in that it is in the carrier containing alkylammonium ions to a modified Bentonite-type silicate, preferably montmorillonite-type. 6. Perfume molded body according to one of claims 1 to 5, characterized in that the carrier that crosslinks an anionic, at least two-dimensionally Has partial structure and contains alkylammonium ions, at least 3% by weight,  preferably at least 5 and in particular more than 7% by weight of the fragrance Molded body. 7. Perfume molded body according to one of claims 1 to 6, characterized in that that the carrier that crosslinks an anionic, at least two-dimensionally Has partial structure and contains alkylammonium ions, less than 80% by weight, preferably less than 70 and in particular less than 50% by weight of the Perfume molded body. 8. Perfume shaped body according to one of claims 1 to 7, characterized in that the moldings have a bulk density above 600 g / l, preferably above of 700 g / l and an average particle size distribution in the range of 0.3 have up to 5.0 mm, preferably from the range of 0.5 to 3.0 mm. 9. Fragrance molded article according to one of claims 1 to 8, characterized in that the molded articles contain, in addition to the ingredients mentioned, a substance which improves the absorption of the fragrance on surfaces, which is one or more substances from the group of Paraffins, the quaternary ammonium compounds, the soil-release polymers, in particular the copolymeric polyesters and other polymers, such as in particular polyvinylpyrrolidone and block copolymers with blocks (-CH ₂ -CH ₂ -O) _n - with n <2. 10. Perfume molded article according to one of claims 1 to 9, characterized in that that the molded body as a component of the carrier material a) one or more Substances from the group of surfactants, surfactant compounds, di- and polysaccharides, Contains silicates, zeolites, carbonates, sulfates and citrates, and this component in Amounts from 30 to 80 wt .-%, preferably from 40 to 75 wt .-%, each based on the weight of the molded body, is included. 11. A process for the production of perfume moldings, in particular fragrance pearls, a solid and essentially water-free premix consisting of

• a) 20 to 92% by weight of detergent base granules,
• b) 0 to 10% by weight of excipient (s),
• c) 5 to 25% by weight of perfume and
• d) 3 to 60% by weight of carrier material which has an anionic, at least 2-dimensionally crosslinked partial structure and contains alkylammonium ions,

is subjected to granulation or press agglomeration. 12. The method according to claim 11, characterized in that the solid and in essential water-free premix of a press agglomeration, preferably one Extrusion, a roller compaction or a pelletization is subjected. 13. The method according to any one of claims 11 or 12, characterized in that the Premix has a total water content of not more than 15% by weight, this water is not in free form and preferably the content of water not bound to zeolite and / or silicates not more than 10% by weight and in particular not more than 7% by weight. 14. The method according to any one of claims 11 to 13, characterized in that the Basic detergent granules one or more substances from the group of surfactants, Surfactant compounds, di- and polysaccharides, silicates, zeolites, carbonates, sulfates and contains citrate in amounts, and the base granules in amounts of 30 to 80 % By weight, preferably from 40 to 75% by weight, in each case based on the weight of the resulting molded body is used. 15. The method according to any one of claims 11 to 14, characterized in that as Excipient (s) one or more substances from the group of polyethylene glycols, the Fatty alcohol alkoxylates and fatty acid alkoxylates in amounts of 1 to 10% by weight, preferably from 2 to 9% by weight and in particular from 5 to 7% by weight, in each case based on the weight of the molded article that is used. 16. The method according to any one of claims 11 to 15, 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 quantities 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. 17. Detergent or cleaning agent containing perfume shaped articles according to one of the Claims 1 to 10 or fragrance molded body according to a method of claims 11 to 16 were produced, in amounts of more than 0.5% by weight, preferably more than 1% by weight and in particular more than 2% by weight, in each case based on the detergent or cleaning agent. 18. Use of carrier materials that are anionic, at least 2-dimensional have cross-linked substructure and contain the alkylammonium ions for Improvement of the fragrance impression leave the fragrances on surfaces.