DE102004006135A1 - Method for applying micro/nano quantity of odorants on a medium (e.g. washing agents) comprises spraying a mixture of the odorants and carbon dioxide and condensing the odorants in liquid or solid form on the medium by cooling - Google Patents

Abstract

Method for applying micro/nano quantity of odorants on a medium (preferably washing-, cleaning-preserving agents and/or their precursors) comprises spraying a mixture (in the form of liquid or paste) of the odorants and carbon dioxide at a pressure where the carbon dioxide is released in the form of gas and condensing the odorants in liquid or solid form on the medium by cooling. Independent claims are also included for: (1) a medium comprising the odorants obtained by the method; (2) aromatic substance comprising the medium (preferably in solid form) containing 10 (preferably 50) wt.% of the total aroma material related to the total weight of the aroma material; (3) the preparation of the odorants; (4) odorants in micro/nano quantity obtained by the method; and (5) a product comprising product medium and the odorants.

Description

The The present invention relates to micro / nanoscale perfume particles, in particular micro / nanoscale perfume particles having agents and products comprising such agents as detergents, cleaning care products and / or precursors thereof, and a process for producing such micro- / nanoscale perfume particles and a method of preparation such agents with micro / nanoscale perfume particles.

In order to for example, freshly washed laundry also smells "fresh", detergents are numerous fragrances added. Fragrances do not only affect the sense of smell. she can in too high doses may also lead to irritation, the manifest in symptoms such as stinging, burning or tingling, similar to one Allergy. Furthermore People who already suffer from allergies take these chemicals often stronger true or more responsive thereon. Although fragrances in individual products or items are only in extremely small Contain quantities. Due to the multitude of fragrant products that When we use it in everyday life, it can lead to an accumulation of the fragrance amount come. For example, there is a great need for the fragrance experience of funds over to optimize a long-lasting period, for example by achieving it a particular scent sequence or the scent experience over a long period of time to keep virtually constant as well as simultaneously the one for that needed Reduce the amount of fragrance.

Usually become particulate Detergents or cleaning agents prepared by spray drying. Devices for spray drying aqueous compositions are known in the art known. Often Devices used are, for example, spray towers with atomizing nozzles, which especially in liquid Starting materials, such as solutions, Suspensions or melts to provide a powdered product be used. Here, the aqueous liquid is usually atomized with pressure nozzles and then it dries in the hot gas in cocurrent or countercurrent. Then the dry product is through Cyclones or filters deposited.

at the production of powdered Detergents become common in a first step an aqueous one Slurry "slurry" formed. The slurry contains thermally stable detergent ingredients that are among the Conditions of spray drying neither volatilize still decompose like surfactants and builders. Subsequently, will the slurry over Pumping in a spray tower promoted and over located in the head of the spray tower Nozzles sprayed. through rising air with a temperature of 200 to 350 ° C is the Slurry dried and the adhering water evaporates, leaving the Detergent ingredients at the outlet of the tower, where temperatures of 80-120 ° C occur, be obtained as a powder. The powder will then become more temperaturlabile Ingredients such as bleach or fragrances, mixed. at the spray-drying known in the art is disadvantageous, that the fragrances added to the powder at a relatively late date become.

In EP-A1 0 200 881 describes washing and cleaning agents, being the washing and cleaning agent comprising fine microparticles, wherein the fine microparticles have a or more detergent and cleaner ingredients.

The Known in the art fine microparticles have a at most low fragrance content, since by means of the usual Manufacturing process micro / nanoscale perfume particles with high perfume content can not be produced. It is well known that with increasing Fragrance content, the particle size of the microparticles clearly increases, especially aqueous spray-fragrance mixtures already due to their low perfume solubility no high perfume levels allow. Also, the temperatures of 200 ° C to 350 ° C are those of the detergent slurry dried too high to fragrances as such to be dried spray product added, since the fragrances would evaporate at least for the most part. Further tend usual known in the art known perfume having microparticles with increasing perfume content to increased stickiness, resulting in a Agglomeration of microparticles leads, so that with conventional Process no very finely divided microparticles with a high Make perfume fraction produce. These include in particular oily perfumes. Furthermore can be finely divided microparticles, the fragrances with low Flash point not included with that required for the production facility Safety, since due to the low flash point at the processing considerable dangers, such as fire or explosion, consist. Consequently, so far in the state of or explosion, consist. Consequently, so far in the prior art no produce finely divided microparticles, the fragrances both with low flashpoint, as well as having a high flash point.

Generally For example, finely divided detergent particles by means of spray in the spray tower. A disadvantage of the known spraying method in the spray tower are in particular high mass losses during spraying because volatile Components of the spray product be entrained at least partially with the exhaust air stream. Especially For components with high vapor pressure, such as fragrances, you have to Application of conventional spraying in the spray tower expect a bad yield.

task It is the object of the present invention to provide micro / nanoscale fragrance particles, in particular micro / nanoscale perfume particles having agents as well as products comprising such agents as washing, cleaning Care products and / or precursors thereof, and a method for manufacturing Such micro / nanoscale fragrance particles and agents with to provide micro / nanoscale perfume particles, so that the overcome the aforementioned disadvantages of the prior art at least partially become.

The Object of the present invention is by means of a method for applying fragrances in micro / nanoscale form to compositions in particular washing, cleaning care particles and / or precursors of it, solved, wherein one is a pressurized liquid or pasty perfume / e-carbon dioxide mixture at lower pressure to release the carbon dioxide in the form of carbon dioxide gas in the presence of the agent sprayed, wherein the forming micro / nanoscale fragrance particles are submerged Cooling on the medium in liquid or solid form.

In addition, let by means of the method according to the invention create micro / nanoscale perfume particles by placing an under Pressurized fluid or pasty Perfume / e-carbon dioxide mixture below Release of carbon dioxide in the form of carbon dioxide gas Cooling sprayed whereby the micro / nanoscale fragrance particles form.

at the agents with applied micro- / nanoscale perfume particles For the purposes of this invention, it is preferably a direct one Spray drying product with applied micro- / nanoscale perfume particles or um a detergent ingredient with applied micro- / nanoscale Fragrance particles, wherein the agents with applied micro- / nanoscale Perfume particles preferably in the form of particles, such as primary particles, secondary Particles and / or agglomerates are present.

Primary particles are particles that are not used as a direct spray-drying product itself particles with a larger diameter form. By contrast, secondary particles are particles under magnification of the Diameter to larger particles agglomerate.

Under the wording "means with applied micro- / nanoscale perfume particles "is in the sense of this Invention to understand that perfume particles with micro- / nanoscale Particle size on the Means, wherein the agent is preferably in the form of particles, such as Particles, powders, granules and / or agglomerates, is applied with the micro / nanoscale particle size on the Agent applied perfume particles, as far as they are liquid at room temperature or are flowable, these are subsequently submerged by the agent Loss of their previous particle shape ad- and / or absorbed can.

in the The scope of the present invention is under a "direct Spray-drying agent "with applied micro / nanoscale perfume understood a means by which one a pressurized liquid or pasty Fragrance / e-carbon dioxide mixture at lower pressure with release of the carbon dioxide in the form of carbon dioxide gas in the presence of the agent sprayed wherein the forming agents with applied micro- / nanoscale Fragrance particles, preferably in the form of particles, without further After treatment can be obtained.

The Agent with applied micro- / nanoscale perfume particles but in the context of this invention can also direct spray-drying with applied micro / nanoscale fragrance particles comprising subsequently after-treatment or mixtures of direct spray-drying agent with applied micro- / nanoscale perfume particles and after-treated Spray drying agent contain or consist of.

Products For the purposes of this invention, agents with applied micro / nano-scale include Fragrance particles, wherein the agents with applied micro- / nanoscale Fragrance particles preferably in the form of particles.

Under the formulation "micro- / nanoscale Fragrance particles " Understood perfume particles that can be produced by one pressurized liquid or pasty Perfumes - carbon dioxide - mixture releasing the carbon dioxide in the form of carbon dioxide gas under cooling sprayed whereby the micro / nanoscale fragrance particles form.

in the With regard to the fineness of the micro / nanoscale perfume particles it is pointed out that the specified particle size distributions on the direct micro / nanoscale fragrance particle spray drying product refer, i. without further treatment. Here it is special advantageous that the micro- / nanoscale fragrance particles a to a relatively large extent uniform Kornspektrum show, without further usual, from the state of the art known post-treatments such as crushing and / or screening of larger components or screening dust particles are required. Such measures to lead in a large-scale Production always to a complexing of the procedure, whereby usually one Reduction of the product yield and thus an increase in the price of the product Associated with the product.

fragrances For the purposes of this invention, fragrances include those in humans trigger a sense of smell, for example perfumes, fragrant natural oils, essences and / or flavors.

According to the invention preferred Fragrances include fragrances that have a pleasant odor in humans trigger.

• – eine Kopfnote gebildet vorzugsweise aus den flüchtigsten Bestandteilen und bestimmen den ersten Dufteindruck; und/oder
• – eine Herznote, vorzugsweise gebildet aus den schweren, süßen Blütenaromen; und/oder
• – eine Basisnote, schwer auf Anhieb wahrnehmbar, machen die sinnlichsten Töne aus.

Fragrances according to the invention may comprise at least a part, preferably three parts of the following fragrance notes:

• A top note preferably formed from the most volatile components and determine the first fragrance impression; and or
• - A heart note, preferably formed from the heavy, sweet flower aromas; and or
• - a base note, difficult to perceive right away, make the most sensual sounds.

It was now surprising found that micro / nanoscale perfume particles with high perfume content obtained when you produce a slurry that acts as a solvent Having carbon dioxide. For the preparation of a solvent Carbon dioxide-containing slurry can be carbon dioxide of the perfume-containing composition, preferably as solid carbon dioxide under atmospheric pressure, or as Gas or liquid under Add pressure. Subsequently the mixture is adjusted to the pre-processing temperature, wherein the pressure rises. By means of the addition of carbon dioxide, as a result its comparatively very low viscosity and surface tension, there is a decrease in the viscosity and the surface tension containing the fragrance in high concentration slurries, so that it possible in this way is, fine perfume droplets to spray, for example in mixers.

Furthermore let yourself as a result of spraying occurring evaporation cold by the evaporating carbon dioxide the mass balance of the micro- / nanoscale Fragrance particles and the micro / nanoscale perfume particles significantly improve means by means of the method according to the invention, because the temperature of the perfume droplets is significantly lower than the usual spraying of the oil at ambient temperature.

The pressurized carbon dioxide containing solvent as slurries with a high proportion of perfume Contain water, for example, when processing a fragrance emulsion. The water content of the slurries containing carbon dioxide as a solvent with high perfume content, which may be liquid or pasty but preferably ≤ 50 wt .-%, preferably ≤ 40 Wt .-%, more preferably ≤ 30 Wt .-% and also preferably ≤ 20 Wt .-%, based on the total weight of the slurries be.

Of the pressurized carbon dioxide containing solvent as a slurry with a high proportion of perfume may preferably also be anhydrous.

in the Meaning of this invention means "anhydrous Slurry "that one Water content of ≤ 1 Wt .-%, based on the total weight of the slurry, is not exceeded, but mostly is significantly lower or exactly zero.

According to the invention, carbon dioxide can be added to the perfume as a solid under atmospheric pressure, as a gas or in liquid form under excess pressure. The slurry is then brought to the desired processing temperature, in most cases brought to temperatures between 15 ° C and 40 ° C, with temperatures near the critical temperature (about 32 to 33 ° C) are preferred. The slurry with high Fragrance component takes after tempering a pressure, at most the corresponding vapor pressure of carbon dioxide at; ie a pressure of between 1.5 and 150 bar, preferably at a pressure of between 40-80 bar.

The amount of carbon dioxide which is added to the high perfume slurry makes preferably 10 to 1000 g CO ₂ / l slurry, preferably 50 to 200 g CO ₂ / l slurry.

By the carbon dioxide addition as well as the temperature control becomes the slurry pressure built up. The slurry pressure should preferably be at least as high be that the slurry has as a solvent liquid carbon dioxide. It is preferred that ≥ 75 Wt .-% of the solvent of the slurries liquid Carbon dioxide is.

Of the Total content of carbon dioxide, i. liquid and non-liquid carbon dioxide, based on the total weight of the solvent of the slurries but also ≥ 60 Wt .-%, preferably ≥ 50 Wt .-%, preferably ≥ 40 Wt .-%, more preferably ≥ 30 Wt .-% and more preferably ≥ 20 % By weight.

The Carbon dioxide can be added to the slurry with a high proportion of fragrance, at a temperature of the slurries of 10 ° C to 45 ° C, preferably 15 ° C to 33 ° C, add.

It but it is also possible in the pressurized slurry with high fragrance content To produce carbon dioxide gas chemically, for example by reaction a carbonate and / or a bicarbonate compound with an acid, an acidic compound or by appropriate heat, for example by partial thermal decomposition.

Further one can carbon dioxide as gas, in liquid form and / or in supercritical Condition in the riser of a spray tower, in the pressure line a spray tower, in a spray agglomeration plant and / or the coating plant, for example, at a pressure of 1.5 to 80 bar, admit.

Of the Addition of carbon dioxide as Slurrylösemittel leads to a reduction of viscosity and the surface tension of the slurries. This allows higher slurry perfume concentrations to adjust. Furthermore decreases as a result of reducing the surface tension of carbon dioxide as a solvent Slurries containing the drop size in the spray, when spraying the so produced slurries with high perfume content, for example when spraying in a mixer, clearly off.

About the The amount of carbon dioxide added to the fragrance slurry can be reduced the viscosity of the slurries, for example in the range of between 1.5 mPas to Set 80 mPas, preferably 5 mPas to 30 mPas.

The viscosity was at 20 ° C determined in a rotational viscometer at an adjusted shear rate.

The Adjustment of viscosity of the slurries with high perfume content by adding carbon dioxide as solvent is advantageous because you over the viscosity the slurries with high fragrance content the drop size and / or the particle size of the micro / nanoscale Can control fragrance particles.

Produced according to the invention Fragrance particles in the form of micro / nanoscale perfume particles can perfume from 0.05% to 2% by weight, based on the total weight of the micro / nanoscale Perfume particles.

The Fragrances can before the carbon dioxide addition as a liquid oil, as an aqueous emulsion and / or as Blend with an organic substance that has a melting point of 30 ° C to 70 ° C, available.

Micro / nanoscale according to the invention disk-based Fragrance particles can Perfume with 0.05 wt .-% to 10 wt .-%, based on the total weight the micro / nanoscale perfume particles.

The Micro / nanoscale invention Fragrance particles can 0.03 wt .-% to 1.5 wt .-% perfume with high vapor pressure based on the total weight of the micro / nanoscale perfume particles.

The micro- / nanoscale perfume particles according to the invention may contain 0.02% to 1.5% by weight of low vapor pressure fragrance, based on the total weight of the micro / nanoscale fragrance particle kel.

The Micro / nanoscale invention Fragrance particles can From 0.02% to 15% by weight of carrier, preferably 0.5% by weight to 1.5% by weight, based on the total weight the micro / nanoscale, supported Perfume particles.

The bulk weight the micro / nanoscale invention Perfume particles can make up a maximum of 1150 g / l. It is preferred when the bulk density at least 250 g / l.

According to one preferred embodiment The invention may relate to the perfume / e-carbon dioxide mixture on the total weight of the perfume / e-carbon dioxide mixture, the Perfume / s in excess exhibit.

• – ≥ 0 Gew.-% bis ≤ 50 Gew.-% Wasser, vorzugsweise ≥ 1 Gew.-% bis ≤ 40 Gew.-% Wasser, bevorzugt ≥ 2 Gew.-% bis ≤ 30 Gew.-% Wasser, weiter bevorzugt ≥ 3 Gew.-% bis ≤ 25 Gew.-% Wasser, noch bevorzugt ≥ 5 Gew.-% bis ≤ 20 Gew.-% Wasser und am meisten bevorzugt ≥ 6 Gew.-% bis 15 Gew.-% Wasser;
• – ≥ 1 Gew.-% bis ≤ 75 Gew.-% Kohlendioxid, vorzugsweise ≥ 3 Gew.-% bis ≤ 60 Gew.-% Kohlendioxid, bevorzugt ≥ 5 Gew.-% bis ≤ 50 Gew.-% Kohlendioxid, weiter bevorzugt ≥ 7 Gew.-% bis ≤ 40 Gew.-% Kohlendioxid, noch bevorzugt ≥ 10 Gew.-% bis ≤ 30 Gew.-% Wasser und am meisten bevorzugt ≥ 15 Gew.-% bis 20 Gew.-% Kohlendioxid; und
• – ≥ 1 Gew.-% bis ≤ 95 Gew.-% Duftstoff/e, vorzugsweise ≥ 5 Gew.-% bis ≤ 80 Gew.-% Duftstoffe, bevorzugt ≥ 10 Gew.-% bis ≤ 70 Gew.-% Duftstoff/e, weiter bevorzugt ≥ 15 Gew.-% bis ≤ 60 Gew.-% Duftstoff/e, noch bevorzugt ≥ 20 Gew.-% bis ≤ 50 Gew.-% Duftstoff/e und am meisten bevorzugt ≥ 30 Gew.-% bis 40 Gew.-% Duftstoff/e, wobei die Gewichtsanteile an Wasser, Duftstoff/e und Kohlendioxid so gewählt sind, dass der Gesamtgewichtsanteil maximal 100 Gew.-% ausmacht.

It has proven to be advantageous if the perfume / e-carbon dioxide mixture, based on the total weight of the perfume / e-carbon dioxide mixture, comprises:

• - ≥ 0 wt .-% to ≤ 50 wt .-% water, preferably ≥ 1 wt .-% to ≤ 40 wt .-% water, preferably ≥ 2 wt .-% to ≤ 30 wt .-% water, more preferably ≥ 3 wt .-% to ≤ 25 wt .-% water, still preferably ≥ 5 wt .-% to ≤ 20 wt .-% water and most preferably ≥ 6 wt .-% to 15 wt .-% water;
• - ≥ 1 wt .-% to ≤ 75 wt .-% carbon dioxide, preferably ≥ 3 wt .-% to ≤ 60 wt .-% carbon dioxide, preferably ≥ 5 wt .-% to ≤ 50 wt .-% carbon dioxide, more preferably ≥ 7 wt .-% to ≤ 40 wt .-% carbon dioxide, more preferably ≥ 10 wt .-% to ≤ 30 wt .-% water and most preferably ≥ 15 wt .-% to 20 wt .-% carbon dioxide; and
• - ≥ 1 wt .-% to ≤ 95 wt .-% perfume / e, preferably ≥ 5 wt .-% to ≤ 80 wt .-% fragrances, preferably ≥ 10 wt .-% to ≤ 70 wt .-% perfume / e, more preferably ≥ 15 wt .-% to ≤ 60 wt .-% perfume / e, still preferably ≥ 20 wt .-% to ≤ 50 wt .-% perfume / e and most preferably ≥ 30 wt .-% bis 40 wt .-% fragrance / e, wherein the weight proportions of water, perfume / s and carbon dioxide are chosen so that the total weight fraction is at most 100 wt .-%.

through the method according to the invention can be micro / nanoscale fragrance particles with high fragrance concentration which are obtained on middle particles, preferably a larger particle diameter Apply as the micro / nanoscale fragrance particles can.

The Micro / nanoscale perfume particles can be used immediately at and / or after their formation on middle particles, preferably a larger particle diameter as the micro / nanoscale perfume particles, applied become. It is also possible the formed micro / nanoscale fragrance particles at a later time apply to appropriate agent particles.

at preferred micro / nanoscale perfume particles is the direct one micro / nanoscale fragrance particle product anhydrous.

The Perfume-containing agent according to the invention and / or product is preferably selected from the group comprising detergents, cleaners, care products, Hair treatment products, hair dyes, Medicines, plant protection products, foodstuffs, cosmetics, fertilizers, Building material, glue, bleach, disinfectant, fragrance and / or precursors of the aforementioned agents, wherein the agent micro / nanoscale Having perfume particles. Most preferred is when the agent and / or product in the form of particles.

Prefers is especially when the perfume containing the inventive agent a fine particulate Solid, preferably a particulate, preferably fine particulate, washing, Cleaning care products and / or precursors thereof.

The term "particle size" or "particle size", which are used interchangeably in the context of the present text, in the context of the present invention is understood to mean the value commonly referred to as "d ₅₀ ", ie the value of about 50% of the particles smaller diameter and about 50% of the particles have a larger diameter.

In principle, all particle measuring methods, for example measuring methods which rest on the principle of light diffraction, are suitable for determining this value. The particle size data given in the context of the present invention relate to measurements with the MASTERSIZER X instrument, by Malvern Instruments, Herrsching, Germany, (version 1.2b). The operation of this apparatus is based on the diffraction of a light beam by the particle size is associated with the diffraction angle.

Further Methods for the determination of particle sizes are for example the Granulometry, in which in a suitable dispersant a uniform slurry one small amount of the powder to be tested is produced and this is then exposed to sedimentation. From the one according to the Stokes law given relationship between size and density of the particles assumed to be spherical and their rate of sinking can be over the course of time the sedimentation on the percentage distribution of the grain sizes closed become. Further methods for determining the particle size are Microscopy, electron microscopy, sieve analysis, sedimentation analysis, Determination of the density of the surface and the same.

The middle particles to which micro- / nanoscale perfume particles according to the invention can be applied preferably have a particle diameter d ₅₀ of 0.1 μm-25 μm, preferably a particle diameter d ₅₀ of 0.2 μm-15 μm, preferably a particle diameter d ₅₀ of 0, 3 μm-10 μm, more preferably a particle diameter d ₅₀ of 0.4 μm-5 μm, and more preferably a particle diameter d ₅₀ of 0.5 μm-2 μm.

in view of the small particle size of the micro- / nanoscale Fragrance particles in proportion to their particle surface can be applied to the agent amount of micro / nanoscale Significantly reduce fragrance to a substantially same Odor impression, even over an extended one Period, to ensure.

Advantageous is also that one the direct micro / nanoscale perfume particles on the middle particles can spread well, so that is preferable a substantially uniform distribution the micro / nanoscale particles with a high proportion of perfume on ensure the middle particles leaves. It is therefore particularly preferred when the agent or the middle particles in the spray the fragrance / e-carbon dioxide mixture brings, preferably blows.

One Another advantage results from the occurring evaporation cold at the evaporation or evaporation of the carbon dioxide of the micro / nanoscale Perfume particles.

For example can be so festiform produce micro / nanoscale fragrance particles that are normally at room temperature as a liquid, especially as oil, would be present. Due to the occurring evaporation cold these micro / nanoscale Duftstoffparti cle initially but in the form of frozen particles and thus as a solid micro / nanoscale Perfume particles before. These frozen solid-shaped micro / nanoscale Perfume particles can be applied to the surface of the agent, in particular Medium particles, with such direct micro- / nanoscale Perfume particles after they have thawed, at least in part from the middle particles, losing their previous particle shape ad- and / or absorbed. In this case, it is particularly advantageous that is an agglomeration of the direct with fragrance particles reduce or even prevent contaminated agent particles because the frozen micro / nanoscale Fragrance particles compared significantly lower adhesion properties to non-frozen micro- / nanoscale fragrance particles. This applies to both solid at room temperature, as well as for liquid at room temperature micro / nanoscale perfume particles.

Yet Another advantage of the present invention is that that scents with a low flash point in this way, for example in the spray tower, because of a fire or explosion hazard due to the frozen state of the micro- / nanoscale perfume particles the processing can be practically excluded. As already mentioned above, can so even at room temperature liquid, especially oily, micro / nano-scale perfume particles, preferably with a high proportion of fragrance, by the method according to the invention because the middle particles contain these fragrance particles, once they become fluid, admit and / or absorb.

At the Therefore, it is most preferred, the micro / nanoscale perfume particles in the solidified and / or iced state, on the means, being the agent preferably detergents, cleaning care particles and / or precursors this includes applying.

In this case, it is advantageous that a high proportion of the sprayed micro- / nanoscale perfume particles can be precipitated on the agents, preferably middle particles, by means of the method according to the invention, since the perfume particles can be readily applied to the middle particles in the frozen state. The share of Perfume particles which are entrained as a loss, for example in the spray tower, with the exhaust air can be significantly reduced by the method according to the invention.

The Inventive fragrance having agent may at least 10 wt .-% of the perfume, preferably at least 20% by weight of the perfume, preferably at least 30% by weight of the Perfume, more preferably at least 40% by weight of the perfume, even more preferably at least 50% by weight of the perfume, based on the total weight of the composition, in the form of the invention applied micro- / nanoscale perfume particles having.

The inventive agent with applied micro / nanoscale perfume can the perfume with a low flash point, advantageously of ≤ 60 ° C and ≥ 20 ° C, preferably of ≤ 55 ° C, more preferred of ≤ 50 ° C and still more preferably of ≤ 45 ° C.

The inventive agent with applied micro / nanoscale perfume can the perfume with a high flash point, advantageously of> 60 ° C and ≤ 200 ° C, preferably of ≥ 70 ° C, on preferably from ≥ 80 ° C and still more preferably of ≥ 100 ° C.

The inventive agent with applied micro / nanoscale perfume fragrance / e having a low flash point and / or high flash point.

The inventive agent with applied micro / nanoscale perfume may have a fragrance vapor pressure at 20 ° C from 0.001 mbar to 2 mbar, preferably 0.01 mbar to 1.0 mbar and preferably 0.05 mbar to 0.5 mbar.

The inventive agent with applied micro / nanoscale perfume can after a Storage for 24 hours at 20 ° C in the air a fragrance vapor pressure at 20 ° C from 0.001 mbar to 2 mbar, preferably 0.005 mbar to 0.8 mbar and preferably 0.01 mbar to 0.4 mbar.

The produced according to the invention Agent with applied micro- / nanoscale perfume can after a Storage for 48 hours at 20 ° C in the air a fragrance vapor pressure at 20 ° C of 0.001 mbar to 1.5 mbar, preferably 0.003 mbar to 0.7 mbar and preferably 0.01 mbar to 0.3 mbar.

The inventive method allows multiple fragrances in a slurry or spread on to spray several slurries simultaneously or in succession.

Around For example, to extend the period of time over which the middle particles according to the invention with applied micro / nanoscale perfume / s your fragrance or develop perceptible odor, one can carry micro / nanoscale perfume / e spray, the carriers preferably selected are from the group comprising paraffins, surfactants, especially ethoxylated Fatty alcohols, fatty acids, silicone oils and / or fatty alcohol. Particularly preferred carriers are lipophilic substances with a melting point above 25 ° C.

at Addition of carrier substances with a melting point between 30 ° C and 70 ° C, the perfume oil solidifies Cooling and stays in the usual Adhere to temperature ranges of storage as a solid particle on the surface.

According to the invention you can micro- / nanoscale perfume particles whose scent odor you have over a long time sustained period, separated from micro / nanoscale Fragrance particles whose fragrance smell perceive over a shorter lasting period can spray, so that the respectively forming micro / nanoscale perfume particles time after time to be reflected on the mean.

According to the above versions It is also possible according to the invention one by using supported ones micro / nanoscale particles and unsupported micro / nanoscale Particles over an extended one Period even odor experience can achieve by perfumes, preferably made the most fleeting Ingredients - so-called "top note" - that the first fragrance impression determine by adding a suitable carrier with respect to Fragrance release rate delayed.

By using suitable carriers, the release of the fragrances or the odor development can be individually controlled by the micro / nanoscale fragrance particles depending the fragrances contained, for example, top note, middle note and / or base note, respectively different carriers added in the slurry which regulate the odor or fragrance unfolding accordingly, ie, if necessary, delay or extend.

suitable usable carriers can Be substances that extend the odor or fragrance unfolding time or shorten can. Such carriers which delay the odor development or extend can are known in the art and are listed below by way of example.

The produced according to the invention Agent with applied micro / nanoscale perfume can be micro / nanoscale Have perfume particles, preferably at room temperature solid-form excipient exhibit.

• – wenigstens einen Duftstoff mit niedrigen Dampfdruck gemessen bei 20° C, vorzugsweise mit einem Dampfdruck bei 20° C von ≤ 0,1 mbar und ≥ 0,001 mbar; und/oder
• – wenigstens einen Duftstoff mit hohem Dampfdruck, vorzugsweise mit einem Dampfdruck von ≥ 0,1 mbar und ≤ 2 mbar.

The fragrance-containing agent according to the invention may preferably have micro / nano-scale supported fragrance particles, with:

• - At least one fragrance with low vapor pressure measured at 20 ° C, preferably with a vapor pressure at 20 ° C of ≤ 0.1 mbar and ≥ 0.001 mbar; and or
• - At least one perfume with high vapor pressure, preferably with a vapor pressure of ≥ 0.1 mbar and ≤ 2 mbar.

The relationship fragrance particles with high vapor pressure in the form of micro / nanoscale, supported perfume particles and fragrance particles with high vapor pressure in the form of micro / nanoscale, unsupported perfume particles can be from 100: 1 to 1: 100.

The relationship Perfume / e to carrier / e Can with a carrier Perfume (s) from 20: 1 to 1:10, preferably 5: 1 to 10: 1 and preferably 3: 1.

Of the Weight fraction of carrier of the micro- / nanoscale perfume particle, based on the micro / nanoscale excipient containing perfume particles may contain at least 10% by weight of excipient, preferably at least 20% by weight of carrier, preferably at least 30% by weight of carrier, more preferably at least 40% by weight of carrier, more preferably at least 50% by weight of carrier and particularly preferably make up at least 60% by weight of carrier.

The Micro / nanoscale invention Perfume particles and / or agents according to the invention can be at least a carrier having the period of perfume delivery of the micro- / nanoscale supported Perfume particles compared to the otherwise same, the same Containing fragrance amount, unsupported micro- / nanoscale Fragrance particle, by at least 10%, preferably at least 30%, preferably at least 50%, more preferably at least 100%, more preferably at least 300%, and most preferred extended by at least 500%.

At Place of carrier / s or additionally to at least one carrier / s you can spray it Fragrance / e-carbon dioxide mixture and at least one emulsifier and / or thickeners.

• – ≥ 0 Gew.-% bis ≤ 3 Gew.-% Emulgator, vorzugsweise ≥ 0,1 Gew.-% bis ≤ 2 Gew.-% Emulgator, bevorzugt ≥ 0,2 Gew.-% bis ≤ 1 Gew.-% Emulgator, weiter bevorzugt ≥ 0,3 Gew.-% bis ≤ 0,8 Gew.-% Emulgator und am meisten bevorzugt ≥ 0,4 Gew.-% bis 0,6 Gew.-% Emulgator; und/oder
• – ≥ 0 Gew.-% bis ≤ 3 Gew.-% Verdicker, vorzugsweise ≥ 0,01 Gew.-% bis ≤ 2 Gew.-% Verdicker, bevorzugt ≥ 0,05 Gew.-% bis ≤ 1 Gew.-% Verdicker, weiter bevorzugt ≥ 0,08 Gew.-% bis ≤ 0,8 Gew.-% Verdicker und am meisten bevorzugt ≥ 0,1 Gew.-% bis 0,5 Gew.-% Verdicker.

According to a preferred embodiment of the process according to the invention, it is possible to add to the fragrance / e-carbon dioxide slurry mixture, based on the total weight of the fragrance / e-carbon dioxide slurry mixture:

• - ≥ 0 wt .-% to ≤ 3 wt .-% emulsifier, preferably ≥ 0.1 wt .-% to ≤ 2 wt .-% emulsifier, preferably ≥ 0.2 wt .-% to ≤ 1 wt .-% Emulsifier, more preferably ≥0.3 wt% to ≤0.8 wt% emulsifier, and most preferably ≥0.4 wt% to 0.6 wt% emulsifier; and or
• - ≥ 0 wt .-% to ≤ 3 wt .-% thickener, preferably ≥ 0.01 wt .-% to ≤ 2 wt .-% thickener, preferably ≥ 0.05 wt .-% to ≤ 1 wt .-% Thickener, more preferably ≥ 0.08 wt .-% to ≤ 0.8 wt .-% thickener and most preferably ≥ 0.1 wt .-% to 0.5 wt .-% thickener.

The to be sprayed Fragrance / e-carbon dioxide mixture should preferably be under a Pressure of 3 bar to 150 bar, preferably 15 bar to 120 bar and preferably 30 bar to 75 bar stand.

The Perfume / e-carbon dioxide slurry can be applied under a pressure of 0.01 bar to 5 bar, preferably 0.1 bar to 3 bar and preferably 0.5 spray bar up to 1 bar.

Preference is given to the sprayed fragrance / e-carbon dioxide mixture on a carrier / e and / or agent which is under a pressure of 0.01 bar to 5 bar, preferably 0.1 bar to 3 bar and preferably 0.5 bar to 1 bar, spray.

The spray chamber, in the one to be sprayed Perfume / e-carbon dioxide slurry preferably under a pressure of 3 bar sprayed to 150 bar is preferably atmospheric pressure exhibit. But it is possible that you have a slight overpressure or negative pressure in the spray chamber adjusting, for example, the rate of carbon dioxide evaporation or distance to regulate, for example, an influence on the particle size of the perfume particles may have.

The to be sprayed Perfume / e-carbon dioxide mixture may have a temperature of ≥ -10 ° C and ≤ 100 ° C, preferably ≥ -5 ° C and ≤ 70 ° C, further preferably from ≥ 0 ° C and ≤ 50 ° C, still preferably ≥ 5 ° C and ≤ 35 ° C, especially preferably from ≥ 5 ° C and ≤ 35 ° C and on Most preferably ≥ 10 ° C and ≤ 25 ° C.

The to be sprayed Perfume / e-carbon dioxide slurry can be obtained in the presence of an ambient temperature of ≥ 0 ° C and ≤ 80 ° C, preferably ≥ 5 ° C and ≤ 60 ° C, further preferably from ≥ 10 ° C and ≤ 50 ° C, still preferably ≥ 20 ° C and ≤ 40 ° C, especially preferably from ≥ 25 ° C and ≤ 30 ° C and on most preferably at room temperature, spray. Preferably one sprays the Perfume / e-carbon dioxide slurry in a spray chamber, for example in the spray chamber a spray tower, the spray chamber an ambient temperature of ≥ 0 ° C and ≤ 80 ° C.

The micro- / nanoscale perfume particles obtained in the method according to the invention can have a particle size d ₅₀ of ≥ 0.1 μm and ≤ 25 μm, preferably a particle size d ₅₀ of ≥ 0.2 μm and ≤ 15 μm, preferably a particle size d ₅₀ of ≥ 0.3 μm and ≤ 10 μm, more preferably a particle size d ₅₀ of ≥ 0.4 μm and ≤ 5 μm, and particularly preferably have a particle size d ₅₀ of ≥ 0.5 μm and ≤ 2 μm.

In the context of the present invention, the term "d ₅₀ " means that about 50% of the particles have a smaller diameter and about 50% of the particles have a larger diameter.

However, the micro- / nanoscale perfume particles obtained in the method according to the invention may also have a particle size d ₇₀ of ≥ 0.1 μm and ≤ 30 μm, preferably a particle size d ₇₀ of ≥ 0.2 μm and ≤ 15 μm, preferably a particle size d ₇₀ of ≥ 0.3 μm and ≤ 10 μm, more preferably a particle size d ₇₀ of ≥ 0.4 μm and ≤ 5 μm, and particularly preferably have a particle size d ₇₀ of ≥ 0.5 μm and ≤ 2 μm.

In the context of the present invention, the term "d ₇₀ " means that about 70% of the particles have a smaller diameter and about 30% of the particles have a larger diameter.

However, the micro- / nanoscale perfume particles obtained in the method according to the invention may also have a particle size d ₉₀ of ≥ 0.1 μm and ≤ 30 μm, preferably a particle size d ₉₀ of ≥ 0.2 μm and ≤ 15 μm, preferably a particle size d ₉₀ of ≥ 0.3 μm and ≤ 10 μm, more preferably a particle size d ₉₀ of ≥ 0.4 μm and ≤ 5 μm, and particularly preferably have a particle size d ₉₀ of ≥ 0.5 μm and ≤ 2 μm.

In the context of the present invention, the term "d ₉₀ " means that about 90% of the particles have a smaller diameter and about 10% of the particles have a larger diameter.

The Particle diameter of the micro / nanoscale perfume particles according to the invention were determined on the basis of sieving numbers. Here you can based on the sieve sizes used for each sieve residue determine the particle diameter.

• – 0 bis 5 Gew.-% der mikro-/nanoskaligen Duftstoffpartikel einen Partikeldurchmesser von < 500 nm,
• – 1 bis 10 Gew.-% der mikro-/nanoskaligen Duftstoffpartikel einen Partikeldurchmesser von < 800 nm bis 1000 nm,
• – 5 bis 20 Gew.-% der mikro-/nanoskaligen Duftstoffpartikel einen Partikeldurchmesser von < 900 nm bis 2000 nm,

bezogen auf das Gesamtgewicht der mikro-/nanoskaligen Duftstoffpartikel, aufweisen.For a preferred embodiment of the micro / nano-scale perfume particles, the following screen numbers result, wherein

• 0 to 5% by weight of the micro- / nanoscale perfume particles have a particle diameter of <500 nm,
• 1 to 10% by weight of the micro- / nanoscale perfume particles has a particle diameter of <800 nm to 1000 nm,
• 5 to 20% by weight of the micro- / nanoscale perfume particles have a particle diameter of <900 nm to 2000 nm,

based on the total weight of the micro / nanoscale perfume particles.

• – 0 bis 5 Gew.-% der Duftstoff aufweisenden Mittelpartikel einen Partikeldurchmesser von < 0,1 mm,
• – 3 bis 40 Gew.-% der Duftstoff aufweisenden Mittelpartikel einen Partikeldurchmesser von < 0,2 mm bis 0,1 mm,
• – 10 bis 55 Gew.-% der Duftstoff aufweisenden Mittelpartikel einen Partikeldurchmesser von < 0,4 mm bis 0,2 mm,
• – 20 bis 70 Gew.-% der Duftstoff aufweisenden Mittelpartikel einen Partikeldurchmesser von < 0,8 mm bis 0,4 mm,
• – 3 bis 30 Gew.-% der Duftstoff aufweisenden Mittelpartikel einen Partikeldurchmesser von < 1,6 mm bis 0,8 mm, und
• – 0 bis 10 Gew.-% der Duftstoff aufweisenden Mittelpartikel einen Partikeldurchmesser von mindestens 1,6 mm, bezogen auf das Gesamtgewicht des Duftstoff aufweisenden Mittels in Form eines feinpartikulären Feststoffs, aufweisen.

For a preferred embodiment of fragrance-containing composition according to the invention in the form of a fine particulate solid, the following sieving numbers result, wherein

• 0 to 5% by weight of the perfume-containing middle particles have a particle diameter of <0.1 mm,
• 3 to 40% by weight of the perfume-containing middle particles have a particle diameter of <0.2 mm to 0.1 mm,
• 10 to 55% by weight of the perfume-containing middle particles have a particle diameter of <0.4 mm to 0.2 mm,
• 20 to 70% by weight of the perfume-containing middle particles have a particle diameter of <0.8 mm to 0.4 mm,
• From 3 to 30% by weight of the perfume-containing agent particles have a particle diameter of from <1.6 mm to 0.8 mm, and
• - 0 to 10 wt .-% of the perfume having the middle particles have a particle diameter of at least 1.6 mm, based on the total weight of the perfume having agent in the form of a fine particulate solid having.

As a general rule All conceivable suitable fragrances can be used according to the invention. This can be from a variety of plant sources Attracting fragrances, for example from flowers of lavender, roses, jasmine, neroli; for example, stems and leaves of geranium, patchouli, Petit grain; from fruits, for example anise, coriander, caraway, juniper; from fruit peel for example, of citrus fruits such as bergamot, lemons, oranges; out Seeds, for example, macis, angelica, celery, cardamom; Root, for example Angelika, Costus, Iris, Calmus; made of wood, for example Sandal, guaiac, cedar, rosewood; from herbs and grasses, for example Tarragon, lemongrass, sage, thyme; from needles and branches, for example of spruces, firs, pines, pines; from resins and balm for example from galbanum, elemi, benzoin, myrrh, olibanum and opoponax.

But also from animal raw materials can be inventively suitable Raw materials, for example ambergris, are extracted from the sperm whale pathological metabolism product; Musk, the glands content a Central Asian antlerless deer; Civet, the glandular secretion the civet cat; and Castoreum, a gland secretion from the Canadian beaver.

For the isolation of the perfume concentrates from the raw materials, various methods are used, for example, pressing the fruit peels for citrus oils, extraction of resinoids from resins, balsams, lichens and mosses by means of volatile solvents such as alcohol or hexane, steam distillation previously prepared crushed plant parts for recovery of essential oils. The enfleurage, which has been known since ancient times, is an extraction of the especially delicate floral fragrances by means of odor-neutral fats, is rarely used today, but the particularly gentle removal by means of supercritical gases, for example CO ₂ , has become increasingly important.

From semi-synthetic fragrances obtained by chemical modification of natural raw materials can including isoeugenol from eugenol, the main constituent of clove oil, vanillin from isoeugenol, hydroxycitronellal from citronellal, citronellol from geraniol or citronellal, geranyl acetate from geraniol, Jonone and citral methylionones are used in the invention.

at The fully synthetic fragrances are nature-identical as well those whose molecular structures are without natural Model are. Some of these products give the odor notes more natural Fragrances again, but many have no odor model in the nature. They allow the creation of various fantasy fragrance compositions.

For the odor directions, there is no generally binding classification. Mostly a distinction is made between "scent families" of certain notes:
"Green notes" are herb-fresh scents and smell of leaves, grasses, meadows etc;
"Citrus notes" usually consist of the essential oils of citrus fruits with a refreshing character;
"Lavender notes" are contained in many compositions and form the main ingredient of "lavender waters".

"Floral notes" are predominant composed of several single flower notes, for example of the directions jasmine, lilac, rose, lily-of-the-valley, iris / violet, carnation.

"Aldehyde notes" are predominantly based on synthetic fragrances with flowery, partly also woody, balsamic and animal character; they are part of many Fashion perfume.

"Chypre notes" (moss notes) predominantly exist from oak moss extracts, partly in combination with bergamot oil and have tart-fresh character.

"Fougere notes" (fern notes) are related to the chypre notes.

"Spice Notes" contain spice extracts of, for example, thyme, pepper, nutmeg, cinnamon, cloves, ginger, Marjoram, cardamom, coriander, etc., some synthetic fragrances and especially combined spice bases.

"Oriental notes" combine spice notes with heavy, sweet, balsamic or animal notes to scents with spicy-sweet to too sweetish-heavy Character.

"Wood notes" are based on, for example Cedar, Sandel u.a. Wood and root oils and vary from herb-fresh to woody-herb.

"Tobacco notes" are available in many Variations of fresh-tart-spicy to heavy honey-sweet, originally based on the scent of tobacco blossoms and fermented tobacco.

"Leather notes" remind of the Odor of the finest leather goods, for example the scent direction Juchten.

Natural essences or with natural Flavored essences are preparations whose odoriferous or flavor-active ingredients exclusively natural Origin.

Next the above listed Fragrances can be as fragrances but also essences of fruits, fruit parts and / or other parts of plants, such as herbs, drugs, as well as it recovered essential oils, also terpene-free oils use according to the invention.

It can but also artificial Essences used in the invention are made from synthetic odorants or flavors are. It can the synthetic products are identical to the natural flavorings For example, vanillin, menthol, biacetyl, eucalyptol and like.

Farther can as fragrances also aromas are used according to the invention. suitable Flavors include essential oils, such as anise oil, Bitter almond oil, fennel oil and caraway oil. Further are mixes of single, generally synthetically produced - one speaks here of "nature identical" - components of these oils as fragrances usable according to the invention. There are currently about 600 natural ones and about 4200 nature-identical flavorings for food and pharmaceutical Products. As such, hydrocarbons, Heterocycles, alcohols, aldehydes, ketones, acetals, esters, phenols and phenol ethers, as well as sulfides and thiols.

When Flavorings are preferably peppermint oil, spearmint oil, aniseed oil, star aniseed oil, caraway oil, eucalyptus oil, fennel oil, lemon oil, wintergreen oil, clove oil, menthol and the like are suitable for use in the invention.

Fragrances which can be used in the context of the present invention are individual fragrance compounds, for example the synthetic products of the ester type, ethers, aldehydes, ketones, alcohols and hydrocarbons. Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethylmethylphenyl glycinate, allylcyclohexyl propionate, styrallyl propionate and benzyl salicylate. The ethers include, for example, benzyl ethyl ether, to the aldehydes, for example, the linear alkanals having 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones, for example, the ionone, isomethylionone and methyl cedrylketone, the alcohols include anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol; the hydrocarbons mainly include the terpenes such as limonene and pinene. Preferably, however, mixtures of different fragrances are used, which together produce an attractive fragrance. Such perfumes also include perfume oils, which may also contain natural fragrance mixtures such as those available from vegetable sources, such as 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, lime 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 usable fragrances (see above) generally represents the different substance classes of Odoriferous substances. To be perceptible, a fragrance must be volatile, besides the nature of the functional groups and the structure the molecular weight of the chemical compound also plays an important role plays. So most perfumes have molecular weights up to about 200 Dalton, while Molar masses of 300 daltons and above rather an exception. Due to the different volatility changed by fragrances the smell of a compound of several fragrances perfumes or perfume during of evaporation, whereby the odor impressions as already mentioned above in "top note", "heart or middle note" (middle note or body) and "Ba sisnote" (end note or dry divided out). Because the smell perception to a large extent also on the smell intensity is based, the top note of a perfume or fragrance is not alone from volatile Connections while the base note for the most part from less volatile, d. H. adherent fragrances. When composing perfumes can be easier volatile For example, fragrances can be bound to specific fixatives. which prevents it from evaporating too quickly. At the following Classification of the fragrances in "lighter volatile or "adherent" fragrances So over the smell impression and about it, whether the corresponding perfume perceived as a head or middle note nothing is said.

By a suitable choice of said fragrances can be made in this way for agents according to the invention both the smell of the product and, after the cleaning and maintenance process, in addition, for example the laundry smell to be influenced. For the latter odor impression is the use of more adhesive fragrances advantageous while for product scenting also more volatile fragrances can be used are. Adhesive-resistant fragrances, which are within the scope of the present invention can be used, for example, the essential oils such as angelica root oil, aniseed oil, arnica blossom oil, basil oil, bay oil, bergamot oil, Champacablütenöl, Edeltannöl, Edeltannenzapfenapfen, Elemiöl, eucalyptus oil, fennel oil, spruce alder oil, galbanum, geranium oil, ginger grass, guaiac wood, Gurjunbalsamöl, Helichrysumöl, Ho oil , Ginger oil, iris oil, cajeput oil, calamus oil, chamomile oil, camphor oil, kanaga oil, cardamom oil, cassia oil, pine oil, copaiba balsam, coriander oil, spearmint oil, caraway oil, cumin oil, lavender oil, lemongrass oil, lime oil, tangerine oil, lemon balm oil, musk kernel 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, Pimento Oil, Pine Oil, Rose Oil, Rosemary Oil, Sandalwood Oil, Celery Oil, Spik Oil, Star Aniseed Oil, Turpentine Oil, Thuja Oil, Thyme Oil, Verbena Oil, Vetiver Oil, Juniper Berry Oil, Vermouth Oil , Wintergreen oil, Ylang-ylang oil, hyssop oil, cinnamon oil, cinnamon leaf oil, lemon oil, lemon oil as well Cypress oil. But also the higher boiling or solid odoriferous natural or of synthetic origin in the context of the present invention as adherent fragrances or Fragrance mixtures, so fragrances are used. To this Counting connections the following compounds as well as mixtures of these: Ambrettolide, α-amylcinnamaldehyde, Anethole, anisaldehyde, anisalcohol, anisole, methyl anthranilate, Acetophenone, benzylacetone, benzaldehyde, ethyl benzoate, benzophenone, Benzyl alcohol, benzyl acetate, benzyl benzoate, benzyl formate, benzyl valerate, Borneol, bornyl acetate, α-bromostyrene, n-decyl aldehyde, n-dodecyl aldehyde, Eugenof, eugenol methyl ether, Euka lyptol, farnesol, Fenchone, fenchyl acetate, geranyl acetate, geranyl formate, heliotropin, Heptincarbonsäuremethylester, Heptaldehyde, hydroquinone dimethyl ether, hydroxycinnamaldehyde, hydroxycinnamyl alcohol, Indole, iron, isoeugenol, isoeugenol methyl ether, isosafrole, jasmon, Camphor, Karvakrol, Karvon, p-cresol methyl ether, coumarin, p-methoxyacetophenone, Methyl n-amyl ketone, methyl anthranilate, p-methyl acetophenone, Methylchavikol, p-methylquinoline, methyl-β-naphthylketone, methyl-n-nonylacetaldehyde, Methyl n-nonyl ketone, Muskon, β-naphthol ethyl ether, β-naphthol methyl ether, Nerol, nitrobenzene, n-nonylaldehyde, nonyl alcohol, n-octylaldehyde, p-oxy-acetophenone, pentadecanolide, β-phenylethyl alcohol, phenylacetaldehyde dimethyacetal, phenylacetic acid, Pulegone, safrol, salicylic acid isoamyl ester, methyl salicylate, Salicylsäurehexylester, Salicylsäurecyclohexylester, Santalol, skatole, terpineol, thymen, thymol, γ-undelactone, vaniline, veratrum aldehyde, Cinnamaldehyde, cinnamyl alcohol, cinnamic acid, cinnamate, Zimtsäurebenzylester. To the more volatile Include fragrances especially the lower-boiling fragrances natural or synthetic origin used alone or in mixtures can be.

Examples for easier volatile Fragrances are alkyl isothiocyanates (alkyl mustard oils), butanedione, limonene, linalool, Linayl acetate and propionate, menthol, menthone, methyl-n-heptenone, Phellandrene, phenylacetaldehyde, terpinyl acetate, citral, citronellal.

Suitable excipients for the fragrances used according to the invention, such as perfumes, are meltable or softenable substances from the group of waxes, paraffins, polyalkylene glycols and the like. The meltable or softenable substances preferably have a melting range of between about 45 ° C and about 75 ° C. That is, in the present case, the melting range occurs within the specified temperature interval and does not indicate the width of the melting range.

excipient can especially selected be from the group comprising paraffins, surfactants, fatty acids, fatty alcohols and silicone oils.

Under "waxing" is a series naturally or artificial understood substances which melt usually above 40 ° C without decomposition and already a little above the melting point, relatively low viscosity and not are thread-pulling. They have a strong temperature-dependent consistency and solubility on. According to their origin, the waxes are divided into three groups, the natural ones Waxes, chemically modified waxes and the synthetic waxes.

To the natural one Count waxing for example, vegetable waxes such as candelilla wax, carnauba wax, Japan wax, esparto wax, cork wax, guaruma wax, rice germ oil wax, Sugarcane wax, ouricury wax, or montan wax, animal waxes such as beeswax, shellac wax, spermaceti, lanolin (wool wax), or uropygial fat, Mineral waxes such as Ceresin or Ozokerit (Erdwachs), or petrochemical waxes such as petrolatum, paraffin waxes or microwaxes.

To The chemically modified waxes include, for example, hard waxes such as montan ester waxes, Sassol waxes or hydrogenated jojoba waxes.

Synthetic waxes are generally understood as meaning polyalkylene waxes or polyalkylene glycol waxes. It is also possible to use as meltable or softenable substances for the compositions which cure by cooling, and compounds of other substance classes which fulfill the stated requirements with regard to the softening point. As suitable synthetic compounds have, for example, higher esters of phthalic acid, in particular dicyclohexyl, which is commercially available under the name Unimoll 66 ^® (Bayer AG), proved. Are also suitable Synthetic waxes of lower carboxylic acids and fatty alcohols, such as dimyristyl tartrate, sold under the name Cosmacol ^® ETLP (Condea). Conversely, synthetic or partially synthetic esters of lower alcohols can be used with fatty acids from natural sources. This class of substances includes, for example, ^Tegin® 90 (Goldschmidt), a glycerol monostearate palmitate. Shellac, for example shellac KPS three-ring SP (Kalkhoff GmbH) can also be used according to the invention as meltable or softenable substances.

Likewise to the waxes in the context of the present invention, for example, the so-called wax alcohols are calculated. Wax alcohols are higher molecular weight, water-insoluble fatty alcohols having generally about 22 to 40 carbon atoms. The wax alcohols are, for example, in the form of wax esters of higher molecular weight fatty acids (wax acids) as the main constituent of many natural waxes. Examples of wax alcohols are lignoceryl alcohol (1-tetracosanol), cetyl alcohol, myristyl alcohol or melissyl alcohol. Other suitable melting and softenable substances are the wool wax alcohols which are understood to be triterpenoid and steroid alcohols, for example lanolin, which is available for example under the trade name Argowax ^® (Pamentier & Co). In the context of the present invention, fatty acid glycerol esters or fatty acid alkanolamides but optionally also water-insoluble or only slightly water-soluble polyalkylene glycol compounds may likewise be used as part of the meltable or softenable substances.

Especially preferred meltable or softenable carriers are those of Group of polyethylene glycols (PEG) and / or polypropylene glycols Contains (PPG), wherein polyethylene glycols having molecular weights between 1500 and 36,000 preferably, those having molecular weights of from 2000 to 6000 are particularly preferred and those having molecular weights of 3,000 to 5,000 are particularly preferred are. Corresponding methods, which are characterized that the plastically deformable mass (s) at least one Substance from the group of polyethylene glycols (PEG) and / or polypropylene glycols Contains (PPG), are preferred.

in this connection Particularly preferred are compositions which are the only meltable or softenable Substances Propylene Glycols (PPG) and / or Polyethylene Glycols (PEG) contain. Usable according to the invention Polypropylene glycols (abbreviated PPG) are polymers of propylene glycol, those of the following general formulas, where n values between 10 and 2000 can accept. Preferred PPGs have molecular weights between 1000 and 10,000, corresponding to values of n between 17 and about 170, on.

Polyethylene glycols (abbreviation PEG) which can preferably be used as the carrier according to the invention are polymers of ethylene glycol which satisfy the general formula H- (O-CH ₂ -CH ₂ ) _n -OH, where n values between 20 and about 1000 can take. The abovementioned preferred molecular weight ranges correspond to preferred ranges of the value n in formula IV of from 30 to 820, in particular from 34 to 818, particularly preferably from 40 to 150, in particular from 45 to 136 and more preferably from 70 to 120, in particular from 68 to 113th

In a further preferred embodiment contain the fused and softenable carriers in the vast majority Proportion of paraffin wax. This means, that at least 50 wt .-% of the total contained melt or softenable substances, preferably more, consist of paraffin wax. Paraffin wax contents (based on the total amount of melted or softenable substances) of about 60% by weight, about 70% by weight. or about 80 wt .-%, with even higher proportions of, for example more than 90 wt .-% are particularly preferred. In a particular embodiment invention, the total amount of melting agent used is or softenable substances of at least one mass exclusively Paraffin wax.

paraffin waxes opposite the other mentioned, natural Grow in the context of the present invention has the advantage that In an alkaline detergent environment, no hydrolysis of the waxes takes place (as you would expect, for example, in the wax esters is), since paraffin wax contains no hydrolyzable groups.

paraffin waxes exist mainly from alkanes, as well as low proportions of iso- and cycloalkanes. The invention to be used Paraffin preferably has substantially no components with it a melting point of more than 70 ° C, more preferably more as 60 ° C on. Shares of high melting alkanes in the paraffin can at Not below this melting temperature in the cleaning agent fleet desirable Wax residues on the surfaces to be cleaned or leave the goods to be cleaned. Such wax residues lead into usually a nasty one Appearance of the cleaned surface and should therefore be avoided.

Prefers Meltable or softenable carriers or carrier mixtures to be processed contain at least one paraffin wax with a melting range from 50 ° C up to 60 ° C, preferred methods being characterized in that the deformable mass (s) a paraffin wax with a melting range from 50 ° C up to 55 ° C contains / contain.

Preferred carriers suitable for use with the fragrances may also comprise solvents or dispersants selected from the group of water-soluble polymers, of which only the most important are to be enumerated:
water-soluble nonionic polymers (polyvinylpyrrolidones, vinylpyrrolidone / vinylester copolymers, cellulose ethers); Water-soluble amphoteric polymers (alkylacrylamide / acrylic acid copolymers, alkylacrylamide / methacrylic acid copolymers, alkylacrylamide / methylmethacrylic acid copolymers, alkylacrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, alkylacrylamide / methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, alkylacrylamide / methylmethacrylic acid / Alkylaminoalkyl (meth) acrylic acid copolymers, alkylacrylamide / alkymethacrylate / alkylaminoethylmethacrylate / alkylmethacrylate copolymers); Copolymers of unsaturated carboxylic acids, cationically derivatized unsaturated carboxylic acids, optionally further ionic or nonionic monomers; water-soluble zwitterionic polymers (acrylamidoalkyltrialkylammonium chloride / acrylic acid copolymers and their alkali metal and ammonium salts, acrylamidoalkyltrialkylammonium chloride / methacrylic acid copolymers and their alkali metal and ammonium salts, methacroylethylbetaine / methacrylate copolymers); water-soluble anionic polymers (vinyl acetate / crotonic acid copolymers, vinylpyrrolidone / vinyl acrylate copolymers, acrylic acid / ethyl acrylate / N-tert-butylacrylamide terpolymers, graft polymers of vinyl esters, esters of acrylic acid or methacrylic acid alone or in a mixture copolymerized with crotonic acid, acrylic acid or methacrylic acid Polyalkylene oxides and / or polyalkylene glycols); grafted and crosslinked copolymers (from the copolymerization of a) at least one nonionic-type monomer, b) at least one ionic-type monomer, c) from polyethylene glycol, and d) a crosslinked one; copolymers obtained by copolymerization of at least one monomer of each of the following three groups: a) esters of unsaturated alcohols and short-chain saturated carboxylic acids and / or esters of short-chain saturated alcohols and unsaturated carboxylic acids, b) unsaturated carboxylic acids, c) esters of long-chain carboxylic acids and unsaturated alcohols and / or esters from the carboxylic acids from the group of saturated or unsaturated, straight-chain or branched C _8-18 -alcohols; Terpolymers of crotonic acid, vinyl acetate and an allyl or methallyl ester; Tetra- and pentapolymers from a) crotonic acid or allyloxyacetic acid, b) vinyl acetate or vinyl propionate, c) branched allyl or methallyl esters, d) vinyl ethers, vinyl esters or straight-chain allyl or methallyl esters; Crotonic acid copolymers with one or more monomers from the group consisting of ethylene, vinylbenzene, vinylmethyl ether, acrylamide and their water-soluble sal ze; Terpolymers of vinyl acetate, crotonic acid and vinyl esters of a saturated aliphatic x-branched monocarboxylic acid); water-soluble cationic polymers (quaternized cellulose derivatives, polysiloxanes with quaternary groups, cationic guar derivatives, polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid, copolymers of vinylpyrrolidone with quaternized derivatives of dialkylamino acrylate and methacrylate, vinylpyrrolidone-methoimidazolinium chloride copolymers , quaternized polyvinyl alcohol, under the INCI names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27. Polymers in the form of water-soluble polymers in the context of the invention are those polymers which at room temperature in water to more than 2.5 wt. -% are soluble.

The preferred solution or dispersant carriers from the group of non-aqueous Solvent, waxes, paraffins, polyalkylene glycols or the water-soluble Polymers can in the method according to the invention used alone or as mixtures.

One Preferred subject of the present application is therefore a Process in which a perfume-containing Slurry containing non-aqueous solvents and / or waxes and / or paraffins and / or polyalkylene glycols and / or water-soluble Polymers of at least 5% by weight, preferably at least 15% by weight and more preferably from at least 20% by weight to a maximum of 40% Wt .-%, based on the total weight of the slurries is used.

in the For the purposes of this invention, data refer to the agent according to the invention in% by weight, unless otherwise stated, on the total weight of the agent according to the invention.

Can be produced according to the invention Agents, in particular washing, care and cleaning agents, preferably have Surfactants, inorganic and optionally organic builders and optionally further customary Ingredients, wherein the contained inorganic constituents are preferably water-soluble.

The produced according to the invention Means has at least one, preferably several components, selected from the group comprising as washing, care and / or cleaning active Substances anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, builders, bleaches, bleach activators, Bleach stabilizers, bleach catalysts, enzymes, polymers, cobuilders, Alkalizing agent, acidifying agent, anti redeposition agent, Silver protectants, colorants, optical brighteners, UV protectants, softeners and / or rinse aids, as well optionally further admixed ingredients.

As anionic surfactants, for example, those of the sulfonate type and sulfates are used. The surfactants of the sulfonate type are preferably C _9-13 -alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as are obtained, for example, from C _12-18 -monoolefins having terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products into consideration. Also suitable are alkanesulfonates which are obtained from C _12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Likewise, the esters of α-sulfo fatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids are suitable.

Further Suitable anionic surfactants are sulfated fatty acid glycerol esters. Among fatty acid glycerol esters are to understand the mono-, di- and triesters and their mixtures, such as they are produced by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol to be obtained. Preferred sulfated fatty acid glycerol esters are included the sulphonated products of saturated fatty acids with 6 to 22 carbon atoms, for example the caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or Behenic acid.

Alk (en) ylsulfates are the alkali metal salts and in particular the sodium salts of the sulfuric monoesters of C ₁₂ -C ₁₈ fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ oxo alcohols and those half-esters of secondary alcohols of these chain lengths are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials. Of washing technical interest are the C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates and C ₁₄ -C ₁₅ alkyl sulfates before Trains t. 2,3-alkyl sulfates can be obtained as commercial products from Shell Oil Company under the name DAN ^®, are suitable anionic surfactants.

The sulfuric acid monoesters of straight-chain or branched C _7-21 -alcohols ethoxylated with from 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C _9-11- alcohols having on average 3.5 mol of ethylene oxide (EO) or C _12-18 . Fatty alcohols with 1 to 4 EO are suitable. Due to their high foaming behavior, they are only used in detergents in relatively small amounts, for example in amounts of from 1 to 5% by weight.

Further suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain C _8-18 fatty alcohol residues or mixtures of these. Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which in themselves constitute nonionic surfactants (see description below). Sulfosuccinates, whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred. Likewise, it is also possible to use alk (en) ylsuccinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

Of the Content of the agent according to the invention the anionic surfactants mentioned are preferably from 2 to 30% by weight and in particular 5 to 25 wt .-%, wherein concentrations above of 10% by weight and even above 15% by weight of particular preference Find.

In addition to The said anionic surfactants may contain soaps. Particularly suitable are saturated Fatty acid soaps, like the salts of lauric acid, myristic, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid and in particular of natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures. The content of the agent in soaps is preferably no longer as 3 wt .-% and in particular 0.5 to 2.5 wt .-%.

The anionic surfactants and soaps in the form of their sodium, potassium or ammonium salts and as soluble salts organic bases, such as mono-, di- or triethanolamine. Preferably, they are in the form of their sodium or potassium salts, especially in the form of the sodium salts. Anionic surfactants and Soaps can also be prepared in situ by being spray dried Composition of the anionic surfactant acids and optionally fatty acids are introduced, which then by the alkali carriers in the spray-drying Composition be neutralized.

nonionic Surfactants are common in direct spray-dried agents according to the invention - if at all - only in Subordinate quantities available. For example, their salary up to 2 or 3 wt .-% amount. For a more detailed description of the Nonionic surfactants will be post-treated on the description Products referenced below. In this context is still important, of course also agents prepared by granulation or compounding can be treated and usable according to the invention are.

The usable according to the invention Agents, such as cleaning, care and detergent may optionally also contain cationic surfactants. Suitable cationic surfactants are for example, surface-active quaternary Compounds, in particular with an ammonium, sulfonium, phosphonium, Iodonium or arsonium group, as described, for example, by K. H. Wallhäußer in "Praxis der Sterilisation, Disinfection-preservation: germ identification-industrial hygiene "(5th ed. - Stuttgart; New York: Thieme, 1995) as antimicrobial agents. Through the use of quaternary surfactants Compounds with antimicrobial activity may be the agent with a antimicrobial effect be designed or its optionally due to other ingredients already existing antimicrobial Effect can be improved.

Particularly preferred cationic surfactants are the quaternary, partially antimicrobial ammonium compounds (QAV, INCI quaternary ammonium compounds) according to the general formula (R ^I ) (R ^II ) (R ^III ) (R ^IV ) N ⁺ X ^- , in which R ^I to R ^IV identical or different C _1-22 -alkyl radicals, C _7-28 -aralkyl radicals or heterocyclic radicals, where two or in the case of an aromatic inclusion as in pyridine even three radicals together with the nitrogen atom, the heterocycle, for example a pyridinium or imidazolinium compound, and X ^{- are} halide ions, sulfate ions, hydroxide ions or like anions. For optimum antimicrobial activity, preferably at least one of the radicals has a chain length of 8 to 18, in particular 12 to 16, carbon atoms.

QAC are tertiary by implementation Amines with alkylating agents, e.g. Methyl chloride, benzyl chloride, Dimethyl sulfate, dodecyl bromide, but also ethylene oxide produced. The alkylation of tertiary Amines with a catch alkyl residue and two methyl groups succeed especially easy, also the quaternization of tertiary amines with two long residues and one methyl group can be made with the help of methyl chloride be carried out under mild conditions. Amines, over three are long alkyl radicals or hydroxy-substituted alkyl radicals little reactive and are preferably quaternized with dimethyl sulfate.

Suitable QACs are, for example, benzalkonium chloride (N-alkyl-N, N-dimethylbenzylammonium chloride, CAS No. 8001-54-5), benzalkone B (m, p-dichlorobenzyl-dimethyl-C ₁₂ -alkylammonium chloride, CAS No. 58390-78 -6), benzoxonium chloride (benzyldodecyl-bis (2-hydroxyethyl) ammonium chloride), cetrimonium bromide (N-hexadecyl-N, N-timethyl-ammonium bromide, CAS No. 57-09-0), benzetonium chloride (N, N Dimethyl N- [2- [2- [p- (1,1,3,3-tetramethylbutyl) phenoxy] ethoxy] ethyl] benzyl ammonium chloride, CAS No. 121-54-0), dialkyldimethylammonium chlorides such as di-n decyl dimethyl ammonium chloride (CAS No. 7173-51-5-5), didecyldimethyl ammonium bromide (CAS No. 2390-68-3), dioctyl dimethyl ammonium chloric, 1-cetyl pyridinium chloride (CAS No. 123-03-5 ) and thiazoline iodide (CAS No. 15764-48-1) and mixtures thereof. Preferred QACs are the benzalkonium chlorides having C ₈ -C ₁₈ -alkyl radicals, in particular C ₁₂ -C ₁₄ -alkyl-benzyldimethylammonium chloride. A particularly preferred QAC Kokospentaethoxymethylammoniummethosulfat (INCI PEG-5 Cocomonium Methosulfate; Rewoquat CPEM ^®).

to Avoidance of possible incompatibilities the antimicrobial cationic surfactants with in the agent according to the invention anionic surfactants contained as possible anionic surfactant and / or preferably little cationic surfactant used or in a particular embodiment the invention entirely dispensed with antimicrobial cationic surfactants.

When For example, antimicrobials can be used instead Parabens, benzoic acid and / or Benzoate, lactic acid, salicylic acid and / or lactates are used. Particularly preferred are benzoic acid and / or Lactic acid.

The agent according to the invention, such as cleaning, care and detergent, can be one or more cationic Surfactants in amounts, based on the total composition, of 0 to 5 wt .-%, greater 0 to 5 Wt .-%, preferably 0.01 to 3 wt .-%, in particular 0.1 to 1 wt .-% contain.

Likewise, the agents according to the invention, such as cleansing, care and washing agents, may also contain amphoteric surfactants. Suitable amphoteric surfactants are, for example, betaines of the formula (R ¹⁾ (R ²⁾ (R ³⁾ N ⁺ CH ₂ CO ^- in which R ¹ is an optionally interrupted by hetero atoms or hetero atom groups alkyl radical having 8 to 25, preferably 10 to 21 carbon atoms, and R ² and R ^{3 are} identical or different alkyl radicals having 1 to 3 carbon atoms, in particular C ₁₀ -C ₂₂ -Alkyldimethylcarboxymethylbetain and C ₁₁ -C ₁₇ -Alkylamidopropyldimethylcarboxymethylbetain. Furthermore, the use of Alkylamidoalkylaminen, alkyl-substituted amino acids, acylated amino acids or biosurfactants as amphoteric surfactants in the inventive compositions, such as cleaning, care and detergent conceivable.

The agent according to the invention, such as cleaning, care and laundry detergents, one or more amphoteric Surfactants in amounts, based on the total composition, of 0 to 5 wt .-%, greater 0 to 5 Wt .-%, preferably 0.01 to 3 wt .-%, in particular 0.1 to 1 wt .-% contain.

Further Ingredients of the agents according to the invention can be inorganic and optionally organic builders. The inorganic builders include water-insoluble or not water-soluble Ingredients, such as aluminosilicates and especially zeolites. In a preferred embodiment contains the agent of the invention no phosphate and / or no zeolite.

It but it is also possible that the agent contains zeolite, this is preferably this zeolite content, based on the total weight the average, less than 5 wt .-%, preferably at most 4 wt .-%, at most 3 wt .-% or at most 2 wt .-% is.

It can also be provided that the inventive agent has a zeolite content of at least 10 wt .-%.

When soluble Builder can the agent of the invention 10 wt% to 30 wt%, preferably 15 wt% to 25 wt%, and especially preferably from 18% by weight to 20% by weight, based on the total weight of the Mean, with sodium carbonate being particularly preferred as a soluble builder is.

The finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P. As zeolite P, for example, zeolite MAP ^(R) (commercial product from Crosfield) is particularly preferred. Also suitable however are zeolite X and mixtures of A, X and / or P. Of particular interest is a co-crystallized sodium / potassium aluminum silicate of zeolite A and zeolite X, which as VEGOBOND AX ^® (a product of Condea Augusta SpA) Trade is available. This product is described below. The zeolite can be used as a spray-dried powder or else as undried, still moist, stabilized suspension of its preparation. 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 wt .-%, based on zeolite, of ethoxylated C ₁₂ -C ₁₈ fatty alcohols having 2 to 5 ethylene oxide groups , C ₁₂ -C ₁₄ fatty alcohols having 4 to 5 ethylene oxide groups or ethoxylated isotridecanols. Suitable zeolites have an average particle size of less than 10 μm (volume distribution, measuring method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

When other particularly suitable zeolites are zeolites of the faujasite type to call. Together with the zeolites X and Y belongs the mineral Faujasite to the faujasite types within the zeolite structure group 4, which are characterized by the double-six-membered subunit D6R (Compare Donald W. Breck: "Zeolite Molecular Sieves, John Wiley & Sons, New York, London, Sydney, Toronto, 1974, page 92). To the zeolite structure group 4 count in addition to the mentioned faujasite types, the minerals chabazite and gmelinite and the synthetic zeolites R (chabazite type), S (gmelinite type), L and ZK-5. The latter two synthetic Zeolites have no mineral analogues.

Faujasite-type zeolites are composed of β-cages linked tetrahedrally via D6R subunits, with the β-cages resembling the carbon atoms in the diamond. The three-dimensional network of the faujasite-type zeolites useful in the present invention has pores of 2.2 and 7.4 Å, the unit cell also contains 8 wells of about 13 Å in diameter, and can be represented by the formula Na ₈₆ [(AlO ₂ ). ₈₆ (SiO ₂ ) ₁₀₈ ]. 264 H ₂ O describe. The network of zeolite X contains a void volume of about 50%, based on the dehydrated crystal, which represents the largest void space of all known zeolites (zeolite Y: about 48% void volume, faujasite: about 47% void volume). (All data from: Donald W. Breck: "Zeolite Molecular Sieves", John Wiley & Sons, New York, London, Sydney, Toronto, 1974, pages 145, 176, 177).

in the In the context of the present invention, the term "faujasite-type zeolite" denotes all three zeolites, which form the faujasite subgroup of the zeolite structure group 4. In addition to zeolite X, the invention also includes zeolite Y and faujasite as well as mixtures of these compounds, the pure zeolite X is preferred.

Also Mixtures or cocrystallizates of faujasite-type zeolites with other zeolites, not necessarily the zeolite structure group 4 belong have to, are suitable according to the invention preferably at least 50 wt .-% of zeolites zeolites from Faujasite type are.

The suitable aluminum silicates are commercially available, and the methods for their presentation are in standard monographs described.

Examples of commercially available X-type zeolites can be described by the following formulas: Na ₈₆ [(AlO ₂ ) ₈₆ (SiO ₂ ) ₁₀₆ ] .xH ₂ O, K ₈₆ [(AlO ₂ ) ₈₆ (SiO ₂ ) ₁₀₆ ] .xH ₂ O, Ca ₄₀ Na ₆ [(AlO ₂ ) ₈₆ (SiO ₂ ) 106] xH ₂ O, Sr ₂₁ Ba ₂₂ [(AlO ₂ ) ₈₆ (SiO ₂ ) 106] x H ₂ O, where x can take values greater than 0 to 276. These zeolites have pore sizes of 8.0 to 8.4 Å.

Also suitable is, for example, the zeolite A-LSX described in the European patent application EP-A-816 291, which corresponds to a co-crystallizate of zeolite X and zeolite A and in its anhydrous form Form has the formula (M _{2 / n} O + M ' _{2 / n} O) · Al ₂ O ₃ · zSiO ₂ , where M and M' may be alkali or alkaline earth metals and z is a number from 2.1 to 2.6 is. Commercially available this product is under the brand name VEGOBOND AX by the company CONDEA Augusta SpA

Y-type zeolites are also commercially available and can be obtained, for example, by the formulas Na ₅₆ [(AlO ₂ ) ₅₆ (SiO ₂ ) ₁₃₆ ] * x H ₂ O, K ₅₆ [(AlO ₂ ) ₅₆ (SiO ₂ ) ₁₃₆ ] xH ₂ O, where x is numbers greater than 0 to 276. These zeolites have pore sizes of 8.0 Å.

The Particle sizes of suitable zeolites of the faujasite type is in the range of 0.1 μm to to 100 μm, preferably 0.5 μm up to 50 μm and in particular of 1 μm up to 30 μm, each with standard particle size determination methods measured.

In another basic embodiment The invention, however, the contained inorganic constituents water soluble be. In these embodiments Therefore, other builders than the mentioned zeolites used.

In cases In which a phosphate content is tolerated, phosphates can also be used especially pentasodium triphosphate, if appropriate Pyrophosphates and orthophosphates, primarily as precipitants for lime salts Act. Phosphates become predominant in automatic dishwashing detergents, partly but also used in detergents.

Alkali metal phosphates is the summary term for the alkali metal (especially sodium and potassium) salts of various phosphoric acids, in which one can distinguish metaphosphoric acids (HPO ₃ ) _n and orthophosphoric H ₃ PO _{4 in} addition to higher molecular weight representatives. The phosphates combine several advantages: they act as alkali carriers, prevent lime deposits on machine parts or lime incrustations in fabrics and also contribute to the cleaning performance.

Sodium dihydrogen phosphate, NaH ₂ PO ₄ , exists as a dihydrate (density 1.91 gcm ^-3 , melting point 60 °) and as a monohydrate (density 2.04 gcm ^-3 ). Both salts are white powders which are very soluble in water and which lose their water of crystallization when heated and at 200 ° C into the weak acid diphosphate (disodium hydrogen diphosphate, Na ₂ H ₂ P ₂ O ₇ ), at higher temperature in sodium trimetaphosphate (Na ₃ P ₃ O ₉ ) and Maddrell's salt (see below). NaH ₂ PO _{4 is} acidic; It arises when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed. Potassium dihydrogen phosphate (potassium phosphate primary or monobasic potassium phosphate, KDP), KH ₂ PO ₄ , is a white salt of 2.33 gcm ^-3 density, has a melting point of 253 ° [decomposition to form potassium polyphosphate (KPO ₃ ) _x ] and is light soluble in water.

Disodium hydrogen phosphate (secondary sodium phosphate), Na ₂ HPO ₄ , is a colorless, very slightly water-soluble crystalline salt. It exists anhydrous and with 2 moles (density 2.066 gcm ^-3 , loss of water at 95 °), 7 moles (density 1.68 gcm ^-3 , melting point 48 ° with loss of 5 H ₂ O) and 12 moles water ( Density 1.52 gcm ^-3 , melting point 35 ° with loss of 5 H ₂ O) becomes anhydrous at 100 ° C and, upon increased heating, passes into the diphosphate Na ₄ P ₂ O ₇ . Disodium hydrogen phosphate is prepared by neutralization of phosphoric acid with soda solution using phenolphthalein as an indicator. Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K ₂ HPO ₄ , is an amorphous, white salt that is readily soluble in water. Trisodium phosphate, tertiary sodium phosphate, Na ₃ PO ₄ , are colorless crystals which have a density of 1.62 gcm ^-3 as dodecahydrate and a melting point of 73-76 ° C (decomposition), as decahydrate (corresponding to 19-20% P ₂ O ₅ ) have a melting point of 100 ° C and in anhydrous form (corresponding to 39-40% P ₂ O ₅ ) have a density of 2.536 gcm ^-3 . Trisodium phosphate is readily soluble in water under alkaline reaction and is prepared by evaporating a solution of exactly 1 mole of disodium phosphate and 1 mole of NaOH. Tripotassium phosphate (tertiary or tribasic potassium phosphate), K ₃ PO ₄ , is a white, deliquescent, granular powder of density 2.56 gcm ^-3 , has a melting point of 1340 ° and is readily soluble in water with an alkaline reaction. It arises, for example, when heating Thomasschlacke with coal and potassium sulfate. Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred over the corresponding sodium compounds in the detergent industry.

Tetrasodium diphosphate (sodium pyrophosphate), Na ₄ P ₂ O ₇ , exists in anhydrous form (density 2.534 gcm ^-3 , melting point 988 °, also indicated 880 °) and as decahydrate (density 1.815-1.836 gcm ^-3 , melting point 94 ° with loss of water) , Both substances are colorless crystals which are soluble in water with an alkaline reaction. Na ₄ P ₂ O ₇ is formed on heating of disodium phosphate to> 200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dewatering the solution by spraying. The decahydrate complexes heavy metal salts and hardness agents and therefore reduces the hardness of the water. Potassium diphosphate (potassium pyrophosphate), K ₄ P ₂ O ₇ , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 gcm ^-3 , which is soluble in water, the pH being 1% Solution at 25 ° 10.4.

Condensation of NaH ₂ PO ₄ or KH ₂ PO ₄ results in higher mol. Sodium and potassium phosphates, in which one can distinguish cyclic representatives, the sodium or Kaliummetaphosphate and chain types, the sodium or potassium polyphosphates. In particular, for the latter are a variety of names in use: hot or cold phosphates, Graham's salt, Kurrolsches and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.

The technically important pentasodium triphosphate, Na ₅ P ₃ O ₁₀ (sodium tripolyphosphate), is an anhydrous or with 6 H ₂ O crystallizing, non-hygroscopic, white, water-soluble salt of the general formula NaO- [P (O) (ONa) -O] _n -Na with n = 3. In 100 g of water dissolve at room temperature about 17 g, at 60 ° about 20 g, at 100 ° around 32 g of the salt water-free salt; after two hours of heating the solution to 100 ° caused by hydrolysis about 8% orthophosphate and 15% diphosphate. In the preparation of pentasodium triphosphate, phosphoric acid is reacted with soda solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dehydrated by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentakaliumtriphosphat, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate), for example, in the form of a 50 wt .-% solution (> 23% P ₂ O ₅ , 25% K ₂ O) in the trade. The potassium polyphosphates are widely used in the washing and cleaning industry. There are also sodium potassium tripolyphosphates which can also be used in the context of the present invention. These arise, for example, when hydrolyzed sodium trimetaphosphate with KOH: (NaPO ₃ ) ₃ + 2 KOH → Na ₃ K ₂ P ₃ O ₁₀ + H ₂ O

These are exact according to the invention such as sodium tripolyphosphate, potassium tripolyphosphate or mixtures can be used from these two; also mixtures of sodium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium tripolyphosphate used according to the invention.

In a preferred embodiment however, as inorganic builders in particular carbonates and silicates used.

Mention should be made here crystalline, 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 1.6 to 4, preferably 1.9 to 4.0 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4. However, since such crystalline silicates at least partially lose their crystalline structure in a spray-drying process, crystalline silicates are preferably subsequently added to the direct or post-treated spray-drying product. 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 is sodium and x assumes the values 2 or 3. In particular, both β- and 6-sodium disilicates Na ₂ Si ₂ O ₅ .yH ₂ O are preferred. Such compounds are commercially available, for example, under the name ^SKS® (from Clariant). Thus, it is SKS-6 ^® primarily a δ-sodium having the formula Na ₂ Si ₂ O ₅ · yH ₂ O, SKS-7 ^® primarily the β-sodium disilicate. Reaction with acids (eg citric acid or carbonic acid) gives kanemite NaHSi ₂ O ₅ .yH ₂ O, commercially available under the names SKS- ^9® and SKS- ^10® (from Clariant) from the δ-sodium disilicate. It may also be advantageous to use chemical modifications of these phyllosilicates. For example, the alkalinity of the layered silicates can be suitably influenced. Phyllosilicates doped with phosphate or with carbonate have altered crystal morphologies in comparison with the δ-sodium disilicate, dissolve more rapidly and show increased calcium binding capacity in comparison with δ-sodium disilicate. Thus, phyllosilicates of the general empirical formula x Na ₂ O.y SiO ₂ .z P ₂ O ₅ in which the ratio x to y is a number 0.35 to 0.6, the ratio x to z a number from 1.75 to 1200 and the ratio y to z a number from 4 to 2800 corresponds to the patent application DE-A-196 01 063 described. The solubility of the layered silicates can also be increased by using particularly finely divided layered silicates. Also compounds from the crystalline layer silicates with other ingredients can be used. In particular, compounds with cellulose derivatives which have advantages in the disintegrating action, and compounds with polycarboxylates, for example citric acid, or polymeric polycarboxylates, for example copolymers of acrylic acid, may be mentioned.

The preferred builder substances also include amorphous sodium silicates having a modulus Na ₂ O: SiO _{2 of} 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 have secondary washing properties. In the context of this invention, the term "amorphous" is also understood to mean "X-ray amorphous". This means that the silicates do not yield sharp X-ray reflections typical of crystalline substances in X-ray diffraction experiments, but at most one or more maxima of the scattered X-rays which have a width of several degrees of diffraction angle. However, it may well even lead to particularly good builder properties if the silicate particles provide blurred or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of size 10 to a few hundred nm, with values of 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 dissolution delay compared with conventional water glasses, are described, for example, in German patent application DE-A-44 00 024. Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates. The content of (X-ray) amorphous silicates in the zeolite-free compositions is preferably 1 to 10% by weight.

Especially preferred inorganic water-soluble However, builders are alkali metal carbonates and alkali metal bicarbonates, wherein sodium and potassium carbonate and especially sodium carbonate to the preferred embodiments counting. The content of the alkali metal carbonates in the particular zeolite-free agents can vary within a very wide range and is preferably 5 to 40 wt .-%, in particular 8 to 30 wt .-%, where usually the content of alkali metal carbonates is higher than on (X-ray) amorphous Silicates.

useful organic builders For example, they are in the form of their alkali and especially sodium salts usable polycarboxylic acids, like citric acid, adipic acid, Succinic acid, glutaric, Tartaric acid, Sugar acids, amino carboxylic acids, nitrilotriacetic (NTA), if such an operation is not for environmental reasons is objectionable, as well as mixtures of these. Preferred salts are the salts of polycarboxylic acids like citric acid, adipic acid, Succinic acid, glutaric, Tartaric acid, sugar acids and mixtures of these.

Further suitable organic builders are polymeric polycarboxylates, for example the alkali metal salts of polyacrylic acid or of polymethacrylic acid, for example those having a relative molecular mass of 500 to 70,000 g / mol. For the purposes of this document, the molecular weights stated for polymeric polycarboxylates are weight-average molar masses M _{w of} the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the polymers investigated. These data differ significantly from the molecular weight data, in which polystyrene sulfonic acids are used as standard. The molar masses measured against polystyrenesulfonic acids are generally significantly higher than the molecular weights specified in this document.

The agents according to the invention and especially the carriers can also contain polymers. Suitable polymers, also known as carriers may be used in conjunction with perfume include in particular Polyacrylates, which preferably has a molecular weight of 2,000 to 20,000 g / mol exhibit. Because of their superior solubility can from this group again the short-chain polyacrylates, the molecular weights of 2000 to 10,000 g / mol, and more preferably from 3,000 to 5,000 g / mol, be preferred.

Suitable are furthermore copolymeric polycarboxylates, especially those of acrylic acid with methacrylic acid and the acrylic acid or methacrylic acid with maleic acid. Particularly suitable are copolymers of acrylic acid with maleic which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid. Your molecular weight, based on free acids, is in general from 2000 to 70000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol.

Of the Content of the organic builder substances may also be vary in a wide context. Preference is given to contents of 2 to 20 wt .-%, wherein in particular for cost reasons, contents of not more than 10 Gew .-% in particular appeal.

The agents according to the invention can Furthermore Components from the classes of the grayness inhibitors (dirt carrier), the Neutral salts and the fabric softening agent (see above Cationic surfactants).

graying have the task of removing the dirt from the fiber in the fleet to keep it suspended, thus allowing the dirt to be recovered prevent. These are water-soluble Colloids mostly organic nature suitable, for example, the water-soluble Salts of polymeric carboxylic acids, glue, Gelatin, salts of ether carboxylic acids or ether sulfonic acids the strength or the cellulose or salts of acidic sulfuric acid esters cellulose or starch. Also water-soluble, Acidic group-containing polyamides are suitable for this purpose. Farther can be soluble Starch preparations and other than the aforesaid starch products use, e.g. degraded starch, aldehyde etc .. Also, polyvinylpyrrolidone is useful. However, preference is given Cellulose ethers, such as carboxymethyl cellulose (Na salt), methyl cellulose, Hydroxyalkylcellulose and mixed ethers, such as methylhydroxyethylcellulose, Methylhydroxypropylcellulose, methylcarboxymethylcellulose and their Mixtures, and polyvinylpyrrolidone, for example, in amounts of 0.1 to 5 wt .-%, based on the means used.

When typical example of a suitable representative of the neutral salts is the sodium sulfate already mentioned to call. It can be used in amounts of, for example, 2 to 45% by weight. be used.

suitable Plasticizers are, for example, swellable phyllosilicates of the Type of corresponding montmorillonites, for example bentonite.

Of the Content of water on average preferably 0 to less than 10 wt .-% and in particular 0.5 to 8 wt .-%, with values of at most 5 wt .-% special preference Find. Not included in this was if necessary existing aluminosilicates such as zeolite adhering water.

The inventive agent can have an excellent trickling behavior.

The Particles of the invention produced By means of after treatment, for example by mixing the particles of the agent rounded. The rounding can be done in a standard roundabout. Preferably the rounding time not more than 4 minutes, in particular no longer than 3.5 minutes. Rounding times of a maximum of 1.5 minutes or less are particularly preferred. The rounding will be another Unification of the grain spectrum achieved, where appropriate resulting agglomerates are crushed.

The Means can be before rounding with nonionic surfactants, perfume and / or Foam inhibitors or preparation forms containing these ingredients contain, preferably with amounts up to 20 wt .-% of active substance, in particular with amounts of 2 to 18 wt .-% of active substance, respectively based on the post-treated product, in per se conventional Way, preferably in a mixer or possibly a fluidized bed, have been treated.

Especially can the agent of the invention with solids, preferably in amounts of up to 15 wt .-%, in particular in amounts of 2 to 15 wt .-%, each based on the total weight the post-treated agent, nachbehanden.

When Solids can be preferably bicarbonate, carbonate, zeolite, silica, Citrate, urea or mixtures thereof, in particular in quantities from 2 to 15% by weight, based on the total weight of the post-treated Products, use. The aftertreatment can be advantageously in a mixer and / or by means of mills.

In the post-treatment step, it is therefore possible to use the agent with a Solid, for example silicas, zeolites, carbonates, Bicarbonates and / or sulfates, citrates, urea or mixtures from it, as it sufficiently from the state of the art is known. This can either be done directly after leaving the agent taken from the tower in a mixer or in the muller. there It is preferred to include solids, especially bicarbonate and soda Amounts of up to 15 wt .-% and in particular in amounts of 2 to 15 wt .-%, in each case based on the aftertreated product to use.

In a preferred embodiment invention, the composition according to the invention comprises nonionic surfactants, which contain, for example, optical brighteners and / or hydrotropes can, Perfume, a solution of optical brightener and / or foam inhibitors or preparation forms, which may contain these ingredients. Preferably these ingredients or formulations containing these ingredients contained, in liquid, melted or pasty Form applied to the agent. Advantageously, the means with up to 20 wt .-%, advantageously with 2 to 18 wt .-% and in particular with 5 to 15 wt .-% of active ingredient of the ingredients mentioned treated. The quantities are in each case based on the aftertreated Product. It is preferred that the aftertreatment with the substances mentioned here in a conventional mixer, only for example in a 2-wave mixer within a maximum of 1 minute, preferably within 30 seconds and, for example, within 20 seconds, with the times at the same time for Addition and mixing time is done. By such measures can you the flowability of the product.

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten. In particular, however, alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, palm kernel, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred. The preferred ethoxylated alcohols include, for example, C ₁₂ -C ₁₄ -alcohols with 3 EO or 4 EO, C ₉ -C ₁₁ -alcohols with 7 EO, C ₁₃ -C ₁₅ -alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C ₁₂ -C ₁₈ -alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C ₁₂ -C ₁₄ -alcohol with 3 EO and C ₁₂ -C ₁₈ -alcohol with 7 EO. The degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number.

preferred Alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic Surfactants can fatty alcohols with more than 12 EO can also be used. Examples therefor are (tallow) fatty alcohols with 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO.

In addition, as further nonionic surfactants and alkyl glycosides of the general formula RO (G) _x can be used in which R is a primary straight-chain or methyl-branched, especially in the 2-position methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number from 1 to 10; preferably x is 1.1 to 1.4.

Another class of preferred nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants, in particular together with alkoxylated fatty alcohols and / or alkyl glycosides, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably from 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl esters, as described for example in Japanese Patent Application JP 58/217598 or which are preferably prepared according to the method described in International Patent Application WO-A-90/13533. Particularly preferred are C ₁₂ -C ₁₈ fatty acid methyl esters having an average of 3 to 15 EO, in particular having an average of 5 to 12 EO.

Also nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamide can be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half from that.

For machine dishwashing, suitable surfactants are in principle all surfactants. However, the nonionic surfactants described above and, above all, the low-foaming nonionic surfactants are preferred for this purpose. Particularly preferred are the alkoxylated alcohols, especially the ethoxylated and / or propoxylated alcohols. The skilled worker generally understands alkoxylated alcohols, the reaction products of alkylene oxide, preferably ethylene oxide, with alcohols, preferably in the context of the present invention, the longer-chain alcohols (C ₁₀ to C ₁₈ , preferably C ₁₂ to C ₁₆ , such as C ₁₁ -, C ₁₂ -, C ₁₃ -, C ₁₄ -, C ₁₅ -, C ₁₆ -, C ₁₇ - and C ₁₈ -alcohols). As a rule, n moles of ethylene oxide and one mole of alcohol, depending on the reaction conditions, form a complex mixture of addition products of different degrees of ethoxylation. A further embodiment consists in the use of mixtures of the alkylene oxides, preferably the mixture of ethylene oxide and propylene oxide. Also you can desired if, by a conclusive etherification with short-chain alkyl groups, such as preferably the butyl group, to the substance class of the "closed" alcohol ethoxylates, which can also be used in the context of the invention. Very particularly preferred for the purposes of the present invention are highly ethoxylated fatty alcohols or mixtures thereof with end-capped fatty alcohol ethoxylates.

Further conceivable additives are foam inhibitors, for example foam-inhibiting paraffin oil or foam-inhibiting silicone oil, for example dimethylpolysiloxane. The use of mixtures of these agents is possible. At room temperature and solid additives, particularly in the above-mentioned foam-inhibiting agents, paraffin waxes, silicas, which may have been rendered hydrophobic in a known manner, and from C _2-7 -diamines and C _{12- 22} carboxylic acids bisamides derived.

Suitable foam-inhibiting paraffin oils for use in admixture with paraffin waxes are generally complex mixtures without a sharp melting point. For characterization, the melting range is usually determined by differential thermal analysis (DTA) as described in "The Analyst". 87 (1962), 420, and / or the solidification point. This is the temperature at which the paraffin passes from the liquid to the solid state by slow cooling. Paraffins with less than 17 carbon atoms are not useful in the invention, their proportion in the paraffin oil mixture should therefore be as low as possible and is preferably below the limit significantly measurable by conventional analytical methods, for example gas chromatography. Preferably before paraffins are used, which solidify in the range of 20 ° C to 70 ° C. It should be noted that even at room temperature appearing paraffin wax mixtures may contain different proportions of liquid paraffin oils. In the case of the paraffin waxes which can be used according to the invention, the liquid fraction at 40 ° C. is as high as possible, without already being 100% at this temperature. Preferred paraffin wax mixtures have at 40 ° C a liquid content of at least 50 wt .-%, in particular from 55 wt .-% to 80 wt .-%, and at 60 ° C, a liquid content of at least 90 wt .-% to. This has the consequence that the paraffins are flowable and pumpable at temperatures down to at least 70 ° C, preferably down to at least 60 ° C. It should also be ensured that the paraffins contain as far as possible no volatile components. Preferred paraffin waxes contain less than 1 wt .-%, in particular less than 0.5 wt .-% at 110 ° C and atmospheric pressure vaporizable fractions. According to Paraffins for example, under the trade names Luna Flex ^® from Fuller and Deawax ^® DEA Mineralöl AG are based.

The paraffin oils can bisamides solid at room temperature, which differ from saturated ones fatty acids with 12 to 22, preferably 14 to 18 carbon atoms and of alkylenediamines with 2 to 7 carbon atoms derived. Suitable fatty acids are Laurin, myristic, stearic, arachinic and behenic acid as well their mixtures, as they are made of natural Greases or hardened oils, such as Tallow or hydrogenated palm oil, available are. Suitable diamines are, for example, ethylenediamine 1,3-propylenediamine, Tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, p-phenylenediamine and toluenediamine. Preferred diamines are ethylenediamine and hexamethylenediamine. Particularly preferred bisamides are bis-myristoyl-ethylenediamine, bis-palmitoyl-ethylenediamine, Bis-stearoyl-ethylenediamine and mixtures thereof and the corresponding Derivatives of hexamethylenediamine.

In some embodiments of the invention the said foam inhibitors may be contained in the composition.

In a further embodiment of the invention can be post-treated with said ingredients and optionally rounded agents with solids, preferably Bicarbonate and / or soda, especially in amounts of from 2 to 15% by weight, be post-treated based on the post-treated product.

According to one preferred embodiment have the inventively prepared Means as well the advantage that the containing agent is rapidly soluble.

The agent and / or the aftertreatment agents described above may comprise further constituents of washing, care and / or cleaning agents, in particular being mixed therewith. From the broad state of the art is generally known which ingredients of detergents and cleaning agents and which raw materials are usually blended, such as bleaching agents based on per-compounds, bleach activators and / or bleach catalysts, enzymes from the class proteases, lipases and amylases; or bacterial strains or fungi, foam inhibitors in optionally granular and / or compounded form, perfumes, temperature-sensitive dyes and the like, which expediently mixed with the previously dried compositions and optionally post-treated products become.

Also, the agent may have UV absorbers which are applied to the treated fabrics and improve the light fastness of the fibers and / or the lightfastness of other formulation ingredients. Under UV absorber are organic substances (sunscreen) to understand, which are able to absorb ultraviolet rays and the absorbed energy in the form of longer-wave radiation, eg heat to give back. Compounds having these desired properties include, for example, the non-radiative deactivating compounds and derivatives of benzophenone having substituents in the 2- and / or 4-position. Also suitable are substituted benzotriazoles, phenyl-substituted acrylates (cinnamic acid derivatives) in the 3-position, optionally with cyano groups in the 2-position, salicylates, organic Ni complexes and natural substances such as umbelliferone and the body's own urocanic acid. Of particular importance are biphenyl and especially Stilbenderivate as described for example in the EP 0728749 A are described and are available as Tinosorb FD ^{® ®} or Tinosorb FR ex Ciba commercially. As UV-B absorber are 3-benzylidene camphor or 3-Benzylidennorcampher and its derivatives, for example 3- (4-methylbenzylidene) camphor, as in EP 0693471 B1 described; 4-aminobenzoic acid derivatives, preferably 2-ethylhexyl 4- (dimethylamino) benzoate, 2-octyl 4- (dimethylamino) benzoate and 4- (dimethylamino) benzoic acid ester; Esters of cinnamic acid, preferably 4-methoxycinnamic acid 2-ethylhexyl ester, 4-methoxycinnamic acid propyl ester, 4-methoxycinnamic acid isoamyl ester, 2-cyano-3,3-phenylcinnamic acid 2-ethylhexyl ester (octocrylene); Esters of salicylic acid, preferably 2-ethylhexyl salicylate, 4-isopropylbenzyl salicylate, homomenthyl salicylate; Derivatives of benzophenone, preferably 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone; Esters of benzalmalonic acid, preferably di-2-ethylhexyl 4-methoxybenzmalonate; Triazine derivatives such as 2,4,6-trianilino (p-carbo-2'-ethyl-1'-hexyloxy) -1,3,5-triazine and octyl triazone, as described in U.S. Pat EP 0818450 A1 Dioctyl Butamido Triazone or described (Uvasorb HEB ^®); Propane-1,3-diones such as 1- (4-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1,3-dione; Ketotricyclo (5.2.1.0) decane derivatives as described in U.S.P. EP 0694521 B1 described. Also suitable are 2-phenylbenzimidazole-5-sulfonic acid and its alkali metal, alkaline earth metal, ammonium, alkylammonium, alkanolammonium and glucammonium salts; Sulfonic acid derivatives of benzophenones, preferably 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its salts; Sulfonic acid derivatives of 3-Benzylidencamphers, such as 4- (2-oxo-3-bomylidenemethyl) benzenesulfonic acid and 2-methyl-5- (2-oxo-3-bomylidene) sulfonic acid and salts thereof.

As a typical UV-A filter in particular derivatives of benzoylmethane are suitable, such as 1- (4'-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1,3-dione, 4-tert-butyl 4'-methoxydibenzoylmethane (Parsol 1789), 1-phenyl-3- (4'-isopropylphenyl) -propane-1,3-dione, and enamine compounds as described in U.S.P. DE 19712033 A1 (BASF). Of course, the UV-A and UV-B filters can also be used in mixtures. In addition to the soluble substances mentioned, insoluble photoprotective pigments, namely finely dispersed, preferably nano-metal oxides or salts, are also suitable for this purpose. Examples of suitable metal oxides are in particular zinc oxide and titanium dioxide and, in addition, oxides of iron, zirconium, silicon, manganese, aluminum and cerium and mixtures thereof. As salts silicates (talc), barium sulfate or zinc stearate can be used. The oxides and salts are already used in the form of the pigments for skin-care and skin-protecting emulsions and decorative cosmetics. The particles should have an average diameter of less than 100 nm, preferably from 5 to 50 nm and in particular from 15 to 30 nm. They may have a spherical shape, but it is also possible to use those particles which have an ellipsoidal or otherwise deviating shape from the spherical shape. The pigments can also be surface-treated, ie hydrophilized or hydrophobized. Typical examples are coated titanium dioxides, for example Titandioxid T 805 (Degussa) or Eusolex ^® T2000 (Merck). Suitable hydrophobic coating agents are in particular silicones and in particular trialkoxyoctylsilanes or simethicones. Preferably, micronized zinc oxide is used. Further suitable UV photoprotective filters can be found in the review by P.Finkel in SÖFW-Journal 122, 543 (1996).

The UV absorbers are usually in amounts of 0.01% by weight to 5% by weight, preferably of 0.03% by weight to 1 wt .-%, used. In exceptional cases, they can also be in the mean be included.

However, other constituents, for example so-called speckles, which by their color and / or their shape stand out from the appearance of the other components of the composition, may also be contained in the composition. The speckles may have a different color. It is also possible that the speckles have the same composition as the other components of the composition, are not stained, but have a different shape. Ultimately, however, it is preferred that speckles differ from the latter in color and optionally additionally in their shape. In these cases, the speckles are only intended to make the appearance of the finished washing, care and / or cleaning agents even more attractive Stalten.

In a further and quite preferred embodiment of the invention however, the speckles have a different chemical composition than the other components containing the agent. Right here may be due to a different color and / or a different shape of the Consumers should be advised that certain ingredients for certain Purposes, such as bleaching or care aspects in the final product are included. These speckles can not only spherical to be rod-shaped, you can also represent completely different figures. At this point is on the Disclosure of International Applications WO 97/08290 and WO 00/23556 pointed.

The admixed speckles or else other ingredients may for example be spray-dried, agglomerated, granulated, pelletized or extruded. With regard to extrusion processes, particular reference is made here to the disclosures in the European patent EP 0486592 B1 and International Patent Application WO 98/12299. Since it is preferable to use an agent having an excellent dissolving rate even at relatively cold water of 30 ° C, it is of course preferable to mix such other ingredients and / or raw materials which also have an excellent dissolving speed. Therefore, in a preferred embodiment of the invention, raw materials are added to the agent which have been prepared according to the disclosure of international patent application WO 99/28433.

Of the The present invention is based on the following Examples 1 to 5 further explained.

Examples 1 to 3:

For the experiment was a heatable autoclave from the company Haage with a volume content of 1.5 liters used. In the autoclave were presented:

example 1

200 ml perfume oil Geraniol, pressed with 75 bar nitrogen (= comparative experiment)

Example 2

200 ml of perfume oil, spiked with 200 g of dry ice (carbon dioxide), was heated to about 32 - 33 ° C, measured value 75th bar.

Example 3

200 ml of a mixture of 66.66% perfume oil and 33.33% dodecanol with 360 g of dry ice, was heated to about 33 ° C, measured value 75 bar; the supply line to the nozzle was at 30 ° C heated.

The Perfume oil or the Mixture according to the examples 1, 2 and 3 were each about a hollow cone nozzle Fa. Schlick (type 121) with an opening diameter of 0.1 mm atomized. The drop size distribution is with a laser diffraction spectrometer from Malvern (type 1600s) centrally within the symmetrical spray cone with an axial distance determined by 30 mm to the nozzle opening Service.

The Sauter diameter ds represents the average spherical size corresponding to the specific surface area of the entire droplet collective and characterizes the distribution. The diameter d 5 indicates that 5% by weight of the total collective is less than d 5.

Of the Experiment c, compared to the other two experiments, a relatively broad distribution, but with increased proportions of very fine and coarser ones Droplet.

Example 4 and 5:

to Determination of the evaporation rate were in each case 2 kg of detergent tower powder with 100 g perfume oil in the technical center in a clay ploughshare mixer according to experiment a) and experiment b) sprayed. One sample each was subjected to thermogavrimetric analysis. TGA analysis with Al crucible, open; 3 l N2 / h; Heating rate: 1 ° K / min; Sample size 4a: 67.9950 mg; Sample size 5c): 60.0570 mg.

Example 4, sprayed after test a), referred to as 4a (comparative example): Example 5, sprayed after test c), designated as 5c (example of the invention):
Normalized evaporation rate (1 / s) at 30 ° C: 4a = 0.0008 at 70 ° C: 4a = 0.0062
normalized evaporation rate (1 / s) at 30 ° C: 5c = 0.0004 at 70 ° C: 5c = 0.0027

The Differences in the evaporation rate will be below temperatures of 26 ° C (Melting point of the mixture) even larger, because the oil of the example 5c is fixed.

Claims (70)

Method of applying fragrances in micro / nanoscale Mold on means, in particular washing, cleaning care particles and / or precursors thereof, characterized in that one pressurized liquid or pasty Perfume / e-carbon dioxide mixture releasing the carbon dioxide in the form of carbon dioxide gas sprayed in the presence of the agent, wherein the forming micro / nanoscale fragrance particles are under cooling on the medium in liquid or solid form. Method according to claim 1, characterized in that that the fragrances before the carbon dioxide addition as a liquid oil, as an aqueous emulsion and / or as a blend with an organic substance having a melting point of 30 ° C up to 70 ° C is present. Method according to one of the preceding claims, wherein the agent is a fine particulate Solid, preferably a particulate, preferably fine particulate, washing, Cleaning Care Products and / or precursors thereof. Method according to one of the preceding claims, wherein the perfume / e-carbon dioxide mixture, based on the total weight the fragrance / e-carbon dioxide mixture comprising: 0% by weight to ≤ 50 Wt .-% water, preferably ≥ 1 Wt .-% to ≤ 40 Wt .-% water, preferably ≥ 2 wt .-% to ≤ 30 Wt .-% water, more preferably ≥ 3 Wt .-% to ≤ 25 Wt .-% water, even more preferably ≥ 5 wt .-% to ≤ 20 wt .-% Water and most preferably ≥ 6 % By weight to 15% by weight of water; and or - ≥ 1 wt .-% to ≤ 75 wt .-% Carbon dioxide, preferably ≥ 3 Wt .-% to ≤ 60 Wt .-% carbon dioxide, preferably ≥ 5 Wt .-% to ≤ 50 % By weight of carbon dioxide, more preferably ≥ 7% by weight to ≦ 40% by weight Carbon dioxide, even more preferably ≥ 10% by weight to ≤ 30% by weight Water, and most preferably ≥ 15 % By weight to 20% by weight of carbon dioxide; and or - ≥ 1% by weight to ≤ 95 % By weight of perfume (s), preferably ≥ 5 Wt .-% to ≤ 80 % By weight of perfume (s), preferably ≥ 10 Wt .-% to ≤ 70 % By weight of perfume (s), more preferably ≥ 15% by weight to ≤ 60% by weight Perfume / s, more preferably ≥ 20 wt .-% to ≤ 50 wt .-% perfume / e and most preferably ≥ 30 % By weight to 40% by weight of perfume (s), the weight proportions of water, Perfume / e and carbon dioxide are chosen so that the total weight fraction at most 100% by weight. Method according to one of the preceding claims, wherein the perfume / e-carbon dioxide mixture, based on the total weight the perfume / e-carbon dioxide mixture having perfumes in excess. Method according to one of the preceding claims, wherein fragrance (s) with a low flashpoint and / or high flashpoint sprayed. Method according to one of the preceding claims, wherein perfume (s) with a high flash point of> 60 ° C and ≤ 200 ° C, preferably from ≥ 70 ° C, continue preferably from ≥ 80 ° C and still more preferably sprayed from ≥ 100 ° C. Method according to one of the preceding claims, wherein one fragrance / s with a low flash point of ≤ 60 ° C and ≥ 20 ° C, preferably from ≤ 55 ° C, further preferably from ≤ 50 ° C and still more preferably sprayed from ≤ 45 ° C. Method according to one of the preceding claims, wherein one carried micro / nanoscale perfume / e sprayed, wherein the carrier / e preferably selected are from the group comprising paraffins, surfactants, especially ethoxylated Fatty alcohols, fatty acids, silicone oils and / or fatty alcohol, preferably lipophilic substances, lipophilic Substances with a melting point above 25 ° C especially are preferred. Method according to one of the preceding claims, wherein the micro / nanoscale carrier-based Perfume particles fragrance with 0.05 wt .-% to 10 wt .-%, based on the total weight of the micro / nanoscale perfume particles, exhibit. Method according to one of the preceding claims, wherein The relationship Perfume / e to carrier / e in a supported Perfume (s) from 20: 1 to 1:10, preferably 5: 1 to 10: 1 and preferably 3: 1. Method according to one of the preceding claims, wherein one to be sprayed Perfume-carbon dioxide mixture at least one emulsifier and / or Add thickener. Method according to one of the preceding claims, wherein one to be sprayed Perfume-carbon dioxide mixture at least one substance added, which extends the period over the the scent odor of the micro / nanoscale precipitated on the middle Perfume particles is maintained. Method according to one of the preceding claims, wherein one micro / nano-scale perfume particles whose fragrance odor one over long-lasting period may be separated from micro / nanoscale perfume particles their smell of scent you over a shorter one sustained period can be sprayed, so that the respectively forming micro / nanoscale Perfume particles precipitate in succession on the agent. Method according to one of the preceding claims, wherein the fragrance / e-carbon dioxide mixture, based on the total weight of the perfume / e-carbon dioxide mixture, having: - ≥ 0% by weight up to ≤ 3% by weight Emulsifier, preferably ≥ 0.1 Wt .-% to ≤ 2 Wt .-% emulsifier, preferably ≥ 0.2 Wt .-% to ≤ 1 % By weight of emulsifier, more preferably ≥ 0.3% by weight to ≦ 0.8% by weight Emulsifier, and most preferably ≥ 0.4 wt% to 0.6 wt% emulsifier; and or - ≥ 0% by weight up to ≤ 3% by weight Thickener, preferably ≥ 0.01 Wt .-% to ≤ 2 % By weight of thickener, preferably ≥ 0.05 Wt .-% to ≤ 1 % By weight of thickener, more preferably ≥ 0.08% by weight to ≦ 0.8% by weight Thickener and most preferably ≥ 0.1 wt .-% to 0.5 wt .-% thickener. Method according to one of the preceding claims, wherein the one to be sprayed Perfume / e-carbon dioxide mixture under a pressure of 3 bar to 150 bar, preferably 15 bar to 120 bar and preferably 30 bar to 75 bar. Method according to one of the preceding claims, wherein the one to be sprayed Perfume / e-carbon dioxide mixture a temperature of ≥ -10 ° C and ≤ 100 ° C, preferably ≥ -5 ° C and ≤ 70 ° C, further preferably from ≥ 0 ° C and ≤ 50 ° C, still preferably ≥ 5 ° C and ≤ 35 ° and most preferably ≥ 10 ° C and ≤ 25 ° C. Method according to one of the preceding claims, wherein to spray it Perfumes-carbon dioxide mixture on an agent that is under one Pressure of 0.01 bar to 5 bar, preferably 0.1 bar to 3 bar and preferably 0.5 bar to 1 bar, sprayed. Method according to one of the preceding claims, wherein the means to apply the fragrance / e-carbon dioxide mixture a temperature of ≥ 0 ° C and ≤ 80 ° C, preferably ≥ 5 ° C and ≤ 60 ° C, further preferably from ≥ 10 ° C and ≤ 50 ° C, still preferably ≥ 20 ° C and ≤ 40 °, especially preferably from ≥ 25 ° C and ≤ 30 ° C and on most preferably at room temperature. Method according to one of the preceding claims, wherein the micro- / nanoscale perfume particles have a particle size d ₅₀ of ≥ 0.1 microns and ≤ 25 microns, preferably a particle size d ₅₀ of ≥ 0.2 microns and ≤ 15 microns, preferably a particle size d ₅₀ of ≥ 0.3 μm and ≤ 10 μm, more preferably a particle size d ₅₀ of ≥ 0.4 μm and ≤ 5 μm, and particularly preferably have a particle size d ₅₀ of ≥ 0.5 μm and ≤ 2 μm. Method according to one of the preceding claims, wherein the micro- / nanoscale perfume particles a Particle size d ₇₀ of ≥ 0.1 microns and ≤ 30 microns, preferably a particle size d ₇₀ of ≥ 0.2 microns and ≤ 15 microns, preferably a particle size d ₇₀ of ≥ 0.3 microns and ≤ 10 microns, still preferably a particle size d ₇₀ of ≥ 0.4 μm and ≤ 5 μm, and particularly preferably have a particle size d ₇₀ of ≥ 0.5 μm and ≤ 2 μm. Method according to one of the preceding claims, wherein the micro- / nanoscale perfume particles have a particle size d ₉₀ of ≥ 0.1 microns and ≤ 30 microns, preferably a particle size d ₉₀ of ≥ 0.2 microns and ≤ 15 microns, preferably a particle size d ₉₀ of ≥ 0.3 μm and ≤ 10 μm, more preferably a particle size d ₉₀ of ≥ 0.4 μm and ≤ 5 μm, and particularly preferably have a particle size d ₉₀ of ≥ 0.5 μm and ≤ 2 μm. Method according to one of the preceding claims, wherein one the micro / nanoscale fragrance particles in the solidified and / or iced state, on the means, the means preferably Washing, cleaning, care agent particles and / or precursor thereof includes, applies. Perfume-containing agent, preferably washing, Cleaning, care and / or precursor thereof, can be produced according to one of the preceding claims. Perfume-containing agent according to one of the previous Claims, preferably in the form of a fine particulate solid, wherein the agent has micro / nanoscale perfume particles. Perfume-containing agent according to one of the previous claims 24 or 25, preferably in the form of a fine particulate solid, wherein the fragrance-containing agent is in the form of particles. Perfume-containing agent according to one of the previous claims 24 to 26, preferably in the form of a fine particulate solid, wherein the fragrance having agent at least 10 wt .-%, preferably at least 20 wt .-%, preferably at least 30 wt .-%, more preferably at least 40 wt .-%, more preferably at least 50 wt .-% of the total Perfume of the perfume having agent, based on the total weight the fragrance-containing agent, in the form of micro- / nanoscale applied fragrance having. Perfume-containing agent according to one of the previous claims 24 to 27, preferably in the form of a fine particulate solid, wherein the agent perfume having a flash point of ≤ 60 ° C and ≥ 20 ° C, preferably from ≤ 55 ° C, further preferably from ≤ 50 ° C and still more preferably of ≤ 45 ° C. Perfume-containing agent according to one of the previous claims 24 to 28, preferably in the form of a fine particulate solid, wherein the agent perfume having a flash point of> 60 ° C and ≤ 200 ° C, preferably from ≥ 70 ° C, further preferably from ≥ 80 ° C and still more preferably of ≥ 100 ° C. Perfume-containing agent according to one of the previous claims 24 to 29, preferably in the form of a fine particulate solid, the fragrance having a fragrance vapor pressure of 0.001 at 20 ° C mbar to 2 mbar, preferably 0.01 mbar to 1.0 mbar and preferred 0.05 mbar to 0.5 mbar. Perfume-containing agent according to one of the previous claims 24 to 30, preferably in the form of a fine particulate solid, the fragrance having agent at 20 ° C after a storage of 24 hours at 20 ° C in the air a fragrance vapor pressure of 0.001 mbar to 2 mbar, preferably 0.005 mbar to 0.8 mbar and preferably 0.01 mbar to 0.4 mbar. Perfume-containing agent according to one of the previous claims 24 to 31, preferably in the form of a fine particulate solid, the fragrance having agent at 20 ° C after 48 hours storage in the air at 20 ° C a fragrance vapor pressure of 0.001 mbar to 1.5 mbar, preferably 0.003 mbar to 0.7 mbar and preferably 0.01 mbar to 0.3 mbar. Perfume-containing agent according to one of the previous claims 24 to 32, wherein the agent micro / nanoscale applied perfume particles wherein the applied micro / nanoscale perfume particles a solid at room temperature excipient exhibit. Fragrance-containing agent according to one of the preceding claims 24 to 33, preferably in the form of a fine particulate solid, wherein the carrier of the agent at least 10 wt .-% carrier, preferably at least 20 wt .-% carrier, preferably at least 30 wt .-% carrier, more preferred at least 40% by weight of carrier, even more preferably at least 50% by weight of carrier and more preferably at least 60% by weight of carrier, based on the total weight of the perfume-containing agent. Perfume-containing agent according to one of the previous claims 24 to 34, preferably in the form of a fine particulate solid, wherein the carrier selected is from the group comprising paraffins, surfactants, fatty acids, fatty alcohols and silicone oils. Perfume-containing agent according to one of the previous claims 24 to 35, preferably in the form of a fine particulate solid, wherein the carrier extends the period of fragrance delivery. Perfume-containing agent according to one of the previous claims 24 to 36, preferably in the form of a fine particulate solid, wherein the carrier the period of perfume delivery compared to the otherwise same, the same amount of fragrance containing, unsupported perfume having at least 10%, preferably at least 30%, preferably at least 50%, more preferably at least 100%, more preferably at least 300%, and most preferred extended by at least 500. Perfume-containing agent according to one of the previous claims 24 to 37, preferably in the form of a fine particulate solid, being the supported one Perfume-containing agent comprises: - at least one perfume with a low flash point, preferably with a flash point of ≤ 60 ° C and ≥ 20 ° C, preferably from ≤ 55 ° C, further preferably from ≤ 50 ° C and still more preferably of ≤ 45 ° C; and or - at least a fragrance with a high flash point, preferably with a flash point of> 60 ° C and ≤ 200 ° C. Perfume-containing agent according to one of the previous claims 24 to 38, preferably in the form of a fine particulate solid, being the supported one Perfume-containing agent comprises: - at least one perfume with low vapor pressure, measured at 20 ° C, preferably with a vapor pressure of ≤ 0.1 mbar and ≥ 0.001 mbar; and or - at least a fragrance with high vapor pressure, preferably with a vapor pressure of ≥ 0.1 mbar and ≤ 2 mbar. Perfume-containing agent in the form of a fine particulate solid according to one of the preceding claims 24 to 39, with the agent carried Fragrance particles with high vapor pressure and / or unsupported perfume particles comprising high vapor pressure. Perfume-containing agent in the form of a fine particulate solid according to one of the preceding claims 24 to 40, the ratio of supported ones Fragrance particles with high vapor pressure and unsupported perfume particles with high vapor pressure 100: 1 to 1: 100. Perfume-containing agent in the form of a fine particulate solid according to one of the preceding claims 24 to 41, where - 0 to 5% by weight of the perfume-containing middle particles have a particle diameter of <0.1 mm, - 3 to 40 wt .-% of the perfume having middle particles a particle diameter from <0.2 mm to 0.1 mm, - 10 Up to 55 wt .-% of the fragrance-containing agent particles have a particle diameter from <0.4 mm to 0.2 mm, - 20 to 70 wt .-% of the fragrance-containing agent particles have a particle diameter from <0.8 mm to 0.4 mm, - 3 to 30% by weight of the fine particulate Solid a particle diameter of <1.6 mm to 0.8 mm, and - 0 to 10 wt .-% of the fragrance-containing agent particles have a particle diameter of at least 1.6 mm, based on the total weight of the agent in the form of a fine particulate Solid, exhibit. Perfume-containing agent in the form of a fine particulate solid according to one of the preceding claims, wherein at least 80 wt .-%, preferably at least 90 wt .-%, and preferably at least 95% by weight of the fine particulate solid, based on the total weight of the fine particulate solid, a particle diameter from 0.1 mm - 1.6 mm, preferably have a particle diameter of 0.2 mm - 1.0 mm. Process for the preparation of fragrances in micro / nanoscale form, characterized in that spraying a pressurized liquid or pasty perfume / e-carbon dioxide mixture with release of carbon dioxide in the form of carbon dioxide gas with cooling, forming micro- / nanoscale perfume particles. Method according to claim 44, characterized in that that the fragrances before the carbon dioxide addition as a liquid oil, as an aqueous emulsion and / or as a blend with an organic substance having a melting point of 30 ° C up to 70 ° C is present. A method according to claim 44 or 45, wherein the perfume / e-carbon dioxide mixture, based on the total weight of the perfume / e-carbon dioxide mixture, having: - 0 Wt .-% to ≤ 50 Wt .-% water, preferably ≥ 1 Wt .-% to ≤ 40 Wt .-% water, preferably ≥ 2 wt .-% to ≤ 30 Wt .-% water, more preferably ≥ 3 Wt .-% to ≤ 25 Wt .-% water, even more preferably ≥ 5 wt .-% to ≤ 20 wt .-% Water and most preferably ≥ 6 % By weight to 15% by weight of water; and or - ≥ 1 wt .-% to ≤ 75 wt .-% Carbon dioxide, preferably ≥ 3 Wt .-% to ≤ 60 Wt .-% carbon dioxide, preferably ≥ 5 Wt .-% to ≤ 50 % By weight of carbon dioxide, more preferably ≥ 7% by weight to ≦ 40% by weight Carbon dioxide, even more preferably ≥ 10% by weight to ≤ 30% by weight Water, and most preferably ≥ 15 % By weight to 20% by weight of carbon dioxide; and or - ≥ 1% by weight to ≤ 95 % By weight of perfume (s), preferably ≥ 5 Wt .-% to ≤ 80 % By weight of perfume (s), preferably ≥ 10 Wt .-% to ≤ 70 % By weight of perfume (s), more preferably ≥ 15% by weight to ≤ 60% by weight Perfume (s), even more preferably ≥ 20 wt% to ≤ 50 wt% perfume (s) and most preferably ≥ 30 % By weight to 40% by weight of perfume (s), the weight proportions of water, Perfume / e and carbon dioxide are chosen so that the total weight fraction at most 100% by weight. Method according to one of the preceding claims 44 to 46, wherein the perfume / e-carbon dioxide mixture, based on the Total weight of the perfume / e-carbon dioxide mixture, the perfume / e in excess. Method according to one of the preceding claims 44 to 47, wherein one scent / e with a low flash point and / or sprayed high flash point. Method according to one of the preceding claims 44 to 48, wherein one perfume / e with a high flash point of> 60 ° C and ≤ 200 ° C, preferably of ≥ 70 ° C, on preferably from ≥ 80 ° C and even further preferably sprayed from ≥ 100 ° C. Method according to one of the preceding claims 44 to 49, wherein fragrance / s having a low flash point of ≤ 60 ° C and ≥ 20 ° C, preferably from ≤ 55 ° C, further preferably from ≤ 50 ° C and still more preferably sprayed from ≤ 45 ° C. Method according to one of the preceding claims 44 to 50, where you carried micro- / nanoscale perfume / e sprayed wherein the carrier / e preferably selected are from the group comprising paraffins, surfactants, especially ethoxylated Fatty alcohols, fatty acids, silicone oils and / or fatty alcohol, preferably lipophilic substances, lipophilic Substances with a melting point above 25 ° C especially are preferred. Method according to one of the preceding claims 44 to 51, the ratio Perfume / e to carrier / e in a supported Perfume (s) from 20: 1 to 1:10, preferably 5: 1 to 10: 1 and preferably 3: 1. Method according to one of the preceding claims 44 to 52, wherein the one to be sprayed Perfume / e-carbon dioxide mixture at least one emulsifier and / or Add thickener. Method according to one of the preceding claims 44 to 53, wherein the one to be sprayed Perfume / e-carbon dioxide mixture at least one substance added, which extends the period over the maintained the fragrance odor of micro / nanoscale perfume particles remains. Method according to one of the preceding claims 44 to 54, wherein the fragrance-carbon dioxide mixture used, based on the total weight of the perfume / e-carbon dioxide mixture, comprises: - ≥ 0 wt .-% to ≤ 3 wt .-% emulsifier, preferably ≥ 0.1 wt.% to ≤ 2 wt.% emulsifier, preferably ≥ 0.2 wt.% to ≤ 1 wt.% emulsifier, more preferably ≥ 0.3 wt.% to ≤ 0, 8 wt .-% emulsifier and on most preferably ≥ 0.4 wt .-% to 0.6 wt .-% emulsifier; and / or - ≥ 0 wt .-% to ≤ 3 wt .-% thickener, preferably ≥ 0.01 wt .-% to ≤ 2 wt .-% thickener, preferably ≥ 0.05 wt .-% to ≤ 1 wt % Thickener, more preferably ≥0.08 wt% to ≤0.8 wt% thickener and most preferably ≥0.1 wt% to 0.5 wt% thickener. Method according to one of the preceding claims 44 to 55, wherein the sprayed Fragrance / e-carbon dioxide mixture under a pressure of 3 bar to 150 bar, preferably 15 bar to 120 bar and preferably 30 bar to 75 bar stands. Method according to one of the preceding claims 44 to 56, wherein the sprayed Fragrance / e-carbon dioxide mixture a temperature of ≥ -10 ° C and ≤ 100 ° C, preferably ≥ -5 ° C and ≤ 70 ° C, more preferably from ≥ 0 ° C and ≤ 50 ° C, still preferably ≥ 5 ° C and ≤ 35 ° and most preferably ≥ 10 ° C and ≤ 25 ° C. Method according to one of the preceding claims 44 to 57, wherein the micro- / nanoscale perfume particles have a particle size d ₅₀ of ≥ 0.1 microns and ≤ 25 microns, preferably a particle size d ₅₀ of ≥ 0.2 microns and ≤ 15 microns, preferably one Particle size d ₅₀ of ≥ 0.3 μm and ≤ 10 μm, more preferably a particle size d ₅₀ of ≥ 0.4 μm and ≤ 5 μm, and particularly preferably a particle size d ₅₀ of ≥ 0.5 μm and ≤ 2 μm, exhibit. Method according to one of the preceding claims 44 to 58, wherein the micro- / nanoscale perfume particles have a particle size d ₇₀ of ≥ 0.1 microns and ≤ 30 microns, preferably a particle size d ₇₀ of ≥ 0.2 microns and ≤ 15 microns, preferably one Particle size d ₇₀ of ≥ 0.3 μm and ≤ 10 μm, more preferably a particle size d ₇₀ of ≥ 0.4 μm and ≤ 5 μm, and particularly preferably a particle size d ₇₀ of ≥ 0.5 μm and ≤ 2 μm, exhibit. Method according to one of the preceding claims 44 to 59, wherein the micro- / nanoscale perfume particles have a particle size d ₉₀ of ≥ 0.1 microns and ≤ 30 microns, preferably a particle size d ₉₀ of ≥ 0.2 microns and ≤ 15 microns, preferably one Particle size d ₉₀ of ≥ 0.3 μm and ≤ 10 μm, more preferably a particle size d ₉₀ of ≥ 0.4 μm and ≤ 5 μm, and particularly preferably a particle size d ₉₀ of ≥ 0.5 μm and ≤ 2 μm, exhibit. Micro / nanoscale fragrance particles produced according to one of the preceding claims 44 to 60. Micro- / nanoscale perfume particles after one the previous claims, wherein the fragrance from 0.05 wt .-% to 2 wt .-%, based on the total weight the micro / nanoscale perfume particles. Micro- / nanoscale perfume particles after one the previous claims, wherein the high vapor pressure fragrance is 0.03% to 1.5% by weight, based on the total weight of the micro / nanoscale perfume particles, accounts. Micro- / nanoscale perfume particles after one the previous claims, wherein the low vapor pressure fragrance is 0.02 wt% to 1.5 Wt .-%, based on the total weight of the micro / nanoscale perfume particles, accounts. Micro- / nanoscale perfume particles after one the previous claims, wherein the carrier From 0.02% to 15%, preferably from 0.5% to 1.5%, by weight, based on the total weight of the micro- / nanoscale, supported perfume particles, accounts. Micro- / nanoscale perfume particles after one the previous claims, the bulk density of the micro- / nanoscale perfume particles at least 250 g / l and / or maximum 1150 g / l. Micro- / nanoscale perfume particles after one the previous claims, in which - 0 to 5 wt .-% of the micro / nanoscale perfume particles a particle diameter of <500 nm, - 1 to 10% by weight of the micro / nanoscale perfume particles have a particle diameter from <800 nm to 1000 nm, - 5 to 20 wt .-% of the micro / nanoscale perfume particles a particle diameter from <900 nm to 2000 nm, based on the total weight of the micro / nanoscale Perfume particles. Micro- / nanoscale perfume particles after one the previous claims, wherein the direct micro- / nanoscale perfume particulate product is anhydrous is. Product, the product being one of the means previous claims and / or micro / nanoscale perfume particles according to one of the preceding claims includes. The product of claim 69, wherein the product is a Detergents, cleansers, conditioners, hair treatment preparations, hair dyes, Medicines, plant protection products, foodstuffs, cosmetics, fertilizers, building materials, Adhesive, bleach, disinfectant and / or fragrance is.