DE102004035552A1 - Non-ionic and / or perfume-containing soda-free particles for use in detergents or cleaners - Google Patents

Abstract

In particular with detergents and cleaning agents, the fragrance may change during storage. To avoid this disadvantage, the provision of nonionic surfactant and / or perfume containing soda-free particles is proposed, these particles having as an essential component a carrier material selected from the group comprising silicate, copolymer, soap, phosphonate, phosphate and / or sulfate, wherein the soda-free particles contain 1% by weight to 50% by weight of nonionic surfactant and / or 0.5% by weight to 15% by weight of perfume, based on the total weight of the soda-free particles.

Description

The The present invention relates to nonionic surfactant and / or perfume soda-free particles, and a process for their preparation. The The invention further relates to a mixture comprising discrete nonionic surfactants and / or Perfume containing soda-free particles and discrete soda-containing particles. Furthermore The invention relates to a finished product comprising nonionic surfactant and / or Perfume having soda-free particles and optionally additionally soda-containing Particle.

It is known to be particulate Agents, such as washing, cleaning or care products by spray drying method can be produced. In the production of powdery In a first step, detergents are formed into an aqueous slurry "slurry." The slurry contains thermally stable detergent ingredients that are among the Conditions of spray drying essentially neither volatilize still decompose like surfactants and builders. Subsequently, will the slurry over Pumping in a spray tower promoted and over in the upper part of the spray tower located nozzles sprayed. By means of ascending air with high temperature becomes 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, obtained as a powder become. The powder is then further temperature-labile components, such as bleach, nonionic surfactants or fragrances, mixed so that soda-containing particles can absorb nonionic surfactant and / or perfumes.

devices for spray drying aqueous compositions are known in the art known. Often devices used are, for example, spray towers with atomizing nozzles, in particular at 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 dries with hot gas in cocurrent or countercurrent. Then the dry product is through Cyclones or filters deposited. If a melt is atomized and frozen in cold gas, this is called a Prill Tower.

Further known spray dryers are disk towers. These are - like also the nozzle towers - short-term dryers. They use for atomization rotating discs and are compared to the nozzle tower of squat design. The advantage of the atomizer disk is their insensitivity to blockage of the "nozzles" and highly variable Liquid flow rates.

Known are as well spray dryer with integrated fluidized bed. By installing a fluidized bed at the bottom of the spray tower The product can be dried and sifted there. The drying gas with the fine dust, for example, in the upper part of the tower deducted at the top of the tower and the fine dust is after the separation returned to the tower. Therefore can also processed comparatively sticky and slowly drying starting materials become. The product obtained is readily dispersible particles, the bigger and thus mostly dustier as the powders of the nozzle and especially the disk towers are.

in the further meaning are also to be counted among the spray dryers Fluidized bed spray granulators ("agglomeration dryers"), which are the manufacture from granules in the range of 0.3 mm to several mm of atomizable Solutions, Serve suspensions and melts. For atomization often two-fluid nozzles are used. The product is usually compact and resistant to abrasion and by a relative characterized by high bulk density. The dissolution rate is therefore lower compared to other spray-drying products. Such a granulator can also be used for coating granules, so-called "coating", used then it is usually operated discontinuously.

The international patent applications WO 00/77148 (EP-A1 1 10 48 03), WO 00/7149 (EP-A1 1 10 48 04), WO 00/77158 (EP-A1 1 10 48 06), WO 00/23560 (EP-A1 1 04 11 39), WO 98/10052 (EP-A1 0 93 62 69), here in full For example, granules are described as a carrier material of surfactants for Laundry detergent.

The have known in the prior art detergents and cleaners in addition to a variety of washing and cleaning substances under other nonionic surfactant and / or perfume on. Furthermore these detergents and cleaners contain a high proportion of soda, because soda has the property to absorb high levels of water.

adversely is that with such usually used detergents and cleaners unwanted odor impairments or changes may occur, so much effort was made, odorless changes of detergents and cleaners. For example, were the washing and cleaning agent components with high degrees of purity processed by an odor impairment or change to avoid the washing and cleaning agents. Furthermore, washing and detergents stored in moisture proof containers and the like. Ultimately, these efforts do not have the desired effect Success led, since it despite these measures again and again to odor impairments or changes of washing and cleaning agents comes.

task The present invention was to have nonionic surfactant and / or perfume Particles available whose odor, i. Fragrance note or perfume note, yourself for example, not caused by a chemical reaction changed adversely by particle components.

object The invention in a first embodiment are therefore at least a nonionic surfactant and / or at least one perfume containing soda-free particles, wherein the particles as an essential component of a carrier material have selected from the group comprising silicate, polymer, soap, phosphonate, phosphate and / or sulfate, wherein the soda-free particles 1 wt .-% to 50 wt .-% Nonionic surfactant and / or from 0.5% to 15% by weight perfume, based on the total weight the soda-free particles.

• – 2 Gew.-% bis 45 Gew.-% Niotensid, vorzugsweise 5 Gew.-% bis 35 Gew.-% Niotensid, bevorzugt 8 Gew.-% bis 25 Gew.-% Niotensid, weiter bevorzugt 10 Gew.-% bis 20 Gew.-% Niotensid, besonders bevorzugt 12 Gew.-% bis 18 Gew.-% Niotensid und am meisten bevorzugt 14 Gew.-% bis 17 Gew.-% Niotensid; und/oder
• – 2 Gew.-% bis 10 Gew.-% Parfüm, besonders bevorzugt 2 Gew.-% bis 5 Gew.-% Parfüm und am meisten bevorzugt 3 Gew.-% bis 4 Gew.-% Parfüm, bezogen auf das Gesamtgewicht der sodafreien Partikel.

Due to the high absorption capacity of the support materials used according to the invention, soda-free particles according to the invention having high nonionic surfactant contents and / or perfume parts can be made available. For example, soda-free particles of the invention may comprise nonionic surfactant and / or perfume, as indicated below, based on the total weight of the soda-free particles:

• 2 wt% to 45 wt% nonionic surfactant, preferably 5 wt% to 35 wt% nonionic surfactant, preferably 8 wt% to 25 wt% nonionic surfactant, more preferably 10 wt% to 20% by weight of nonionic surfactant, more preferably 12% by weight to 18% by weight of nonionic surfactant, and most preferably 14% by weight to 17% by weight of nonionic surfactant; and or
• From 2% by weight to 10% by weight of perfume, more preferably from 2% by weight to 5% by weight of perfume and most preferably from 3% by weight to 4% by weight of perfume, based on the total weight of the perfume soda-free particles.

olfactory impairments or changes mean in the sense of this invention that a change the fragrance note or the perfume note of perfume and / or nonionic surfactant-containing particles are not or at least not change significantly. The review of Scent is carried out by 10 adult human subjects.

It it is preferred that the invention, with perfume and / or Nonionic surfactant-laden, soda-free particles mixed with others Particles, for example mixed with soda-containing particles, and / or in the finished product at least partially and preferably substantially, as separate, i. as discrete perfume and / or nonionic surfactant loaded, soda-free particles.

The according to the invention, with Perfume and / or nonionic surfactant-laden, soda-free particles are preferred, except at least one nonionic surfactant, no other surfactants such as anions, Cation and / or Zwitterionic surfactants on.

Surprisingly was found that the aforementioned disadvantages by the Use of soda-free particles containing at least one nonionic surfactant and / or at least one perfume exhibit, avoid.

Without being committed to a particular theory is believed that soda leads to a chemical decomposition, albeit minor of nonionic surfactant and / or perfume or optionally proportionate hard-to-remove impurities these aforementioned substances to form undesirable smelling Perfumes, what a change the fragrance note or perfume note leads.

Of the Term "perfume" in the sense of this Invention stands for at least one perfume, preferably perfume mixture of at least 2 fragrances, preferably up to 10 fragrances. Possibly can the perfume also have more than 10 fragrances.

Prefers have the inventive, with Perfume and / or nonionic surfactant-free, soda-free particles exclusively nonionic surfactants on.

The according to the invention, with Perfume and / or nonionic surfactant-laden, soda-free particles can be used, for example 1 to 10, preferably 2 to 8 and preferably 3 to 5 different types Have nonionic surfactants.

It is possible, however that the soda-free particles linear alkyl benzene sulfonate / e (LAS) can have Preferably, the proportion by weight of linear alkylbenzenesulfonates ≥ 0 wt .-% and ≤ 25 Wt .-%, preferably ≥ 5 Wt .-% and ≤ 15 Wt .-%, more preferably ≥ 5 Wt .-% and ≤ 10 Wt .-% and most preferably 0 wt .-% and ≤ 5 wt .-%, based on the total weight the soda-free particles, make up.

The the aforementioned invention, at least a nonionic surfactant and / or at least one perfume containing soda-free particles can have, inter alia, at least one of the following advantages.

For example can these particles have significantly reduced adhesive properties, even if these soda-free particles high levels of nonionic surfactant and / or Perfume have recorded.

One Another advantage of at least one nonionic surfactant according to the invention and / or at least one perfume soda-free particles is that, if any, only one at most have a low tendency to form agglomerates.

It was further found that the inventive at least a nonionic surfactant and / or at least one perfume containing soda-free particles a high dissolution rate, improved flowability, have reduced sedimentation and / or low clump test values can. In particular, at least according to the invention a nonionic surfactant and / or at least one perfume containing soda-free particles with high bulk density a sufficiently good flowability can be observed.

Yet an advantage is that according to the invention at least one nonionic surfactant and / or at least one perfume having soda-free particles practically do not tend to a so-called "clustering" what the Avoids danger of gelling. This is advantageous as a Greater to increased Residues in the Einspülkammer and / or detergent residues with washed fabrics can. It should be emphasized that such a gag already by a plurality of and / or a few surfactant-related adhesives not according to the invention Particles can be caused.

The soda-free carrier can as a direct spray-drying product then at least one nonionic surfactant and / or at least a perfume be applied. In the context of the present invention is under a direct spray-drying product a product understood by spray drying without further treatment is obtained.

The soda-free carrier can as tower powder, preferably overdried Tower powder, present, then at least one nonionic surfactant and / or at least one perfume be applied.

Even though Surfactant particles are known a bad dissolution rate as surfactant particles usually are sticky and larger particles agglomerate, it has now been found that the inventive at least a nonionic surfactant and / or at least one perfume containing soda-free particles not or have a significantly lower tendency to each other To form agglomerates. At least one nonionic surfactant according to the invention and / or at least one perfume having soda-free particles can therefore preferred as primary fine particulate Surfactant particles and / or secondary soda-free particles are present. Primary soda-free invention Particles are particles that do not self-assemble with particles larger diameter agglomerate, although this is due to the nonionic surfactant and / or perfume concentrations would expect. At primary nonionic surfactant according to the invention and / or perfume containing soda-free particles are thus discrete Particle.

On the other hand are secondary nonionic surfactant according to the invention and / or perfume containing soda-free particles around particles, due to their non-sensory and / or perfumery-related adhesive Properties under magnification of the Diameter to larger particles agglomerate.

The proportion of primary and secondary at least one nonionic surfactant and / or at least one perfume having soda-free particles may be of different levels. For example, at least 10% by weight may be present preferably at least 30% by weight, preferably at least 50% by weight, more preferably at least 70% by weight and particularly preferably at least 90% by weight of the soda-free particles are present as primary soda-free particles, based on the total weight of the soda-free particles ,

It But is depending on the way of making the at least one Nonionic surfactant and / or at least one perfume containing soda-free particles possible, that at least 50 wt .-%, preferably at least 40 wt .-%, preferably at least 30% by weight, more preferably at least 20% by weight, and more preferably at least 10% by weight of the at least one nonionic surfactant and / or at least one perfume containing soda-free particles as secondary soda-free particles, based on the total weight of soda-free particles.

• – 25 Gew.-% bis 65 Gew.-% Silikat, besonders bevorzugt 30 Gew.-% bis 50 Gew.-% Silikat und am meisten bevorzugt 40 Gew.-% bis 45 Gew.-% Silikat; und/oder
• – 4 Gew.-% bis 54 Gew.-% Polymer, besonders bevorzugt 10 Gew.-% bis 40 Gew.-% Polymer und am meisten bevorzugt 25 Gew.-% bis 30 Gew.-% Polymer; und/oder
• – 0 Gew.-% bis 15 Gew.-% Phosphonat, bevorzugt 1 Gew.-% bis 12 Gew.-% Phosphonat und am meisten bevorzugt 3 Gew.-% bis 9 Gew.-% Phosphonat, wobei

die Gewichtsgehalte der Trägermaterialien der sodafreien Partikel einschließlich der Gewichtsgehalte von Niotensid und/oder Parfüm, soweit enthalten, 100 Gew.-% nicht übersteigen.It has been found that one can significantly or even completely reduce adhesiveness, particularly at the surface of the perfume and / or nonionic surfactant-laden soda-free particles of the invention, by selecting the weight fraction of carrier material of the soda-free particles as indicated below soda-free particles of support material include:

• 25% by weight to 65% by weight of silicate, more preferably 30% by weight to 50% by weight of silicate and most preferably 40% by weight to 45% by weight of silicate; and or
• From 4% by weight to 54% by weight of polymer, more preferably from 10% by weight to 40% by weight of polymer, and most preferably from 25% by weight to 30% by weight of polymer; and or
• - 0 wt .-% to 15 wt .-% phosphonate, preferably 1 wt .-% to 12 wt .-% phosphonate and most preferably 3 wt .-% to 9 wt .-% phosphonate, wherein

the weight contents of the carrier materials of the soda-free particles, including the weight contents of nonionic surfactant and / or perfume, if included, do not exceed 100% by weight.

If Unless otherwise indicated, the weight percentages refer to on the active content.

It it is preferred that the total weight fraction (wt.%) of carrier material, exceeds the total weight fraction (% by weight) of nonionic surfactant and / or perfume, preferably at least a factor of 1.5, preferably at least by a factor of 2, and even more preferably at least by a factor 3 to 5.

It can also it may be preferred that the total weight fraction (% by weight) of perfume is lower is the total weight fraction (% by weight) of nonionic surfactant.

At least according to the invention a nonionic surfactant and / or at least one perfume containing soda-free particles can a nonionic surfactant and / or perfume concentration gradient wherein the nonionic surfactant and / or perfume concentration indicated in% by weight, decreasing in the direction of the particle core.

According to the invention preferred is when the outer upper surface the inventive at least a nonionic surfactant and / or at least one perfume containing soda-free particles free of nonionic surfactant and / or perfume is. Since the carrier material used the particle absorbent is applied to the soda-free particles nonionic surfactant and / or Perfume absorbed by the particles into the interior of the particles.

In addition, the at least according to the invention a nonionic surfactant and / or at least one perfume containing soda-free particles be aftertreated by applying the surface with carrier material or other soda-free Powdered off components so as to obtain a particle surface, which have no or virtually no adhesive properties. As components for the post-treatment can be solids such as zeolite, silica, citrate, Urea or mixtures of these, in particular in amounts of 2 to 15 wt .-%, based on the total weight of the aftertreated Products, use.

Of the Nonionic surfactant and / or perfume fraction in wt .-%, based on the total weight of the inventive, with Perfume and / or nonionic surfactant-laden, soda-free particles, may be soda-free on the outer surface of the invention Particles ≥ 0 Wt .-% to at most 1 wt .-%, preferably ≥ 0.01 wt .-% to 0.5 wt .-% and preferably ≥ 0 Wt .-% and ≤ 0.02 Make up wt .-%.

In the context of the present invention, "d ₅₀ " is understood to mean that 50% of the perfume and / or nonionic surfactant-laden, soda-free particles according to the invention have a smaller diameter and 50% of the soda-free particles laden with perfume and / or nonionic surfactant according to the invention Have diameter.

It may be preferred according to the invention that the soda-free particles have a particle diameter d ₅₀ of 0.01 mm to 2 mm, preferably 0.02 mm to 1 mm and particularly preferably from 0.05 to 0.4 mm.

The according to the invention, with Perfume and / or nonionic surfactant-laden, soda-free particles may have a low Have water content. It may thus be advantageous, so-called over-dried to feed soda-free particles with nonionic surfactant and / or perfume. nonionic surfactant and / or perfume For example, by spraying on soda-free particles and / or by mixing nonionic surfactant and / or perfume with soda-free Particles are applied. The invention, with perfume and / or Nonionic surfactant-laden, soda-free particles may contain large amounts of nonionic surfactant and / or Perfume absorb or absorb.

Around a high absorption capacity of nonionic surfactant and / or perfume to ensure, it may be preferred if the soda-free particles have a water content of ≥ 0% by weight and ≤ 15 Wt .-%, preferably ≥ 1 Wt .-% and ≤ 10 Wt .-%, more preferably ≥ 3 Wt .-% and ≤ 8 Wt%, and most preferably ≥ 4 wt% and ≦ 7% by weight, based on the total weight of soda-free particles, based on the total weight of soda-free particles. The water content of the soda-free particles can also be ≥ 5 wt .-% and ≦ 6% by weight turn off.

Around a sufficiently high absorption capacity of nonionic surfactant and / or perfume by means of to ensure the soda-free particles are the usable carrier materials really important. Suitable carrier materials may be at least a silicate, wherein the silicate is selected from the group comprising amorphous sodium silicates, aluminosilicates, in particular zeolites, preferably zeolite A, zeolite P, zeolite X, swellable phyllosilicates, Montmorillonite and / or bentonite.

suitable support materials can but also at least one polymer, in particular homopolymer, wherein the polymer is selected is selected from the group comprising polycarboxylate, polyacrylate, as well Copolymers of polyacrylate, such as copolymers of acrylic acid with methacrylic acid, acrylic acid or methacrylic acid with maleic acid are suitable. An inventively usable Polymer, in particular homopolymer, preferably has a molecular weight of 500 g / mol to 20,000 g / mol, and preferably 1,000 g / mol to 10,000 g / mol. But it is also possible that the polymer has a molecular mass from 500 to 2,000,000 g / mol, preferably one molecular weight of 1,000 to 1,000,000 g / mol, more preferably one molecular weight of 1,000 to 1,000,000 g / mol, more preferably a molecular mass of 10,000 to 500,000 g / mol and particularly preferably a molecular mass of 15,000 to 50,000 g / mol.

Further suitable carrier materials are soaps, preferably at least one soap of the carrier material selected is from the group comprising saturated Fatty acid soaps, in particular salts of lauric acid, myristic, palmitic acid, stearic acid, hydrogenated erucic acid and / or behenic acid. Further preferred soap (s) are formed from natural fatty acids, in particular Coconut, palm kernel or tallow fatty acids, derived soap mixtures, the soaps preferably in the form their sodium, potassium and / or ammonium salts and as soluble salts organic bases, such as mono-, di- or triethanolamine, may be present.

• – Trimethylenphosphonsäure;
• – Hydroxyethyliden-1,1-diphosphonsäure;
• – Ethylendiamintetramethylenphosphonsäue;
• – Hexamethylendiamintetramethylenphosphonsäure;
• – Diethylentriaminpentamethylenphosphonsäure;
• – Polyaminomethylenphosphonsäure;
• – Hexamethylentriaminpentamethylenphosphonsäure;
• – Phosphonobutantricarboxylsäure; und/oder
• – neutral-Salze der vorgenannten Phosphonate.

According to the invention, at least one phosphonate can also be used as the carrier material. Suitable phosphonates are, for example, the compounds mentioned below:

• Trimethylene phosphonic acid;
• Hydroxyethylidene-1,1-diphosphonic acid;
• Ethylenediamine tetramethylenephosphonic acid;
• Hexamethylenediamine tetramethylenephosphonic acid;
• Diethylenetriaminepentamethylenephosphonic acid;
• - polyaminomethylenephosphonic acid;
• Hexamethylenetriaminepentamethylenephosphonic acid;
• - phosphonobutane tricarboxylic acid; and or
• Neutral salts of the abovementioned phosphonates.

The Phosphonic / phosphonates can as watery solution present and so as a carrier material the other carrier materials be added.

According to the invention can as support material also used at least one sulfate, for example sodium sulfate become.

According to the invention can as support material also at least one phosphate can be used, wherein at least a phosphate of the carrier material selected is from the group comprising pentasodium triphosphate, pyrophosphates, Orthophosphates and / or alkali metal phosphates, in particular Sodium and potassium salts of various phosphoric acids especially are preferred.

Especially suitable carrier material mixtures are given in Table 1 below.

Table 1

The Support materials those for use according to the invention are suitable, have a high absorption capacity for liquids, such as perfume and / or Nonionic surfactant. For example, you can for use according to the invention suitable carrier materials an oil number, based on the absorption of hexane, of at least 100 ml / 100 g, preferably at least 200 ml / 100 g, more preferably at least 250 ml / 100 g, more preferably at least 300 ml / 100 g and most preferably from 350 ml / 100 g to a maximum of 400 ml / 100 g on.

• – 0 Gew.-% der sodafreien Träger einen Partikeldurchmesser von ≥ 1,6 mm,
• – 0 Gew.-% der sodafreien Träger einen Partikeldurchmesser von ≥ 0,8 mm,
• – ≥ 0 Gew.-% bis 25 Gew.-%, vorzugsweise ≥ 0,5 Gew.-% bis 20 Gew.-% und bevorzugt ≥ 1 Gew.-% bis 18 Gew.-% der sodafreien Träger einen Partikeldurchmesser von < 0,4 mm bis 0,2 mm,
• – ≥ 60 Gew.-% bis 80 Gew.-%, vorzugsweise ≥ 63 Gew.-% bis 75 Gew.-% und bevorzugt ≥ 66 Gew.-% bis 70 Gew.-% der sodafreien Träger einen Partikeldurchmesser von < 0,2 mm bis 0,1 mm,
• – ≥ 0 Gew.-% bis 5 Gew.-%, vorzugsweise ≥ 1 Gew.-% bis 4 Gew.-% und bevorzugt ≥ 2 Gew.-% bis 3 Gew.-% der sodafreien Träger einen Partikeldurchmesser von < 0,1 mm,

bezogen auf das Gesamtgewicht der sodafreien Träger aufweisen, wobei die jeweiligen Gewichtsanteile der sodafreien Träger so gewählt sind, dass diese zusammen maximal 100 Gew.-% ausmachen.The soda-free carriers which are suitable for the loading according to the invention with fragrances and / or nonionic surfactants can have the following particle size distribution, wherein:

• 0% by weight of the soda-free carrier has a particle diameter of ≥ 1.6 mm,
• 0% by weight of the soda-free carrier has a particle diameter of ≥ 0.8 mm,
• - ≥ 0 wt .-% to 25 wt .-%, preferably ≥ 0.5 wt .-% to 20 wt .-% and preferably ≥ 1 wt .-% to 18 wt .-% of the soda-free carrier has a particle diameter of < 0.4 mm to 0.2 mm,
• - ≥ 60 wt .-% to 80 wt .-%, preferably ≥ 63 wt .-% to 75 wt .-% and preferably ≥ 66 wt .-% to 70 wt .-% of the soda-free carrier has a particle diameter of <0, 2 mm to 0.1 mm,
• - ≥ 0 wt .-% to 5 wt .-%, preferably ≥ 1 wt .-% to 4 wt .-% and preferably ≥ 2 wt .-% to 3 wt .-% of the soda-free carrier has a particle diameter of <0, 1 mm,

based on the total weight of the soda-free carrier, wherein the respective weight proportions of the soda-free carrier are selected so that together make up a maximum of 100 wt .-%.

by virtue of the good recording capacity the carrier materials the inventive, with Perfume and / or Non-surfactant loaded, soda-free particles have these after loading with perfume and / or nonionic surfactant at most low adhesive properties on the particle surface, so that the invention, with perfume and / or Non-surfactant loaded, soda-free particles have a bulk density of 100 g / l to 500 g / l, preferably 150 g / l to 400 g / l and preferably 200 g / l to 300 g / l. The bulk density the inventive, with Perfume and / or nonionic surfactant-laden, soda-free particles can be, for example also ≥ 250 g / l and ≤ 270 make out g / l.

The according to the invention, with Perfume and / or nonionic surfactant-laden, soda-free particles have a very high low dust level, since the nonionic surfactant and / or perfume a ensure good cohesion of the respective soda-free particles. In particular, due to the high content of nonionic surfactant / s and / or perfume is a especially low dust value of the invention, with perfume and / or Nonionic surfactant loaded, soda-free particles reached.

The according to the invention, with Perfume and / or nonionic surfactant-laden, soda-free particles may have a dust level of> 0% and <1%, preferably of ≥ 0.01% and ≤ 0.5% and particularly preferably ≥ 0.05% and ≤ 0.25% exhibit. The dust value of the invention, with perfume and / or However, nonionic surfactant-laden, soda-free particles can also account for ≥ 0.06% and ≤ 0.11%.

The according to the invention, with Perfume and / or nonionic surfactant-laden, soda-free particles can be free-flowing of at least 40%, in particular of at least 50%, preferably at least 70% and preferably 90% to ≤ 100%. The good flowability is particularly due to the low surface adhesion of the invention, with Perfume and / or nonionic surfactant-laden, soda-free particles.

For the invention, with Perfume and / or nonionic surfactant-laden, soda-free particles can be selected from the abovementioned establish also a low Klumptestwert be obtained. The invention, with perfume and / or Non-surfactant-loaded, soda-free particles may have a Klumpptestwert of ≥ 0 g and ≤ 50 g, preferably ≤ 20 g, preferably ≤ 10 g and particularly preferably ≦ 1 g have.

For the invention, with Perfume and / or nonionic surfactant-laden, soda-free particles may be subjected to the sedimentation test a value of ≥ 0 ml and ≤ 5 ml, preferably ≥ 0.01 ml and ≤ 3 ml, preferably ≥ 0.05 ml and ≤ 2 ml and more preferably ≦ 0.1 ml.

One Another advantage of the invention, with perfume and / or Nonionic surfactant-laden, soda-free particles are their high solubility. So can the invention, with Perfume and / or nonionic surfactant-laden, soda-free particles at a water temperature of 10 ° C a release time of a maximum of 300 seconds, preferably a maximum of 60 seconds and / or at a water temperature of 30 ° C a release time of a maximum of 90 seconds, and preferably of a maximum of 10 seconds.

For example can 1 g of the invention, with Perfume and / or nonionic surfactant, soda-free particles have a residue behavior in 200 ml at 10 ° C tempered tap water with 15 ° d of ≥ 0% and ≤ 10%, preferably ≥ 0.01% and ≤ 5%, preferably ≥ 0.05% and ≤ 1% and especially preferably of ≥ 0.075% and ≤ 0.5% and / or 1 g of the invention, with Perfume and / or nonionic surfactant-laden, soda-free particles can residue behavior in 200 ml at 30 ° C tempered tap water with 15 ° d of ≥ 0% and ≤ 8%, preferably ≥ 0.005% and ≤ 4%, preferably ≥ 0.01% and ≤ 1% and especially preferably ≥ 0.05% and ≤ 0.1% exhibit.

If Unless stated otherwise, the water hardness is given in degrees of German hardness.

The Measurements of the residue value, of the clot test and the sedimentation test are included below the information on the methods of measurement described.

The according to the invention, with Perfume and / or nonionic surfactant-laden, soda-free particles may vary the particle size distribution different, but it is not mandatory that the carrier after the inclusion of nonionic surfactant and / or perfume to form the inventive, with Perfume and / or nonionic surfactant, soda-free particles are in the particle size distribution differ.

• – 1 Gew.-% der sodafreien Partikel einen Partikeldurchmesser von ≥ 1,6 mm,
• – ≥ 10 Gew.-% bis 30 Gew.-%, vorzugsweise ≥ 15 Gew.-% bis 25 Gew.-% und bevorzugt ≥ 19 Gew.-% bis 20 Gew.-% der sodafreien Partikel einen Partikeldurchmesser von ≥ 0,8 mm,
• – ≥ 30 Gew.-% bis 45 Gew.-%, vorzugsweise ≥ 35 Gew.-% bis 40 Gew.-% und bevorzugt ≥ 37 Gew.-% bis 39 Gew.-% der sodafreien Partikel einen Partikeldurchmesser von > 0,4 mm,
• – ≥ 25 Gew.-% bis 40 Gew.-%, vorzugsweise ≥ 30 Gew.-% bis 35 Gew.-% und bevorzugt ≥ 33 Gew.-% bis 34 Gew.-% der sodafreien Partikel einen Partikeldurchmesser von > 0,2 mm,
• – ≥ 1 Gew.-% bis 15 Gew.-%, vorzugsweise ≥ 5 Gew.-% bis 10 Gew.-% und bevorzugt ≥ 6 Gew.-% bis 8 Gew.-% der sodafreien Partikel einen Partikeldurchmesser von > 0,1 mm, und
• – 0 Gew.-% bis 2 Gew.-%, vorzugsweise ≤ 1 Gew.-% der sodafreien Partikel einen Partikeldurchmesser von ≤ 0,1 mm, bezogen auf das Gesamtgewicht der sodafreien Partikel, aufweisen, wobei die jeweiligen Gewichtsanteile der sodafreien Partikel so gewählt sind, dass diese zusammen maximal 100 Gew.-% ausmachen.

Advantageous embodiments of the invention, loaded with perfume and / or nonionic surfactant, soda-free particles have, for example, the following particle size distribution, wherein:

• 1% by weight of the soda-free particles have a particle diameter of ≥ 1.6 mm,
• - ≥ 10 wt .-% to 30 wt .-%, preferably ≥ 15 wt .-% to 25 wt .-% and preferably ≥ 19 wt .-% to 20 wt .-% of soda-free particles have a particle diameter of ≥ 0, 8 mm,
• From ≥30% to 45%, preferably ≥35% to 40% and preferably ≥37% to 39% by weight of the soda-free particles have a particle diameter of> 0, 4 mm,
• - ≥ 25 wt .-% to 40 wt .-%, preferably ≥ 30 wt .-% to 35 wt .-% and preferably ≥ 33 wt .-% to 34 wt .-% of the soda-free particles have a particle diameter of> 0, 2 mm,
• - ≥ 1 wt .-% to 15 wt .-%, preferably ≥ 5 wt .-% to 10 wt .-% and preferably ≥ 6 wt .-% to 8 wt .-% of soda-free particles have a particle diameter of> 0, 1 mm, and
• - 0 wt .-% to 2 wt .-%, preferably ≤ 1 wt .-% of the soda-free particles have a particle diameter of ≤ 0.1 mm, based on the total weight of the soda-free particles, wherein the respective weight fractions of the soda-free particles so are chosen that together make up a maximum of 100 wt .-%.

The according to the invention, with Perfume and / or nonionic surfactant-laden, soda-free particles can have a whiteness Y. > 90%, for example ≥ 90.8 or ≥ 90.9.

As a general rule can the soda-free particles have all the perfume (s) for the consumer give a pleasant fragrance smell.

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, auf Anhieb schwer wahrnehmbar, welches die sinnlichen Töne ausmacht.

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

• A top note, formed preferably of the most volatile constituents and determining the first fragrance impression; and or
• - A heart note, preferably formed from the heavy, sweet flower aromas; and or
• - a base note, difficult to discern right away, which makes up the sensual notes.

As a general rule All conceivable suitable fragrances can be used according to the invention. This can be from a variety of plant sources usable according to the invention 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 suitable fragrances amber, for example, amber, a sperm whale secreted 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.

To isolate the fragrance (s) from the raw materials, various methods are used, for example, squeezing the fruit peels for citrus oils, extracting resinoids from resins, balsams, lichens and mosses by means of volatile solvents such as alcohol or hexane, steam distillation of previously prepared comminuted 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.

• – "Grün-Noten" sind herb-frische Düfte und riechen nach Blättern, Gräsern, Wiesen usw;
• – "Citrus-Noten" bestehen meist aus den etherischen Ölen der Citrus-Früchte mit erfrischendem Charakter;
• – "Lavendel-Noten" sind in vielen Kompositionen enthalten und bilden den Hauptbestandteil der "Lavendel-Wässer";
• – "Blumige Noten" sind überwiegend zusammengesetzt aus mehreren Einzelblumen-Noten, beispielsweise der Richtungen Jasmin, Flieder, Rose, Maiglöckchen, Iris/Veilchen, Nelke;
• – "Aldehyd-Noten" basieren überwiegend auf synthetischen Riechstoffen mit blumigem, zum Teil auch holzigem, balsamischen und animalischem Charakter; sie sind Bestandteil vieler Modeparfüms;
• – "Chypre-Noten" (Moos-Noten) bestehen überwiegend aus Eichenmoos-Extrakten, zum Teil in Kombination mit Bergamotteöl und haben herb-frischen Charakter;
• – "Fougere-Noten" (Farn-Noten) sind den Chypre-Noten verwandt;
• – "Gewürz-Noten" enthalten Gewürz-Extrakte von beispielsweise Thymian, Pfeffer, Muskat, Zimt, Nelken, Ingwer, Majoran, Kardamom, Koriander usw., zum Teil auch synthetische Riechstoffe und speziell kombinierte Gewürz-Basen;
• – "Orientalische Noten" kombinieren Gewürz-Noten mit schweren, süßen, balsamischen oder animalischen Noten zu Düften mit würzig-süßem bis zu süßlich-schwerem Charakter;
• – "Holz-Noten" basieren auf beispielsweise Zedern-, Sandel- u.a. Holz- und Wurzel-Ölen und variieren von herb-frisch bis holzig-herb;
• – "Tabak-Noten" gibt es in vielen Variationen von frisch-herb-würzig bis schwer-süß-honigartig, ursprünglich basierend auf dem Duft von Tabakblüten und fermentiertem Tabak;
• – "Leder-Noten" erinnern an den Geruch feinster Lederwaren, beispielsweise der Duftrichtung Juchten;
• – „Metall-Noten" erinnern an den Geruch von Metall.

For the odor directions, there is no generally binding classification. Mostly a distinction is made between "scent families" of certain notes:

• - "Green notes" are fresh and harsh 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";
• - "Flowery notes" are predominantly composed of several single floral notes, for example, the directions of jasmine, lilac, rose, lily of the valley, iris / violet, carnation;
• - "aldehyde notes" are predominantly based on synthetic fragrances with floral, partly also woody, balsamic and animal character; they are part of many fashion perfumes;
• - "Chypre notes" (moss notes) consist predominantly of oak moss extracts, partly in combination with bergamot oil and have a 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., in part also synthetic fragrances and especially combined spice bases;
• - "Oriental notes" combine spice notes with heavy, sweet, balsamic or animalistic Notes to scents with spicy-sweet to sweet-heavy character;
• - "wood notes" are based on, for example, cedar, sandal, etc. wood and root oils and vary from herb-fresh to woody-herb;
• - "Tobacco notes" are available in many variations from fresh-tart-spicy to heavy-sweet-honey, originally based on the scent of tobacco blossoms and fermented tobacco;
• - "Leather notes" reminiscent of the smell of fine leather goods, such as the scent direction Juchten;
• - "Metal notes" reminiscent of the smell of metal.

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.

When Fragrances can in the context of the present invention, individual fragrance compounds, For example, the synthetic products of the ester, ether, Aldehydes, ketones, alcohols and hydrocarbons are used. Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzyl-carbinyl acetate, Phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methyl phenyl glycinate, Allyl cyclohexyl propionate, styrallyl propionate and benzyl salicylate. Count to the Ethern for example, benzyl ethyl ether, to the aldehydes, for example the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, Hydroxycitronellal, Lilial and Bourgeonal, for example, to the ketones the Jonone, isomethylionone and methylcedryl ketone, to the alcohols Anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons mainly include the terpenes such as limonene and pinas. However, mixtures of different fragrances are preferred used, which together create an appealing scent. Such Perfumes also include perfume oils, wherein this also natural May contain fragrance mixtures, as they are accessible from plant sources, for example Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also Muscat, sage, chamomile, clove, lemon balm, mint, cinnamon, lime, juniper, vetiver, olibanum, galbanum and labdanum oils are also suitable Orange blossom oil, neroliol, Orange peel oil and sandalwood oil.

The general description of the usable fragrances is doing in general the different substance classes of fragrances represents.

To be perceptible, a fragrance, also called fragrance, must be volatile, whereby in addition to the nature of the functional groups and the structure of the chemical compound and the molecular weight plays an important role. For example, most odorants have molecular weights up to about 200 daltons, while molecular weights of 300 daltons and above are more of an exception. Due to the different volatility of fragrances, the smell of a perfume or fragrance composed of several fragrances changes during evaporation, whereby the odor impressions as already mentioned in "top note", "heart or middle note" (middle note or body) and "base note" (end note or dry out). Since odor perception is also largely based on odor intensity, the top note of a perfume or fragrance does not consist solely of volatile compounds, while Base note for the most part consists of less volatile, ie adherent fragrances. For example, in the composition of perfumes, more volatile fragrances can be bound to certain fixatives, preventing them from evaporating too quickly. In the subsequent classification of the fragrances in "more volatile" or "adherent" fragrances so nothing about the olfactory impression and whether the corresponding fragrance is perceived as a head or middle note, nothing 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 or textile air.

For the latter Odor impression, the use of more adhesive fragrances is advantageous, while to Product scenting also more volatile Fragrances can be used.

Tenacious Fragrances that can be used in the context of the present invention are, 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 oil, geranium oil, ginger grass oil, guaiac wood oil, Gurjunbalsamöl, Helichrysumöl, Ho oil, Ginger oil, iris oil, cajeput oil, calamus oil, camomile 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-Ylan g oil, hyssop oil, cinnamon oil, cinnamon leaf oil, lemon oil, lemon oil and cypress oil.

But also the higher-boiling ones 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, eucalyptol, Farnesol, fenchone, fenchyl acetate, geranyl acetate, geranyl formate, Heliotropin, heptincarboxylic acid methyl ester, 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.

• – Essenzen aus Früchten, Fruchtteilen und/oder anderen Pflanzenteilen, vorzugsweise Kräutern, Drogen, daraus gewonnene etherische Öle, bevorzugt terpenfreie Öle; und/oder
• – künstliche Essenzen, vorzugsweise aus synthetischen Geruchs- und/oder Geschmacksstoffen, besonders bevorzugt Vanillin, Menthol, Biacetyl und/oder Eucalyptol; und/oder
• – Aromen, vorzugsweise ätherische Öle, Anisöl, Sternanisöl, Bittermandelöl, Eukalyptusöl, Fenchelöl, Pfefferminzöl, Citronenöl, Wintergrünöl, Nelkenöl, Menthol und/oder Kümmelöl; und/oder
• – synthetische Riechstoffverbindungen vom Typ der Ester, vorzugsweise Benzylacetat, Phenoxyethylisobutyrat, p-tert.-Butylcyclohexylacetat, Linalylacetat, Dimethylbenzyl-carbinylacetat, Phenylethylacetat, Linalylbenzoat, Benzylformiat, Ethylmethylphenyl-glycinat, Allylcyclohexylpropionat, Styrallylpropionat und/oder Benzylsalicylat; und/oder
• – synthetische Riechstoffverbindungen vom Typ der Ether, vorzugsweise Benzylethylether; und/oder
• – synthetische Riechstoffverbindungen vom Typ der Aldehyde, vorzugsweise lineare Alkanale mit 8–18 C-Atomen, Citral, Citronellal, Citronellyloxyacetaldehyd, Cyclamenaldehyd, Hydroxycitronellal, Lilial und/oder Bourgeonal; und/oder
• – synthetische Riechstoffverbindungen vom Typ der Ketone, vorzugsweise Jonone, Isomethylionon und/oder Methyl-cedrylketon; und/oder
• – synthetische Riechstoffverbindungen vom Typ der Alkohole, vorzugsweise Anethol, Citronellol, Eugenol, Geraniol, Linalool, Phenylethylalkohol und/oder Terpineol; und/oder
• – synthetische Riechstoffverbindungen vom Typ der Kohlenwasserstoffe, vorzugsweise Terpene, bevorzugt Limonen und Pinien; und/oder
• – natürliche Riechstoffgemische aus pflanzlichen Quellen, vorzugsweise Pine-, Citrus-, Jasmin-, Patchouly-, Rosen- oder Ylang-Ylang-Öl, Muskateller, Salbeiöl, Kamillenöl, Nelkenöl, Melissenöl, Minzöl, Zimtblätteröl, Lindenblütenöl, Wacholderbeeröl, Vetiveröl, Olibanumöl, Galbanumöl, Labdanumöl, Orangenblütenöl, Neroliol, Orangenschalenöl und/oder Sandelholzöl; und/oder
• – metallische Riechstoffverbindungen umfassend Oxacyclododecan-2-on, 4,5-Decamethylenoxazol, Sclarene, Derivate davon und/oder Vorstufen davon, wobei die Derivate vorzugsweise in Form von Estern und/oder Ethern vorliegen.

It is particularly preferred if the soda-free particles have at least one perfume which is selected from the group comprising:

• - essences of fruits, fruit parts and / or other parts of plants, preferably herbs, drugs, essential oils derived therefrom, preferably terpene-free oils; and or
• Artificial essences, preferably of synthetic odorants and / or flavorings, more preferably vanillin, menthol, biacetyl and / or eucalyptol; and or
• Flavorings, preferably essential oils, aniseed oil, star aniseed oil, bitter almond oil, eucalyptus oil, fennel oil, peppermint oil, lemon oil, wintergreen oil, clove oil, menthol and / or caraway oil; and or
• Synthetic fragrance compounds of the ester type, preferably benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethylmethylphenyl glycinate, allyl cyclohexyl propionate, styrallyl propionate and / or benzyl salicylate; and or
• Synthetic fragrance compounds of the ether type, preferably benzyl ethyl ether; and or
• Synthetic fragrance compounds of the aldehyde type, preferably linear alkanals of 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and / or bourgeonal; and or
• - Synthetic fragrance compounds of the ketone type, preferably ionone, isomethylionone and / or methyl cedrylketone; and or
• Synthetic fragrance compounds of the alcohol type, preferably anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and / or terpineol; and or
• Synthetic perfume compounds of the hydrocarbon type, preferably terpenes, preferably limonene and pine; and or
• - Natural fragrance mixtures from plant sources, preferably pine, citrus, jasmine, patchouly, rose or ylang-ylang oil, muscatel, sage oil, camomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, lime blossom oil, juniper berry oil, vetiver oil, olibanum oil , Galbanum oil, labdanum oil, orange blossom oil, neroliol, orange peel oil and / or sandalwood oil; and or
• - Metallic fragrance compounds comprising oxacyclododecan-2-one, 4,5-decamethyleneoxazole, Sclarene, derivatives thereof and / or precursors thereof, wherein the derivatives are preferably in the form of esters and / or ethers.

Around a slower release of fragrance for long-lasting fragrance of according to the invention, with Perfume and / or Nonionic surfactant loaded, soda-free particles provide, you can as a carrier, for example Add cyclodextrins, wherein the forming cyclodextrin-perfume complexes optionally in addition can still be coated with other excipients.

The according to the invention, with Perfume and / or nonionic surfactant-loaded, soda-free particles can, as accomplished Nonionic surfactant, also referred to as nonionic surfactants. Preferably, at least one nonionic surfactant is selected from the group comprising alkoxylated fatty alcohols, alkyl glycosides, fatty acid alkyl esters and / or amine oxides, where alkoxylated fatty acid alkyl esters, ethoxylated fatty acid alkyl esters or ethoxylated and propoxylated fatty acid alkyl esters are preferred.

As nonionic surfactants, called nonionic surfactants in the following, preferably alkoxylated, preferably ethoxylated, especially primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol used in which the alcohol radical linear or preferably in 2-position may be methyl-branched or may contain linear and methyl-branched radicals in the mixture, 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, fatty alcohols with more than 12 EO can also be used. Examples include (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, in particular Fettsäuremethyles ter, as described for example in Japanese Patent Application JP 58/217598 or preferably according to the in the international patent 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 soda-free particles according to the invention, in particular suitable for machine dishwashing, the low-foaming nonionic surfactants are particularly suitable as nonionic surfactants. 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. Optionally, a final etherification with short-chain alkyl groups, such as preferably the butyl group, may also yield the class of "closed" alcohol ethoxylates which can likewise 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.

The nonionic surfactant according to the invention and / or perfume containing soda-free particles can at least one, preferably have several of the ingredients listed below, selected from the group comprising 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, fabric softeners and / or rinse aids, and optionally other admixed ingredients.

It However, it is not mandatory that the nonionic surfactant and / or perfume according to the invention have soda-free particles further ingredients, hereinafter also as additives or as components.

suitable nonionic surfactant according to the invention and / or perfume having soda-free particles can for example, free of 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, fabric softeners and / or rinse aids.

It may also be preferred that the nonionic surfactant of the invention and / or perfume optionally containing no further admixed soda-free particles Have constituents.

ingredients the soda-free particles can in addition to the ingredients already mentioned also anionic surfactants, cationic surfactants, amphoteric surfactants (= zwitterionic surfactants) it being preferred that the inventive, with Perfume and / or nonionic surfactant-laden, soda-free particles besides nonionic surfactants no further surfactants, such as anionic surfactants, cationic surfactants and / or amphoteric surfactants.

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. Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and mixtures thereof, as used in the preparation by Veres obtained from a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol. Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example 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 technology interest, the C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates and C ₁₄ -C ₁₅ alkyl sulfates are preferred. 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.

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 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 adding to the composition anionic surfactant and optionally fatty acids are introduced, which then by the carrier materials in the spray-drying Composition be neutralized.

to Avoidance of possible incompatibilities the antimicrobial cationic surfactants with the invention contained anionic surfactants are possible most compatible and / or as possible little cationic surfactant used or in a particular embodiment the invention entirely antimicrobial cationic surfactants omitted. As antimicrobial effective substances can Parabens, benzoic acid and / or benzoate, lactic acid and / or lactates are used. Particularly preferred are benzoic acid and / or Lactic acid.

Further Ingredients of the nonionic surfactant according to the invention and / or perfume containing soda-free particles may be inorganic and optionally be organic builders.

The inorganic builder substances also include non-water-soluble ingredients such as aluminosilicates and in particular zeolites. 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 X Zeo lith which as VEGOBOND AX ^® (a product of Condea Augusta SpA) is commercially 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 ) ₁₀₆ ] · 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 For the purposes of the present invention, the term "zeolite faujasite type "all three zeolites containing the faujasite subgroup of the zeolite structure group 4 form. In addition to the Zeo lith X according to the invention therefore also 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 wherein preferably at least 50 wt .-% of the zeolites of the 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 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. 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 ] xH 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.

With particular advantage the washing or cleaning agents condensed as water-softening substances Contain phosphates. These substances form a group of - due also known as melting or annealing phosphates - phosphates, which is derived from acid salts of orthophosphoric acid (phosphoric acids) Allow condensation to dissipate. Leave the condensed phosphates into the metaphosphates [Mnn (PO3) n] and polyphosphates (Mln + 2PnO3n + 1 or MnnH2PnO3n + 1).

Of the Term "metaphosphates" was originally the general term for condensed phosphates of the composition Mn [PnO3n] (M = monovalent Metal), but today is usually limited to salts with cyclic cyclo (poly) phosphate anions. At n = 3, 4, 5, 6, etc. one speaks of tri-, tetra-, penta-, hexa-metaphosphates etc. According to the systematic nomenclature of isopolyanions z. B. called the anion with n = 3 as cyclo triphosphate.

metaphosphates receives one as accompanying substances of - wrongly called sodium hexametaphosphate - Graham's salt by melting NaH 2 PO 4 to temperatures above 620 ° C, where intermediately also so-called Maddrell'sches Salt is produced. This and Kurrol'sches Salt is linear polyphosphates, which are not usually used today Metaphosphates count, but in the context of the present invention also with preference as water-softening Substances are used.

The crystalline, water-insoluble Maddrell salt, (NaPO3) x with x> 1000, which can be obtained at 200-300 ° C from NaH2PO4, turns into the cyclic metaphosphate [Na3 (PO3) 3] at about 600 ° C melting at 620 ° C. The quenched, glassy melt is, depending on the reaction conditions, the water-soluble Graham's salt, (NaPO 3) 40-50, or a glassy condensed phosphate of the composition (NaPO 3) 15-20, known as Calgon. Both products still use the misleading name nexametaphosphate. The so-called Kurrol's salt, (NaPO3) n with n »5000, is formed if from the 600 ° C hot melt of Maddrell's salt, if this is left for a short time at about 500 ° C. It forms high polymer water-soluble fibers.

Particularly preferred water-softening substances from the above classes of condensed phosphates, the "hexametaphosphates" Budit ^® H6 and H8 from. Budenheim have proven.

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 ₇ 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 the NaH ₂ PO ₄ or the KH ₂ PO ₄ results in higher molecular weight sodium and potassium phosphates, in which one can distinguish cyclic representatives, the sodium or potassium metaphosphates 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.

A Substance class with cobuilder properties represent the phosphonates These are in particular hydroxyalkane or aminoalkanephosphonates. Among the hydroxyaliphosphonates is 1-hydroxyethane-1,1-diphosphonate (HEDP) of particular importance as a co-builder. It is preferably as Sodium salt used, wherein the disodium salt neutral and the Tetrasodium salt alkaline (pH 9) reacts. As aminoalkanephosphonates preferably, ethylenediamine tetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher Homologous in question. They are preferably in the form of neutral reacting Sodium salts, e.g. B. as hexasodium salt of EDTMP or hepta- and octa-sodium salt of DTPMP. As a builder will be there from the class of phosphonates preferred HEDP used. The aminoalkane phosphonates also have a pronounced Heavy metal binding capacity. Accordingly, it may, especially if the means also bleach be preferred, Aminoalkanphosphonate, in particular DTPMP, to use or mixtures of the phosphonates mentioned.

In a preferred embodiment however, as inorganic builders in particular alkali carriers be present. As alkali carrier alkali metal hydroxides, alkali metal carbonates, alkali metal bicarbonates, Alkali metal sesquicarbonates, alkali silicates, alkali metal silicates, and mixtures of the aforementioned substances, wherein for the purposes of this invention preferably the alkali metal carbonates, in particular sodium carbonate, sodium bicarbonate or sodium sesquicarbonate. The invention, with Perfume and / or nonionic surfactant loaded, soda - free particles, the substances mentioned above, with the exception of soda.

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 one Number is 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 δ-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 of 1.75 to 1200 and the ratio y to z of a number from 4 to 2800 corresponds to that described in the patent application DE-A-196 01 063. The solubility of the layered silicates can also be increased by using particularly finely divided layered silicates. It is also possible to use substances from the crystalline layered silicates with other ingredients. In particular, substances with cellulose derivatives which have advantages in the disintegrating action, as well as substances 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 in X-ray diffraction experiments do not give sharp X-ray reflections typical of crystalline substances but at best one or more maxima of the scattered X-radiation which are several angstroms in width of the diffraction angle. However, it may well even lead to particularly good builder properties if the silicate particles provide washed-out or even sharp diffraction maxima in electron diffraction experiments. This is so too interpret that the products have microcrystalline regions of size 10 to a few hundred nm, with values up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray-amorphous silicates, which likewise have a dissolution delay compared to the 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 the (X-ray) amorphous silicates in the zeolite-free direct spray-drying products is preferably 1 to 10% by weight.

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.

suitable Polymers are in particular polyacrylates, which preferably have a molecular mass of 2000 to 20,000 g / mol. Because of their superior solubility can from this group again the short-chain polyacrylates, the molecular weights from 2000 to 10000 g / mol, and more preferably from 3000 to 5000 g / mol, may 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.

The (co) polymeric polycarboxylates can either as a powder or as an aqueous one solution be used.

Especially Biodegradable polymers of more than two are also preferred various monomer units, for example, those as monomers Salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or as monomers Salts of acrylic acid and 2-alkylallyl sulfonic acid and sugar derivatives. Further preferred copolymers are those containing as monomers preferably acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.

As well are as further preferred builders polymeric aminodicarboxylic acids whose Salts or their precursors to call. Particular preference is given to polyaspartic acids or their salts and derivatives, in addition to cobuilder properties also have a bleach-stabilizing effect.

Further Suitable builders are polyacetals, which by reaction of dialdehydes with polyol carboxylic acids containing 5 to 7 carbon atoms and at least 3 hydroxyl groups can be obtained. preferred Polyacetals are made from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic receive.

Further suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary, for example acid or enzyme catalyzed processes. Preferably, it is hydrolysis products having average molecular weights in the range of 400 to 500,000 g / mol. In this case, a polysaccharide with a dextrose equivalent (DE) in the range of 0.5 to 40, in particular of 2 to 30, where DE is a common measure of the reducing effect of a polysaccharide compared to dextrose which has a DE of 100. Usable are both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 and so-called yellow dextrins and white dextrins with higher molecular weights in the range from 2000 to 30,000 g / mol.

at the oxidized derivatives of such dextrins are their reaction products with oxidants, which are able are at least one alcohol function of the saccharide ring to the carboxylic acid function to oxidize. A product oxidized at C6 of the saccharide ring can be particularly advantageous.

Also Oxydisuccinates and other derivatives of disuccinates, preferably Ethylenediamine disuccinate are other suitable cobuilders. there becomes ethylenediamine-N, N'-disuccinate (EDDS) preferably used in the form of its sodium or magnesium salts. Also preferred in this context are glycerol disuccinates and glycerol trisuccinates.

Further useful organic cobuilders are, for example, acetylated hydroxy or their salts, which may also be present in lactone form can and which at least 4 carbon atoms and at least one hydroxy group and a maximum of two acid groups contain.

Of the Content of organic builder substances of the fine-particle surfactant particles according to the invention, particles and / or finished product may also vary widely. Preference is given to contents of from 2 to 20% by weight, in particular from cost reasons Contents of a maximum of 10 wt .-% in particular appeal.

In addition, the according to the invention, with Perfume and / or nonionic surfactant, soda-free particles also components containing, for example, the oil and Fettauswaschbarkeit from textiles positively influence (so-called soil repellents). This effect becomes particularly noticeable when a fabric becomes dirty, that previously several times with a detergent according to the invention, that this oil and fat dissolving component contains was washed. Among the preferred oil and fat dissolving components counting for example, nonionic cellulose ethers such as methyl cellulose and methylhydroxypropylcellulose with a proportion of methoxyl groups from 15 to 30% by weight and of hydroxypropoxyl groups from 1 to 15 Wt .-%, each based on the nonionic cellulose ether, and the known from the prior art polymers of phthalic acid and / or of terephthalic acid or of their derivatives, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionically modified derivatives of these. Especially preferred of these are the sulfonated derivatives of phthalic acid and the terephthalic acid polymers.

To the usable soil-release compounds containing the inventive, with Perfume and / or nonionic surfactant-laden, soda-free particles may include all known in the art compounds. Particularly suitable are cationic polymers such as hydroxypropyltrimethylammonium guar; Copolymers of aminoethyl methacrylate and acrylamide and copolymers of dimethyldiallylammonium chloride. and acrylamide, polymers with Imino groups, cationic Cellulose derivatives, cationic homo- and / or copolymers (monomer units: quaternized ammonium alkyl methacrylate groups).

Further can the nonionic surfactant according to the invention and / or perfume containing soda-free particles as optical brightener derivatives the diaminostilbene disulfonic acid or their alkali metal salts. Suitable are e.g. salts 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or the like built-up compounds that instead of the morpholino group a Diethanolamino group, a methylamino group, an anilino group or carry a 2-methoxyethylamino group. Furthermore, brighteners of the type of substituted diphenylstyrene, e.g. the Alkali salts of 4,4'-bis (2-sulfostyryl) -diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) -diphenyls. Also Mixtures of the aforementioned brighteners can be used.

Out more usual for the rest of the groups Detergent ingredients are included in the use of the nonionic surfactant of the invention and / or perfume containing soda-free particles, in particular ingredients the classes of the grayness inhibitors (soil carrier), the Neutral salts and fabric softening aids.

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.

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 total weight of the nonionic surfactant of the invention and / or Perfume containing soda-free particles used.

It can but also silver protectants selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, Alkylaminotriazole and the transition metal salts or complexes are used. Particularly preferable to use are benzotriazole and / or alkylaminotriazole.

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

Among the compounds which serve as bleaches and deliver H ₂ O ₂ in water, sodium perborate monohydrate or tetrahydrate and sodium percarbonate have particular significance. Other useful bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -forming peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid. The content of bleaching agents in the composition is from 0 to 30% by weight and in particular from 5 to 25% by weight, it being advantageous to use perborate monohydrate or percarbonate.

Around when washing or cleaning at temperatures of 60 ° C and below To achieve an improved bleaching effect, bleach activators can be incorporated become. As bleach activators can Compounds which, under perhydrolysis conditions, are aliphatic peroxycarboxylic acids preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid, are used. Suitable substances are the O- and / or N-acyl groups of the mentioned C atom number and / or optionally substituted benzoyl groups wear. Preference is given to polyacylated alkylenediamines, in particular Tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated Phenolsulfonates, especially n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran.

In addition to The conventional bleach activators or in their place may also so-called bleach catalysts are incorporated. In these Substances are bleach-enhancing transition metal salts or transition metal complexes such as Mn, Fe, Co, Ru or Mo saline complexes or carbonyl complexes. Also Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes usable as bleach catalysts.

Suitable enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof. Particularly suitable are bacterial strains or fungi, such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus derived enzymatic agents. Preferably, subtilisin-type proteases and in particular proteases derived from Bacillus lentus are used. Enzyme mixtures, for example from protease and amylase or protease and lipase or protease and cellulase or from cellulase and lipase or from protease, amylase and lipase or protease, lipase and cellulase, but in particular cellulase-containing mixtures are of particular interest. Peroxidases or oxidases have also proved suitable in some cases. The enzymes may be adsorbed to carriers and / or embedded in encapsulants to protect against premature degradation. The proportion of enzymes, enzyme mixtures or enzyme granules in the moldings according to the invention can be, for example, about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight. The most commonly used enzymes include lipases, amylases, cellulases and proteases. Preferred proteases are, for. B. BLAP ^® 140 from. Biozym, Optimase ^® -M-440 and Opticlean ^® -M-250 from. Solvay enzyme; Maxacal ^® CX and Maxapem ^® or Esperase ^® from Novo. Gist Brocades or Savinase ^® from.. Particularly suitable cellulases and lipases are Celluzym ^® 0.7 T and Lipolase ^® 30 T of Messrs. Novo Nordisk. Particular use as amylases Duramyl ^® and Termamyl ^® 60 T and Termamyl ^® 90 T from. Novo, Amylase-LT ^® from. Solvay Enzymes or Maxamyl ^® P5000 Messrs. Gist Brocades. Other enzymes can also be used.

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.

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. As at room temperature solid additives, in particular in the said foam-inhibiting agents, paraffin waxes, silicas, which also hydrophobic in a known manner and bisamides derived from C _2-7 diamines and C _12-22 carboxylic acids.

For use eligible foam inhibiting paraffin oils blended with paraffin can be present generally provide 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 freezing point. By this one understands the temperature, at the paraffin by slow cooling from the liquid in the solid state passes. Paraffins with less than 17 carbon atoms are not according to the invention useful, their share in the paraffin oil mixture should therefore be so low as possible and is preferably below that with conventional analytical methods, for example, gas chromatography, significantly measurable limit. Preferably Paraffins are used, which solidify in the range of 20 ° C to 70 ° C. It should be noted that even at room temperature seemingly solid Paraffin wax mixtures contain different proportions of liquid paraffin oils can. In the invention useful Paraffin waxes is the liquid fraction at 40 ° C preferably high, without already 100% at this temperature. preferred Paraffin wax mixtures have a liquid content of at least 50 at 40 ° C Wt .-%, in particular from 55 wt .-% to 80 wt .-%, and at 60 ° C a liquid content of at least 90% by weight. This has the consequence that the paraffins at temperatures down to at least 70 ° C, preferably down to to at least 60 ° C. flowable and pumpable are. Furthermore Care should be taken to ensure that the paraffins are not volatile Shares included. 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 also in the nonionic surfactant according to the invention and / or perfume containing soda-free particles and / or particle mixture containing particles according to the invention and / or finished product.

The according to the invention, with Perfume and / or nonionic surfactant-laden, soda-free particles can be dyes containing the amount of one or more dyes so low to choose is that after application of the agent no visible residues remain. Preferably, however, the agent according to the invention is free of dyes.

preferred Dyes whose selection does not present any difficulty to the skilled person have a high storage stability and insensitivity to the rest Ingredients of the agents and against light and no pronounced substantivity to textile fibers, so as not to stain them.

A another embodiment The invention relates to a mixture in addition to nonionic surfactant according to the invention and / or perfume containing soda-free particles additionally soda-containing particles having.

It is preferred according to the invention, that the soda-containing particles have no nonionic surfactant and / or no perfume.

It is further preferred according to the invention that the soda-containing particles at least one anionic surfactant, cationic surfactant and / or zwitterionic surfactant, it being preferred that the soda-containing particles contain at least one anionic surfactant. Most preferred is when the soda-containing particles as surfactant exclusively have at least one anionic surfactant.

The mixture according to the invention can soda-containing particles with ≥ 0 wt .-% and ≤ 25 wt .-% anionic surfactant, preferably ≥ 1 wt .-% and ≤ 20 wt .-% anionic surfactant, more preferably ≥ 5 wt .-% and ≤ 17 % By weight of anionic surfactant, and most preferably ≥ 10% by weight and ≤ 15% by weight of anionic surfactant, based on the total weight of the soda-containing particles.

Of the Weight fraction of the soda-free particles, based on the total weight the mixture according to the invention, can> 0 wt .-% to at most 25% by weight, preferably 1% to 22% by weight, preferably 3% by weight to 20% by weight, more preferably 5% by weight to 18% by weight and most preferably from 10% to 15% by weight.

The soda-containing particles can at least one, preferably more ingredients, selected from the group comprising washing, care and / or cleaning substances, anionic surfactants, cationic surfactants, amphoteric surfactants, builders, Bleaching agents, bleach activators, bleach stabilizers, bleach catalysts, Enzymes, polymers, cobuilders, alkalizing agents, acidifying agents, anti redeposition agents, Silver protectants, colorants, optical brighteners, UV protectants, fabric softeners, foam inhibitors and / or rinse aid, and optionally further admixed ingredients. The above listed In detail, ingredients are already mentioned in the introduction to the nonionic surfactant according to the invention and / or Perfume containing soda-free particles described in detail, so that This reference is hereby fully incorporated by reference.

As already described above, it is preferred according to the invention that the soda-containing Particles have no nonionic surfactant and / or no perfume.

In addition, the aftertreated particles containing at least one component be, wherein the component amount is preferably up to 10 wt .-%, in particular 1 wt .-% to 5 wt .-%, each based on the total weight of post-treated particles. As components for the aftertreatment can be solids preferably bicarbonate, carbonate, zeolite, silica, Citrate, urea or mixtures thereof, in particular in quantities from 2 to 15 wt .-%, based on the total weight of the aftertreated Products, use.

According to the invention is a Mixture preferred, which is the invention, with perfume and / or nonionic surfactant loaded, soda-free particles to soda-containing particles in a weight ratio of 1: 10 to 10: 1, preferably 1: 8 to 8: 1, preferably 1: 6 to 6: 1, and more preferably 1: 5 to 5: 1, and most preferably the soda-free particles to soda-containing particles in a weight ratio of 1: 3 to 3: 1 contains.

A another embodiment The invention relates to a finished product, the nonionic surfactant according to the invention and / or perfume having soda-free particles or mixtures of nonionic surfactant according to the invention and / or Perfume containing soda-free particles and additionally soda-containing particles, as already described above.

It is preferred according to the invention, that the soda-containing particles have no nonionic surfactant and / or no perfume.

At the Most preferred are finished products, wherein exclusively the according to the invention, with Perfume and / or Non-surfactant laden, soda-free particles have nonionic surfactant and / or perfume.

at a finished product according to the invention It can be a detergent, a cleaning agent for hard and / or soft surfaces, a stainless steel cleaner, a household cleaner, an oven cleaner, a conditioner, a laundry detergent, a laundry care product, a fragrance, a hair treatment composition, a hair dye, a conditioner, a fabric softener, a conditioning substrate, a drug, a pesticide, a food, a cosmetic, a fertilizer, a building material, an adhesive, a bleach, a disinfectant and / or a precursor of the aforementioned finished products act.

A finished product according to the invention may comprise, in addition to the soda-free particles laden with perfume and / or nonionic surfactant according to the invention or in addition to the mixture according to the invention comprising soda-free particles with perfume and / or nonionic surfactant and soda-containing particles at least one, preferably more ingredients selected from the group comprising as washing, care and / or cleaning substances anionic surfactants, cationic surfactants, amphoteric surfactants, builders, bleach, bleach activators, bleach stabilizers, bleach catalysts, enzymes, polymers, cobuilders, alkalizing, Acidifizierungsmittel, Antiredepositionsmittel, silver protectants, colorants, optical brightener, UV Protective substances, fabric softeners, foam inhibitors and / or rinse aid, and optionally other admixed ingredients.

The listed above In detail, ingredients are already at the beginning of the nonionic surfactant according to the invention and / or perfume containing soda-free particles described in detail, so that This reference is hereby fully incorporated by reference.

It is preferred when the finished product according to the invention, in particular Washing, cleaning and / or care product, at least 1 wt .-% and at most 30 wt .-%, preferably at least 25 wt .-%, preferably at least 20% by weight, more preferably at least 15 Wt .-%, more preferably at least 12 wt .-% and most preferably at least 10 wt .-% soda-free particles according to the invention, based on the total weight of the finished product, with the respective Weight shares chosen are that together make up a maximum of 100 wt .-%.

One preferred finished product of the invention relates to tablets or moldings the soda-free invention Particles or a mixture of inventive, with perfume and / or Nonionic surfactant-laden, soda-free particles and soda-containing particles having.

As "tablet" or "shaped body" are in the frame independent of the present application Form-stable, solid body called by the nature of their preparation. Such bodies can be, for example, by crystallization, molding, injection molding, reactive or thermal sintering, (co) extrusion, compounding, pastillation, or compaction processes such as calendering or tableting produce. The preparation of the "tablets" or "shaped bodies" by tableting is particularly preferred in the context of the present application. The Tablet or shaped body So it is preferably made of compressed, particulate material. It is preferred according to the invention, that in the tablets or moldings optionally contained soda-containing particles have no nonionic surfactant and / or no perfume. Most preferred are tablets or shaped articles in which exclusively the according to the invention, with Perfume and / or nonionic surfactant-laden, soda-free particles nonionic surfactant and / or Perfume exhibit.

The having the above-described nonionic surfactant and / or perfume according to the invention soda-free particles or the mixtures according to the invention described above from soda-free and soda-containing particles are outstanding for incorporation in detergent tablets, such as detergent tablets for washing of textiles, detergent tablets for automatic dishwashing or the cleaning of hard surfaces, Bleach moldings for use in washing machines or dishwashers, water softening tablets or Stain remover tablets.

One preferred subject of the present invention is therefore the Use of nonionic surfactant and / or perfume containing soda-free particles or the mixtures of soda-free mixtures according to the invention described above and soda-containing particles, which after mixing with finely divided Preparation components in a conventional manner to washing and Detergent tablets be pressed, to stabilize and solubility improvement of detergent tablets.

By the use of the nonionic surfactant according to the invention and / or perfume containing soda-free particles or those described above mixtures according to the invention from soda-free and soda-containing particles, which after mixing with compressed further components to detergent tablets can, can the physical properties of the moldings, in particular the mechanical stability and the solubility behavior, be significantly improved. This can be done with low Press Press Detergent tablets produce sufficient mechanical stability in packaging, Transport and handling exhibit. That way you can directly stable tablets at lower pressures, so that the Wear on the tableting machines significantly reduced and their lifetime extended becomes.

One Another object of the present invention also relates to and detergent tablets of compacted particulate Detergents and cleaners containing the nonionic surfactant and / or perfume of the invention soda-free particles or the mixtures according to the invention described above from soda-free and soda-containing particles. It is preferred according to the invention that the soda-containing particles have no nonionic surfactant and / or no perfume. Most preferred are detergent tablets, wherein exclusively the according to the invention, with Perfume and / or nonionic surfactant-laden, soda-free particles nonionic surfactant and / or Perfume exhibit.

The nonionic and / or perfume containing soda-free particles or those described above Mixtures of soda-free and soda-containing particles according to the invention may be present in varying amounts in the shaped bodies depending on the intended use of the washing and cleaning agent tablets according to the invention. Here, detergent tablets are preferred which, based on the weight of the shaped body, 10 to 90 wt .-%, preferably 20 to 80 wt .-% and in particular 25 to 70 wt .-% of nonionic surfactant and / or perfume having soda-free Contain particles or the above-described mixtures of soda-free and soda-containing particles according to the invention.

Around It is to facilitate the disintegration of highly compressed moldings possible, Disintegration aids, so-called tablet disintegrants, in to incorporate these to shorten the disintegration times. Under Tablet disintegrants or disintegrants are used according to Römpp (9. Auflage, Bd. 6, p. 4440) and Voigt "Textbook of Pharmaceutical Technology" (6th edition, 1987, Pp. 182-184) Understood excipients for the rapid disintegration of tablets into water or gastric juice and for release provide the pharmaceuticals in resorbable form.

These Substances that are also referred to as "explosives" due to their effect increase when water enters their volume, on the one hand increasing the intrinsic volume (swelling), on the other hand also about the Release of gases can create a pressure on the tablet can disintegrate into smaller particles. Well-known Disintegration aids are, for example, carbonate / citric acid systems, although other organic acids can be used. Swelling disintegration aids are for example synthetic Polymers such as polyvinylpyrrolidone (PVP) or natural polymers or modified Natural substances such as cellulose and starch and their derivatives, alginates or casein derivatives.

In a preferred variant of the invention include the washing and Cleaning tablets no disintegration aids. You alone by the Incorporation of the nonionic surfactant of the invention and / or Perfume containing soda-free particles or those described above mixtures according to the invention From soda-free and soda-containing particles a sufficiently high dissolution rate on.

In another, likewise preferred variant contain the washing and detergent tablets 0.5 to 10 wt .-%, preferably 3 to 7 wt .-% and in particular 4 to 6 wt .-% of one or more disintegration aids, respectively based on the molding body weight.

When preferred disintegrants are within the scope of the present invention Invention disintegrating agent used on cellulose basis, so that preferred detergent tablets and cleaning agent such a disintegrating agent based on cellulose in amounts of 0.5 to 10 wt .-%, preferably Contain 3 to 7 wt .-% and in particular 4 to 6 wt .-%. Pure Cellulose has the formal gross composition (C6H10O5) n and formally represents a β-1,4-polyacetal of cellobiose, which in turn consists of two molecules of glucose is constructed. Suitable celluloses consist of about 500 to 5000 glucose units and therefore have average molecular weights from 50,000 to 500,000. As disintegrating agent based on cellulose it is also possible to use cellulose derivatives in the context of the present invention, which are obtainable by polymer-analogous reactions of cellulose. Such chemically modified celluloses include, for example Products of esterifications or etherifications in which substituted hydroxy hydrogen atoms were. But also celluloses in which the hydroxy groups against functional groups that do not have over an oxygen atom are bonded, can be as Use cellulose derivatives. In the group of cellulose derivatives For example, alkali celluloses, carboxymethylcellulose (CMC), Cellulose esters and ethers and aminocelluloses. The cellulose derivatives mentioned are preferably not used alone as cellulose disintegrating agents used but used in mixture with cellulose. The salary these mixtures of cellulose derivatives is preferably below 50 Wt .-%, more preferably below 20 wt .-%, based on the Cellulose-based disintegrant. Particularly preferred used as cellulose-based disintegrating agent pure cellulose, which is free of cellulose derivatives.

The cellulose used as a disintegration aid is preferably not used in finely divided form, but converted into a coarser form, for example granulated or compacted, before it is added to the premixes to be tabletted. Detergents and cleaning agent tablets containing disintegrators in granular or optionally cogranulated form are described in the German patent applications DE 197 09 991 and DE 197 10 254 and International Patent Application WO98 / 40463. Further details of the production of granulated, compacted or cogranulated cellulose explosives can be found in these publications. The particle sizes of such disintegrating agents are usually above 200 .mu.m, preferably at least 90 wt .-% between 300 and 1600 .mu.m and in particular at least 90 wt .-% between 400 and 1200 microns. The coarser disintegration aids based on cellulose mentioned above and described in more detail in the cited documents are within the scope of the present invention tion preferably used as disintegration aids and commercially available, for example, under the name Arbocel ^® TF-30-HG from Rettenmaier.

When another disintegrating agent based on cellulose or as an ingredient This component can be used microcrystalline cellulose. This microcrystalline cellulose is made by partial hydrolysis of Celluloses obtained under such conditions, only the amorphous ones Areas (about 30% of the total cellulose mass) of the celluloses attack and completely dissolve, the crystalline areas (about 70%) but leave undamaged. A subsequent disaggregation of the resulting from the hydrolysis microfine celluloses provide the microcrystalline celluloses, the primary particle sizes of approx. 5 μm and compactable, for example, to granules having an average particle size of 200 microns are.

in the In addition, detergents and cleaning agent tablets preferred according to the present invention contain a Disintegration aid, preferably a disintegration aid based on cellulose, preferably in granular, cogranulated or compacted form, in amounts of 0.5 to 10 wt .-%, preferably from 3 to 7% by weight and especially from 4 to 6% by weight, respectively based on the molding body weight.

Next having the said components nonionic surfactant and / or perfume soda-free particles or the mixtures according to the invention described above from soda-free and soda-containing particles as well as disintegration aids can the detergent tablets according to the invention additionally a or several substances from the groups of bleaches, bleach activators, Enzymes, pH modifiers, fluorescers, dyes, foam inhibitors, Silicone oils, Anti redeposition agents, optical brighteners, grayness inhibitors, Color transfer inhibitors, Contain corrosion inhibitors and silver protectants. These substances are described below.

Among the compounds which serve as bleaches and deliver in water H ₂ O ₂ , the sodium perborate tetrahydrate, the sodium perborate monohydrate and the sodium percarbonate have particular significance. Other useful bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -forming peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid. Even when using the bleaching agents, it is possible to dispense with the use of surfactants and / or builders, so that pure bleach tablets can be produced. If such bleach tablets are to be used for textile washing, a combination of sodium percarbonate with sodium sesquicarbonate is preferred, regardless of which other ingredients are contained in the tablets.

Become Cleaning or bleaching tablets for machine dishwashing prepared, so can Also bleach from the group of organic bleach used become. Typical organic bleaches are the diacyl peroxides, such as. Dibenzoyl. Other typical organic bleaches are the peroxyacids, Examples being the alkyl peroxyacids and the aryl peroxyacids. Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted Derivatives, such as alkyl peroxybenzoic acids, but also peroxy-α-naphthoic acid and Magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, like peroxylauric acid, Peroxystearic acid, ε-phthalimidoperoxycaproic acid [phthaloiminoperoxyhexanoic acid (PAP)], o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinates, and (c) aliphatic and araliphatic peroxydicarboxylic, such as 1,12-diperoxy carboxylic acid, 1,9-diperoxyazelaic acid, Diperocysebacinsäure, diperoxybrassylic, the diperoxyphthalic acids, 2-decyldiperoxybutane-1,4-dioic acid, N, N-Terephthaloyl-di (6-aminopercapronate) can be used.

When Bleaching agents in moldings for the automatic dishwashing can Chlorine or bromine releasing substances are used. Among the suitable chlorine or bromine releasing materials come for example, heterocyclic N-bromo and N-chloroamides, for example Trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric (DICA) and / or their salts with cations such as potassium and sodium into consideration. Hydantoin compounds, such as 1,3-dichloro-5,5-dimethylhydanthoin are also suitable.

Further can Bleach activators, as for the invention, with Perfume and / or nonionic surfactant-laden, soda-free particles described above, incorporated into the detergent tablets according to the invention become.

In addition to or in place of the conventional bleach activators, so-called bleach catalysts, as for the perfume and / or nonionic surfactant-laden, soda-free materials of the present invention may also be used Particles described above, are incorporated into the moldings.

In addition, all Enzymes, as for the invention, with Perfume and / or nonionic surfactant-laden, soda-free particles described above, be used.

In addition, the Detergent tablets Also contain components that the oil and Fettauswaschbarkeit from textiles positively influence (so-called repellents). As suitable components, the oil and Fettauswaschbarkeit from textiles positively affect all components usable, already mentioned above for the invention, with Perfume and / or nonionic surfactant-loaded, soda-free particles have been described are.

The moldings can also optical brightener derivatives, as already for the inventive, with perfume and / or Nonionic surfactant-loaded, soda-free particles described above, contain.

color and fragrances, as described in the beginning, may be added to the washing and detergent tablets be added to the aesthetic Improve the impression of the products and the consumer in addition to the Softness performance is a visually and sensory "typical and unmistakable" product available too put.

The Fragrances can directly into the agents according to the invention incorporated, but it can also be beneficial, the fragrances to apply to substrates, the adhesion of the perfume on the Laundry strengthen and by a slower release of fragrance for long-lasting fragrance of Provide textiles. As such substrates have, for example Cyclodextrins proven, the cyclodextrin-perfume complexes additionally can still be coated with other excipients.

Around the aesthetic Impression of the agents according to the invention to improve with suitable dyes, as already mentioned for the invention, with Perfume and / or nonionic surfactant loaded, soda-free particles carried out, dyed.

Dishwashing agents according to the invention, in particular dishwashing detergent tablets, can be used for protection of the items to be washed or the machine contain corrosion inhibitors, taking particular Silver protection agent in the field of automatic dishwashing have special meaning. Suitable useful silver protectants were already in the beginning for the invention, with Perfume and / or nonionic surfactant loaded, soda-free particles listed on which is referred to here.

The agents according to the invention can about that In addition, active chlorine-containing substances, the corrosion of the silver surface significantly can lessen be added. In chlorine-free agents, such as cleaners, are especially oxygen- and nitrogen-containing organic redox-active Compounds such as di- and trihydric phenols, e.g. Hydroquinone, Pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol or Derivatives of these classes of compounds. Also salt and complex Inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are common Use. Preferred here are the Übergangsmetaflsalze which are selected from the group of manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammin) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes; the chlorides of cobalt or manganese and manganese sulfate. Also, zinc compounds can help prevent it corrosion on the items to be washed be used.

Special Ingredients used in machine dishwashing moldings according to the invention or the cleaning of hard surfaces can be used are substances that prevent the re-soiling of surfaces and / or the soil removal after one-time use (so-called "soil release compounds"). Suitable components therefor were already prominent for the invention, with Perfume and / or nonionic surfactant-laden, soda-free particles mentioned on the is fully incorporated herein by reference.

The cationic polymers are particularly preferably selected from cationic polymers of copolymers of monomers such as trialkylammonium alkyl (meth) acrylate or acrylamide; Dialkyldiallyldiammoniumsalze; polymer-analogous reaction products of ethers or esters of polysaccharides with pendant ammonium groups, in particular guar, cellulose and starch derivatives; Polyadducts of ethylene oxide with ammonium groups; quaternary ethyleneimine polymers and polyesters and polyamides with quaternary side groups as soil release compounds. Exceptionally preferred in the context of this application are also natural polyuronic acids and related substances, as well as polyampholytes and hydrophobized poly ampholytes, or mixtures of these substances.

In The moldings of the invention can all ingredients described above are used; in addition to the phosphate compounds according to the invention can also other builders in the moldings be included. In the detergent tablets according to the invention, in addition to the phosphate compounds water-soluble and water-insoluble Builder mainly used for binding calcium and magnesium become. Here are for Detergent Tablets water-soluble builder preferred because They usually do less on crockery and hard surfaces tend to form insoluble residues. Usual builders, in the context of the invention between 10 and 90 wt .-% based on the Whole preparation may be present, in addition to the already mentioned above Build the low molecular weight polycarboxylic acids and their salts, the carbonates and silicates. To water insoluble Counting builders the zeolites, which can also be used, as well as mixtures the abovementioned builder substances. Preference is given in addition to the phosphate compounds according to the invention Trisodium citrate and / or sodium carbonate and / or sodium bicarbonate and / or gluconates and / or silicatic builders of the class the disilicates and / or metasilicates or the phyllosilicates used.

In Inventive detergent tablets for machine Cleaning dishes can be also other bleaching agents are used. Preferably, the Bleaching performance of bleach-containing moldings such as detergent tablets, Detergent tablets or bleach tablets through the use of Increased bleach activators. Suitable usable bleaching agents and bleach activators have already been mentioned in the introduction for the invention Perfume and / or nonionic surfactant loaded, soda-free particles listed on which is referred to here.

Next the active substances, such as anionic and / or nonionic and / or cationic and / or amphoteric surfactants, preferably contain the detergent tablets according to the invention still granules additives, which particularly preferably originate from the group of builders. Granules additives can be anionic and / or nonionic surfactants and builders and may contain total surfactant levels of at least 10% by weight, preferably at least 20% by weight and in particular at least 25% by weight.

ever According to the purpose of the molding according to the invention, the proportion of Surfactant granules and the surfactant content of the granules higher or lower. contains the shaped body according to the invention in addition the soda-pure nonionic surfactant and / or perfume containing particles separately Of these already tensides, these are in the calculation of the total surfactant content to take into account. Usually the surfactant content of detergent tablets is between 10 and 40 wt .-%, preferably between 12.5 and 30 wt .-% and in particular between 15 and 25 wt .-% while Detergent tablets for automatic dishwashing between 0.1 and 10% by weight, preferably between 0.5 and 7.5% by weight and in particular between 1 and 5 wt .-% surfactants. Bleach tablets and water softener tablets are common free of surfactants.

These surfactants Substances come from the group of anionic, nonionic, zwitterionic or cationic surfactants, with anionic surfactants from economic establish and are clearly preferred due to their power spectrum. suitable usable anionic, nonionic, zwitterionic or cationic Surfactants have already been mentioned in the introduction for the invention Perfume and / or nonionic surfactant loaded, soda-free particles listed on which is referred to here.

Independently of, whether anionic or optionally amphoteric or cationic surfactants in the soda-containing surfactant granules, moldings according to the invention are preferred, in which the anionic or optionally amphoteric or cationic Surfactant content of the soda-containing granules 5 to 60 wt .-%, preferably 10 to 50 wt .-% and in particular 15 to 40 wt .-%, each based on the surfactant granules. Moldings.

Above has already been mentioned that in the moldings Other builders may be included. Accordingly, can It may also be preferred within the scope of the invention that these further Builders; preferably at least one aluminosilicate and / or a layered silicate, with the molded body components be mixed. Suitable useful builders were already in the beginning for the invention, with Perfume and / or nonionic surfactant loaded, soda-free particles listed on which is hereby incorporated by reference.

As already mentioned above, the shaped bodies according to the invention, such as washing and cleaning gungsformkörper, other ingredients of detergents and cleaning agents. A preferred in the context of the present invention premix of a shaped article additionally has a disintegration aid, preferably a disintegration aid based on cellulose, preferably in granular, cogranulated or compacted form, in amounts of 0.5 to 10 wt .-%, preferably from 3 to 7 wt. % and in particular from 4 to 6 wt .-%, each based on the weight of the premix of the molding on, wherein it is additionally preferred that the premix of the molding additionally one or more substances from the group of enzymes, pH adjusting agent , Perfumes, perfume carriers, fluorescers, dyes, foam inhibitors, silicone oils, antiredeposition agents, optical brighteners, grayness inhibitors, dye transfer inhibitors, corrosion inhibitors and silver protectants.

In front the compression of the particulate Premix to moldings, such as detergent tablets, the premix be "powdered" with finely divided surface treatment agents. This can for the Texture and physical properties of both the premix (Storage, compression) and the finished detergent tablets of Be an advantage. Finely divided powdering agents are known in the art well-known, with mostly zeolites, silicates or other inorganic salts be used. However, the premix is preferred with finely divided Zeolite "powdered", using zeolites of the faujasite type are preferred. In the context of the present invention the term "zeolite faujasite type "all three zeolites containing the faujasite subgroup of the zeolite structure group 4 (Compare Donald W. Breck: "Zeolite Molecular Sieves", John Wiley & Sons, New York, London, Sydney, Toronto, 1974, page 92). In addition to the zeolite X are including zeolite Y and faujasite and mixtures of these compounds can be used, wherein 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, can be used as a powdering agent, it being advantageous if at least 50% by weight of the powdering agent consists of a zeolite consist of faujasite type.

The Production of the shaped body according to the invention takes place first by the dry mixing of the ingredients, in whole or in part can be pre-granulated, and subsequent Informing, in particular compression to tablets, wherein conventional Method used can be. For the preparation of the shaped body according to the invention, the premix is in a so-called matrix between two stamps to a solid Compacted compressed. This process, hereinafter referred to briefly as Tableting is divided into four sections: Dosing, compaction (elastic deformation), plastic deformation and Ejecting.

First, will introduced the premix in the die, wherein the filling amount and thus the weight and the shape of the resulting molded body the position of the lower punch and the shape of the pressing tool be determined. The constant dosage even at high molding throughputs is preferably over reached a volumetric dosage of the premix. In the further Touched the course of tableting the upper stamp the pre-mix and lower in the direction of of the lower punch. In this compression, the particles become closer to the premix pressed together wherein the void volume within the filling between the punches decreases continuously. From a certain position of the upper punch (and thus from a certain pressure on the premix) begins the plastic deformation, in which the particles flow together and it for the formation of the molding comes. Depending on the physical properties of the premix Part of the premix particles is also crushed and it comes at even higher pressures a sintering of the premix. With increasing pressing speed, So high throughput, the phase of elastic deformation ever shorter, so that the resulting shaped body more or less big cavities can have. In the last step of tabletting the finished molding is through pushed out the lower punch from the die and by subsequent transport facilities carried away. At this time, only the weight of the molded article is finally determined, there the compacts due to physical processes (re-expansion, crystallographic Effects, cooling etc.) can change their shape and size.

The Tableting is done in commercial Tablet presses, in principle with single or double punches equipped could be. In the latter case, not only the upper punch for pressure build-up also the lower punch moves during the pressing process on the upper temple too, while the upper punch presses down.

For small production quantities preferably eccentric tablet presses are used, in which the one or more punches are attached to an eccentric disc, which in turn on an axis with a bestimm rotational speed is mounted. The movement of these dies is comparable to the operation of a conventional four-stroke engine. The compression can be done with a respective upper and lower punch, but it can also be attached more stamp on an eccentric disc, the number of Matrizenbohrungen is extended accordingly. The throughputs of eccentric presses vary depending on the type of a few hundred to a maximum of 3000 tablets per hour.

For larger throughputs, choose Rotary tablet presses in which on a so-called die table A larger number of matrices circular is arranged. The number of matrices varies depending on the model 6 and 55, although larger matrices available in the stores are. Each die on the die table is a top and bottom stamp assigned, in turn, the pressing pressure active only by the Upper or lower stamp, but also constructed by both stamps can be. The die table and the stamps move around one common vertical axis, with the stamps with the help rail-like curved tracks during of circulation in the positions for filling, Compression, plastic deformation and ejection are brought. In the places where a particularly serious increase or decrease in the Stamp is required (filling, Compacting, ejecting), These curves are through additional low pressure pieces, Nierderzugschienen and lifting tracks supported. The filling the matrix is over a rigidly arranged supply device, the so-called filling shoe, the one with a reservoir for the Premix is connected. The pressing pressure on the premix is about the compression paths for upper and Lower punch individually adjustable, whereby the pressure build-up by the rolling of the punch shaft heads on adjustable pressure rollers happens.

Rotary presses can to increase the throughput with two filling shoes be provided, wherein for the preparation of a tablet only one Semicircle must be traversed. To produce two-layered and multi-layered shaped bodies, several filling shoes are used arranged one behind the other, without the slightly pressed first Layer before further filling pushed out becomes. By suitable process control are on coat and point tablets produced this way, the one have onion-like structure, in the case of the point tablets not covering the top of the core or core layers and thus remains visible. Also rotary tablet presses are Equipped with single or multiple tools, so that, for example an outer circle with 50 and an inner circle with 35 holes at the same time for pressing to be used. The throughputs modern rotary tablet presses amount to over one million moldings per Hour.

in the According to the present invention suitable tabletting machines are available from, for example the companies Apparatebau. Holzwarth GbR, Asperg, Wilhelm Fette GmbH, Schwarzenbek, Hofer GmbH, Weil, KILIAN, Cologne, KOMAGE, Kell am See, KORSCH Press GmbH, Berlin, Mapag Maschinenbau AG, Berne (CH) and Courtoy N.V., Halle (BE / LU). For example, the hydraulic is particularly suitable Double printing press HPF 630 of the company LAEIS, D.

The moldings can manufactured in a predetermined spatial form and predetermined size become. As a form of space virtually all useful manageable Embodiments into consideration, for example, the training as a blackboard, the bar or bar form, cubes, cuboids and the like Room elements with flat side surfaces and in particular cylindrical Embodiments with circular or oval section. This last embodiment detects the presentation form of the tablet to compact cylinder pieces with a relationship of height to diameter above 1.

The portioned compacts can each formed as separate individual elements be that of the predetermined dosage amount of detergents and / or cleaning agents equivalent. But it is also possible compacts form a plurality of such mass units in one compact connect, in particular by predetermined breaking points the easy separability of portioned smaller units provided is. For the use of laundry detergents in machines common in Europe Type with horizontally arranged mechanics can be the training of the portioned compacts be useful as tablets, in cylindrical or cuboidal form, being a diameter / height ratio in the Range of about 0.5: 2 to 2: 0.5 is preferred. Commercial hydraulic presses, Eccentric presses or rotary presses are suitable devices, in particular for the production of such Preßtinge.

The Room shape of another embodiment the molded body is in its dimensions of the dispenser of commercial Household washing machines adapted so that the moldings without Dosing aid directly into the dispenser can be metered in, where they are during the flushing process dissolves. Of course it is but also a use of detergent tablets via a dosing easily possible and preferred in the context of the present invention.

One another preferred shaped body, which can be produced, has a plate-like or tabular structure with alternately thick long and thin short segments, so that individual segments of this "bar" at the predetermined breaking points, the short ones thin Display segments, aborted and entered into the machine can be. This principle of the "bar-shaped" molding detergent can also be in other geometric shapes, such as vertical standing triangles, which alongside only one of their sides connected with each other, be realized.

Is possible It is also true that the various components are not one compressed uniform tablet be, but that shaped body be obtained, the several layers, so at least two layers, exhibit. It is also possible that these different layers have different dissolution rates exhibit. From this you can advantageous performance properties of the molded articles result. For example, if components are contained in the moldings that are mutually negatively affect, so it is possible the one component in the faster soluble Layer and integrate the other component into a slower one soluble Incorporate layer so that the first component is already reacted has, if the second in solution goes. The layer structure of the molded body can be both stacked take place, being a solution process the inner layers) already takes place at the edges of the shaped body, when the outer layers not yet complete solved but it can also be a complete covering of the inner layers) through each further outward lying (n) layers), resulting in a prevention the early one solution of constituents of the inner layers).

disintegration aid can be present in one or more layers. If disintegration aid present in multiple layers, the disintegration aids optionally present in different amounts.

In a further preferred embodiment The invention consists of a molded body from at least three layers, so two outer and at least one inner layer, wherein at least in one of the inner layers a peroxy bleach is contained, while in the stacked shaped body the both outer layers and the envelope-shaped body the outermost However, layers are free of peroxy bleach. Furthermore is it also possible Peroxy bleach and optionally present bleach activators and / or enzymes spatially in a shaped body separate from each other. Such multilayer moldings have the advantage of not only having a dispenser or over a metering device, which is added to the wash liquor, can be used; rather, it is in such cases also possible, the shaped body in direct contact with the textiles in the machine without giving that stains caused by bleach and the like are to be feared.

Similar Effects can also be achieved by coating ("coating") individual components of the material to be pressed Achieve detergent and cleaner composition or the entire Formkör pers. You can do this the bodies to be coated for example with aqueous solutions or Emulsions be, or over the process of melt coating obtained a coating.

To the pressing, the detergent tablets have a high stability on. The breaking strength of cylindrical shaped bodies can over the Measured variable of the diametrical Breaking stress detected become. This can be determined by σ = 2PπDt.

Here in σ stands for the diametrical one Diametral fracture stress (DFS) in Pa, P is the force in N, which leads to the pressure exerted on the molded body, the the breakage of the molding D is the shape diameter in meters and t is the height the molded body.

The nonionic surfactant according to the invention and / or perfume containing soda-free particles, or the nonionic surfactant and / or perfume containing soda-free particles and / or soda-containing particles of the mixture according to the invention or finished product, for example moldings, can be aftertreated, For example, by the respective soda-free and / or soda-containing Particles rounded.

The Rounding can be done in a usual way Run rounder. Preferably, the rounding time is included no longer than 4 minutes, especially not more than 3.5 minutes. rounding of not more than 1.5 minutes or less are particularly preferred. The rounding becomes a further standardization of the grain spectrum achieved because any resulting coarse particles are crushed.

In particular, according to the invention particles and / or finished product can then be solid aftertreatment, preferably in amounts of up to 15% by weight, in particular in amounts of from 2 to 15% by weight, based in each case on the total weight of the post-treated particles or finished product. Suitable usable components for the aftertreatment have already been mentioned above for the soda-free particles according to the invention loaded with perfume and / or nonionic surfactants, to which reference is made in their entirety.

The After-treatment with the substances mentioned here can be carried out in a conventional manner Mixer, for example, in a 2-wave mixer within for a maximum of 1 minute, preferably within 30 seconds and for example within 20 seconds, whereby the time and mixing time stands.

Yet An object of the present invention relates to a method for the preparation of the invention, with perfume and / or Nonionic surfactant-laden, soda-free particles containing nonionic surfactant and / or Perfume.

• – Herstellung feinteiliger sodafreier Träger,
• – Aufbringung von wenigstens einem Niotensid und/oder wenigstens einem Parfüm; wobei die sodafreien Partikel das Niotensid und/oder Parfüm aufsaugen.

A preferred method comprises the steps:

• - production of finely divided soda-free carriers,
• Application of at least one nonionic surfactant and / or at least one perfume; wherein the soda-free particles soak up the nonionic surfactant and / or perfume.

The Preparation of soda-free particles can be achieved by means of spray-drying, Granulation, for example in mixers or by other known Procedure done.

Also The application of surfactant and / or perfume can basically after all methods known in the art, so far these are suitable.

below are the measuring methods stated

Principle of dust value determination

It were each 50 g sample of the invention, with perfume and / or Nonionic surfactant-loaded, soda-free particles of the mixture according to the invention from the aforementioned soda-free surfactant according to the invention and / or Perfume containing particles and soda-containing particles and inventive finished product examined separately from each other, in which the respective sample on a vibrating trough has applied, wherein the frequency of the vibrating trough was 50 Hz and the opening gap adjusted so that the sample passes through the vibratory chute in 1 minute so that the sample through the funnel and the filler pipe in the cylinder falls and collect in the vessel, while the dust is outside of this vessel the bottom plate collects. Any remaining sample in the funnel By carefully knocking the funnel into the cylinder over the Transfer tube transferred. To a settling time of 2 minutes was on the polished bare Ground plate deposited dust with a spatula transferred to a weighing dish and balanced.

Of the Construction of the experimental apparatus for determining the dust value was such that the sample has a vibrating conveyor and funnel into a sealed cylinder, centered over one filler pipe was dropped, with the drop height measured from the filler pipe outlet opening to to the upper outer bottom plate 50 cm made. While so coarse portions of the sample are perpendicular to the bottom of the cylinder, Centrally located under the funnel collecting vessel with a Height of 10 cm and a diameter of 18 cm collected, distributed the fines - dust - on the entire bottom plate of the cylinder. After settling leave the Dust in the cylinder was the dust with a spatula on the base plate of the cylinder pushed together, collected in a vessel and weighed.

Equipment:

It became a laboratory standard vibrating conveyor used, manufacturer AEG type DR 50 220 V, 50 Hz, 0.15 A.

Of the used funnels made of sheet iron with a wall thickness of 2 mm had a top diameter of 15 cm and the diameter the spout was 1.8 cm. The length of the funnel tube was 8 cm.

The used filling pipe made of brass with a wall thickness of 1 mm had a length of 30 cm and a diameter of 2.5 cm. The immersion depth of the tube in the outer cylinder was 20 cm. The immersion depth of the pipe is by a soldered to the outer wall of the filler pipe brass disc with Diameter of 15 cm and a thickness of 1 mm kept constant.

Of the used cylinder had a height of 70 cm, diameter 40 cm, closed at the top, open at the bottom. The Cover plate of the cylinder was in the middle with a circular opening, Diameter about 3 cm, provided for receiving the funnel outlet pipe. The lower edge of the cylinder was to eliminate the sharp edge outward beaded and soldered. The cylinder was made of galvanized sheet steel with a wall thickness of 1 mm.

The had used vessel a height of 10 cm and a diameter of 18 cm. The vessel was up open and closed down. The lower edge of the vessel was Crimped and soldered to remove the sharp edge. The Vessel was off Galvanized steel sheet with a wall thickness of 1 mm.

The used base plate made of bare aluminum with a thickness of 1 mm had a round shape with a diameter of 48 cm.

Of the used 2 mm thick sheet iron spatula had a worktop width of 11 cm.

The The analytical balance used had an accuracy of 0.01 g.

to Weight determination of the dust content became a laboratory standard Used weighing dishes.

Of the Dust content was in% based on the weight of each sample specified.

aggregation test

at the also carried out Klumpptest 15 ml of each sample to be examined, i. the inventive, with Perfume and / or nonionic surfactant-laden, soda-free particles of the mixture according to the invention from the aforementioned soda-free surfactant according to the invention and / or Perfume containing particles and soda-containing particles and inventive finished product separated from each other, into a hollow cylinder with an inner diameter transferred from 25 mm and by means of a stamp, in addition is loaded with 500 g while Pressed for 30 minutes. The ejected under appropriate precautions cylindrical compact will follow in vertical position under defined conditions until breaking loaded. The applied load in grams is a measure of the lumping tendency.

The Values of the clumping test were given in g.

solution behavior

The Determination of the solution behavior was done as follows. In a beaker (volume 500 ml) are added for each sample to be examined 200 ml each at 30 ° C and 10 ° C tempered tap water (15 ° d) with the help of a motor driven stirrer, with 4 at an angle from 30 ° to equipped below curved impellers is stirred with a constant number of revolutions of 700 rpm. Of the Distance of the stirring blades to Bottom of the vessel is 2.5 cm. 1 g of the sample, i. the invention, with perfume and / or Nonionic surfactant-loaded, soda-free particles of the mixture according to the invention from the aforementioned soda-free surfactant according to the invention and / or Perfume containing particles and soda-containing particles and finished product according to the invention, becomes separated from each other carefully and avoiding lumping in a stirring cone poured. After 90 seconds, the solution becomes through a tared sieve with a mesh size of 0.1 mm and a 7 cm diameter cast and sucked off with a suction bottle. Remains of substance in the beaker are by means of possible little injected water transferred to the sieve. The sieve becomes after a Drying time of 24 hours in the air reweighed.

The residue formation as well as the solved Sample content at 30 ° C and 10 ° C was given in%.

sedimentation test

In a beaker, 90 ml of tap water at 16 ° d were introduced and with vigorous stirring 10 g of the respective sample to be tested, ie the invention, perfume and / or nonionic surfactant loaded, soda-free particles, the inventive mixture of the aforementioned soda-free surfactant and / or perfume-containing particles and soda-containing particles and inventive Finished product, separated from each other in small portions. Thereafter, it is stirred for 15 minutes at room temperature. The solution is then filled into a graduated cylinder and allowed to stand. During the service life, the measuring cylinder is covered with a foil. After 20 h, the quotient of the sediment volume V _S and total volume V is determined.

Equipment:

Cups:

• 250 ml, diameter 70 mm

stirrer:

• Three-bladed propeller stirrer, diameter 50 mm, speed 700-1000 min ^-1

measuring cylinder:

• 100 ml glass measuring cylinder according to DIN

The Values of the sedimentation test were expressed in ml.

migration test

It were the flow time of 1000 ml of inventive sample, the inventive, with Perfume and / or nonionic surfactant-laden, soda-free particles of the mixture according to the invention from the aforementioned soda-free surfactant according to the invention and / or Perfume containing particles and soda-containing particles and finished product according to the invention, measured separately from a standard funnel and against compared the exit speed of standard test sand. The flow time dry test sand from the Rieselapparatur was set to 100%. The flow time the sample from the Rieselapparatur were put into relation to it and as% efflux time compared to the test sand.

Characteristics of the test sand:

• bulk weight 1460 g / l

Particle size distribution:

• > 1.6 mm = 0.2%
• > 0.8 mm and ≤ 1.6 mm = 11.6%
• > 0.4 mm and ≤ 0.8 mm = 56.2%
• > 0.2 mm and ≤ 0.4 mm = 26.6%
• > 0.1 mm and ≤ 0.2 mm = 4.8%
• <0.1 mm = 0.6

The Grain spectrum of the test sand is weighed out from fractionated building sand and is an average distribution a washing powder modeled.

Of the Test Sand is before the calibration of the Rieseltrichters by Probeteilung from a larger storage bottle to divide to a volume of 1000 ml.

equipment

• Bulk density apparatus with 1000 ml beaker
• Rieseltestapparatur (consisting of trickle funnel and tripod)

stopwatch

• Powder funnel (for filling the apparatus)
• 2 liter plastic can (to collect the spilled material)

execution

• Calibration of the trickle test apparatus

For the trickle test apparatus becomes the flow time of the test sand determined by the flow time of 1000 ml of test sand 5 determined. The average runtime is set as 100%. It is important to pay attention to the flow time of the test sand 50 seconds. Otherwise, the outlet opening of the funnel to correct.

Measurement of a sample according to the invention

1000 ml sample, i. the inventive, with Perfume and / or nonionic surfactant-laden, soda-free particles of the mixture according to the invention from the aforementioned soda-free surfactant according to the invention and / or Perfume containing particles and soda-containing particles and finished product according to the invention are transferred separately from each other in the trickle test apparatus. For easier filling of the Rieseltrichters was the particles of the invention using a huge Pulvertrichters filled in the apparatus. While the sample from the top in the vertical Rieselapparatur is filled, is the lower outlet opening of the funnel to close the trickle test apparatus (finger). After release the outlet opening the funnel of the Rieselapparatur became the time with a stopwatch in seconds measured in the particle sample completely off runs out of the trickle funnel.

The Outflow time of 1000 ml sample according to the invention was determined 5 times and the mean is calculated.

The Flow time of the test sand in seconds multiplied by 100 and divided by the flow time of the 1000 ml of sample according to the invention in seconds, the trickle test results in%.

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

example 1

Soda-free invention particle

By Addition of 3.5% by weight of perfume on one at the spray tower prepared carrier the composition 54.3% by weight of sodium silicate, 34.7% by weight of polyacrylic acid Na salt, 5 wt% sodium sulfate and 6 wt% water were in a Lödigemischer soda-free perfumed Particles made.

A change the perfume note after storage of 100 g of sample in an open 500 ml glass dish at 35 ° C for 4 weeks at a room humidity of 80% did not occur.

The review of Scent note was performed by 10 adult human subjects none of the 10 subjects noticed a change in the scent have, compared to an immediately produced fresh Detergent sample and a stored as described above Sample.

Example 2

Inventive mixture comprising soda-free and soda-containing particles

It were 13 wt .-% of the soda-free particles of the invention according to Example 1 with 87 wt .-% of a 26 wt .-% soda, based on the granules, containing granules, wherein the weights the soda-free particles and the soda-containing granules on the total weight of the mixture.

A change the perfume note after storage of 100 g of sample in an open 500 ml glass dish at 35 ° C for 4 weeks at a room humidity of 80% did not occur.

The review of the fragrance was carried out by human sensory 10 adult subjects where none of the 10 subjects found a change in fragrance compared to an immediately prepared fresh detergent sample and a sample stored as described above.

Example 3

Inventive finished product

There were 69 wt .-% of the mixture obtained according to Example 2, with 2 wt .-% C ₁₂ -C ₁₈ fatty alcohol with 7 EO and 29 wt .-% detergent additives, filled to produce the finished product, wherein the weights refer to the total weight of the finished product.

When detergent additives became usual Amounts of sodium carbonate, carboxymethyl cellulose Na, defoamers, enzymes, sodium carbonate peroxohydrate and tetraacetylethylenediamine and hydroxypropane-1,2,3-tricarboxylic acid Mixture added.

A change the perfume note after storage of 100 g of sample in an open 500 ml glass dish at 35 ° C for 4 weeks at a room humidity of 80% did not occur.

The review of Scent note was performed by 10 adult human subjects none of the 10 subjects noticed a change in the scent have, compared to an immediately produced fresh Detergent sample and a stored as described above Sample.

Example 4

Soda-free invention particle

By adding 2.6 wt .-% perfume, based on the total weight of perfume-free carrier, and 16.9 wt .-% C ₁₂ -C ₁₈ fatty alcohol with 7 EO, based on the total weight of the surfactant-free carrier, on an am 54.3% by weight of sodium silicate, 34.7% by weight of polyacrylic acid Na salt, 5% by weight of sodium sulfate and 6% by weight of water were used in a Lödigemischer soda-free, perfume and nonionic surfactant containing Particles made.

A change the perfume note after storage of 100 g of sample in an open 500 ml glass dish at 35 ° C for 4 weeks at a room humidity of 80% did not occur.

The review of Scent note was performed by 10 adult human subjects none of the 10 subjects noticed a change in the scent have, compared to an immediately produced fresh Detergent sample and a stored as described above Sample.

Example 5

Inventive mixture comprising soda-free and soda-containing particles

to Preparation of the mixture according to the invention were 15.9 wt .-% soda-free particles of the invention obtained according to Example 2, to 84.1 wt .-% of a 25.2 wt .-% soda-containing granules mixed, with the weights of soda-free particles and the soda-containing granules on the total weight of the mixture Respectively.

A change the perfume note after storage of 100 g of sample in an open 500 ml glass dish at 35 ° C for 4 weeks at a room humidity of 80% did not occur.

The review of Scent note was performed by 10 adult human subjects none of the 10 subjects noticed a change in the scent have, compared to an immediately produced fresh Detergent sample and a stored as described above Sample.

Example 6

Inventive finished product

There were 71.4 wt .-% of the mixture obtained according to Example 5, with 2 wt .-% C ₁₂ -C ₁₈ fatty alcohol filled with 7 EO and 26.6 wt .-% detergent additives, for the preparation of the finished product, wherein the weights are based on the total weight of the finished product.

When detergent additives were the same detergent additives as described in Example 3, used.

A change the perfume note after storage of 100 g of sample in an open 500 ml glass dish at 35 ° C for 4 weeks at a room humidity of 80% did not occur.

The review of Scent note was performed by 10 adult human subjects none of the 10 subjects noticed a change in the scent have, compared to an immediately produced fresh Detergent sample and a stored as described above Sample.

Example 7

Soda-free invention particle

By adding 20 wt .-% C ₁₂ -C ₁₈ fatty alcohol with 7 EO on a support prepared at the spray tower of the composition 43.3 wt .-% sodium sulfate, 0.14 wt .-% NaOH, 12 wt .-% polyacrylic acid Na salt, 18.8% by weight of sodium silicate and 5.76% by weight of water, the weight data being based on the surfactant-loaded particles, soda-free, nonionic-containing particles were prepared in a Lödigemischer.

The following values were determined for the soda-free, nonionic surfactant-containing particles: bulk weight 270 g / l dust test 0.11% whiteness 90.8% aggregation test 0

A change the odor note after storage of 100 g of sample in an open 500 ml glass dish at 35 ° C for 4 weeks at a room humidity of 80% did not occur.

The review of Odor note was human sensory by 10 adult subjects carried out, none of the 10 subjects noticed a change in the scent have, compared to an immediately produced fresh Detergent sample and a sample stored as described above.

Example 8

Soda-free invention particle

By adding 20 wt .-% C ₁₂ -C ₁₈ fatty alcohol with 7 EO on a support prepared at the spray tower of the composition 50.14 wt .-% sodium sulfate, 0.14 wt .-% NaOH, 12 wt .-% polyacrylic acid Na salt, 13.2% by weight of sodium silicate and 4.52% by weight of water, the weight data being based on the surfactant-loaded particles, soda-free, nonionic-containing particles were prepared in a Lödiger mixer.

A change the odor note after storage of 100 g of sample in an open 500 ml glass dish at 35 ° C for 4 weeks at a room humidity of 80% did not occur.

For the soda-free, nonionic-containing particles, the following pitches were determined: bulk weight 250 g / l dust test 0.06% whiteness 90.9% aggregation test 0

Example 9

Soda-free invention particle

By addition of 5.34 wt .-% C ₁₂ -C ₁₈ fatty alcohol with 7 EO on a support prepared at the spray tower of the composition 49.51 wt .-% sodium sulfate, 0.04 wt .-% NaOH, 15 wt. % Polyacrylic acid Na salt, 23.50 wt .-% sodium silicate and 6.61 wt .-% water, wherein the weights are based on the surfactant-loaded particles, were prepared in a Lödigemischer soda-free, nonionic surfactant particles.

A change the odor note after storage of 100 g of sample in an open 500 ml glass dish at 35 ° C for 4 weeks at a room humidity of 80% did not occur.

The review of Scent note was performed by 10 adult human subjects none of the 10 subjects noticed a change in the scent have, compared to an immediately produced fresh Detergent sample and a stored as described above Sample.

Comparative Example 10

• – 60 Gew.-% Soda enthaltendes Granulat gemäß Beispiel 1;
• – 8,7 Gew.-% des auf einen am Sprühturm hergestellten Trägers nach Beispiel 1;
• – 2,6 Gew.-% Parfüm;
• – 0,3 Gew.-% C₁₂-C₁₈-Fettalkohol mit 7 EO; und
• – übliche Waschmittelzusätze wie in Beispiel 3 auf 100 Gew.-% aufgefüllt.

A comparative product was produced in a Lödigemischer comprising:

• - 60 wt .-% soda-containing granules according to Example 1;
• 8.7% by weight of the carrier prepared according to Example 1 on a spray tower;
• - 2.6% by weight of perfume;
• - 0.3 wt .-% C ₁₂ -C ₁₈ fatty alcohol with 7 EO; and
• - Usual detergent additives as in Example 3 made up to 100 wt .-%.

at the mixture according to Example 3 came a change the perfume note after storage of 100 g of sample in an open 500 ml glass dish at 35 ° C for 4 weeks at a room humidity of 80%.

The review of Scent note was performed by 10 adult human subjects Each of the 10 subjects noticed a significant change in the scent have, compared to an immediately produced fresh Detergent sample and a stored as described above Sample.

Claims (39)

Nonionic surfactant and / or perfume containing soda-free particles, characterized in that the particles comprise as an essential constituent a carrier material selected from the group comprising silicate, copolymer, soap, phosphonate, phosphate and / or sulfate, wherein the soda-free particles 1 wt .-% to 50% by weight of nonionic surfactant and / or 0.5% by weight to 15% by weight of perfume, based on the total weight of the soda-free particles. Soda-free particles according to Claim 1, characterized that the soda-free particles include: From 2% to 45% by weight of nonionic surfactant, preferably 5% by weight to 35% by weight of nonionic surfactant, preferably 8% by weight to 25% by weight of nonionic surfactant, more preferably 10% by weight to 20% by weight of nonionic surfactant, especially preferably from 12% to 18% by weight of nonionic surfactant, and most preferably 14% by weight to 17% by weight of nonionic surfactant; and or 2% by weight up to 10% by weight of perfume, more preferably from 2% to 5% by weight of perfume, and most preferably 3% by weight to 4% by weight of perfume, based on the total weight of soda-free particles. Soda-free particles according to claim 1 or 2, characterized in that the soda-free particles have a particle diameter d ₅₀ of 0.01 mm to 2 mm, preferably 0.02 mm to 1 mm and particularly preferably from 0.05 to 0.4 mm. Soda-free particles according to any one of claims 1 to 3, characterized in that the soda-free particles comprise: - 25 wt .-% to 65 wt .-% silicate, more preferably 30 wt .-% to 50 wt .-% silicate and most preferably from 40% to 45% by weight of silicate; and / or - from 4% to 54% by weight of polymer, more preferably from 10% to 40% by weight of polymer, and most preferably from 25% to 30% by weight of polymer; and or - 0 wt .-% to 15 wt .-% phosphonate, preferably 1 wt .-% to 12 wt .-% phosphonate and most preferably 3 wt .-% to 9 wt .-% phosphonate, wherein the weight content of the support materials of the soda-free particles, including the weight contents of nonionic surfactant and / or perfume, if included, do not exceed 100% by weight. Soda-free particles according to one of claims 1 to 4, characterized in that the soda-free particles are linear Alkylbenzenesulfonate / e (LAS), preferably makes the weight fraction linear alkylbenzenesulfonates ≥ 0 Wt .-% and ≤ 25 Wt .-%, preferably ≥ 5 Wt .-% and ≤ 15 Wt .-%, more preferably ≥ 5 wt .-% and ≤ 10 Wt .-%, and most preferably ≥ 0 Wt .-% and ≤ 5 Wt .-%, based on the total weight of the soda-free particles from. Soda-free particles according to one of claims 1 to 5, characterized in that the soda-free particles have a water content of ≥ 0% by weight and ≤ 15 Wt .-%, preferably 1 wt .-% and ≤ 10 Wt .-%, more preferably ≥ 3 Wt .-% and ≤ 8 Wt .-%, and most preferably ≥ 4 Wt .-% and ≤ 7 % By weight, based on the total weight of the soda-free particles. Soda-free particles according to one of claims 1 to 6, characterized in that the soda-free particles have a bulk density from 100 g / l to 500 g / l, preferably 150 g / l to 400 g / l, and preferred 200 g / l to 300 g / l have. Soda-free particles according to one of claims 1 to 7, characterized in that the soda-free particles have a dust value of> 0% and <1%, preferably of ≥ 0.01% and ≤ 0.5% and particularly preferably ≥ 0.05% and ≤ 0.25% exhibit. Soda-free particles according to one of claims 1 to 8, characterized in that the soda-free particles have a flowability of at least 40%, in particular of at least 50%, preferably at least 70% and preferably 90% to ≤ 100%. Soda-free particles according to one of claims 1 to 9, characterized in that the soda-free particles have a Klumpptestwert of ≥ 0 g and ≤ 50 g, preferably ≤ 20 g, preferably ≤ 10 g and more preferably ≦ 1 g have. Soda-free particles according to one of claims 1 to 10, characterized in that for the soda-free particles of the Sedimentation test a value of ≥ 0 ml and ≤ 5 ml, preferably ≥ 0.01 ml and ≤ 3 ml, preferably ≥ 0.05 ml and ≤ 2 ml and more preferably ≦ 0.1 ml. Soda-free particles according to one of claims 1 to 11, characterized in that at least 10 wt .-%, preferably at least 30% by weight, preferably at least 50% by weight, more preferably at least 70% by weight and more preferably at least 90% by weight of the soda-free Particles as primary soda-free particles, based on the total weight of soda-free Particles, present; and / or at least 50% by weight, preferably at least 40% by weight, preferably at least 30% by weight, more preferably at least 20% by weight and more preferably at least 10% by weight of the soda-free particles as a secondary soda-free particles, based on the total weight of soda-free Particles are present. Soda-free particles according to one of claims 1 to 12, characterized in that the soda-free particles in a Water temperature of 10 ° C a release time of a maximum of 300 seconds, preferably a maximum of 60 seconds and / or at a water temperature of 30 ° C a release time of a maximum of 90 seconds, and preferably of a maximum of 10 seconds. Soda-free particles according to one of claims 1 to 13, characterized in that 1 g of the soda-free particles residue behavior in 200 ml at 10 ° C tempered tap water with 15 ° d of ≥ 0% and ≤ 10%, preferably ≥ 0.01% and ≤ 5%, preferably ≥ 0.05% and ≤ 1% and especially preferably ≥ 0.075% and ≤ 0.5% exhibit. Soda-free particles according to one of claims 1 to 14, characterized in that 1 g of soda-free particles residue behavior in 200 ml at 30 ° C tempered tap water with 15 ° d of ≥ 0% and ≤ 8%, preferably ≥ 0.005% and ≤ 4%, preferably ≥ 0.01% and ≤ 1% and especially preferably ≥ 0.05% and ≤ 0.1% exhibit. Soda-free particles according to one of claims 1 to 15, characterized in that - 1 wt .-% of the soda-free particles have a particle diameter of ≥ 1.6 mm, - ≥ 10 wt .-% to 30 wt .-%, preferably ≥ 15 wt .-% to 25 wt .-% and preferably ≥ 19 wt % to 20 wt .-% of soda-free particles have a particle diameter of ≥ 0.8 mm, - ≥ 30 wt .-% to 45 wt .-%, preferably ≥ 35 wt .-% to 40 wt .-% and preferably ≥ 37 wt .-% to 39 wt .-% of soda-free particles have a particle diameter of> 0.4 mm, - ≥ 25 wt .-% to 40 wt .-%, preferably ≥ 30 wt .-% to 35 wt. % and preferably ≥ 33 wt .-% to 34 wt .-% of soda-free particles have a particle diameter of> 0.2 mm, - ≥ 1 wt .-% to 15 wt .-%, preferably ≥ 5 wt .-% to 10 Wt .-% and preferably ≥ 6 wt .-% to 8 wt .-% of soda-free particles have a particle diameter of> 0.1 mm, and - 0 wt .-% to 2 wt .-%, preferably ≤ 1 wt. % of the soda-free particles have a particle diameter of ≤ 0.1 mm, based on the total weight of the soda-free particles, wherein the jewe iligen parts by weight of soda-free particles are chosen so that together make up a maximum of 100 wt .-%. Soda-free particles according to one of claims 1 to 16, characterized in that the soda-free particles have a whiteness Y from ≥ 90, preferably of ≥ 90.8 and preferably ≥ 90.9 exhibit. Soda-free particles according to one of claims 1 to 17, characterized in that the nonionic surfactant and / or perfume part in wt .-%, based on the total weight of the perfume and / or Nonionic surfactant loaded soda-free particles, on the outer surface of the soda-free particles ≥ 0 Wt .-% to at most 1 wt .-%, preferably ≥ 0.01 wt .-% to 0.5 wt .-% and preferably ≥ 0 Wt .-% and ≤ 0.02 Wt .-% makes up. Soda-free particles according to one of claims 1 to 18, characterized in that at least one silicate of the carrier material selected is from the group comprising amorphous sodium silicates, aluminosilicates, in particular zeolites, preferably zeolite A, zeolite P and / or Zeolite X, swellable Phyllosilicates, preferably montmorillonites, in particular bentonite. Soda-free particles according to one of claims 1 to 19, characterized in that at least one polymer of the carrier material a homopolymer, especially polycarboxylate or a copolymer is, selected is from the group comprising acrylic acid with methacrylic acid, acrylic acid or methacrylic acid with maleic acid, wherein the polymer preferably has a molecular weight of 500 g / mol to 20,000 g / mol and preferably 1,000 g / mol to 10,000 g / mol. Soda-free particles according to one of claims 1 to 20, characterized in that at least one soap of the carrier material selected is from the group comprising saturated Fatty acid soaps, in particular salts of lauric acid, myristic, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, preferably soap / s of natural fatty acids, especially coconut, palm kernel or tallow fatty acids, derived soap mixtures, the soaps are preferably in the form of their sodium, potassium and / or Ammonium salts and as soluble Salts of organic bases, such as mono-, di- or triethanolamine, are present. Soda-free particles according to one of claims 1 to 21, characterized in that at least phosphate of the carrier material selected is from the group comprising pentasodium triphosphate, pyrophosphates, Orthophosphates, alkali metal phosphates, especially sodium and Potassium salts of various phosphoric acids. Soda-free particles according to one of claims 1 to 22, characterized in that at least one nonionic surfactant is selected from the group comprising alkoxylated fatty alcohols, alkyl glycosides, fatty acid alkyl ester and / or amine oxides, wherein alkoxylated fatty acid alkyl esters, ethoxylated fatty acid alkyl ester or ethoxylated and propoxylated fatty acid alkyl esters are preferred. Soda-free particles according to one of claims 1 to 23, characterized in that at least one perfume is selected from the group comprising perfume (s) with green note notes, Citrus notes, Lavender notes, Flowery notes, Aldehyde notes, Chypre notes, Fougere notes, spice notes, Oriental notes, wood notes, tobacco notes, leather notes and / or metal notes. Soda-free particles according to any one of claims 1 to 24, characterized in that at least one perfume is selected from the group comprising: - essences of fruits, fruit parts and / or other parts of plants, preferably herbs, drugs, essential oils derived therefrom, preferably terpene-free oils; and / or - artificial essences, preferably of synthetic odorants and / or flavoring agents, especially preferably vanillin, menthol, biacetyl and / or eucalyptol; and / or aromas, preferably essential oils, aniseed oil, star aniseed oil, bitter almond oil, eucalyptus oil, fennel oil, peppermint oil, lemon oil, wintergreen oil, clove oil, menthol and / or caraway oil; and / or synthetic fragrance compounds of the ester type, preferably 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 / or benzyl salicylate; and / or synthetic fragrance compounds of the ether type, preferably benzyl ethyl ether; and / or - synthetic fragrance compounds of the aldehyde type, preferably linear alkanals of 8-18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and / or bourgeonal; and / or - synthetic fragrance compounds of the ketone type, preferably ionone, isomethylionone and / or methyl cedryl ketone; and / or synthetic fragrance compounds of the alcohol type, preferably anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and / or terpineol; and / or synthetic fragrance compounds of the hydrocarbon type, preferably terpenes, preferably limonene and pine; and / or - natural fragrance mixtures from plant sources, preferably pine, citrus, jasmine, patchouly, rose or ylang-ylang oil, muscatel, sage oil, chamomile oil, clove oil, balm oil, mint oil, cinnamon leaf oil, lime blossom oil, juniper berry oil, Vetiver oil, olibanum oil, galbanum oil, labdanum oil, orange blossom oil, neroliol, orange peel oil and / or sandalwood oil; and / or - metallic fragrance compounds comprising oxacyclododecan-2-one, 4,5-decamethyleneoxazole, Sclarene, derivatives thereof and / or precursors thereof, wherein the derivatives are preferably in the form of esters and / or ethers. Mixture comprising discrete soda-free particles after one of the claims 1 to 25 and discrete soda-containing particles. Mixture according to Claim 25, characterized that the soda-containing particles have no nonionic surfactant and / or perfume. Mixture according to Claim 26 or 27, characterized in that the soda-containing particles have at least one anionic surfactant. Mixture according to one of Claims 26 to 28, characterized that the soda-containing particles ≥ 0 Wt .-% and ≤ 25 Wt .-% anionic surfactant, preferably ≥ 1 Wt .-% and ≤ 20 % By weight of anionic surfactant, more preferably ≥5% by weight and ≤17% by weight. Anionic surfactant, and most preferably ≥10% by weight and ≤15% by weight of anionic surfactant, based on the total weight of the soda-containing particles. Mixture according to one of Claims 26 to 29, characterized that the proportion by weight of the soda-free particles, based on the Total weight of the mixture, at least> 0 wt .-% to a maximum of 25 wt .-%, preferably 1 wt .-% to 22 wt .-%, preferably 3 wt .-% to 20 wt .-%, more preferably from 5% to 18%, and most preferably 10%, by weight to 15 wt .-% makes up. Mixture according to one of Claims 26 to 30, characterized that the soda-containing particles at least one, preferably a plurality Have components selected from the group comprising washing, care and / or cleaning active Substances, in particular anionic surfactants, cationic surfactants, amphoteric 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, fabric softeners, foam inhibitors and / or rinse aid, and optionally further admixed ingredients. Mixture according to one of Claims 26 to 31, characterized that the soda-containing particles and / or soda-free particles with at least one component after-treated, wherein the component quantity preferably up to 10% by weight, in particular 1% by weight to 5% by weight, in each case based on the total weight of the aftertreated particles, accounts. Mixture according to one of claims 26 to 32, characterized in that the mixture, the soda-free particles to soda-containing particles in a weight ratio of 1: 10 to 10: 1, preferably 1: 8 to 8: 1, preferably 1: 6 to 6: 1 and more preferably 1: 5 to 5: 1 and most preferably the soda-free ones Particles containing soda-containing particles in a weight ratio of 1: 3 to 3: 1. Finished product comprising particles or particle mixtures according to one of the claims 1 to 33, characterized in that the finished product is a detergent, a cleaning agent for hard and / or soft surfaces, a stainless steel cleaner, a household cleaner, an oven cleaner, a conditioner, a laundry detergent, a laundry care product, a fragrance, a hair treatment composition, a hair dye, a conditioner, a fabric softener, a conditioning substrate, a drug, a pesticide, a food, a cosmetic, a fertilizer, a building material, a Glue, a bleach, a disinfectant and / or a Preproduct of the aforementioned finished products. Finished product according to claim 34, characterized that the finished product in addition to the particles or particle mixtures according to one of claims 1 to 33 has at least one, preferably a plurality of components selected from the group comprising as washing, care and / or cleaning active Substances anionic surfactants, cationic surfactants, amphoteric surfactants, Builders, bleaches, bleach activators, bleach stabilizers, Bleach catalysts, enzymes, polymers, cobuilders, alkalizers, Acidifiers, anti redeposition agents, silver protectants, dye, optical brighteners, UV protectants, fabric softeners, foam inhibitors and / or rinse aid, and optionally further admixed ingredients. Finished product according to claim 34 or 35, characterized characterized in that the finished product, in particular washing, cleaning, and / or ready-to-use product, at least 1% by weight and at most 30% Wt .-%, preferably at least 25 wt .-%, preferably at least 20% by weight, more preferably at least 15% by weight, even more preferably at least 12% by weight and most preferably at least 10% by weight soda-free particles according to any one of claims 1 to 26, based on the Total weight of the finished product, wherein the respective Weight shares chosen are that together make up a maximum of 100 wt .-%. Process for the preparation of soda-free particles containing nonionic surfactant and / or perfume according to one of claims 1 to 25, comprising the steps: - Production of finely divided soda-free carrier, - application at least one nonionic surfactant and / or at least one perfume; in which the soda-free particles absorb the nonionic surfactant and / or perfume. Process for the preparation of soda-free particles containing nonionic surfactant and / or perfume according to claim 37, wherein said soda-free carrier an oil number, based on the absorption of hexane, of at least 100 ml / 100 g, preferably at least 200 ml / 100 g, more preferably at least 250 ml / 100 g, more preferably at least 300 ml / 100 g and most preferably from 350 ml / 100 g to a maximum of 400 ml / 100 g have. Soda-free particles according to claim 37 or 38, characterized characterized in that 0 wt .-% of the soda-free carrier has a particle diameter of ≥ 1.6 mm, - 0 % By weight of the soda-free carrier a particle diameter of ≥ 0.8 mm, - ≥ 0% by weight to 25 wt .-%, preferably ≥ 0.5 Wt .-% to 20 wt .-% and preferably ≥ 1 wt .-% to 18 wt .-% of soda-free carrier a particle diameter of <0.4 mm to 0.2 mm, - ≥ 60% by weight to 80% by weight, preferably ≥ 63 Wt .-% to 75 wt .-% and preferably 66 wt .-% to 70 wt .-% of soda-free carrier a particle diameter of <0.2 mm to 0.1 mm, - ≥ 0% by weight to 5 wt .-%, preferably ≥ 1 Wt .-% to 4 wt .-% and preferably ≥ 2 Wt .-% to 3 wt .-% of soda-free carrier a particle diameter of <0.1 mm on the total weight of the soda-free carrier, wherein the respective Parts by weight of the soda-free carrier are chosen so that these together make up a maximum of 100 wt .-%.