WO2007118733A1 - Washing or cleansing agent granulates - Google Patents

Abstract

The method for the manufacture of washing or cleansing agents is described in which a refined shell material is granulated onto core material whereby the raw materials used in the granulation stage are at least partially passed through a mill drying unit. The diameter of the product, the core material, and the shell material coming from the mill drying stage preferably stand in a specific relationship to each other. The resulting end products of the manufacturing process are aesthetically pleasing and very stable in storage.

Description

 "Detergent or cleaning agent granules"

The present invention relates to a process for the preparation of detergents or cleaners, in which a finer shell material is granulated onto a particulate core material, wherein the raw materials entering the granulation stage are passed at least partially through a grinding drying plant.

Granulation processes are state of the art in a wide variety of industries, and there are a large number of standard monographs and patent literature on this subject. In the context of the present invention, it is important that an important contribution to product design can be made via the granulation process.

Due to the enormous variety of goods offered for all the needs of everyday life, the consumer is often faced with the problem of choosing from a variety of products that is almost unimaginable just what suits his needs the most. Here, product design can make it easier for the consumer to make a purchase decision.

The purchase decision is generally based on very different criteria, but above all on the price of the presented goods and their quality. As an additional criterion for the purchase decision, however, product design is becoming increasingly important. Consumers usually want to use a product that also appeals to their aesthetic sensibilities. For this reason, many products are equipped with visually appealing packaging. The product itself is also of great interest, for example with regard to its color and shape. About the shape of the product, the aesthetic sensibility of consumers can be particularly easily addressed, which is especially true for powdered detergents and / or cleaning products. A visually very appealing product from this area is, for example, a detergent powder which consists exclusively of almost spherical particles. Due to its high symmetry and homogeneous appearance in the eyes of the consumer, such a detergent powder of almost identical and almost spherical particles indicates great care in the preparation and high competence in the processing of the washing powder, whereas a powder consisting of very irregularly shaped particles exists, the consumer does not trigger corresponding positive associations.

Against this background, the object of the present invention was to provide aesthetically pleasing granules. This object is achieved by the subject matter of the invention, which is a process for the production of detergents or cleaners, in which a finer shell material is granulated onto a particulate core material, wherein the raw materials to be used in the granulation stage at least partially by a Mahltrocknungsanlage be guided.

The mill-drying should advantageously serve to reduce the mean grain diameter and the partial drying of the shell material in question. According to a preferred embodiment, the core material is not subjected to grinding drying.

The shell material can be obtained from suitable raw materials and / or from recycled material of the granulation process. Preferably, a mixture of both components is used. The recycling material in question comes from a screening after granulation and optional drying and consists of the undersize and / or the oversize. Both can be subjected to grinding drying and used as a shell material.

Suitable solid raw materials for both the core and shell materials are e.g.

(A) builders, such as preferably zeolite (compounds), polycarboxylate (compounds), Na acrylic / maleic acid copolymer, nitrilotriacetic acid, ethylenediaminetetraacetic acid or their sodium salts

(b) carbonates, such as preferably soda,

(C) hydrogencarbonates, in particular alkali metal and / or alkaline earth metal hydrogencarbonates

(d) sulfates, especially alkali and / or alkaline earth sulfates

(e) builders such as silicates and phosphates, e.g. Na silicate, soda silicates, disilicates, tripolyphosphate, phyllosilicates

(f) anionic surfactant compounds (including, for example, fatty alcohol sulfates, alkylbenzenesulfonates, alkanesulfonates, alkyl ether sulfates, alkyl sulfates, α-olefin sulfonates and / or ester sulfonates, in particular methyl ester sulfonates, and / or mixtures thereof), soaps

(g) bleach activators, in particular N, N, N ', N'-tetraacetylethylenediamine,

(c) citrates, preferably alkali metal and / or alkaline earth metal citrates, in particular sodium, potassium and / or magnesium

Citrates, and / or citric acid (i) tower powders or spray drying products,), e.g. containing mixtures thermally stable

Ingredients of detergents or cleaners (j) polymers, such as in particular cellulose ethers (derivatives) or, preferably, linear hydrophilic polyethylene terephthalate-polyoxyethylene terephthalate block copolymers (PET-POET polymers),

(k) antifoam powder, preferably comprising substances such as natural fats and / or oils, petroleum derivatives and / or silicone oils

(I) fabric softener, bentonites, esterquat compounds

(m) discoloration inhibitors (PVP, etc.)

Typical and preferred (liquid) components which may enter or be included in the granulation aids are or may include e.g. Nonionic surfactants (ethoxylates, APG), anionic surfactant acids / pastes, cationic compounds / surfactants, phosphonates, phosphonic acids, Sokalan (maleic acid acrylic acid copolymer sodium salt (30:70)) solution, fatty acids, caustic soda, water glass, silicones, skin care oils.

Typical and preferred (liquid) components for an optional coating layer of the granules may be e.g. Zeolite powder, shell material, powder, nonionic surfactant, water, PEG, glycerin, buffer system for pH adjustment, e.g. Citric acid / citrate, dye solution, mica, iridescent and / or shiny substances.

The optionally coated granules may finally be treated with zeolite powder and / or

Shell material to be recycled.

As separate admixing components for the optionally coated granules, bleaching agents, e.g. Percarbonate, bleach enhancers, enzymes are added.

The core material can be obtained, for example, by screening out of the raw materials or materials to be used. It is also possible and preferred to screen out from the granules produced in size suitable particles which are to be reused as core material. The core material is thus preferably sieved (e) raw material (s), recirculated, sieved granules originating from the process, having a suitable size for use as core material or mixtures of both. In order that the granulation process with regard to grain quality and particle size distribution can proceed advantageously within the intended time frame, a core material must be submitted. As our experiments show, preferably at least 3 to 5 wt .-% core material, based on the granules, be present. More preferably 10 to 35 wt .-%, in particular 15 to 25 wt.% Core material, based on the granules. More than 35% by weight of core material is not necessary, although the method also allows higher than 35% by weight, even more than 50% by weight.

The process product advantageously has a diameter d ₅₀ which is at least 5% and at most 66% greater than the diameter d _{50 of} the core material and at least fifteen times the average diameter (d ₅₀ ) of the shell material originating from a grinding drying stage. With the method according to the invention, the average diameter of the products can be adjusted in a controlled manner.

Due to the special nature and guidance of the granulation, which is a build-up granulation, very round particles can be produced. In this case, preferably the raw materials, which are part of the shell material, finely ground. This is preferably done together with recirculated oversized and undersized grain of the process (recycled material) in a grinding drying stage. The good grain can then be refined by applying further solid and / or liquid substances (shell material).

If both sifted undersize and oversized particles are subjected to a grinding drying process after the granulation / drying step and returned to the process as part of the shell material, then a preferred embodiment is present.

Likewise, a preferred embodiment is present when the product stream is screened from the product flow and / or undersize and then fed into the process as core material.

In the granulation stage, the build-up granulation takes place, in which the fine shell material is preferably adhered to a preferably screened core material with preferably one or more rolling movements with the addition of one or more granulation aids. The built-up granulation preferably runs at Froude numbers of 1.5 to 25, advantageously from 2 to 15, more preferably from 2 to 10, more preferably from 2.5 to 8, in particular from 2.5 to 4 in the desired manner from. Particularly with these Froude numbers, particularly beautiful, round granules are obtained. The Froude number is given by the relation (w ² - r) / g (w = angular velocity, r = length of the tools from the central axis, g = acceleration due to gravity).

This type of granulation can be easily controlled via the operating parameters so that the product has a diameter d ₅₀ which is at most 66% greater than the diameter d _{50 of} the core material and at least fifteen times the average diameter (d ₅₀ ) of the mill drying stage originating shell material.

Granulation aids used are preferably one or more granulation liquids, for example neutralized surfactant and / or builder acids, complexing liquid (s) (for example containing phosphonates such as HEDP etc.), solution (s) of natural and / or synthetic polymers, water glass solution (s) , Anionic surfactant pastes and nonionic surfactants, salt solutions.

Foaming agents may preferably also be used as granulating aids.

A process according to the invention in which several, chemically distinguishable granulation aids are added simultaneously or preferably in succession, preferably in the form of solutions, suspensions, dispersions, foams and / or (nano) emulsions, represents a preferred embodiment of the invention.

The milling process for providing the shell material is advantageously carried out in a mill drying stage. This simplifies the fluidized bed drying of the granules or it can be dispensed with in some cases entirely to this stage. The shell and recycling material is preferably conveyed with air into the mill. Here, at the same time, the grinding and the drying takes place. In particular, by a possible warming of the conveying air to preferably 30 to 120 ⁰ C, in particular 35 to 70 ⁰ C, the degree of drying of the shell material can be adjusted specifically. The feed air may also have a minimum temperature of eg 40 ° C, 42 ° C, 44 ° C, 46 ° C, 48 ° C, 50 ⁰ C, 52 ° C, 54 ° C, 56 ° C, 58 ° C or 60 ⁰ C have. It is also possible that the conveying air has a maximum temperature of 68 ° C, 66 ° C, 64 ° C or 62 ° C. Accordingly, the conveying air may, for example, also assume values of 42 ° C. to 64 ° C. or values corresponding to another possible combination of previously mentioned temperatures. It is also possible that conveying air is used, which was not heated. The mill-drying is particularly effective for the recirculated material (recycled material from undersize and oversize granulation), which before the mill drying, a residual moisture content of preferably about 8 to 11 wt .-% and then preferably about 4 to 8 wt .-% may have , Wt .-% based on the material.

In granulation, the advantage of the dried-on-dried particles can be optimally utilized, in particular by the use of a high-viscosity granulation auxiliary, since such remains on the (large) surface and hardly penetrates. Therefore, in addition to the possibility of spraying granulation liquid (s), preferably limited to granulation aids having maximum viscosities of about 500 mPas, the method is particularly advantageous when using highly viscous (viscosity preferably> 1000 mPas).

(a) granulation foams

(B) highly viscous liquids, suspension, paste, dispersion, which are preferably poured into the jet / pumped

(c) high viscosity granulation aids pumped around a mill / chopper.

A preferred embodiment is working with several granulation aids, which are at different locations (continuous process) or at different times (batch process).

Process) are added. Preferably, 2, 3, 4 or more granulation aids are usable, e.g. when

Granulation Aid 1: Neutralized acids, e.g. as a foam,

Granulation agent 2: water glass as a highly viscous liquid (viscosity preferably> 1000 mPas), Granulation assistant 3: polymer solution, likewise as highly viscous liquid (viscosity preferably> 1000 mPas),

Granulating agent 4: (nano) emulsion, preferably as a low-viscosity liquid (viscosity advantageously <250 mPas, preferably <75 mPas, in particular <10 mPas). Viscosities measured in each case with the Brookfield viscometer at 25 ^° C.

When 0.05 to 6 wt .-%, preferably up to 5 wt .-%, advantageously up to 4 wt .-%, in a further advantageous manner to 3 wt .-% of water are removed in the mill-drying stage, based on the shell material, so is a preferred embodiment of the invention. It is also possible that larger amounts of water are removed, e.g. to 10% by weight or to 15% by weight.

The average particle size of the granulate which can be produced by the method according to the invention can be adjusted within wide limits because it can be essentially determined by the grain size of the core material. Fine, dust-free products preferably have a d ₅₀ of 0.25 to 0.30 mm. Here, advantageously core materials in amounts of preferably about 10 to 25% in size d ₅₀ of preferably 0.2 to 0.28 mm should be submitted. For relatively coarse products with a d ₅₀ of preferably 1.5 mm, it is preferable to use core materials having a d ₅₀ of about 1.0 to 1.4 mm. The exact value then depends in particular on the amount of shell material and on the guidance of the granulation. The correct screening of the core material has to be determined beforehand through some routine tests in the technical center.

d ₅₀ represents the median value. The median value is defined as the particle size below and above which in each case 50% of the particle quantity lie. Correspondingly, at d _90, 90% of the particle quantity is below the value, ie 10% higher. The ratio d ₅ o / d ₉ o approaches the value of 1 for very narrow particle size distributions, or is well below 0.5 for broad distributions.

Advantageously, the inventive method provides almost spherical and preferably also very abrasion-resistant granules with a very uniform particle size, which can be set very accurately on the selection of the size of the starter grain (particulate core material). It can thereby produce high-quality granules with specific determination of the granule size. The granules obtainable according to the invention are storage-stable. Advantageously, the process according to the invention is energy-efficient in comparison to the usual tower processes (spray-drying). The inventive method also allows by the core-shell concept, a large variety of products and offers the possibilities of so-called "controlled release", for example, by integrating into the shell those components which are to be released first and the later release substances in the In addition, a granulate obtainable in this way can still be provided with a coating.

For the actual granulation, a conventional mixer / granulator can be used. By the term mixer / granulator is meant preferably drum and plate mixers and / or fluidized bed granulators, but also single- and two-shaft mixers with fast to slow rotating shafts and Zig-Zag mixers, especially discontinuous machines with low specific energy input. The particles in the mixer preferably move over the free fall or by introducing a thrust, throw or centrifugal force. Preference is given to using mixers in which the particles are set in rolling motion. The addition of a portion of the granulation liquid can be done before the granulator in a high speed mixer (CB, Schugi). It is also possible to complete the granulation in the fluidized bed with the addition of a residual amount of liquid. Mixers / granulators are described in detail in the relevant patent and specialist literature, in particular via mechanical process engineering. In the broadest sense, the term mixer / granulator means any machinery and apparatus suitable for mixing / granulating.

In a preferred embodiment, the granules which can be produced and subsequently coated by the process according to the invention are essentially dust-free.

According to a preferred embodiment of the invention, the granules which can be produced according to the invention have an average form factor of at least 0.78, preferably 0.81, advantageously 0.83, more preferably 0.85, more preferably 0.87, in particular 0.9 , More about the form factor and possibilities of its determination will be described below.

If the granules which can be produced according to the invention are present in a particle size distribution which is as uniform as possible, at which the ratio of d ₅₀ to d _{90 is} at least 0.5, preferably is at least 0.6, advantageously at least 0.75, in particular at least 0.8, so it is also a preferred embodiment of the invention

At a bulk density of the granules according to the invention in the range of 200-1500 g / l is also a preferred embodiment of the invention. The lower limit for the bulk density may also be at a value of preferably 250, 300, 350, 400, 450, 500, 550, 600, 650, 700 or even 750 g / L. It is also possible that the lower limit is even higher, e.g. at 800g / L. The process also makes it easy to adjust the bulk density, which is difficult for granules, using standard formulations in the range from 520 to 620 g / l.

The upper limit for the bulk density may be at a value of preferably 1450, 1400, 1350, 1300, 1250, 1200, 1150, 1100, 1050, 1000, 950, 900, 850, 800 or 750 g / L. It is also possible that the upper limit is even lower, e.g. at a value of preferably 700, 650, 600, 550 or 500 g / L.

According to a preferred embodiment of the invention, the granules which can be produced according to the invention have a surfactant content of at least 1% by weight, based on the total granules. According to a further preferred embodiment of the invention, the surfactant content is 1-99 wt .-%, preferably 1-95 wt .-%, advantageously 5-50 wt .-%, more preferably 10-40 wt .-%, in particular 15-30 Wt .-%, based on the total granules. However, according to another preferred embodiment, the lower limit of the surfactant content may also be given a value of e.g. preferably 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 Wt .-%, 11 wt .-%, 12 wt .-%, 13 wt .-%, 14 wt .-%, 15 wt .-%, 16 wt .-%, 17 wt .-%, 18 wt. %, 19 wt%, 20 wt%, 21 wt%, 22 wt%, 23 wt%, 24 wt%, 25 wt%, 26 wt% , 27 wt .-%, 28 wt .-%, 29 wt .-% or 30 wt .-%, each based on the total granules. In particular, the lower limit may even be at still higher values, e.g. at a value of e.g. preferably 35 wt .-%, 40 wt .-%, 45 wt .-%, 50 wt .-%, 55 wt .-% or 60 wt .-%, each based on the total granules.

According to a further preferred embodiment, however, the upper limit may also be at a value of, for example, preferably 70% by weight, 71% by weight, 72% by weight, 73% by weight, 74% by weight, 75% by weight. %, 76 wt%, 77 wt%, 78 wt%, 79 wt%, 80 wt%, 81 wt%, 82 wt%, 83 wt%, 84 wt.%, 85 wt.%, 86 wt.%, 87 wt.%, 88 wt.%, 89 wt.%, 90 wt.%, 91 wt.%, 92 wt .-%, 93 wt .-%, 94 wt .-% or 95 wt .-%, each based on the total granules. The lower limit may in particular even be at even lower values, for example, at a value of, for example, preferably 65% by weight, 60% by weight, 55% by weight, 50% by weight, 45% by weight, 40% by weight, 35% by weight, 30 Wt .-% or 25 wt .-% or even only at values such as 20 wt .-%, 15 wt .-% or 10 wt .-%, each based on the total granules.

According to a preferred embodiment of the invention, the granules which can be produced according to the invention have a builder content of at least 1% by weight, based on the total granules. According to a further preferred embodiment of the invention, the builder content of the granulate is 1-99 wt .-%, preferably 1-95 wt .-%, advantageously 5-90 wt .-%. even more advantageously 10-70 wt .-%, more preferably 20-60 wt .-%, based on the total granules, in particular 25-50 wt .-%. However, according to another preferred embodiment, the lower limit of the builder content may also be given a value of e.g. preferably 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 Wt .-%, 10 wt .-%, 11 wt .-%, 12 wt .-%, 13 wt .-%, 14 wt .-%, 15 wt .-%, 16 wt .-%, 17 wt. %, 18 wt%, 19 wt%, 20 wt%, 21 wt%, 22 wt%, 23 wt%, 24 wt%, 25 wt% , 26 wt .-%, 27 wt .-%, 28 wt .-%, 29 wt .-% or 30 wt .-%, each based on the total granules. In particular, the lower limit may even be at still higher values, e.g. at a value of e.g. preferably 35 wt .-%, 40 wt .-%, 45 wt .-%, 50 wt .-%, 55 wt .-% or 60 wt .-%, each based on the total granules.

However, according to another preferred embodiment, the upper limit may also be set at a value of e.g. preferably 70% by weight, 71% by weight, 72% by weight, 73% by weight, 74% by weight, 75% by weight, 76% by weight, 77% by weight, 78 Wt%, 79 wt%, 80 wt%, 81 wt%, 82 wt%, 83 wt%, 84 wt%, 85 wt%, 86 wt% %, 87 wt%, 88 wt%, 89 wt%, 90 wt%, 91 wt%, 92 wt%, 93 wt%, 94 wt% or 95 wt .-%, each based on the total granules. In particular, the lower limit may even be at even lower values, e.g. at a value of preferably 65 wt .-%, 60 wt .-%, 55 wt .-%, 50 wt .-%, 45 wt .-%, 40 wt .-%, 35 wt .-%, 30 wt. -% or 25 wt .-% or even only at a value of 20 wt .-%, 15 wt .-% or 10 wt .-%, each based on the total granules.

According to a preferred embodiment of the invention, each individual granulate which can be produced according to the invention contains a complete detergent or cleaning agent formulation, advantageously with the exception of the enzymes, the foam inhibitor granules and the bleaching agents, in particular percarbonate.

According to a preferred embodiment of the invention, each individual granulate which can be produced according to the invention comprises at least 2, preferably at least 3, advantageously from at least 4, in a further advantageous manner from at least 5, more advantageously from at least 6, even more advantageously from at least 7 and in particular from at least 8 or more chemically distinguishable substances.

According to a preferred embodiment of the invention, the granules which can be produced according to the invention have a content of at least 0.5% by weight, based on the total granules, of sodium citrate.

According to a preferred embodiment of the invention, the granules which can be prepared according to the invention have a content of at least 1% by weight, based on the total granules, of polycarboxylates (polymer and / or copolymer).

According to a preferred embodiment of the invention, the granules which can be produced according to the invention have a free water content of 0-15% by weight, based on the total granules. The upper limit of water may e.g. also at 14 wt%, 13 wt%, 12 wt%, 11 wt%, 10 wt%, 9 wt%, 8 wt%, 7 wt%, 6 wt .-%, 5 wt .-%, 4 wt .-%, 3 wt .-%, 2 wt .-% or 1 wt .-%, based on the total granules on.

According to a preferred embodiment of the invention, the granules which can be produced according to the invention have a perfume content of at least 0.05% by weight, based on the total granules. According to a further preferred embodiment of the invention, the perfume content of the granules 0.1-30 wt .-%, preferably 1-25 wt .-%, advantageously 5-22 wt .-%, in particular 10-20 wt .-%.

According to a preferred embodiment of the invention, the granules produced according to the invention are enzyme-free, which means for the purposes of the invention that the granules less than 30 wt .-%, preferably less than 25 wt .-%, advantageously less than 20 wt .-%, in more advantageously less than 15% by weight, more preferably less than 10% by weight, and in a further advantageous manner less than 5% by weight of enzymes, based on the total granules. In particular, however, the granules are completely enzyme-free, ie they contain 0% by weight of enzyme, based on the total granules.

According to a preferred embodiment of the invention, the granules are bleach-free. According to a preferred embodiment, the product of the process according to the invention has a diameter d ₅₀ which is advantageously at most 64%, 62%, 60%, 58%, 56%, 54%, 52%, 50%, 48%, 46%, 44 %, 42%, 40%, 38%, 36%, 34%, 32%, 30%, 28%, 26%, 24%, 22%, 20%, 18%, 16%, 14%, 12% or 10% larger than the diameter d _{50 of} the core material.

According to a further preferred embodiment, the product of the process according to the invention should have a diameter d ₅₀ which is advantageously at least 6%, 8%, 10%, 12%, 14%, 16%, 18%, 20%, 22%, 24%, 26%, 28% or 30% greater than the diameter d _{50 of} the core material.

Accordingly, the product may, for example, have a diameter d ₅₀ which, for example, is 6-64%, or for example 10-58%, or for example 20-44%, greater than the diameter d _{50 of} the core material. Here, the aforementioned upper and lower limits can be combined accordingly.

According to a further preferred embodiment, the product of the method according to the invention has a diameter d ₅₀ , which advantageously at least 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29 or 30 times the average diameter (d ₅₀ ) of the shell material is.

It also corresponds to a very preferred embodiment of this invention, when the shell material, which is grafted onto the core material, at least partially, in particular in its entirety, emerged from a grinding drying process.

An inventive Mahltrocknungsprozess takes place advantageously in a tube, impact, pen, vibrating, hammer, air jet or roller mill, but preferably in a fluidized air mill, in particular in a working with carrier gas mill with rotating grinding plates. Such mills are known to those skilled in the art. If in the grinding drying process air or another carrier grass having a temperature between 15 and 220 ⁰ C, preferably between 25 and 120 ⁰ C, in particular between 35 and 70 ⁰ C is used, so again is a preferred embodiment. , The minimum temperature of the carrier gas (eg air), for example, advantageously even at 21 ⁰ C, 22 ° C, 23 ° C, 24 ° C, 25 ° C, 26 ° C, 27 ° C, 28 ° C, 29 ° C, 30 ⁰ C, 31 ⁰ C, 32 ° C, 33 ° C, 34 ° C, 36 ° C, 37 ° C, 38 ° C, 39 ° C, 40 ⁰ C, 41 ⁰ C, 42 ° C, 43 ° C , 44 ° C, 45 ° C, 46 ° C, 47 ° C, 48 ° C, 49 ° C or 50 ⁰ C. However, temperatures above room temperature, that is advantageously greater than 22 ° C., are preferred. Particularly preferred are temperatures from 35 ° C. The maximum temperature of the carrier gas (eg air) can advantageously also, for example, at 210 ⁰ C, 200 ⁰ C, 190 ° C, 180 ⁰ C, 170 ° C, 160 ° C, 150 ⁰ C, 140 ° C, 130 ° C, 110 ⁰ C, 100 ° C, 90 ° C, 80 ⁰ C, 70 ° C or 60 ° C.

Advantageously, the core material entering into the process according to the invention is present in a particle size distribution which is as uniform as possible, in which the ratio of d ₅₀ to d _{90 is} preferably at least 0.50. The ratio of d ₅₀ to d ₉₀ may advantageously also be, for example, at least 0.60, 0.65, 0.70, 0.75, or 0.80.

In a further preferred embodiment, in the granulation downstream, optional drying step between 0.1 and 6 wt .-%, preferably up to a maximum of 5 wt .-%, advantageously up to 4 wt .-%, in a further advantageous manner to a maximum 3 wt .-%, in still more advantageous manner to a maximum of 2 wt .-%, in particular to at most 1 wt .-% water removed, the wt .-% is based on the granules after drying.

It is also possible to completely dispense with the subsequent drying step. In a preferred embodiment, a tower process is not part of the process.

If the granulation stage consists of at least one mixer and one fluidized bed, then there is a preferred embodiment.

If the granulation stage consists of a fast and a low-speed mixer and a fluidized bed, so is also a preferred embodiment.

For the purposes of the invention, it is highly preferred if the undersize resulting from the process, as well as the oversize particles, are subjected to a grinding drying process after the granulation and optional drying step and returned to the process as shell material. This leads to particularly high-quality, abrasion-resistant products and corresponds to a particularly preferred embodiment. Under- or oversize grains are those granules called smaller or larger than the so-called good grain. The good grain, however, has the desired granule size. Accordingly, if both sifted undersize and oversized grains are subjected to a grinding drying process after the granulation / drying step and returned to the process as part of the shell material, then a preferred embodiment of the invention is provided.

According to a further preferred embodiment, after the granulation and optional drying step, it is possible to sift out the product stream from the product stream and to reuse it as core material. This, too, corresponds to a preferred embodiment. Thus, if the product and / or undersize particles are removed from the product stream and then fed into the process as core material, then a preferred embodiment is present.

Various granulating aids can be used in the process according to the invention, namely e.g. Liquids in the broadest sense, preferably suspensions, dispersions, emulsions, as well as foams.

A foam is, as one skilled in the art knows, not a liquid, but a structure of gas-filled, spherical or polyhedral cells, which is bounded by liquid, semi-liquid, highly viscous or solid cell webs.

A granulation foam is obtained, for example, by applying a gaseous medium to a flowable component and thus foaming it up. A granulation foam is, for example, a surfactant foam which has been obtained by foaming a flowable, surfactant-containing component with a gaseous medium and can be used as a granulation aid. The granulation foam preferably has mean pore sizes below 10 mm, preferably below 5 mm and in particular below 2 mm. By using a granulation foam instead of conventional granulating liquids even more homogeneous liquid distributions can be achieved during the granulation process. It is preferred if at least one granulation foam and at least one granulation liquid are used in the granulation.

The granules to be granulated can be wetted even better and it may be required even less granulating liquid to form the granules when granulation foam is used. Furthermore, when using granulation foam, an even more homogeneous particle size distribution of the resulting granules is achieved. Possible dust and fines are bound even more effectively.

If the generation of foam (for the production of the granulation foam) takes place under a pressure which is above the pressure in the granulation plant, then there is a particularly advantageous embodiment. Preferably, the pressure during foam generation is at least 0.1 bar, advantageously at least 0.5 bar and in particular at least 0.85 bar above the pressure prevailing in the granulation plant.

Preferably, that flowable component, which is acted upon for foaming with a gaseous medium at 20 ⁰ C, a viscosity of 5 to 1500 mPas, preferably from 10 to 1000 mPas and in particular from 50 to 800 mPas.

Advantageously, the foaming liquid component may contain nonionic surfactant (s) and / or polymer (s) to promote foaming.

A flowable component to be foamed may advantageously contain one or more natural or synthetic polymer (s), which are preferably water-soluble; in particular, such water-soluble polymer (s) may be selected from: i) polyacrylic acids and their salts ii) polymethacrylic acids and their salts iii) polyvinylpyrrolidone, iv) vinylpyrrolidone / vinyl ester copolymers, v) cellulose, starch and guar ethers vi) Polyvinyl acetates, polyvinyl alcohols and their copolymers vii) graft copolymers of polyethylene glycols and vinyl acetate viii) alkylacrylamide / acrylic acid copolymers and their salts ix) alkylacrylamide / methacrylic acid copolymers and their salts x) alkylacrylamide / methylmethacrylic acid copolymers and their salts xi) alkylacrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers and their salts xii) alkylacrylamide / methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers and their

Salts xiii) alkylacrylamide / methylmethacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers and their salts xiv) alkylacrylamide / alkymethacrylate / alkylaminoethylmethacrylate / alkylmethacrylate copolymers and their salts xv) copolymers of xv-i) unsaturated carboxylic acids and their salts xv-ii) cationically derivatized unsaturated carboxylic acids and their salts xvi) acrylamidoalkyltrialkylammonium chloride / acrylic acid copolymers and their alkali metal and

Xvii) acrylamidoalkyltrialkylammonium chloride / methacrylic acid copolymers and their alkali metal and ammonium salts xviii) methacroylethylbetaine / methacrylate copolymers xix) vinyl acetate / crotonic acid copolymers xx) acrylic acid / ethylacrylate / N-tert.butylacrylamide terpolymers xxi) graft polymers of vinyl esters, esters of acrylic acid or methacrylic acid alone or in the

Mixture copolymerized with crotonic acid, acrylic acid or methacrylic acid with

Polyalkylene oxides and / or polyalkylene glycols xxii) graft copolymers obtained from the copolymerization of xxii-i) at least one nonionic-type monomer, xxii-ii) at least one ionic-type monomer, xxiii) by copolymerization of at least one monomer of each of the following three groups Copolymers: xxiii-i) esters of unsaturated alcohols and short-chain saturated carboxylic acids and / or esters of short-chain saturated alcohols and unsaturated carboxylic acids, xxiii-ii) unsaturated carboxylic acids, xxiii-iii) esters of long-chain carboxylic acids and unsaturated alcohols and / or esters of the carboxylic acids of the group d6ii) with saturated or unsaturated, straight-chain or branched C8-18-alcohols. xxiv) biopolymers, especially xanthan, carageenan agar etc.

Advantageously, a flowable component to be foamed, based on its weight, may contain from 0.1 to 40% by weight, preferably from 0.5 to 20% by weight and in particular from 1 to 10% by weight of polymer (e) and / or 0, 01 to 1 wt .-%, in particular nonionic (s) surfactant (s) included.

The amount of gas used for foaming may preferably be one to three hundred times, advantageously five to two hundred times, and in particular ten to one hundred times, the volume of the amount of flowable component to be foamed. For foaming, it is possible to use air, nitrogen or carbon dioxide as the gaseous medium.

The frothy flowable component may advantageously before the foaming temperatures of 15 to 120 ⁰ C, preferably from 25 to 90 ⁰ C and in particular from 50 to 75 ° C, have.

Preferably, a liquid component can be foamed and the resulting foam can then be combined with a foam produced from a further liquid component.

The foam may advantageously have temperatures below 115 ° C, preferably between 20 and 80 ⁰ C and in particular between 30 and 70 ⁰ C.

The foam may advantageously have a density below 0.80 ^"3 , preferably from 0.10 to 0.60 ^{" 3} and especially from 0.30 to 0.55 ^"3 .

The foam may advantageously have average pore sizes below 10 mm, preferably below 5 mm and in particular below 2 mm.

In the present invention, a neutralizing foam may be highly preferred, e.g. obtainable by combining an anionic surfactant in its acid form with a neutralizing agent and foaming to form a neutralizing foam, this foam advantageously having average pore sizes below 10 mm, preferably below 5 mm and in particular below 2 mm. The neutralizing agent may be solid or liquid.

A neutralizing foam may preferably be obtained by combining an anionic surfactant foamed with a gaseous medium in its acid form and a high-concentration, aqueous alkaline component foamed with a gaseous medium. The neutralizing foam can advantageously by combining an anionic surfactant in its acid form, optionally containing further, preferably acidic, ingredients of detergents and cleaners and a neutralizing agent, advantageously comprising substances from the group of carbonates and / or bicarbonates, preferably the alkali metal carbonates and / or alkali metal bicarbonates and in particular from the group sodium carbonate and / or sodium bicarbonate.

As aqueous alkaline component (neutralizing agent) may advantageously also alkali metal hydroxide, preferably sodium hydroxide solutions with concentrations of at least 40 wt .-% NaOH, preferably at least 50 wt .-% NaOH and in particular at least 65 wt .-% NaOH, each based on the foamed aqueous alkaline component used. The aqueous alkaline component may, prior to foaming, advantageously contain further ingredients of detergents and cleaners in amounts of from 0.1 to 80% by weight, preferably from 10 to 75% by weight and in particular from 25 to 70% by weight, in each case based on the weight of the mixture to be foamed, mixed. Surfactants, preferably anionic and / or nonionic surfactants, and in particular ethoxylated alcohols and / or soap, can be added to the aqueous alkaline component before foaming.

As anionic surfactant in acid form, one or more substances from the group of the carboxylic acids, the sulfuric monoesters and the sulfonic acids, preferably from the group of the fatty acids, the fatty alkyl sulfuric acids and the alkylaryl sulfonic acids, can advantageously be used. As anionic surfactant in acid form may preferably C ₈ . ₁₆ -, preferably C _9-13 - alkylbenzenesulfonic acids are used. The anionic surfactant in acid form before foaming other, preferably acidic ingredients of detergents and cleaners in amounts of 0.1 to 40 wt .-%, preferably from 1 to 15 wt .-% and in particular from 2 to 10 wt. %, in each case based on the weight of the mixture to be foamed mixed. The anionic surfactant in acid form before foaming nonionic surfactants in amounts of 0.1 to 40 wt .-%, preferably from 1 to 15 wt .-% and in particular from 2 to 10 wt .-%, each based on the weight of the foamed Mixture, to be mixed.

The neutralizing foam may advantageously have surfactant contents of from 10 to 99% by weight, preferably from 20 to 98% by weight and in particular from 30 to 97% by weight, based in each case on the weight of the foam. As granulation liquids and water or aqueous solutions can be used. However, it is preferred to avoid the use of water as such or water in solutions / dispersions / suspensions / emulsions, ie to manage with as little water as possible in the entire granulation.

Advantageously, other granulation aids than water, for example liquid nonionic surfactants, polyethylene glycols or other organic solvents can be used. Particularly preferred are granulation liquids, for example, salts, water glass, alkyl polyglycosides, carbohydrates, natural polymers, synthetic polymers, eg. Cellulose ethers, starch, polyethylene glycol, polyvinyl alcohol and / or biopolymers such as e.g. Containing xanthan gum. Also possible are organic solvents with swollen polymers. Melting of suitable substances is also possible.

If the granulating agent comprises a liquid of neutralized surfactant and builder acids, preferably with a water content of less than 10% by weight, advantageously less than 6% by weight, based on the granules, then again a preferred embodiment is present.

If, in addition to a granulation liquid (s), further hydrophilic and / or lipophilic granulating agents are present in the granulation step according to the invention as granulation auxiliary

Liquids and / or salts are incorporated, is also a preferred embodiment.

Hydrophilic liquids are known in the art. It is those that show a pronounced interaction with polar solvents, especially water. Typical hydrophilic groups are e.g. anionically charged carboxylate, sulfate and sulfonate as well as optionally substituted cationic ammonium functions or nonionic polyether chains (ethoxylate chains). Lipophilic fluids show a pronounced attractive interaction with fats (lipids). Lipophilic are, for example, the hydrophobic hydrocarbons.

A process according to the invention, in which the granulating aid comprises a solution of polymeric substances, preferably having a water content of less than 10%, preferably below 6% by weight, based on the granules, likewise represents a preferred embodiment.

If at least two different liquids are used as granulation aids, preferably in the form of suspension, dispersion and / or emulsion, which is preferably differ in their viscosity and / or their pH values, so again is a preferred embodiment.

A very preferred liquid for use as a granulation aid is a water glass solution. Another very preferred liquid for use as a granulation aid is a solution of polyacrylic acid sodium salt. According to the invention it is preferred to use as granulating both a water glass solution and a solution of polyacrylic acid sodium salt. According to the invention, it is also preferable to use a foam, preferably a neutralizing foam, in particular producible from acid, comprising advantageously fatty acids, alkylbenzenesulfonic acids and / or etidronic acid, as well as from an alkaline solution, preferably NaOH solution, as granulating auxiliary. In this case it is preferred if the acids, e.g. Fatty acids, alkylbenzenesulfonic acids and / or etidronic acid are mixed first and then combined with the alkaline solution.

Also, a method according to the invention, in which the total granulating a total of less than 12 wt .-%, preferably less than 10 wt .-%, advantageously less than 8 wt .-%, in particular less than 6 wt .-% water, based on the finished granules, represents a preferred embodiment. The granulation as such makes preferably at most 15 wt .-% based on the finished granules.

In a very particularly preferred embodiment, the granulation auxiliary comprises a liquid which contains skin care agents and / or textile care agents, in particular silicone oil.

Advantageously, the granulation aid may comprise solubilizer (hydrotrope). Typical hydrotropes are e.g. Xylene or cumene sulphonate or other substances, e.g. Urea or N-methylacetamide.

Skin care agents may, in particular, be those agents which give the skin a sensory benefit, e.g. by delivering lipids and / or moisturizing factors. Skin care agents may e.g. Proteins, amino acids, lecithins, lipids, phosphatides, plant extracts, vitamins; Likewise, fatty alcohols, fatty acids, fatty acid esters, waxes, petrolatum, paraffins can act as skin care agents. Fabric care agents are e.g. Fabrics for the care of textiles, e.g. Cationic surfactants.

The granules which can be produced according to the invention can be coated in a further step (coating). The optional coating layer (coating) results, for example, from anhydrous or low-water mixtures or suspensions, but may for example be water-containing even when drying, which corresponds in each case to a preferred embodiment. It is important that the coating is a preferred, but still only optional embodiment of the method according to the invention. This only optional character must be taken into account in the following explanations to advantageous embodiments of the coating.

It is preferred if the (optional) coating is applied without subsequent drying, which corresponds to a preferred embodiment.

According to another preferred embodiment, it may also be advantageous if the coating is followed by a post-drying.

The thickness of the (optional) coating is variably adjustable and is preferably in the range of the order of a monomolecular coverage up to 50 microns, but it is highly preferred if the coating thickness is significantly less than 5 microns.

According to a preferred embodiment, the coating applied is a liquid, preferably water-free, in particular anhydrous, liquid, advantageously containing surfactants, such as e.g. preferably nonionic surfactants, amphoteric surfactants and / or cationic surfactants, brighteners, triglycerides, terpenes, glycerol silicone oil, paraffin (oil), perfume, vitamin E, (co) polymer (solutions) and / or natural oils.

Such a liquid advantageously does not remain liquid on the surface of the granulate, but draws on the large surface of the shell material, created by the fine grinding, so that the surface of the granules is advantageously not wet or sticky. Very preferred here is nonionic surfactant, which is advantageously combined with other components. Preferred are e.g. the following combinations:

(a) nonionic surfactant, brightener, optional perfume

(b) nonionic surfactant, silicone oil, optionally paraffin (oil), optionally perfume

(c) silicone oil, whitener, optional perfume, optional nonionic surfactant

(d) nonionic surfactant, vitamin (derivative) such as preferably vitamin E, optional perfume

(e) nonionic surfactant, natural oils, optional perfume

(f) nonionic surfactant, vitamin (derivative), natural oils, optional perfume

(g) mixtures of various surfactants, such as betaines, nonionic surfactants and / or cationic substances.

Low-water means in this context that the coating liquid used contains less than 35 wt .-% water, based on the total coating liquid. In In this case preferred embodiments, this water content upper limit may also be at lower values, for example at a value of preferably 30 wt .-%, 25 wt .-%, 20 wt .-%, 15 wt .-%, 10 wt .-% or 5 wt % or between these values, ie for example at a value of preferably 9, 8, 7 or 6% by weight, based on the total coating liquid.

An anhydrous coating liquid contains a maximum of 4 wt .-%, advantageously at most 3 wt .-%, more preferably at most 2 wt .-%, preferably at most 1 wt .-% or in particular no water based on the total coating liquid. This corresponds to a preferred embodiment.

However, according to another preferred embodiment, the coating liquid may also contain larger amounts of water, that is more than preferably 35 wt .-%, based on the total coating liquid. In preferred embodiments, this minimum water content limit may also be at higher levels, e.g. at a value of preferably 40%, 45%, 50%, 55%, 60% or 65% or between these values, e.g. at a value such as 41, 42, 43 or 44% by weight. based on the entire coating liquid. A highly water-rich liquid, according to a preferred embodiment, may even have an even higher water content upper limit, e.g. with a value of preferably 70 wt .-%, 75 wt .-%, 80 wt .-%, 85 wt .-%, 90 wt .-% or 95 wt .-% water based on the total coating liquid.

According to a preferred embodiment, the (optional) coating contains (co) polymers, in particular water-soluble (co) polymers, optionally modified (co) polymers, such as e.g.

(A) synthetic polymers such as polyethylene glycols, polyvinylpyrrolidones, polyvinyl alcohols, homo- and copolymers of (meth) acrylic acid and its derivatives, the maleic, vinylsulfone, vinylphosphonic acid, polyethyleneimine and / or PAA

(b) naturally-based, optionally modified polymers, e.g. Starch, alginates, pectins, vegetable gums, caseins, gelatin guar, cellulose, cellulose ethers and / or starch ethers

(c) biotechnology. produced products such as e.g. Pullulan, Curdlan and / or Xanthan.

(d) mixtures of the aforementioned.

According to another preferred embodiment, a melt is applied as (optional) coating, preferably melting of (co) polymers, waxes, esters and / or fats. Such a melt advantageously remains on the surface of the granules no melt, but is advantageously solid after drawing and cooling, so that the surface of the granules is advantageously not sticky. The (optional) coating preferably comprises waxes. For waxing, the following may be preferred:

(a) vegetable waxes such as preferably carnauba wax, candelilla wax, espartowax, guaruma wax, Japan wax, cork wax, montan wax, ouricury wax, rice germ oil wax and / or sugarcane wax

(b) animal waxes such as preferably beeswax, rumen grease, wool wax, shellac wax and / or spermaceti

(c) mineral waxes such as preferably ceresin and / or ozokerite

(d) chemically modified waxes, preferably hard waxes, in particular hydrogenated jojoba waxes, montan ester waxes and / or sasol waxes

(e) synthetic waxes, such as preferably paraffin waxes (in particular soft paraffin with a melting point of> 38 ° C.), polyalkylene waxes and / or polyethylene glycol waxes

(F) microwaxes, so preferably higher melting ingredients of petroleum, which in particular consist of a mixture of saturated hydrocarbons (iso-alkanes) and advantageously still contain alkyl-substituted cycloparaffins and alkyl-substituted or naphthene-substituted aromatics, advantageously petrolatum, plastic microwaxes and Hartmikrowachse

(g) mixtures of vegetable waxes, animal waxes, mineral waxes, synthetic waxes, microwaxes and / or chemically modified waxes.

The (optional) coating preferably comprises esters. For esters, the esters of long chain fatty acids are advantageously preferred, especially having at least 22 carbon atoms, e.g. Behenic acid, tetracosanoic acid, cerotic acid and / or triacontanoic acid, etc.

The (optional) coating preferably comprises fats. By fats is preferably meant the solid or semi-solid products which consist essentially of mixed glycerol esters of higher fatty acids.

The (optional) coating preferably comprises (co) polymers. Polyethylene glycols, polyacrylic acids, polyacrylamides, polyvinylpyrrolidones, polyvinyl acetates and polyvinyl alcohols are particularly preferred in the (co) polymers.

Polyethylene glycols having molecular weights of about 200-5000000 g / mol, corresponding polymerization degrees Pn of about 5 to> 100,000 are preferred.

Liquid products with molecular weights <approx. 25,000 g / mol can also be used as a coating material.

The higher molecular weight solid polyethylene glycols, also called polyethylene oxides, are also preferred. In general, it is very preferred if the optional coating contains lipids and / or silicone oils, which corresponds to a preferred embodiment. Preferred lipids are

(a) lipophilic hydrocarbons (such as triacontane, squalene or carotenoids, etc.),

(b) lipophilic alcohols (such as wax alcohols, retinol or cholesterol, etc.),

(c) ether lipids

(d) lipophilic carboxylic acids (fatty acids),

(e) lipophilic esters [such as neutral fats - i. Mono-, Di- u. Triacylglycerols (triglycerides), sterol esters, etc.]

(f) lipophilic amides (such as ceramides, etc.),

(g) waxes

(h) lipids with more than 2 hydrolysis products, e.g. Glycolipids, phospholipids, sphingolipids and / or glycerolipids etc. (i) lipids in the form of higher molecular weight conjugates with more than 2 hydrolysis products, e.g.

Lipoproteins and / or lipopolysaccharides, etc., (j) phosphorus-free glycolipids, e.g. Glycosphingolipids (such as preferably cerebrosides, gangliosides, sulphatides) or as e.g. Glycoglycerolipids (such as preferably glycosyl di- and monoglycerides), etc. (k) carbohydrate-free phospholipids, e.g. Sphingophospholipids (such as preferably sphingo- myelins) or e.g. Glycerophospholipids (such as preferably lecithins, cephalins,

Cardiolipins, phosphatidylinositols and inositol phosphates, etc.) (I) Mixtures of the foregoing.

In a further preferred embodiment, the (optional) coating has unsaponifiably Bares lipid, preferably selected from free fatty acid, isoprenoid lipids, in particular steroids, carotenoids, monoterpenes, etc. and / or tocopherols.

In another preferred embodiment, the (optional) coating comprises saponifiable lipid, preferably selected from mono-, di-, triacylglycerides, phospholipids (phosphatides), glycolipids, diollipids, waxes and / or sterol esters.

In a further preferred embodiment, the (optional) coating each has at least one unsaponifiable and one saponifiable lipid. In another preferred embodiment, the (optional) coating comprises neutral lipid, preferably selected from fatty acids (> C12), mono-, di-, triacylglycerides, sterols, sterol esters, carotenoids, waxes and / or tocopherols.

In another preferred embodiment, the (optional) coating comprises polar lipid, preferably selected from glycerophospholipids, glyceroglycolipids, sphingophospholipids and / or sphingoglycolipids.

In a further preferred embodiment, the (optional) coating has at least one polar and one nonpolar lipid. In another embodiment, the (optional) coating contains a silicone oil.

According to a preferred embodiment, the (optional) coating is applied as a dispersion, thus advantageously as a system of several phases, one of which is continuous (dispersing agent) and at least one further (finely divided) (dispersed phase), preferably as emulsion, aerosol or suspension ,

Most preferred are suspensions, ie dispersions of insoluble solid particles with particle sizes down to colloidal dimensions (<10 ^{~ 6} cm) in liquids, plastic masses or solidified melts.

Particular preference is given to solvent-containing, advantageously aqueous suspensions of pulverulent components, preferably of a few μm diameter, e.g. aqueous suspensions of pigments. Solvent-containing systems preferably contain dispersants, such as in particular

(a) oligomeric titanates and / or silanes,

(b) amphoteric dispersants such as e.g. Soy lecithin etc.

(c) anionic dispersants, e.g. oligomeric or polymeric carboxylic acids, etc.,

(d) cationic dispersants, e.g. Polyamines etc.,

(e) Electroneutral dispersants, such as e.g. Salts of long-chain polyamines and. Polycarboxylic acids, etc., and / or

(f) amine / amide functional polyesters and / or amine / amide functional polyacrylates. Aqueous systems preferably contain dispersants, such as in particular

(A) inorganic dispersants, here preferably so-called Pickering dispersants, ie fine-grained, insoluble inorganic compounds such as CaCO ₃ or Ca ₃ (PO ₄ ) ₂ , polyphosphates, such as preferably salts of the pyro, meta- or. Polyphosphoric acid of the general formula M _{n + 2} P _n O _{3n + I} or. Mn [H ₂ P _n O _{3n + 1} ] with M = Na +, K +, NH ⁴⁺ ; n = 2-10 oligophosphates, eg pentasodium triphosphate Na ₅ P ₃ Oi ₀ , n> 10 polyphosphates (b) modified natural products such as gum arabic, alginates, casein, gelatin, soy lecithin, tannates and / or lignosulfonates and / or

(c) synthetic polymers, for example predominantly water-soluble Na ⁺ or NH ⁴⁺ salts of anionic synthetic polymers with carboxylate, sulfate or sulfonate groups, homopolymers, such as preferably polyacrylic acid, polymethacrylic acid,

(D) copolymers, such as preferably acrylic acid or methacrylic acid with vinyl (ethene), allylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid (AMPS), acrylamide or acrylonitrile, maleic anhydride with ethylene or other 1-alkenes, methyl vinyl ether or styrene, polyaldehydocarboxylic acids , as preferably co-, or terpolymers of acrylic acid, acrylamide, acrylonitrile, in the presence and incorporation of long-chain, branched or linear mercaptans as regulators, naphthalenesulfonate-formaldehyde condensation products.

In a further preferred embodiment, the (optional) coating comprises colored substances or dyes, brighteners and / or pigments, advantageously in the nanoscale range or in the micrometer range, preferably white pigments, in particular selected from titanium dioxide pigments, in particular anatase pigments and / or rutile pigments, zinc sulfide pigments, zinc oxide (zinc white), antimony trioxide (antimony white), basic lead carbonate (lead white) 2PbCO ₃ Pb (OH) ₂ , lithopone ZnS + BaSO ₄ . Preferably, white auxiliaries, such as preferably calcium carbonate, talc 3MgO ^■ 4SiO ₂ ^■ H ₂ O and / or barium sulfate may be included.

In another preferred embodiment, the pigments may be um

(a) colored pigments (preferably inorganic colored pigments, in particular iron oxide pigments, chromate pigments, iron blue pigments, chromium oxide pigments, ultramarine pigments, mixed oxide phase pigments and / or bismuth vanadate pigments),

(b) black pigments (e.g., aniline black, perylene black, iron oxide pigments, manganese black and / or spinel black),

(c) luster pigments (preferably platelet-shaped effect pigments, metallic effect pigments such as aluminum pigments (silver bronze), copper pigments and copper / zinc pigments (gold bronze) and zinc pigments, pearlescent pigments such as magnesium stearate, zinc stearate, lithium stearate or ethylene glycol distearate or Polyethylene terephthalate, interference pigments such as metal oxide mica pigments) and / or

(d) luminescent pigments such as e.g. Azomethine fluorescence yellow, silver-doped and / or copper-doped zinc sulfide pigments act.

The (optional) coating may preferably also comprise the following substances: (a) carbonates, such as preferably chalk, limestone, calcite and / or precipitated calcium carbonate, dolomite and / or barium carbonate

(b) sulphates, such as preferably barite, blanc-fixed and / or calcium sulphates

(c) silicates, such as preferably talc, pyrophyllite, chlorite, hornblende, mica, kaolin wollastonite, slate, precipitated Ca, Al, Ca / Al, Na / Al silicates, feldspars and / or minerals

(D) silicas, such as preferably quartz, fused silica, cristobalite, kieselguhr, Neuburg Siliceous Earth, precipitated silica, fumed silica, glass powder, pumice, perlite, Ca-metasilicates and / or fibers from melting of glass, basalt, slags

(E) oxides, in particular aluminum hydroxide and / or magnesium hydroxide

(F) organic fibers, such as in particular textile fibers, cellulose fibers, polyethylene fibers, polypropylene fibers, polyamide fibers, polyacrylonitrile fibers and / or polyester fibers, preferably with lengths in the nanometer or micrometer range and / or

(g) flours, e.g. Starch flours.

In a preferred embodiment, the (optional) coating lowers the dissolution rate of the entire particles by 5% based on 20 ^° C. cold water, ie the coated granules correspondingly take more time to dissolve completely in cold water in 20 ^° C., based on dissolving 60 grams of the particles in one liter of tap water in a 2 liter beaker, stirring with a stirrer / magnetic stirrer (250 rpm) at 20 ^° C. In other preferred embodiments, lowering the dissolution rate of the total particles at a value of preferably 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90% %, 95% or 100%. At a value of 100%, the complete particle resolution takes twice as long as without coating. According to a further preferred embodiment, the reduction of the dissolution rate of the total particles may even be at an even higher value, preferably at 150%, 200%, 250%, 300%, 350%, 400%, 450% or 500%. If the uncoated particle is already dissolved after 1 minute, the coated tablet would be dissolved at a value of 500% only after 5 minutes.

In a preferred embodiment, in the optionally coated granules, preferably in the core and / or in the shell, effervescent or effervescent components are contained.

An inventive granules consists of a core and surrounding shell material. This does not necessarily mean that the shell material must completely cover the core. It is only necessary that the particles surrounding the core at least partly surround or cover it, so that preferably at least 10%, in Partial meadow at least 15%, more preferably at least 20%, advantageously at least 25%, more preferably at least 30%, very advantageously at least 35%, in a significantly advantageous manner at least 40%, in a very advantageous manner at least 45%, in particular at least 50% of the outer visible surface of the core is covered by the surrounding particles (= degree of coverage), which corresponds to a preferred embodiment.

According to another preferred embodiment, however, the degrees of coverage should not exceed certain maximum values, such maximum values being in particular at a value of 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95 % or 100%, but can also be at a lower value, such as 10%, 15%, 20%, 25%, 30%, 35%, 40% or 45%. According to another preferred embodiment, however, it may also be desirable for the degree of coverage to reach very high levels, preferably the degree of coverage may be at values of at least 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% or 100%.

According to a preferred embodiment of the invention, the core as such is uniform, preferably almost spherical or ellipsoidal. The ellipsoid is similar to the sphere, but the longitudinal axis and the transverse axis are different. However, the core can also be other embodiments

(a) cubic (cube-shaped) or at least approximately cubic-shaped or

(b) shaped parallelepiped (e.g., cuboid) or at least approximately parallelepiped shaped or

(c) lamellar (platy and the like) or at least approximately lamellar or

(d) needle-like or fibrous-shaped, or at least approximately needle-like or fibrous, or

(e) be strand-like or at least approximately strand-like.

According to a further preferred embodiment, the core is designed as such uneven, preferably not spherical or ellipsoidal, but of irregular shape. Such a shape is characterized, for example, by the irregular presence of corners, points, points and edges, bulges and indentations, tears or blisters. From the center of the core, therefore, the majority of the points of the surface are substantially at an unequal distance. Such a shape may, for example, taper to one side, have a dent or have a flat side. A collective of, optionally coated, granules, for example a washing powder consisting of granules, can now be characterized in that

(A) the majority, preferably at least 75%, in particular the total number, the cores of the, optionally coated, granules is substantially uniform, preferably almost spherical or ellipsoidal, or

(b) the majority, preferably at least 75%, in particular the total number, of the cores of the optionally coated granules is unevenly formed, or

(c) mixtures of substantially uniformly and non-uniformly formed cores are present, preferably in the ratio of 200: 1 to 1: 200. This corresponds to a preferred embodiment.

The collective of the optionally coated granules may also be a sub-collective of a larger total collective, i. the collective of, optionally coated, granules forms together with other particles a total collective.

A collective of optionally coated granules, for example a washing powder consisting of granules, may be distinguished by the fact that the cores of the collective

(a) in the majority, preferably at least 75%, in particular the total number of cores, have a more uniform grain size, or

(b) in the majority, preferably at least 75%, in particular the total number of cores, have a rather non-uniform grain size, or

(C) represent a mixture of cores of very uniform grain size with cores of very non-uniform grain size, preferably in the ratio of 200: 1 to 1: 200. This corresponds to a preferred embodiment.

The collective of the optionally coated granules may also be a sub-collective of a larger total collective, i. the collective of, optionally coated, granules forms together with other particles a total collective.

A rather uniform grain size is preferably present when the cores are present substantially in the most uniform particle size distribution, in which the ratio of d ₅₀ to d ₉₀ at least 0.50, preferably at least 0.6, advantageously at least 0.75, in further advantageously at least 0.80.

A collective of optionally coated granules, for example a washing powder consisting of granules, may be distinguished by the fact that the cores of the collective (a) in the majority, preferably at least 75%, in particular the total number of cores, have a more uniform density, or

(b) in the majority, preferably at least 75%, in particular the total number of cores, have a rather different density, or

(c) represent a mixture of cores of very uniform density with nuclei of very non-uniform density, preferably in the ratio of 200: 1 to 1: 200. This corresponds to a preferred embodiment.

The collective of the optionally coated granules may also be a sub-collective of a larger total collective, i. the collective of, optionally coated, granules forms together with other particles a total collective.

A collective of optionally coated granules, for example a washing powder consisting of granules, may be distinguished by the fact that the cores of the collective

(a) in the majority, preferably at least 75%, in particular the total number of cores, have a more uniform structural configuration, i. e.g. either single grains, extrudates or agglomerates, etc., or

(b) in the majority, preferably at least 75%, in particular the total number of cores, have a rather different structural configuration, i. both as extrudates, agglomerates, single grains, etc., or

(c) represent a mixture of cores of very uniform structural composition with nuclei of very inconsistent density. This corresponds to a preferred embodiment.

The collective of the optionally coated granules may also be a sub-collective of a larger total collective, i. the collective of, optionally coated, granules forms together with other particles a total collective.

A collective of optionally coated granules, for example a washing powder consisting of granules, may be distinguished by the fact that the cores of the collective

(a) in the majority, preferably at least 75%, in particular the total number of cores, have a more uniform chemical composition, relative to the collective, or

(b) in the majority, preferably at least 75%, in particular the total number of cores, have a rather non-uniform chemical composition relative to the collective, or (c) a mixture of cores of very uniform chemical composition with cores of a very non-uniform chemical composition, relative to the collective. This corresponds to a preferred embodiment.

The collective of the optionally coated granules may also be a sub-collective of a larger total collective, i. the collective of, optionally coated, granules forms together with other particles a total collective.

Furthermore, the following cases (i) to (iv) represent preferred embodiments of the invention: (i) A collective of optionally coated granules, for example a washing powder consisting of granules, may be characterized in that the cores of the collective are individual objects respectively a homogeneous distribution of at least one (preferably one and the same) contained in them active substance (eg surfactant or builder, etc.), wherein formed in the same optionally coated granules α) also a homogeneous distribution of the relevant active substances (s ) or there is a heterogeneous distribution of the relevant active substance (s) via the collective.

In simple terms, this means that there is a particle collective ψ. In all particles of this collective ψ at least one (preferably one and the same) active substance is homogeneously distributed. In the case α), all particles of the collective ψ also contain the same amount of the active substance in question. This is the case of a homogeneous individual distribution in a homogeneous collective. In the case β), however, the particles contain different amounts of the active substance in question, although the different amounts in each individual particles are homogeneously distributed. This is the case of a homogeneous individual distribution in a heterogeneous collective.

The collective of the optionally coated granules may also be a sub-collective of a larger total collective, i. the collective of, optionally coated, granules forms together with other particles a total collective.

(ii) A collective of optionally coated granules, for example a washing powder consisting of granules, may be distinguished by the fact that the cores of the collective as individual objects each have a heterogeneous distribution of at least one (preferably one and the same) active substance contained in them (eg Surfactant or builder, etc.) (ie having a concentration gradient of the active substance via a particle or local Accumulations of the active substance occur), wherein in the group formed by the same, optionally coated granules χ) also a heterogeneous distribution of the relevant active substances (s) is given by the collective, or δ) a homogeneous distribution of (the) concerned Active substances (s) is given through the collective.

In simple terms, this means that there is a particle collective ξ. In all particles of this collective ξ at least one (one and the same) active substance is distributed heterogeneously. In the case χ) all particles of the collective ξ also contain different amounts of the active substance in question. This is the case of a heterogeneous individual distribution in a heterogeneous collective. In the case δ), however, the particles contain equal amounts of the active substance in question, although the same amounts are distributed inhomogeneous in each individual particles. This is the case of a heterogeneous individual distribution in a homogeneous collective.

The collective of the optionally coated granules may also be a sub-collective of a larger total collective, i. the collective of, optionally coated, granules forms together with other particles a total collective.

(iii) A collective of optionally coated granules, for example a washing powder consisting of granules, can be distinguished by the fact that the cores of the collective as individual objects each have a homogeneous mass distribution (ie there is no density gradient in the individual core), where in the collective formed by the same, optionally coated granules

ε) is also given a homogeneous mass distribution over the collective (ie there is no density gradient across the collective as a whole, so that all the particles forming the collective have almost the same density), or φ) a heterogeneous mass distribution over the collective is given ( ie it is on

Density gradient across the collective as a whole, so that the particles forming the collective do not have nearly the same densities). In simple terms, this means that there is a particle collective $. In none of the particles of this collective 9- is there a density gradient. In the case ε) all particles of the collective 9- also have the same density. This is the case of a homogeneous individual distribution in a homogeneous collective. In the case φ) not all particles of the collective 9- have the same density. This is the case of a homogeneous individual distribution in a heterogeneous collective. In this case, the collective of the optionally coated granules may also be a sub-collective of a larger total collective, ie the collective of the optionally coated granules forms together with further particles a total collective.

(iv) A collective of optionally coated granules, for example a washing powder consisting of granules, may be distinguished by the fact that the cores of the collective each have a heterogeneous mass distribution as individual objects (ie there is a density gradient in each individual nucleus), wherein the group formed by the same, optionally coated, granules γ) is also given a heterogeneous mass distribution over the collective (ie there is a density gradient over the collective as a whole, so that the

Collectively forming particles do not all have the same density), or η) is a homogeneous mass distribution across the collective (i.e., there is no

Density gradient over the collective as a whole before, so that is the the

Collectively forming particles have the same densities).

In simple terms, this means that a particle collective π is present. The individual particles of this collective π have a density gradient. In the case of γ), the particles of the collective π also have different densities in comparison with each other. This is the case of a heterogeneous individual distribution in a heterogeneous collective. In the case η), the particles of the collective π have identical densities in comparison with one another. This is the case of a heterogeneous individual distribution in a homogeneous collective.

The collective of the optionally coated granules may also be a sub-collective of a larger total collective, i. the collective of, optionally coated, granules forms together with other particles a total collective.

It is possible within the scope of the invention that the core is coated as such before it is surrounded by the shell material, ie, for example, it is coated with a solution, dispersion, melt or emulsion of certain active substances. This corresponds to a preferred embodiment. The (optional) coating of the core includes materials comprising nonionic surfactants, cationic surfactants, amphoteric surfactants, silicone oil, triglycerides, Terpene, perfume, glycerin and / or (co) polymer (solutions) in question. Furthermore, all those substances which are disclosed for the coating of the granulate elsewhere in this description are also suitable.

It is also possible that an uncoated granulate per se, before it is optionally coated, is previously impregnated, i. e.g. So impregnated with a solution, dispersion or emulsion of certain active ingredients, to modify the properties of the granules. This corresponds to a preferred embodiment.

Impregnating agents, preferably silicone-containing impregnating agents, ie mixtures which advantageously contain various polysiloxanes with condensable groups, which advantageously make water repellency more or less strong, can be used to impregnate the core or granules. For impregnation, it is preferred to use agents which serve to hydrophobicize the core or the granules. Preferred hydrophobizing agents, in addition to agents containing silicones, are also agents e.g. Paraffins, waxes, metal soaps (sometimes also with additions of aluminum or zirconium salts), quaternary ammonium compounds with long-chain alkyl radicals, urea derivatives, fatty acid-modified melamine resins, chromium complex salts, tin-organic compounds and / or glutaric dialdehyde ,

In principle, of course, a hydrophilization is possible, which corresponds to a preferred embodiment. The hydrophilization is carried out with the aid of hydrophilizing agents, e.g. be applied in the form of aqueous solutions. It is e.g. to formulations of ionic or nonionic polymers, ethoxylation products and the like. It is e.g. it is possible to hydrophilize the core before it is surrounded by the shell.

For impregnation, agents containing lipids are preferably used. Preferred lipids are

(a) lipophilic hydrocarbons (such as triacontane, squalene, or carotenoids, etc.),

(b) lipophilic alcohols (such as wax alcohols, retinol or cholesterol, etc.),

(c) ether lipids

(d) lipophilic carboxylic acids (fatty acids),

(e) lipophilic esters [such as neutral fats - i. Mono-, Di- u. Triacylglycerols (triglycerides), sterol esters, etc.]

(f) lipophilic amides (such as ceramides, etc.),

(g) waxes (h) lipids with more than 2 hydrolysis products, such as glycolipids, phospholipids, sphingolipids and / or glycerolipids etc.

(i) lipids in the form of higher molecular weight conjugates with more than 2 hydrolysis products, e.g. Lipoproteins and / or lipopolysaccharides etc.,

(j) Phosphorus-free glycolipids, e.g. Glycosphingolipids (such as preferably cerebrosides, gangliosides, sulphatides) or as e.g. Glycoglycerolipids (preferably glycosyl di- and monoglycerides), etc.

(k) carbohydrate-free phospholipids, e.g. Sphingophospholipids (such as preferably sphingo- myelins) or e.g. Glycerophospholipids (such as preferably lecithins, cephalins, cardiolipins, phosphatidylinositols and inositol phosphates, etc.) and / or

(I) Mixtures of the foregoing.

In a further preferred embodiment, the impregnating agent comprises unsaponifiable lipid, preferably selected from free fatty acids, isoprenoid lipids, in particular steroids, carotenoids, monoterpenes etc. and / or tocopherols.

In another preferred embodiment, the impregnating agent comprises saponifiable lipid, preferably selected from mono-, di-, triacylglycerides, phospholipids (phosphatides), glycolipids, diollipids, waxes and / or sterol esters.

In a further preferred embodiment, the impregnating agent comprises at least one unsaponifiable and one saponifiable lipid.

In another preferred embodiment, the impregnating agent comprises neutral lipid, preferably selected from fatty acids (> C12), mono-, di-, triacylglycerides, sterols, sterol esters, carotenoids, waxes and / or tocopherols.

In another preferred embodiment, the impregnating agent comprises polar lipid, preferably selected from glycerophospholipids, glyceroglycolipids, sphingophospholipids and / or sphingoglycolipids.

In a further preferred embodiment, the impregnating agent has at least one polar and one nonpolar lipid.

It is also possible in the (optional) coating of the granules to perform a partial hydrophobization, that is to make the surface of the particles hydrophobic by applying water repellents as a coating, preferably agents such as silicones, paraffins, Waxes, metal soaps (sometimes also with additions of aluminum or zirconium salts), quaternary ammonium compounds with long-chain alkyl radicals, urea derivatives, fatty acid-modified melamine resins, chromium complex salts, tin-organic compounds and / or glutaric dialdehyde.

It is also possible in the (optional) coating of the granules to carry out a partial hydrophilization, that is to make the surface of the particles hydrophilic, e.g. by applying aqueous solutions as a coating to the granules, in particular preparations of ionic or nonionic polymers, ethoxylation products and the like. Particularly suitable for hydrophilization are e.g. Polyethylenglykolsorbitanfettsäureester and comparable substances.

The solubility of the shell as such can also be manipulated individually, advantageously via the choice of granulation aid. For example, the granulation aid may be more hydrophobic, with the result that the shell dissolves more slowly in an aqueous environment. In the context of this invention, when the granulating agent is rather hydrophobic, the term "hydrophobically bound" in the context of this invention is more simply referred to, for example, the granulating agent may be rather hydrophilic, with the result that the shell dissolves more quickly in an aqueous environment. If the granulating agent is rather hydrophilic, in the context of this invention in the further description of a "hydrophilic bonded" shell is mentioned.

The freedom of design of the skilled person are virtually unlimited. Of course, the granules which can be produced according to the invention can also be advantageously applied in pouches, bags or sachets. Another object of the invention is a pouch, bag or sack, containing granules according to the invention can be produced.

A further subject of the invention is a shaped body, preferably a tablet, containing granulates preparable according to the invention.

Another object of the invention is a detergent or cleaning agent containing producible granules according to the invention, in particular a detergent containing care components.

Another object of the invention is a cleaning agent containing producible granules according to the invention, preferably containing dishwashing detergent (A) cleaning component containing, for example, surfactants such as preferably alkanesulfonates, alkyl ether sulfates, alkyl polyglucosides and / or cocoamidopropyl betaine

(b) Rinse aid component containing, for example, nonionic surfactants, preferably on a fatty alcohol basis, in particular with additions of lower alcohols as solubilizers and advantageously of citric acid

(c) Softening component comprising, for example, phosphonate, polycarboxylate, sodium gluconate, ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA) and / or aluminosilicates (zeolites)

(d) Optional: other ingredients such as preferably silver / glass protection component

According to a further preferred embodiment, the optional coating of the granules obtainable according to the invention is pH and / or temperature and / or ionic strength-sensitive or contains pH and / or temperature and / or ionic strength-sensitive materials. According to a further embodiment, the shell is pH and / or temperature and / or ionic strength-sensitive or contains pH and / or temperature and / or ionic strength-sensitive materials. According to a further embodiment, the core is pH and / or temperature and / or ionic strength-sensitive or contains pH and / or temperature and / or ionic strength-sensitive materials.

In the following, the terminology of the pH and / or temperature and / or ionic strength sensitivity will be explained primarily by the example of the optional coating. However, it is clear to the person skilled in the art that he can readily apply the same mechanisms to the preparation of the core and shell (shell material). The core may e.g. a granulate which consists of subparticles which are held together by a pH and / or temperature and / or ionic strength-sensitive material. Under adjustable conditions regarding pH and / or temperature and / or ionic strength, the core can thus lose its integrity, ie decay. The shell may e.g. be applied to the core with a pH and / or temperature and / or ionic strength-sensitive granulation liquid. Under adjustable conditions of pH and / or temperature and / or ionic strength, the shell may thus lose its integrity and dissolve.

By the term of pH sensitivity, temperature sensitivity and / or ionic strength sensitivity is meant that the coating or the materials forming the coating with a change in the pH, the temperature and / or the ionic strength in the environment, which is exposed to the coating (eg a wash liquor),

(a) undergoes a change (increase or decrease) in solubility (preferably in water); and or (b) undergoes a change (increase or decrease) in diffusion density; and or

(c) undergoes a change (acceleration or deceleration) in the solution kinetics; and or

(d) undergoes a change (increase or decrease) in mechanical stability.

In addition to the options (a) to (d) mentioned above, the temperature sensitivity also has the additional option (e) according to which the coating or the materials forming the coating change the physical state from solid to liquid when the temperature changes or vice versa, ie the materials melt or solidify.

For this purpose, suitable coating materials for the purposes of the invention may be all those materials whose integrity is a function of the temperature and / or the pH and / or the ionic strength, or also those materials which are subject to mechanical stress as described e.g. occur during an automatic laundry process, lose their integrity. Advantageously, the pH sensitivity of the (optional) coating can be used. The (optional) coating may e.g. be designed so that it dissolves in whole or in part if the pH falls below a critical mark. This can be done in the example of a washing process when the alkaline wash water is removed from the machine and introduced fresh water into the machine, preferably in the rinse cycle of the washing process. On contact with the fresh water, the coating then lose its integrity, in whole or in part, making it possible to penetrate the granules for the water. The pH in question, in which the coating completely or partially disintegrated, can be set arbitrarily, so that the material, for example, then its integrity completely or partially loses when the pH z. B. falls below 9.0, but remains substantially inert, as long as the pH is above 10, 0.

The term "inert" is understood according to the invention in the usual sense, ie in such a way that a physical or chemical reaction of the material of the coating with the surrounding environment does not occur substantially, but the material of the coating is physically and chemically resistant to this, so that the granules from penetration through the environment, eg the wash liquor is substantially protected.

The granules which can be produced according to the invention can have a plurality of shells and a plurality of coatings can be applied to them. According to a preferred embodiment of the invention, therefore, the particles surrounding the core of the granulate are multi-shelled on the Core applied. According to a further preferred embodiment of the invention, the granules are coated several times.

In the context of this application, multi-shelled granules can be obtained if a granulate obtained is taken as a "core" for one (or more) further granulation processes, ie the granules are themselves reused as a new core and surrounded by further particles It is preferred that the shells differ from one another in at least one parameter, for example by physical parameters such as their density, their size, and / or by chemical parameters, ie different chemical substances.

In a preferred embodiment, core materials and shell material also differ in at least one physical and / or chemical parameter.

Granules with several coatings can be obtained by applying one (or more) further coatings to the finished granules on which a coating has already been applied. So you can, for example apply a first nonionic surfactant-containing coating and a subsequent perfume-containing coating, etc ..

According to a further preferred embodiment of the invention, the diameter d _{50 of} the core particles of the agents according to the invention is preferably in the range of 0.05 to 5 mm.

The lower limit of the diameter d _{50 of} the core particles of the agents according to the invention may preferably also at a value such as in particular 0.06 mm, 0.07 mm, 0.08 mm, 0.09 mm, 0.1 mm, 0.1 1 mm , 0.12 mm, 0.13 mm, 0.14 mm, 0.15 mm, 0.16 mm, 0.17 mm, 0.18 mm, 0.19 mm, 0.2 mm, 0.21 mm , 0.22 mm, 0.23 mm, 0.24 mm, 0.25 mm, 0.26 mm, 0.27 mm, 0.28 mm, 0.29 mm, 0.30 mm, 0.4 mm , 0.5 mm, 0.6 mm, 0.7 mm, 0.8 mm, 0.9 mm or 1, 0 mm or even between these values, for example, at 0.35 mm, 0.45 mm, etc. lie ,

Less advantageous, but also possible according to another embodiment, it would also be if the diameter d _{50 of} the core particles of the inventive compositions smaller than 0.05 mm, for example, a value such as preferably 0.01 mm, 0.02 mm, 0.03 mm or 0.04 mm.

The upper limit of the diameter d _{50 of} the core particles of the compositions according to the invention may preferably also be given a value such as in particular 4.8 mm, 4.6 mm, 4.4 mm, 4.2 mm, 4.0 mm, 3.8 mm, 3.6 mm, 3.4 mm, 3.2 mm, 3.0 mm, 2.8 mm, 2.6 mm, 2.4 mm, 2.2 mm, 2.0 mm, 1, 8 mm, 1, 6 mm, 1, 4 mm, 1, 2 mm or 1, 0 mm or even between these values, eg at 4.7 mm, 4.5 mm, etc.

Less advantageous, but it would also be possible according to another embodiment, even if the diameter d _{50 of} the core particles of the inventive compositions greater than 5.0 mm, for example, a value such as in particular 6 mm, 7 mm, 8 mm, 9 mm or 10 mm or values which lie between these values, eg at 5.5 mm, 6.5 mm etc.

The particles surrounding the core are advantageously not powdered. According to general understanding, powder is a kind of flour, ie an accumulation of solid particles having a particle size preferably below 100 nm. It is also advantageous for process-technical reasons, if the particles do not fall below a certain minimum size. According to a preferred embodiment of the invention, therefore, the particles surrounding the core have a particle diameter d ₅₀ which is preferably at least 1/100, advantageously at least 1/80, more preferably at least 1/70, more preferably at least 1/60 even more preferably, at least 1/50, most preferably at least 1/40 and especially at least 1/35 of the particle diameter d _{50 of} the cores.

However, the particle diameter d ₅₀ of the particles surrounding the core is preferably greater than 2, 3, 4 or 5 μm.

According to a further preferred embodiment of the invention, the particles surrounding the core have a largely uniform particle size, wherein advantageously the particle size distribution of the particles surrounding the core is such that the ratio of d ₅₀ to d ₉₀ of the particles surrounding the core is preferably at least 0.5 , more preferably at least 0.6, in particular at least 0.75.

According to a further preferred embodiment of the invention, the compositions according to the invention, that is to say the granulates preparable according to the invention, essentially have an average form factor of at least 0.79, preferably of at least 0.81, advantageously of at least 0.83, more preferably of at least 0.85 , in particular of at least 0.87. According to another preferred embodiment of the invention, the compositions according to the invention, ie the granules which can be produced according to the invention, are present essentially in a particle size distribution which is as uniform as possible, in which the ratio of d ₅₀ to d _{90 is} at least 0.50, preferably at least 0.6, advantageously at least 0.75, in a further advantageous manner is at least 0.80. According to a preferred embodiment, the optionally coated granules (especially those containing pH, ionic strength and / or temperature-sensitive materials) are floatable in water, ie do not submerge in water or in a wash liquor, but float on the water surface ,

In order to make the granules floating, it is preferable to adjust their density to values less than 1 g / cm ³ , if necessary. There is a wide range of options available. For example, gases, in particular air, can be incorporated into the granules. Optionally, the granules per se have a correspondingly low density, so that the additional incorporation of, for example, gases is not necessary, which is likewise preferred. It is likewise preferred to incorporate solids, preferably support materials having a density of less than 1 g / cm ³ into the granules, the supports being substances which are solid at room temperature, preferably builders, carbonates, bicarbonates, sulfates, phosphates and / or at room temperature solid oligocarboxylic acids.

To set a density of less than 1 g / cm ³ preferably hollow microspheres, so very voluminous lightweight fillers, be incorporated into the granules, for example in the core. The hollow microspheres are filled, for example with air, nitrogen or carbon dioxide, the spherical shells consist for example of glass (eg borosilicate glass) or in particular of organic materials, for example of a thermoplastic (eg styrene / acrylate polymer, polyacrylate). They may also be filled with other convenient materials such as vegetable oils (eg almond oil, density about 0.91-0.92 g / cm ³ ). The density of the hollow microspheres is preferably <1 g / cm ³ , preferably 0.176-0.9 g / cm ³ or 0.176-0.8 g / cm ³ or 0.176-0.7 g / cm ³ or 0.176-0.6 g / cm ³ or 0.176-0.5 g / cm ³ or 0.176-0.4 g / cm ³ . The average particle diameter is preferably in the range of 0.4-10 μm. Grain upper limits are preferably 0.4-250 microns. The thermal conductivity is preferably 0.110-0.156 Wm-1 K-1. The internal pressure is preferably about 0.2 bar. At higher shear stress, the hollow spherical shells may preferably burst. In particular, the polyacrylate hollow microspheres are preferably incorporated as an aqueous suspension, for example in the core production, for example by granulation or spray drying, or in the production of granules, for example by agglomeration. To set a density of less than 1 g / cm ³ , for example, cork flour can also be incorporated into the granules. Due to its low density of 0.12-0.25 g / cm ^{3 it} is ideally suited for this purpose.

Cork meal is preferably made by crushing and then screening or sifting cork waste. According to a preferred embodiment, the composition according to the invention (granules producible according to the invention) contains ingredients for the cleaning, care, conditioning and / or after-treatment of textiles.

According to a preferred embodiment, the composition according to the invention (granules producible according to the invention) contains ingredients for cleaning and / or care of dishes, glasses, cutlery and the like.

In a preferred embodiment, the core of the granulate to be prepared according to the invention contains ingredients for the care, conditioning and / or aftertreatment of textiles, preferably selected from the group of the softening agents, fragrances, pH regulators, fluorescers, dyes, hydrotopes, silicone oils, anti redeposition agents, optical brighteners, Graying inhibitors, anti-wrinkling agents, antimicrobial agents, germicides, fungicides, antioxidants, antistatic agents, ironing aids, repellents and impregnating agents, bleaching agents, acidifiers and / or UV absorbers.

In a further preferred embodiment, the core of the granules according to the invention contains one or more skin-care and / or skin-protecting and / or skin-healing active substances.

In a preferred embodiment, the compositions according to the invention are characterized in that the skin-care and / or skin-protecting and / or skin-healing active ingredients contained in the core are released at least partially onto the fibers of the textile laundry and are released during the washing process, preferably in the rinse cycle at least partially remain on this even after completion of the washing process, said skin-care and / or skin-protecting and / or skin-healing active ingredients are at least partially released from the skin to the skin with a correspondingly washed textile and this can benefit the skin to the advantage ,

The granules according to the invention may contain ingredients for the care and / or after-treatment of textiles. In a preferred embodiment, the proportion by weight of the ingredient preferably contained in the core for the care and / or aftertreatment of textiles, more than 5 wt .-%, in particular between 20 and 50 wt .-%, based on the core. In another preferred embodiment, the granules according to the invention, preferably the core, contains retarded fragrance-giving and / or delayed-release biocidal oligomers, polymers and / or copolymers which contain a structural element according to the following formula (1) at least once R ¹ O- Si (R ²⁾ (R ³⁾ - R _A ⁴ - C (R ⁵⁾ (H) - C (R ⁶⁾ (R ⁷⁾ - Si (1),

I wherein R ² , R ³ are each independently an aliphatic or aromatic, straight-chain or branched, saturated or unsaturated, substituted or unsubstituted hydrocarbon radical which may each contain heteroatoms such as oxygen, nitrogen, sulfur or halogens or others, and wherein R _a ^{4 is} a carbon bridge member which is an aliphatic or aromatic, straight-chain or branched, saturated or unsaturated, substituted or unsubstituted hydrocarbon radical which may each contain heteroatoms such as oxygen, nitrogen, sulfur or halogens or others, the run number a 0 to 10, and wherein R ⁵ , R ⁶ , R ⁷ are each independently hydrogen or an aliphatic or aromatic, straight-chain or branched, saturated or unsaturated, substituted or unsubstituted hydrocarbon radical, each heteroatom such as oxygen, S may contain nitrogen, sulfur or halogens or others, and wherein the terminal silicon in the formula (1) independently has any of the remaining three valences of any of the oligomer, polymer or copolymer, and wherein R ¹ O is either a group represented by a fragrance alkoxy group and / or biocide alkoxy group derived from the corresponding fragrance and / or biocide alcohol R ¹ OH, or

R ¹ O represents a radical derived from an enolizable fragrance and / or biocide ester, ketone or aldehyde. Preferably, in the inventively preparable, optionally coated, granules or in the other detergent at least one on hard and / or soft substrate surfaces, preferably, at least one cationic charge bearing compound containing. These retarded fragrance-giving oligomers, polymers and / or copolymers are able to produce an excellent and very long-lasting odor effect on substrates treated therewith, in particular in conjunction with compounds which accumulate on hard and / or soft substrate surfaces and preferably carry at least one cationic charge.

For the purposes of the present invention, the term "perfume" is understood to mean all those fragrances or substances or mixtures thereof which are perceived by humans as odor and trigger a sensation of smell in humans, preferably a pleasant sensation of smell. Accordingly, "fragrance alcohols" in the context of the present invention are perfumes or fragrances which have free hydroxyl groups, regardless of how the molecule is further structured. By analogy, fragrance esters, ketones, aldehydes designate those fragrances which have correspondingly free esters, keto or aldehyde functionalities. This implies that certain molecules, such as salicylic acid esters within the meaning of this invention, For example, they can function both as a fragrance alcohol and as a fragrance ester. Accordingly, biocide alcohol, aldehyde, ester or ketone are understood to mean all compounds which have the corresponding alcohol, aldehyde, ester or keto functionality in the aforementioned sense, and which are capable of at least germ growth to inhibit. Biocides are compounds which inhibit germ growth or at least kill, depending on the individual case, a broad spectrum of organisms, for example of viruses, bacteria, fungi, insects. The dates perfume-alkoxy group or biocide-alkoxy group are explained in the foregoing, these are the corresponding anions of the relevant perfume alcohols or biocide alcohols, which result by abstraction of a hydrogen atom. It has already been described that, in a preferred embodiment, the agent according to the invention contains one or more skin-care and / or skin-protecting and / or skin-healing active substances.

Skin-care active substances are all those active substances which give the skin a sensory and / or cosmetic advantage. Skin-care active substances are preferably selected from the following substances: a) waxes such as, for example, carnauba, spermaceti, beeswax, lanolin and / or derivatives thereof and others. b) Hydrophobic plant extracts c) Hydrocarbons such as squalene and / or squalanes d) Higher fatty acids, preferably those having at least 12 carbon atoms, for example lauric acid, stearic acid, behenic acid, myristic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid, isostearic acid and / or multiple unsaturated fatty acids and others. e) Higher fatty alcohols, preferably those having at least 12 carbon atoms, for example, lauryl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, behenyl alcohol, cholesterol and / or 2-hexadecanol and others. f) esters, preferably such as cetyloctanoates, lauryl lactates, myristyl lactates, cetyl lactates, isopropyl myristates, myristyl myristates, isopropyl palmitates, isopropyl adipates, butyl stearates, decyl oleates, cholesterol stearates, glycerol monostearates, glycerol distearates, glycerol tristearates, alkyl lactates, alkyl citrates and / or alkyl tartrates and others. g) lipids such as cholesterol, ceramides and / or sucrose esters and others. h) vitamins such as vitamins A and E, vitamin C esters, including vitamin C.

Alkyl esters and others, i) sunscreens j) phospholipids k) derivatives of alpha-hydroxy acids I) fragrances m) germicides for cosmetic use, both synthetic and, for example, salicylic acid and / or other natural as well as neem oil and / or other, n) silicones and mixtures of any of the abovementioned components.

In a preferred embodiment, the granules contain both skin-care and / or skin-protecting and / or skin-healing active substances and also textile-softening quaternary ammonium compounds, preferably esterquats. Skin-protecting and / or skin-healing active substances are active substances which give the skin an advantage which goes beyond a mere sensory and / or cosmetic advantage.

The term skin healing or the skin-healing attribute in the context of this invention is most easily defined by the state of healthy human skin. Healthy human skin is characterized by the fact that its intact acid mantle provides sufficient protection against microorganisms, germs and pathogens, that its buffer capacity and alkaline neutralizing capacity are sufficient to ward off harmful influences of surrounding fluids, that there is a high degree of freedom from redness, and that there is freedom from skin damage such as cuts, abrasions and burns, irritation, inflammation and allergies, and that it is neither cracked nor dried out. Furthermore, healthy skin is characterized by the fact that it takes on a depot function for fat, water and blood and plays an important role in the metabolism. Is the skin unable to o. G. To take over functions or shows them obvious damage or itching from the skin, it is no longer considered to be healthy. Skin healing in the context of the present invention is now all that helps the skin to return to its original state. It is also all skin-healing, which stimulates, trains, supports and promotes the self-regulating powers of the skin, so that it is able to perform its functions, by returning to the natural state of equilibrium. In the context of this invention, the term "skin healing" is understood to include all influences which lead to at least alleviate, if not heal, obvious skin diseases such as eczema, rashes, redness, itching, swelling, blistering, oozing, crusting in various forms ,

In turn, the term skin protection means everything that is necessary to maintain the normal performance of the skin in terms of its functions under specific stress situations and goes beyond its own protective mechanisms. Thus, this term differs significantly from the skin care, because the skin care achieved only a cosmetic benefit in terms of sensory needs such as softness or Gloss under normal conditions. The skin protection, however, supports the skin with additional agents that help the skin, for example, even in adverse conditions, to fulfill their multifaceted functions. Such adverse conditions can z. As friction, cold, heat, UV radiation, aggressive ambient fluids, contact with skin-irritating materials. In a preferred embodiment, at least one of the skin-healing and / or skin-protecting active substances contained in the optionally coated granules which can be prepared according to the invention is antiseptic or contains at least one antiseptic substance, wherein the antiseptic substance is preferably an oil, in particular an essential oil is.

In the context of this invention, the attribute of antiseptic efficacy means an effect that is beneficial to the self-regulating forces of human skin. This efficacy is not in its expression with that of classical germicidal or germicidal agents such. Phenols, halogens, alcohols with which z. B. skin u. Mucous membranes Wounds or even medical instruments treated to achieve asepsis (germ-free) compare. The classical antiseptic includes antimicrobial measures at the point of origin or at the portal of entry of a possible infection or at the site of infection on the body surface. However, such strong effectiveness is not sought in the context of the invention, as it undoubtedly o.a. to eliminate harmful germs. would also affect the natural skin flora of humans.

The particular advantage of the antiseptic active substances which can be used according to the invention results from a synergistic interaction of these substances with the general functional mechanisms of human skin, since these substances have a mildly antiseptic action, eg. B. germs, including harmful germs reduce, but not perfect, so to sterility, destroy. So there are enough germs on the skin that are sufficient to train and strengthen the self-regulating powers of human skin. The interaction of the self-regulating forces of the skin with the antiseptic capacity of the active ingredients in the middle of the skin supports the general functioning of the skin. This is of great advantage, especially with regard to already irritated and / or otherwise damaged skin. In already irritated and / or sensitized and / or otherwise damaged or even particularly sensitive skin, the self-regulatory powers of the skin are sometimes no longer able, even temporarily, to ensure skin health on their own. In synergistic interaction with the agents according to the invention and their use according to the invention, these self-regulating forces are supported, trained and strengthened. In this way, the detergent according to the invention or the laundry treated with it supports the natural skin flora of humans. In order not to affect the natural skin flora of humans, it is advantageous to exclude (largely) such substances, which are indeed highly disinfecting or antiseptic effective, such. As glutaraldehyde, but at the same time hold a high allergenic potential and are skin and mucous membrane irritant.

Unexpectedly, optionally coated granules of such an embodiment are particularly useful for their purpose when the antiseptic active is an oil, preferably an essential oil.

This antiseptic oil is preferably an essential oil selected in particular from the group of Angelica fine - Angelica archangelica, Anis - Pimpinella anisum, Benzoin siam - Styrax tokinensis, Cabreuva - Myrocarpus fastigiatus, Cajeput - Melaleuca leucadendron, Cistrose - Cistrus ladaniferus, Copaiba balm - Copaifera reticulata, Costus root - Saussurea discolor, Edeltann needle - Abies alba, Elemi - Canarium luzonicum, Fennel - Foeniculum dulce Spruce needle - Picea abies, Geranium - Pelargonium graveolens, Ho leaves - Cinnamonum camphora, Immortelle (Strawflower) Helichrysum ang., Ginger extra - Zingiber off., St. John's wort - Hypericum perforatum, Jojoba, German chamomile - Matricaria recutita, Chamomile blue fine - Matricaria chamomilla, Chamomile rom. - Anthemis nobilis, Chamomile wild - Ormensis multicaulis, Carrot - Daucus carota, Mountain pine - Pinus mugho, Lavandin - Lavendula hybrida, Litsea Cubeba - (May Chang), Manuka - Leptosperm Melissa officinalis, Sea pine - Pinus pinaster ,, Myrrh - Commiphora molmol, Myrtle - Myrtus communis, Neem - Azadirachta, Niaouli - (MQV) Melaleuca quin, viridiflora, Palmarosa - Cymbopogom martini, Patchouli - Pogostemon patchouli, Peru balsam - Myroxylon balsamum var. Pereirae, Raventsara aromatica, Rosewood - Aniba pink odora, Sage - Salvia officinalis Horsetail - Equisetaceae, yarrow extra - Achillea millefolia, plantain lanceolate - Plantago lanceolata, Styrax - Liquidambar orientalis, Tagetes (Marigold) Tagetes patula, Tea Tree - Melaleuca alternifolia , Tolu balsam - Myroxylon balsamum L., Virginia cedar - Juniperus virgi- niana, Frankincense (Olibanum) - Boswellia carteri, Silver fir - Abies alba.

Another advantage of the aforementioned essential oils lies in their particular multifunctionality, which, in addition to the described mild antiseptic activity, results from a large number of other desirable organoleptic properties attributable to these oils. These oils are in most cases given an expectorant effect because they exert on the mucous membranes of the respiratory organs a mild, positive stimulus. Furthermore, a desirable feeling of warmth can be established. Deodorant, analgesic, circulation-promoting, calming effects could be observed in connection with the use according to the invention of these designated oils and be recognized as particularly advantageous. As a rule, the organoleptic properties of these oils are not from the main components, but from the Neben- od. Trace components marked that often go into the hundreds and sometimes synergistically work together. Another advantage associated with these oils is their harmonizing fragrance and scent, which in many cases leads to positive feelings in people. In this way, for example, supports a corresponding detergent or laundry washed with this not only the natural skin flora of man, but helps the human body to additional benefits just described type. Against this background, especially the tea tree oil is of great advantage for the subject invention. In addition to its considerable germicidal, antiseptic, fungicidal, antiviral, wound-healing, anti-inflammatory, scarring-promoting effect, it has excellent skin compatibility and offers a wide range of other applications, for example with regard to the supportive treatment of colds or diseases of the rheumatic type, gout, muscle pain.

In a preferred embodiment, the skin-protecting active substances contained in the optionally coated granules which can be prepared according to the invention are a skin-protecting oil. The skin-protecting substance is advantageously a skin-protecting oil, eg. B. also to a carrier oil, in particular selected from the group algae oil Oleum Phaeophyceae, aloe vera oil aloe vera brasiliana, apricot kernel oil Prunus armeniaca, arnica oil Arnica montana, avocado oil Persea americana, borage oil Borago officinalis, calendula oil Calendula officinalis, camellia oil Camellia oleifera, safflower oil Carthamus tinctorius, peanut oil Arachis hypogaea, hemp oil cannabis sativa, hazelnut oil Corylus avellana /, currant oil Hypericum perforatum, jojoba oil Simondsia chinensis, carrot oil Daucus carota, coconut oil Cocos nucifera, pumpkin seed oil Curcubita pepo, kukui nut oil Aleurites moluccana, macadamia nut oil Macadamia ternifolia, almond oil Prunus dulcis , Olive oil Olea europaea, pear kernel oil Prunus persica, rapeseed oil Brassica oleifera, castor oil Ricinus communis, black seed oil Nigella sativa, sesame seed oil Sesamium indicum, sunflower oil Helianthus annus, grape seed oil Vitis vinifera, walnut oil Juglans regia, wheat germ oil Triticum sativum, where from these are particularly beneficial to borage oil, hemp oil and almond oil.

All of the oils just listed are natural emollients, ie agents that soften and soften body tissues and reduce the roughness of the skin. So these oils have a skin conditioning effect. On the other hand, it is precisely these oils which have further specific effects which result in a synergistic interaction with the skin and its self-regulating forces and also enable protection under adverse conditions. A particularly preferred oil in the context of this invention is, for example, the hemp oil. Hemp oil, which contains a high proportion of essential fatty acids and also contains up to 6% by weight of valuable γ-linolenic acid (GLA), also has an anti-inflammatory, slightly analgesic, healing, nourishing, skin structure improving, preventing the appearance of old age. It improves tissue regeneration processes and has a high regenerative effect on injured tissue. In addition, it may increase the care properties or other properties of other oils in particular of all oils explicitly mentioned here. Since essential fatty acids play a key role in maintaining the barrier function of the skin because they help to regulate and normalize transepidermal water loss via the skin, hemp oil can play a special role in the context of this invention as a consequence of its high GLA content because localized treatment with GLA results in the greatest reduction in transepidermal water loss in disturbed transepidermal water loss. Furthermore, hemp oil has further positive effects on the human organism in terms of arteriosclerosis, rheumatoid arthritis, diabetic neuropathy to heart problems. Another preferred oil for the purposes of this invention is the borage oil.

Due to its high GLA content (up to 25% by weight) it has comparable properties and advantages to hemp oil.

In a preferred embodiment, the agents according to the invention contain skin-healing active substances which have a minimum content of 0.1% by weight of GLA, preferably of 0.3% by weight, particularly preferably of 0.5% by weight, based on the respective active substance. These include, for example, black cumin oil, Echiumöl, Trichodesmaöl, evening primrose oil and the blackcurrant seed oil.

Another preferred oil is almond oil. It is characterized by the fact that it can enhance the action of other oils, which is why it is advantageously used in combination with other oils.

According to another embodiment of the invention, it is advantageous to combine different oils in the granules, i. So to combine the antiseptic effective with the skin-protecting or even to combine the antiseptic and the skin-protecting one another.

In a preferred embodiment, the agents according to the invention comprise at least 1% by weight, preferably at least 5% by weight, particularly preferably at least 10% by weight, in a very particular manner preferably at least 15% by weight of one or more skin-protecting and / or or skin-healing active substances or oils or essential oils, it being even more advantageous if even at least 20 wt .-%, in particular even more than 25 wt .-%, even better than more than 30 wt .-% of one or more skin-protecting and / or skin-healing active substances or oils or essential oils are contained, in each case based on the total agent (ie granules produced according to the invention).

In a preferred embodiment, the optionally prepared granules which can be prepared according to the invention additionally comprise urea and / or lactic acid and / or citric acid and / or salts thereof.

Urea promotes skin health by providing anti-microbial, water-binding, anti-itching, dandruff-releasing, skin-smoothing, and inhibiting excessive cell growth. Furthermore, it can serve the skin as a moisturizing factor, i. it can help the skin to retain moisture.

Lactic acid and / or citric acid and / or their salts are used inter alia. to support or renew the natural acid mantle or hydrolipid film of the skin. The hydrolipidic film of the skin is attacked or destroyed by alkaline influences, resulting in a loss of the barrier function of the skin, so that microorganisms or pollutants can more easily penetrate into the skin. By virtue of the preferably contained lactic and / or citric acid in the agents according to the invention, e.g. Remove residual alkali from clothing and adjust the pH of the textiles to a pH range around 5. The additional lactic acid, which is already part of the epidermis, has an additional stabilizing effect on the acidic pH of the skin (pH approx. 5.2) and serves as a moisturizing factor, since it can improve the water binding ability of the skin. Furthermore, the lactic acid smoothes the skin and supports the detachment of dander.

In addition to the special moisturizing factors mentioned, in a preferred embodiment the compositions according to the invention may contain further moisturizing factors, for example those selected from the following group: amino acids, chitosan or chitosan salts / derivatives, ethylene glycol, glucosamine, glycerol, diglycerol, triglycerol, uric acid, honey and hardened honey, creatinine, cleavage products of collagen, lactitol, polyols and polyol derivatives (for example, butylene glycol, erythritol, propylene glycol, 1, 2,6-hexane triol, polyethylene glycols such as PEG-4, PEG-6, PEG-7, PEG-8, PEG- 9, PEG-10, PEG-12, PEG-14, PEG-16, PEG-18, PEG-20), pyrrolidone carboxylic acid, sugars and sugar derivatives (e.g., fructose, glucose, maltose, maltitol, mannitol, inositol, sorbitol, sorbitylsilanediol. Sucrose, trehalose, xylose, xylitol, glucuronic acid and salts thereof), ethoxylated sorbitol (sorbeth-6, sorbeth-20, sorbeth-30, sorbeth-40) Starch hydrolysates and mixtures of hardened wheat protein and PEG-20 acetate copolymer, in particular panthenol.

In a preferred embodiment, the skin-protecting and / or skin-healing and / or skin-care active substances preferably contained in the optionally coated granules which can be prepared according to the invention are reversibly fixed to a polymeric carrier, preferably to a silicic acid ester, so that a delayed release of the skin-protecting and / or skin-healing active ingredients is possible.

The skin-healing and / or skin-protecting and / or skin-care active ingredients are thus z. B. reversibly fixed by adsorption on a polymeric carrier, optionally with the participation of surfactants, so that a delayed release of the healing active ingredients is possible. This is particularly advantageous because in this way an even longer-lasting effect can be achieved, which is especially useful for consumers with particularly irritated skin. The fact that the healing and / or protective and / or nourishing substances continuously over a longer period z. B. delivered in relatively low dosage to the skin, it is possible to intervene in a very gentle manner in the particularly sensitive balance of self-regulatory strong irritated skin supportive. The effect of the active ingredients is so mild that, in spite of their effectiveness, it does not overwhelm the already highly irritated skin.

Particularly preferred polymeric carriers belong to the class of silicic acid esters. However, it can also be any conceivable other carrier, with the only provisos that they allow delayed release of active ingredient and as such have no negative or irritating effect on the skin, if used for the purposes of this invention.

According to a preferred embodiment of the invention, the core material of the inventively producible, optionally coated, granules comprises one or more

Ingredients selected from

(n) Turmeric powders (spray drying products), including e.g. Mixtures of thermally stable ingredients of detergents or cleaners

(o) carbonates, such as preferably soda,

(P) hydrogencarbonates, in particular alkali metal and / or alkaline earth metal hydrogencarbonates

(q) sulfates, especially alkali and / or alkaline earth sulfates

(r) anionic surfactant compounds (comprising, for example, fatty alcohol sulfates, alkylbenzenesulfonates, alkanesulfonates, alkyl ether sulfates, alkyl sulfates, α-olefin sulfonates and / or ester sulfonates, in particular methyl ester sulfonates, and / or mixtures thereof), (s) bleach activators, in particular N, N, N ', N'-tetraacetylethylenediamine,

(c) citrates, preferably alkali metal and / or alkaline earth metal citrates, in particular sodium, potassium and / or magnesium

Citrate

Builder (compounds), preferably zeolite (compounds) and / or polycarboxylate (compounds)

The use of inventively producible, optionally coated, granules containing at least one skin-protecting and / or skin-healing active for the preparation of a medically active detergent for finishing textiles for the supportive treatment of irritated and / or sensitized and / or diseased human skin as well as for the prophylactic treatment of healthy skin a preferred embodiment of the invention.

The use of at least one skin-protecting and / or skin-healing active substance for the production of a medically active additive in the form of inventively preparable, optionally coated, granules for detergents for finishing textiles for the supportive treatment of irritated and / or sensitized and / or diseased human skin and for prophylactic treatment healthy skin is a preferred embodiment of the invention.

The invention also relates to the use of a detergent according to the invention which, optionally coated granules, in a laundry process or a machine washing process.

Such a washing process is characterized according to a preferred embodiment in that they are not removed during the washing process in the course of Abpumpvorgängen essentially not from the washing machine and precipitate during the washing process preferably in the course of Abpumpvorgängen on the laundry.

Thus, when using a detergent according to the invention with certain buoyant, inventively produced, optionally coated granules in an ordinary machine laundry process, it was advantageously observed that the compositions according to the invention interrupts the washing program after the main wash and immediately before the rinse and the laundry visually inspected in the laundry drum, deposited well visible on the laundry. At such an observation time, the washing liquor contaminated as a result of the cleaning process is largely pumped out of the machine and the laundry is dripping wet in the washing drum or washing chamber. Although certain certain inventively producible, optionally coated Teten, granules are theoretically pumped with the wash liquor, since they fit, for example, the size of the many small openings of a washing drum, certain inventively produced, optionally coated granules remain in the inventive use according to this preferred embodiment substantially in the washing drum, preferably as a precipitate on the laundry. It could further be observed that, after this optical inspection of the laundry, the washing machine closes again, and continues with the rinse, the certain inventively produced, optionally coated, granules after completion of the rinse and before the spin cycle in the rinse have dissolved. If the washing machine is opened immediately after completion of the rinse cycle and before the start of the spin cycle and the viscous laundry is visually inspected, in the case of this particular embodiment, none of these inventively producible, optionally coated, granules can be seen more on the laundry.

The invention also relates to a washing process in a commercial washing machine, wherein a detergent according to the invention, which contains, optionally coated granules, introduces into the washing machine and brings it there with water and the laundry in contact, preferably in that the detergent in the Einspülkammer introduces the commercially available washing machine and rinsed with water in the washing chamber or drum, and run a conventional washing program, preferably the coating, if present, contained coated granules during the washing of the detergent and during the Vorwaschganges and during the early stages of the main wash cycle retains its integrity in whole or in part, advantageously loses its integrity in the late stages of the main wash cycle and / or rinse.

In a preferred embodiment of the method, the optionally coated, contained in the detergent detergent according to the invention are not substantially removed during the washing process in the course of Abpumpvorgängen from the washing machine, but are preferably in the late stages of the washing process, especially in the course of Abpumpvorgängen down on the wash.

According to another preferred embodiment of the process according to the invention, the optionally coated granules (constructed as final process product) essentially have an average form factor of at least 0.79, preferably at least 0.81, advantageously at least 0.83, in a further advantageous manner at least 0.85, in particular of at least 0.87. "Substantially" means here in particular that at least 80%, preferably at least 90% and more preferably at least 95% the built up granules have the just mentioned form factor. The built-up granules are preferably the entirety of good grain, oversize grain and undersize (fines), which proves that oversize and undersize particles (fines) are preferably too negligible.

The shape factor in the sense of the present invention can be precisely determined by modern particle-measuring techniques with digital image processing. In a typical particle shape analysis, such as with the Camsizer® system by Retsch Technology or with the KeSizer® Kemira is feasible, based on the fact that the particles or the bulk material are irradiated with a light source and detects the particles as projection surfaces , digitized and processed by computer technology. The surface curvature is determined by means of an optical measurement method, which determines the "shadow cast" of the parts to be examined and converts them into a corresponding form factor.The underlying principle for determining the shape factor was described by Gordon Rittenhouse in "A Visual method of estimating two-dimensional sphericity "in Journal of Sedimentary Petrology, Vol. 13, No. 2, pp. 79-81.

The measurement limits of this optical analysis method are 15 μm and 90 mm, respectively. The numerical values for d ₅₀ and d ₉₀ are also available via the aforementioned measuring method.

In this case, the granules according to the invention may preferably contain all the ingredients required or commonly used for a washing and / or cleaning process, so that such granules are in themselves an independent, fully functional and functional washing and / or cleaning agent. An inventively constructed detergent and / or detergent granules is therefore preferably a complete washing and / or cleaning agent.

However, it is also preferred if the granulate according to the invention contains only one particular or several particular detergent and / or cleaning agent constituents. Such a granulate constructed in accordance with the invention would then not be an independent, complete and functional washing and / or cleaning agent, but rather a detergent and / or detergent component. Such a granulate would then be mixed with the other customary components which are necessary for the formation of a complete washing and / or cleaning agent. In such a case, it is preferred if at least two or more granules constructed according to the invention are mixed to form a washing and / or cleaning agent and the resulting fully-fledged washing and / or cleaning agent only consists of consists of these inventively constructed granules, wherein the different granules preferably have different colors.

In the context of the present invention, the term of the optionally coated granules which can be prepared according to the invention also includes washing and / or cleaning agent granules, i. to understand both full-strength detergents and / or detergents as well as detergent and / or detergent components.

Another object of the present invention is the use of the method according to the invention for the transfer of powdery and / or fine-grained multi-component mixtures from the field of detergents and cleaning agents, e.g. commercially available detergents and / or cleaners, in granules provided with an (optional) coating.

In this way, the refinement of conventional detergents to high-quality dosage forms with controlled release of active ingredient, sustained release effect and optically unique quality succeeds.

Although neither the method according to the invention nor the agent according to the invention is fundamentally restricted to the field of detergents and cleaning agents, such agents and / or methods represent particularly preferred embodiments of the invention. Therefore, in the following, more detail on possible ingredients according to the invention will be provided. or detergent granules, ie coated detergent and / or cleaning granules (granules) received.

The constituents contained in the detergent granules (granules) to be produced according to the invention are preferably selected from the group comprising surfactants, fragrances, dyes, builders, pH adjusters, bleaches, bleach activators, soil repellents, optical brighteners, grayness inhibitors , Disintegration aids, conventional ingredients and / or mixtures thereof. Furthermore, all other detergents and / or cleaning agent ingredients known to the person skilled in the art from the prior art can also be any of the customary amounts of constituents of the washing and / or cleaning agent granules (granules) to be prepared according to the invention.

Some of the washing and / or cleaning agent components which are particularly suitable according to the invention will be explained in greater detail below. These ingredients can be added to the washing and / or detergent granules (granules) themselves be contained and / or in appropriate admixtures, which may optionally be added to the detergent granules (granules), if necessary, to obtain a complete washing and / or cleaning agent , All components listed below are purely optional, but may preferably contain sin.

As surfactants, it is possible to use anionic, cationic, amphonic and / or nonionic surfactants for the preparation according to the invention of the washing and / or cleaning agent granules (granules).

For example, anionic surfactants of the sulfonate and sulfates type can be used. The surfactants of the sulfonate type are preferably C ₉ . _13- Alkylbenzolsulfonate, Olefinsulfonate, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as obtained for example from C ₁₂ -i ₈ monoolefins having terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation , considering. Also suitable are alkanesulfonates which are obtained from C _12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Likewise suitable are the esters of .alpha.-sulfo fatty acids (ester sulfonates), for example the .alpha.-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids. Also suitable are sulfonation of unsaturated fatty acids, for example oleic acid, in small amounts, preferably in amounts not above about 2 to 3 wt .-%. In particular, preferred are α-sulfofatty acid alkyl esters which have an alkyl chain having not more than 4 carbon atoms in the ester group, for example, methyl ester, ethyl ester, propyl ester and butyl ester. With particular advantage, the methyl esters of α-sulfo fatty acids (MES), but also their saponified disalts are used.

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 in the preparation by esterification of a monoglycerol with 1 to 3 mol of fatty acid or in the transesterification of triglycerides with 0.3 to 2 mol Glycerol can be obtained. Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids containing 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) yl sulfates are the alkali and especially the sodium salts of Schwefelsäurehalbester the C ₁₂ -C ₁₈ fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or C ₁₀ -C ₂ o Oxo alcohols and those half esters 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.

Suitable further anionic surfactants are fatty acid derivatives of amino acids, for example N-methyltaurine (Tauride) and / or N-methylglycine (sarcosides). Particularly preferred are the sarcosides or the sarcosinates and here especially sarcosinates of higher and optionally monounsaturated or polyunsaturated fatty acids such as oleyl sarcosinate.

As further anionic surfactants are particularly soaps into consideration. Suitable are saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, 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, including the soaps, may be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine. The anionic surfactants are preferably present in the form of their sodium or potassium salts, in particular in the form of the sodium salts.

The anionic surfactants may be present in the detergent and / or detergent granules to be produced according to the invention preferably in amounts of from 1 to 30% by weight and in particular in amounts of from 5 to 25% by weight.

It is also possible to use alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters. Preferred nonionic surfactants are C ₁₂ -C ₁₈ fatty acid methyl esters having an average of from 3 to 15 EO, in particular having an average of from 5 to 12 EO. In particular, C ₁₂ -C ₁₈ fatty acid methyl esters with 10 to 12 EO can be used as surfactants.

Another class of nonionic surfactants which can be advantageously used for the production according to the invention of detergent granules (granules) are the alkylpolyglycosides (APG). Usable Alkypolyglycoside satisfy the general formula RO (G) _Z , in which R is a linear or branched, especially in the 2-position methyl-branched, saturated or unsaturated, aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the Symbol is that for a glycose unit having 5 or 6 C atoms, preferably for glucose. The glycosidation degree z is between 1, 0 and 4.0, preferably between 1, 0 and 2.0 and in particular between 1, 1 and 1, 4.

Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable for the inventive preparation of the detergent granules (granules) ,

Suitable further surfactants for the preparation according to the invention of the washing and / or cleaning agent granules (granules) are so-called gemini surfactants. These are generally understood as meaning those compounds which have two hydrophilic groups and two hydrophobic groups per molecule. These groups are usually separated by a so-called "spacer". This spacer is typically a carbon chain that should be long enough for the hydrophilic groups to be spaced sufficiently apart for them to act independently of each other. Such surfactants are generally characterized by an unusually low critical micelle concentration and the ability to greatly reduce the surface tension of the water. In exceptional cases, however, the term gemini surfactants is understood to mean not only dimeric but also trimeric surfactants. Gemini surfactants for the preparation of detergents and / or cleaning agent granules (granules) according to the invention are, for example, sulfated hydroxy mixed ethers or dimer alcohol bis- and trimer alcohol tris sulfates and ether sulfates. End-capped dimeric and trimeric mixed ethers are especially characterized by their bi- and multi-functionality. Thus, the end-capped surfactants mentioned have good wetting properties and are low foaming, so that they are particularly suitable for use in automatic washing and / or cleaning processes. The laundry and / or cleaning agent granules (granules) which can be prepared according to the invention may contain as builder or builder all builders customarily used in detergents and / or cleaning agents, in particular detergents, in particular zeolites, silicates, carbonates, soda, organic cobuilders and also the phosphates. To avoid particulate residues on textiles, it is particularly advantageous to use builders which are completely water-soluble, such as soda or the like.

Suitable crystalline, layered sodium silicates have the general formula NaMSi _x O _{2x + I} H ₂ O, where M is sodium or hydrogen, x is a number from 1, 9 to 4 and y is a number from 0 to 20 and preferred values for x 2 , 3 or 4 are. 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. It is also possible to use amorphous sodium silicates with a Na ₂ O: SiO ₂ modulus 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. Particularly preferred are amorphous silicates.

A useful fine crystalline, synthetic and bound water-containing zeolite is preferably zeolite A and / or P. As zeolite P zeolite MAP ^® (commercial product from Crosfield) is particularly preferred. Also suitable, however, are zeolite X and mixtures of A, X and / or P. Commercially available and preferably usable in the context of the present invention is, for example, a cocrystal of zeolite X and zeolite A (about 80% by weight of zeolite X) ), which is sold by Condea Augusta SpA under the brand name VEGOBOND AX ^® and the formula:

n Na ₂ O (1-n) K ₂ O Al ₂ O ₃ (2 - 2.5) SiO ₂ (3.5-5.5) H ₂ O.

Suitable zeolites preferably have an average particle size of less than 10 microns (volume distribution, measuring method: Coulter Counter) and preferably contain 18 to 22 wt .-%, in particular 20 to 22 wt .-% of bound water.

The content of the granules of zeolite according to the invention can be up to 60 wt .-%, advantageously up to 40 wt .-% and in a further advantageous manner up to 30 wt .-% according to a preferred embodiment, and it may be even more advantageous if at most 15% by weight, preferably at most 12% by weight, in particular not more than 10% by weight, based in each case on the anhydrous active substance, for example 1 to 8% by weight or 0 to 5% by weight. In a particularly preferred embodiment, the granules which can be prepared according to the invention are free of zeolite.

Of course, a use of the well-known phosphates as builders is possible, unless such use should not be avoided for environmental reasons. Particularly suitable are the sodium salts of orthophosphates, pyrophosphates and in particular tripolyphosphates. The granules according to the invention are preferably not only zeolite but also low in phosphate. Thus, the phosphate content is advantageously at most 15 wt .-%, preferably at most 12 wt .-%, in particular at most 10 wt .-%, for example 1 to 8 wt .-% or 0 to 5 wt .-%. Very particular preference is given to granules which are both free of zeolite and of phosphate. As organic cobuilders, the detergent and / or cleaning agent granules according to the invention may contain, in particular, polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, further organic cobuilders (see below) and also phosphonates. These classes of substances are described below.

Useful organic builder substances are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, and mixtures of these. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof.

The acids themselves can also be used. In addition to their builder effect, the acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents and / or cleaning agents. In particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.

Further suitable builders are polymeric polycarboxylates, for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a relative molecular mass of from 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 weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molar masses of from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, may again be preferred from this group. Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable. Their relative molecular weight, based on free acids, is generally from 2000 to 70000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol.

Also particularly preferred are biodegradable polymers of more than two different monomer units, for example those which contain 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-alkylallylsulfonic acid and sugar derivatives ,

Further preferred copolymers are those which preferably have as monomers acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.

Also to be mentioned as further preferred builders polymeric aminodicarboxylic acids, their salts or their precursors. Particular preference is given to polyaspartic acids or their salts and derivatives which, in addition to cobuilder properties, also have a bleach-stabilizing action.

Further suitable builder substances are polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 C atoms and at least 3 hydroxyl groups. Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.

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 from 0.5 to 40, in particular from 2 to 30 is preferred, DE being a common measure of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100 , is. Both maltodextrins with a DE of between 3 and 20 and dry glucose syrups with a DE of between 20 and 37 and also so-called yellow dextrins and white dextrins with relatively high molecular weights in the range from 2000 to 30 000 g / mol are useful. The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function. A product oxidized to C _{6 of} the saccharide ring may be particularly advantageous.

Oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disucinate, are further suitable co-builders. Ethylenediamine-N, ^{N'-disuccinate} (EDDS) is preferably in the form of its sodium or magnesium salts. Also preferred in this context are glycerol disuccinates and glycerol trisuccinates.

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

Another class of substances with cobuilder properties are the phosphonates. These are, in particular, hydroxyalkane or aminoalkanephosphonates. Among the hydroxyalkane phosphonates, the 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a co-builder. It is preferably used as the sodium salt, the disodium salt neutral and the tetrasodium salt alkaline (pH 9). Preferred aminoalkane phosphonates are ethylenediamine tetramethylene phosphonate (EDTMP), diethylene triamine pentamethylene phosphonate (DTPMP) and their higher homologs. They are preferably in the form of neutral sodium salts, eg. B. as the hexasodium salt of EDTMP or as hepta- and octa-sodium salt of DTPMP used. The builder used here is preferably HEDP from the class of phosphonates. The aminoalkanephosphonates also have a pronounced heavy metal binding capacity. Accordingly, in particular if the washing and / or cleaning agents also contain bleach, it may be preferable to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned for producing the granules.

In addition, all compounds capable of forming complexes with alkaline earth ions can be used as co-builders.

Further suitable builder substances for preparing the detergent granules according to the invention are oxidation products of carboxyl-containing polyglucosans and / or their water-soluble salts. Also suitable are oxidized oligosaccharides. Further builder substances which are suitable for the preparation according to the invention of the detergent granules and / or detergent granules are polyacetals which are prepared by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 C atoms and at least 3 hydroxyl groups. Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.

In order to reduce the pH of detergents and / or cleaning agents, in particular detergents, the granules which can be prepared according to the invention can also have acid salts or slightly alkaline salts. Preferred acidifying components are bisulfates and / or bicarbonates or organic polycarboxylic acids, which can also be used simultaneously as builders. Particularly preferred is the use of citric acid.

The laundry and / or cleaning agent granules which can be prepared according to the invention can also comprise bleaching agents. Among the compounds serving as bleaches in water H ₂ O ₂ , sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Other useful bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.

It is also possible to use bleaching agents from the group of organic bleaching agents for the preparation of the washing and / or cleaning agent granules (optionally coated, granules which can be prepared according to the invention). Typical organic bleaches are the diacyl peroxides such as dibenzoyl peroxide. Other typical organic bleaches are the peroxyacids, examples of which include 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 peroxy acids, such as peroxylauric acid, peroxystearic acid, ε-phthalimido peroxycaproic acid [Phthaloiminoperoxyhexanoic acid (PAP)], o-carboxybenzamido-peroxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate; and (c) peroxydicarboxylic acids such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperocysebacic acid, diperoxybrassic acid, the diperoxyphthalic acids , 2-Decyldiperoxybutan-1, 4-diacid, N, N-terephthaloyl-di (6-aminopercapronic) can be used to prepare the granules of the invention. Chlorine or bromine-releasing substances can also be used as bleaching agents in the detergent and / or detergent granules preparable according to the invention. Suitable chlorine or bromine-releasing materials include, for example, heterocyclic N-bromo and N-chloroamides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium. Hydantoin compounds, such as 1,3-dichloro-5,5-dimethylhydantoin are also suitable.

The content of bleaching agents may preferably be from 0 to 25% by weight and in particular from 1 to 20% by weight, based on the total composition of the detergent and / or detergent granules obtainable according to the invention.

In order to achieve an improved bleaching effect during washing or cleaning at temperatures of 60 ^° C. and below, bleach activators may be present.

As bleach activators for the preparation of the detergent granules according to the invention, it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups. Preference is given to polyacylated alkylene diamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5- di-acetoxy-2,5-dihydrofuran.

In addition to the conventional bleach activators or in their place, so-called bleach catalysts can also be used for the preparation according to the invention of the detergent granules and / or detergent granules. These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo saline complexes or carbonyl complexes. Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes can also be used as bleach catalysts.

Enol esters and acetylated sorbitol and mannitol, acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetyl fructose, tetraacetylxylose and octaacetyl lactose as well as acetylated, optionally N-alkylated glucamine and gluconolactone, can also be used as bleach activators for the preparation of the detergent granules according to the invention. and / or N-acylated lactams, for example N-benzoyl-caprolactam. Hydrophilically substituted acylacetals and acyl lactams are likewise preferably used for the preparation of the washing and / or cleaning agent granules according to the invention. In particular when used in automatic washing processes, it may be advantageous to add to the washing and / or cleaning agent granules customary foam inhibitors. Suitable foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C18-C24 fatty acids. Suitable non-surfactant foam inhibitors are, for example, organopolysiloxanes and mixtures thereof with microfine, optionally silanized silica and paraffins, waxes, microcrystalline waxes and mixtures thereof with silanated silica or bistearylethylenediamide.

According to a preferred embodiment of the invention, the optionally coated, granules according to the invention are free of enzymes, which means for the purposes of the invention that they less than 30 wt .-%, preferably less than 25 wt .-%, advantageously less than 20 wt. -%, more preferably less than 15 wt .-%, more preferably less than 10 wt .-%, in turn advantageously less than 5 wt .-% of enzymes, based on the total, optional coated, granules. In particular, however, they are completely enzyme-free, ie they contain 0% by weight of enzyme based on the total, optionally coated, granules.

According to a preferred embodiment of the invention, the optionally coated granules are bleach-free.

According to a further preferred embodiment of the invention, the core and / or the shell and / or the (optional) coating of the optionally coated granules according to the invention are free of enzymes, which means for the purposes of the invention that in each case the core and / or the shell and / or the coating is less than 30% by weight, preferably less than 25% by weight, advantageously less than 20% by weight, more preferably less than 15% by weight, even more advantageously less than 10 wt .-%, in turn advantageously less than 5 wt .-%, in particular 0 wt .-% of enzymes, based on the respective phase of, optionally coated, granules. However, it is very preferred if both the core and the shell and also the coating are free of enzymes in the just mentioned sense, in particular they each contain 0 wt .-% of enzyme based on the total, optionally coated, granules.

However, it is most preferred if at least the shell of the optionally coated, granules according to the invention is free of enzymes, which means in the context of the invention that the Shell less than 30% by weight, preferably less than 25% by weight, advantageously less than 20% by weight, more preferably less than 15% by weight, even more advantageously less than 10% by weight. %, in a further advantageous manner contains less than 5 wt .-%, in particular 0 wt .-% of enzymes, based on the total, optionally coated, granules.

However, if enzymes should be present, which corresponds to another preferred embodiment, suitable enzymes for the preparation according to the invention of the detergent granules are, in particular, those from the classes of hydrolases such as proteases, esterases, lipases or lipolytic enzymes, amylases, Glykosylhydrolasen and mixtures of the enzymes mentioned in question. All of these hydrolases contribute to the removal of stains such as proteinaceous, fatty or starchy stains.

According to a further preferred embodiment, the optionally coated granules are enzyme-containing, wherein according to a preferred embodiment here advantageously 2 phases of the optionally coated granules according to the invention, namely preferably shell and (optional) coating, are completely free of enzymes, whereas advantageously the third phase, preferably the core, contains enzyme, in particular in amounts greater than 1 wt .-%, but less than 80 wt .-%, preferably less than 70 wt .-%, advantageously less than 60 wt .-%, in further advantageously less than 50% by weight, more preferably less than 40% by weight, again more advantageously less than 30% by weight, more preferably less than 20% by weight, even more advantageously Way less than 10% by weight, based on the total mass of the core.

According to the aforementioned embodiment, a further subject of the invention is the use of the inventive, optionally coated, granules as enzyme granules, which preferably have an enzyme-free shell and / or an enzyme-free coating.

For bleaching oxidoreductases may preferably be used. Particularly suitable for the preparation of detergents and / or cleaning granules are those enzymes which are derived from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus, Coprinus cinereus and Humicola insolens as well as from their genetically modified variants enzymatic agents. Preferably, subtilisin-type proteases and in particular proteases derived from Bacillus lentus are obtained. In this case, enzyme mixtures, for example from protease and amylase or protease and lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytic acting enzymes or protease, lipase or lipolytic enzymes, but in particular protease and / or lipase-containing mixtures or mixtures with lipolytic enzymes of particular interest. Examples of such lipolytic enzymes are the known cutinases. Peroxidases or oxidases have also proved suitable in some cases. Suitable amylases include, in particular, alpha-amylases, iso-amylases, pullulanases and pectinases. Oxireductases are also suitable.

For the preparation according to the invention of the washing and / or cleaning agent granules, in addition to the abovementioned enzymes, cellulases may additionally be considered. Cellulases and other glycosyl hydrolases can contribute to color retention and increase the softness of the fabric by removing pilling and microfibrils. Cellulases used are preferably cellobiohydrolases, endoglucanases and glucosidases, which are also called cellobiases, or mixtures of these. Since different cellulase types differ by their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases.

The proportion of enzymes or enzyme mixtures may, provided that the granules of the invention are not completely free of enzyme, which is preferred, for example, about 0.1 to 5 wt .-%, preferably 0.5 to about 4.5 wt .-%, based on the total, optionally coated, granules amount.

Apart from possibly phosphonates, the laundry and / or cleaning agent granules which can be prepared according to the invention may contain further enzyme stabilizers. For example, the washing and / or cleaning agent granules may contain sodium formate. It is also possible to use proteases which are stabilized with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme. In addition to calcium salts, magnesium salts also serve as stabilizers. However, it is particularly advantageous to use boron compounds, for example boric acid, boron oxide, borax and other alkali metal borates, such as the salts of orthoboric acid (H ₃ BO ₃ ), metaboric acid (HBO ₂ ) and pyroboric acid (tetraboric acid H ₂ B ₄ O ₇ ).

The optionally coated granules may also contain grayness inhibitors. The purpose of scorch inhibitors is to keep the debris loosened from the fiber suspended in the liquor and thus prevent the dirt from being rebuilt. Water-soluble colloids of mostly organic nature are suitable for this purpose, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or of cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Also, water-soluble, acidic groups containing polyamides are for suitable for this purpose. It is also possible to use soluble starch preparations and starch products other than those mentioned above, for example degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone is also useful. However, preference is given to using cellulose ethers, such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose and mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof, and also polyvinylpyrrolidone in the optionally coated granules according to the invention.

In addition, for the production of, optionally coated, granules and soil-repellent substances can be used which positively influence the oil and Fettauswaschbarkeit from textiles (so-called soil repellents). This effect is particularly evident when a textile is dirty, which has been previously washed several times with a detergent according to the invention, which contains this oil and fat dissolving component. Examples of preferred oil and fat dissolving components include nonionic cellulose ethers such as methylcellulose and methylhydroxypropylcellulose having a methoxyl group content of 15 to 30% by weight and hydroxypropoxyl groups of 1 to 15% by weight, based in each case on the nonionic cellulose ether , As well as known from the prior art polymers of phthalic acid and / or terephthalic acid or derivatives thereof, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionic modified derivatives thereof.

These substances, which are also called "whiteners", can be used to produce the, optionally coated, granules. Optical brighteners are organic dyes that convert part of the invisible UV radiation of sunlight into longer-wavelength blue light. The emission of this blue light complements the "gap" in the light reflected by the textile, so that a fabric treated with optical brightener appears whiter and brighter to the eye. Since the mechanism of action of brighteners requires their application to the fibers, a distinction is made depending on the "fibers to be dyed", for example, brighteners for cotton, polyamide or polyester fibers. The commercially available brighteners suitable for the preparation of the optionally coated granules essentially comprise five structural groups, namely the stilbene, diphenylstilbene, coumarin-quinoline, diphenylpyrazoline and the group of the combination of benzoxazole or benzimidazole with conjugated systems. An overview of common brighteners is easy to find in the relevant literature. Suitable are for example salts of 4,4 ^'- bis [(4-anilino-6-morpholino-s-triazin-2-yl) amino] ^{stilbene-2,2'} disulphonic acid compounds or similarly constructed, instead of the morpholino Group a Diethanolaminogruppe, a methylamino group, an anilino group or a 2-Methoxyethylaminogruppe carry. Furthermore, brighteners of the substituted diphenylstyrene type may be present, for example the alkali metal salts of 4,4'-bis (2-sulfostyryl) -diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) -diphenyl, or (4-chloro- styryl) -4 '- (2-sulfostyryl). Mixtures of the aforementioned brightener can be used.

Fragrances can be added to the optionally coated granules to be produced according to the invention in order to improve the aesthetic impression of the resulting granules and to provide the consumer with a sensory "typical and unmistakable" washing and / or cleaning agent in addition to the cleaning performance and the color impression. As perfume oils or fragrances, individual fragrance compounds, e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used. Fragrance compounds of the ester type are known e.g. Benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate, phenylethyl acetate, linalylbenzoate, benzylformate, ethylmethylphenylglycinate, allylcyclohexylpropionate, styrallylpropionate and benzylsalicylate. The ethers include, for example, benzyl ethyl ether, to the aldehydes e.g. the linear alkanals having 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones, e.g. the alcohols include anethole, citronellol, eugenol, geraniol, linalool, phenylethylalcohol and terpineol; the hydrocarbons mainly include the terpenes such as limonene and pinene. However, mixtures of different fragrances are preferably used for the preparation of the optionally coated granules according to the invention, which together produce an attractive fragrance. Such perfume oils may also contain natural fragrance mixtures such as are available from vegetable sources, e.g. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage, chamomile, clove, lemon balm, mint, cinnamon, lime, juniper, vetiver, olibanum, galbanum and labdanum, and orange blossom, neroliol, orange peel and sandalwood.

Granules which can be produced according to the invention can comprise in particular fragrances selected from fragrances with

(a) almond-like odor, such as preferably benzaldehyde, pentanal, heptenal, 5-methylfurfural, methylbutanal, furfural and / or acetophenone or

(b) apple-like odor, preferably (S) - (+) - ethyl-2-methylbutanoate, diethyl malonate, ethyl butyrate, geranyl butyrate, geranyl isopentanoate, isobutyl acetate, linalyl isopentanoate, (E) -β-damascone, heptyl-2-methyl butyrate, methyl 3-methylbutanoate, 2-hexenalpentyl-methyl butyrate, ethylmethyl butyrate and / or methyl 2-methylbutanoate or

(c) apple peel-like odor, such as preferably ethylhexanoate, hexylbutanoate and / or hexylhexanoate or

(d) apricot-like odor, preferably γ-undecalactone, or (e) banana-like odor, such as preferably isobutyl acetate, isoamyl acetate, hexenyl acetate and / or pentyl butanoate or

(f) bitter almond-like odor such as preferably 4-acetyltoluene or (g) blackcurrant-like odor, such as preferably mercaptomethylpentanone and / or methoxymethylbutanethiol or

(h) citrusy odor such as preferably linalyl pentanoate, heptanal, linalyl isopentanoate dodecanal, linalyl formate, α-p-dimethylstyrene, p-cymenol, nonanal, β-cubebene, (Z) -limonoxide, cis-6-ethenyl-tetrahydro-2,2,6- trimethylpyran-3-ol, cis-pyranoidlinalooloxide, dihydrolinalool, 6 (10) -dihydromyrcenol, dihydromyrcenol, β-farnesene, (Z) -β-farnesene, (Z) -cime, (E) -liminene oxide, dihydrotypinyl acetate, (+) -Limonen, (Epoxymethylbutyl) -methylfuran and / or p-cymene or (i) cocoa-like odor such as preferably dimethylpyrazine, butylmethyl butyrate and / or methyl butanal or

(j) coconut-like odor, such as preferably γ-octalactone, γ-nonalactone, methyl laurate, tetradecanol, methyl nonanoate, (3S, 3aS, 7aR) -3a, 4,5,7a-tetrahydro-3,6-dimethylbenzofuran-2 (3H) on, 5-butyldihydro-4-methyl-2 (3H) -furanone, ethyl undecanoate and / or δ-decalactone or (k) creamy odor, preferably diethyl acetal, 3-hydroxy-2-butanone, 2,3-pentadione and / or 4-heptenal or

(I) flower-like odor such as preferably benzyl alcohol, phenylacetic acid, tridecanal, p-anisyl alcohol, hexanol, (E, E) -farnesylacetone, methyl geranate, trans-crotonaldehyde, tetradecylaldehyde, methyl anthranilate, linalooloxide, epoxylinalool, phytol, 10-epi-γ-eudesmol , Nerol oxide, ethyldihydrocinnamate, γ-dodecalactone, hexadecanol, 4-mercapto-4-methyl-2-pentanol, (Z) -oximes, cetyl alcohol, nerolidol, ethyl (E) -cinnamate, elemicin, pinocarveol, α-bisabolol, ( 2R, 4R) -Tetrahydro-4-methyl-2- (2-methyl-1-propenyl) -2H-pyran, (E) -Isoelemicin, methyl 2-methylpropanoate, trimethylphenylbutenone, 2-methylanisole, β-farnesol, ( E) isoeugenol, nitrophenylethane, ethyl vanillate, 6-methoxyeugenol, linalool, β-ionone, trimethylphenylbutenone, ethyl benzoate, phenylethyl benzoate, isoeugenol and / or acetophenones, or (m) freshness odor, preferably methylhexanoate, undecanone, (Z) -imony oxide , Benzyl acetate, ethyl hydroxyhexanoate, isopropyl hexanoate, pentadecanal, β-elemene, α-zingiberene, (E) -lone oxide, (E. ) -p-mentha-2,8-dien-1-ol, menthone, piperone, (E) -3-hexenol and / or carveol or (n) fruit odor, preferably ethylphenylacetate, geranylvalerate, y-heptalactone, ethylpropionate, Diethyl acetal, geranyl butyrate, ethylheptylate, ethyloctanoate, methylhexanoate, dimethylheptenal, pentanone, ethyl-3-methylbutanoate, geranylisovalerate, lobutylacetate, ehoxypropanol, methyl-2-butenal, methylnonanedione, linalylacetate, methylaryanate, ammonium oxide, hdrocinnamic alcohol, ethylsuccinate, ethylhexanoate, ethylmethylpyrazine, ethyl acetate, Cetronellyl butyrate, heyl acetate, nonyl acetate, butyl methyl butyrate, pentenal, isopentyl dimethylpyrazine, p-menth-1-en-9-ol, hexadecanone, octyl acetate, γ-dodecalactone, epoxy-β-ionone, ethyloctenoate, Ethyl isohexanoate, isobornyl propionate, cedrenol, p-menth-1-en-9-yl acetate, cadinadiene, (Z) -3-hexenylhexanoate, ethylcyclohexanoate, 4-methylthio-2-butanone, 3,5-octadienone,

Methylcyclohexanecarboxylate, 2-pentylthiophene, α-ocimene, butanediol, ethylvalerate, pentanol, isopiperiton, butyloctanoate, ethylvanylate, methylbutanoate, 2-methylbutylacetate, propylhexanoate, butylhexanoate, isopropylbutanoate, spathulenol, butanol, δ-dodecalactone, methylquinoxaline, sesquipellandrene, 2- Hexenol, ethylbenzoate.isopropylbenzoate, ethyl lactate and / or citronellyl isobutyrate or

(o) Geranium-like odor, such as preferably geraniol, (E, Z) -2,4-nonadienal, octadienone and / or o-xylene or

(p) grape-like odor such as preferably ethyl decanoate and / or hexanone or (q) grapefruit-like odor such as preferably (+) - 5,6-dimethyl-8-isopropenylbicyclo [4.4.0] dec-1-en-3-one and / or p-menthenethiol or

(r) grassy odor such as preferably 2-ethylpyridine, 2,6-dimethylnaphthalene, hexanal and / or (Z) -3-hexenol or (s) green note, preferably 2-ethylhexanol, 6-decenal, dimethylheptenal, hexanol, heptanol, Methyl-2-butenal, hexyloctanoate, nonanoic acid, undecanone, methyl geranate, isobornylformiate, butanal, octanal, nonanal, epoxy-2-decenal, cis-linalool, pyranoxide, nonanol, alpha, γ-dimethylallylalcohol, (Z) -2-pentene 1-ol, (Z) -3-hexenylbutanoate, isobutylthiazole, (E) -2-nonenal, 2-dodecenal, (Z) -4-decenal, 2-octenal, 2-hepten-1-al, Bicyclogermacrene, 2- Octenal, α-thujene, (Z) -β-farnesene, (-) - γ-elemene, 2,4-octadienal, fucoserrate, hexenyl acetate, geranylacetone, valencene, β-eudesmol, 1-hexenol, (E) -2- Undecenal, artemisia ketone, viridiflorol, 2,6-nonadienal, trimethylphenylbutenone, 2,4-nonadienal, butyl isothiocyanate, 2-pentanol, elemole, 2-hexenal, 3-hexenal, (+) - (E) -lemonone, cis-isocitral , Dimethyloctadienal, bornyl formate, bornyl isovalerate, isobutyraldehyde, 2,4-hexadiene al, trimethylphenylbutenone, nonanone, (E) -2-hexenal, (+) - cis-rose oxides, menthone, coumarin, (epoxymethylbutyl) -methylfuran, 2-hexenol, (E) -2-hexenol and / or carvylacetate or (t ) Green Tea-like odor, preferably (-) - Cubenol or

(u) herbaceous odor, preferably octanone, hexyloctanoate, caryophyllene oxides ,. Methylbutenol, safranal, benzyl benzoate, bornyl butyrate, hexyl acetate, β-bisabolol, piperitol, β-selenene, α-cubebene, p-menth-1-en-9-ol, 1, 5,9,9-tetramethyl-12-oxabicyclododeca- 4,7-diene, T-muurolol, (-) - cubenol, levomenol, ocimene, α-thujene, p-menth-1-en-9-yl acetate, dehydrocarveol, Artemisia alcohol, γ-muurolene, hydroxypentanone, (Z ) -Oximes, β-elemene, δ-cadinol, (E) -β-ocimene, (Z) -dihydrocarvone, α-cadinol, calamine, (Z) -piperitol. Lavandulol, β-bourbonene, (Z) -3-hexenyl-2-methylbutanoate, 4- (1-methylethyl) -benzenemethanol, artemisia ketone, methyl-2-butenol, heptanol, (E) -dihydrocarvone, p-2-menthene -1-ol, α-curcumene, spathulenol, sesquipellandrene, citronellyl valerate, bornyl isovalerate, 1, 5-octadien-3-ol, methyl benzoate, 2,3,4,5-tetrahydroanisole and / or hydroxycalamene or (v) honey-like odor, preferably ethyl cinnamate, β-phenethyl acetate, phenylacetic acid,

Phenylethanal, methylanthranilate, cinnamic acid, β-damascenone, ethyl (E) -cinnamate, 2-

Phenylethylalcohol, Citronellylvalerate, Phenylethylbenzoate and / or Eugenol or

(w) Hyacinth-like odor, preferably Hotrienol or

(x) jasmine-like odor, preferably methyl jasmonate, methyldihydroepijasmonate and / or

Methylepijasmonat or

(y) lavender-like odor, preferably linalyl valerate and / or linalool or

(z) lemon-like odor, preferably neral, octanal, δ-3-carene, limonene, geranial, 4-mercapto-4-methyl-2-pentanol, citral, 2,3-dehydro-1, 8-cineol and / or α -Terpines or

(aa) lily-like odor, preferably dodecanal or

(bb) magnolia-like odor, preferably geranylacetone or

(cc) mandarin-like odor, preferably undecanol or

(dd) melon-like odor, preferably dimethylheptenal or

(ee) mint-like odor, preferably menthone, ethyl salicylate, p-anisaldehyde, 2,4,5,7-tetrahydro-3,6-dimethylbenzofuran, epoxy-p-menthene, geranial, (methylbutenyl) -methylfuran,

Dihydrocarvyl acetate, β-cyclocitral, 1,8-cineole, β-phellandrene, methylpentanone, (+) - limonene,

Dihydrocarveol (-) - carvone, (E) -p-mentha-2,8-dien-1-ol, isopulegyl acetate, piperitone, 2,3-dehydro-

1, 8-cineol, α-terpineol, DL-carvone and / or α-phellandrene or

(ff) nutty odor, preferably 5-methyl- (E) -2-hepten-4-one, γ-heptalactone, 2-acetylpyrrole,

3-octen-2-one, dihydromethylcyclopentapyrazine, acetylthiazole, 2-octenal, 2,4-heptadienal, 3

Octenone, hydroxypentanone, octanol, dimethylpyrazine, methylquinoxaline and / or acetylpyrroline or

(gg) orange-like odor, preferably methyloctanoate, undecanone, decyl alcohol, limonene and / or 2-decenal or

(hh) orange peel-like odor, preferably decanal and / or beta-carene or

(ii) peach-like odor, preferably γ-nonalactone, (Z) -6-dodecene-γ-lactone, δ-decalactone,

R-δ-decenolactone, hexylhexanoate, 5-octanolide, γ-decalactone and / or δ-undecalactone or

Qj) peppermint-like odor, preferably methyl salicylate and / or I-menthol or

(kk) Pine-like odor, preferably α-p-dimethylstyrene, β-pinene, bornyl benzoate, δ-

Terpinene, Dihydroterpinylacetat and / or α-pinene or

(II) pineapple-like odor, preferably propyl butyrate, propyl propanoate and / or ethyl acetate or

(mm) plum-like odor, preferably benzyl butanoate, or

(nn) raspberry-like odor, preferably β-ionone or

(oo) Rose-like odor, preferably β-phenethyl acetate, 2-ethylhexanol, geranyl valerate,

Geranyl acetate, citronellol, geraniol, geranyl butyrate, geranyl isovalerate, citronellyl butyrate, Citronellyl acetate, isogeraniol, tetrahydro-4-methyl-2- (2-methyl-1-propenyl) -2,5-cis-2H-pyran,

Isogeraniol, 2-phenylethyl alcohol, citronellyl valerate and / or citronellyl isobutyrate, or

(pp) spearmint-like odor, preferably carvylacetate and / or carveol, or

(qq) strawberry-like odor, preferably hexylmethyl butyrate, methyl cinnamate, pentenal,

Methyl cinnamate or

(rr) sweet odor, preferably benzyl alcohol, ethyl phenylacetate, tridecanal, nerol,

Methylhexanoate, linalylisovalerate, undecanedehyde, caryophyllene oxide, linalyl acetate, safranal,

Uncinol, phenylethanal, p-anisaldehyde, eudesmol, ethylmethylpyrazine, citronellylbutyrate, 4-

Methyl-3-penten-2-one, nonyl acetate, 10-epi-γ-eudesmol, β-bisabolol, (Z) -6-dodecene-γ-lactone, β-

Farnesene, 2-dodecenal, γ-dodecalactone, epoxy-β-ionone, 2-undecenal, styrene glycol,

Methyl furanane, (-) - cis-rose oxide, (E) -β-octenes, dimethylmethoxyfuranone, 1,8-cineole,

Ethylbenzaldehyde, 2-pentylthiophene, α-farnesene, methionol, 7-methoxycoumarin, (Z) -3-hexenyl-

2-methylbutanoate, o-aminoacetophenone, viridiflorol, isopiperitones, β-sinensal, ethyl vanillate, methyl butanoate, p-methoxystyrene, 6-methoxyeugenol, 4-hexanolide, δ-dodecalactone,

Sesquiphellandrene, diethyl malate, linalyl butyrate, guaiacol, coumarin, methyl benzoate,

Isopropyl benzoate, safroles, durene, γ-butyrolactone, ethyl isobutyrate and / or furfural or

(ss) Vanilla-like odor, preferably vanillin, methyl vanillate, acetovanillon and / or

Ethyl vanillate or

(tt) watermelon-like odor, preferably 2,4-nonadienal or

(uu) woody odor, preferably α-muurolene, cadina-1, 4-dien-3-ol, isocaryophyllene,

Eudesmol, α-ionone, bornyl butyrate, (E) -α-bergamotene, linalooloxide, ethylpyrazine, 10-epi-γ-

Eudesmol, α-ionone, bornyl butyrate, (E) -α-bergamotene, linalooloxide, ethylpyrazine, 10-epi-γ-

Eudesmol, Germacrene B, trans-Sabine hydrate, Dihydrolinalool, Isodihydrocarveol, β-Farnesene, β-Sesquiphellandrene, δ-Elemene, α-Calacorene, Epoxy-β-ionone, Germacrene D,

Bicyclogermacrene, alloaromadendrene, α-thujene, oxo-β-ionone, (-) - γ-elemene. γ-Muurolene,

Sabinene, α-guaienes, α-copenes, γ-cadinene, nerolidol, β-eudesmol, α-cadinol, δ-cadenines,

4,5-dimethoxy-6- (2-propenyl) -1,3-benzodioxole, [1ar (1aalpha, 4aalpha, 7alpha, 7abeta, 7balpha)] - decahydro-1, 1, 7-trimethyl-4-methylene- 1 H-cycloprop [e] azulen, α-gurjunen, guaiol, α-farnesene, γ-selenene, 4- (1-methylethyl) -benzenemethanol, perillen, elemol, α-humulenes, β-caryophyllene and / or β-guaienes or

(vv) mixtures of the above. contain.

In order to facilitate the disintegration of the optionally coated granules which can be prepared according to the invention, for example in tablet form, it is possible to incorporate disintegration aids, so-called tablet disintegrants, into these in order to shorten the disintegration times. Under Tablet disintegrants or disintegrants are generally understood to be adjuvants that ensure the rapid disintegration of tablets in water and for the release of the active ingredients.

These substances, which are also referred to as explosives due to their action, increase their volume upon ingress of water, whereby on the one hand the intrinsic volume increases (swelling), on the other hand a pressure can be generated via the release of gases which causes the tablet to disintegrate into smaller particles. Well-known disintegration aids are, for example, carbonate / citric acid systems, although other organic acids can also 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.

Conventional, optionally coated, granules may advantageously 0.5 to 10 wt .-%, preferably 3 to 7 wt .-% and in particular 4 to 6 wt .-% of one or more disintegration aids, each based on the detergent and / or detergent granules , contain.

As preferred disintegrating agents which are suitable for the production of the optionally coated granules according to the invention, disintegrating agents based on cellulose are used in the context of the present invention. Pure cellulose has the formal gross composition (C ₆ H ₁₀ Os) _n and is formally a β-1,4-polyacetal of cellobiose, which in turn is composed of two molecules of glucose. Suitable celluloses consist of about 500 to 5000 glucose units and therefore have average molecular weights of 50,000 to 500,000. Cellulose-based disintegrating agents which can be used in the context of the present invention are also cellulose derivatives obtainable by polymer-analogous reactions of cellulose. Such chemically modified celluloses include, for example, products of esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. Celluloses in which the hydroxy groups have been replaced by functional groups which are not bonded via an oxygen atom can also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkali metal celluloses, carboxymethylcellulose (CMC), cellulose esters and ethers, and aminocelluloses. The cellulose derivatives mentioned are preferably not used alone as disintegrating agents based on cellulose, but used in admixture with cellulose. The content of these mixtures of cellulose derivatives is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrating agent. It is particularly preferred to use pure cellulose as disintegrating agent based on cellulose for producing the optionally coated granules according to the invention, which is free of cellulose derivatives. As another cellulose-based disintegrant for the production of the optionally coated granules of the invention, microcrystalline cellulose can be used. This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions which attack and completely dissolve only the amorphous regions (about 30% of the total cellulosic mass) of the celluloses, leaving the crystalline regions (about 70%) intact ,

In order to further improve the aesthetic impression of the optionally coated granules which can be prepared according to the invention, the optionally coated granules can be dyed with suitable dyes, preferably the brightener phase (s) containing the total amount of dye (s). contain. Preferred dyes, the selection of which presents no difficulty to the skilled person, have a high storage stability and insensitivity to the other ingredients of detergents and / or detergents and to light and no pronounced substantivity to textile fibers so as not to stain them.

Preferred for the production of the agents according to the invention are all colorants which can be oxidatively destroyed in the washing process and mixtures thereof with suitable blue dyes, so-called blue toners. It has proved to be advantageous to use colorants for the production of the optionally coated granules according to the invention, which are soluble in water or at room temperature in liquid organic substances. Suitable examples are anionic colorants, for example anionic nitrosofarbstoffe. One possible dye is, for example, naphthol green (Color Index (CI) Part 1: Acid Green 1; Part 2: 10020)., That is as a commercial product, for example as Basacid ^® Green 970 from BASF, Ludwigshafen available, as well as mixtures thereof with suitable blue dyes. Further suitable colorants are Pigmosol ^® Blau6900 (CI 74160), Pigmosol ^® Green 8730 (CI 74260), Basonyl ^® Red 545 FL (CI 45170), Sandolan® ^® rhodamine EB400 (CI 45100), Basacid® ^® Yellow 094 (CI 47005), Sicovit ^® Patent Blue 85 E 131 (Cl 42051), Acid Blue 183 (CAS 12217-22-0, Cl Acid Blue 183), Pigment Blue 15 (Cl 74160), Supranol ^® Blue GLW (CAS 12219-32-8, Cl Acidblue 221) , Nylosan Yellow ^® N-7GL SGR (CAS 61814-57-1, Cl Acidyellow 218) and / or Sandolan Blue ^® (Cl Acid Blue 182, CAS 12219-26-0) is used.

When choosing the colorant, it must be taken into account that the colorants do not have too high an affinity for the textile surfaces, and in particular for synthetic fibers. At the same time, it should also be taken into account when choosing suitable colorants that colorants have different stabilities to the oxidation. In general, water-insoluble colorants are more stable to oxidation than water-soluble colorants. Depending on the solubility and thus also on the sensitivity to oxidation, the concentration of the colorant in the, optionally coated, granules varies. For highly soluble dyes, for example, the above-mentioned Basacid ^® Green or the above-mentioned Sandolan ^® Blue are typically colorant Kon-concentrations in the range of a few 10 ^-2 to 10 ^-3 wt .-%, each based on the total detergent and / or detergent granules selected. In the due to their brilliance, particularly preferred, but are less readily water-soluble pigment dyes, for example the above-mentioned Pigmosol ^® - dyes, the appropriate concentration of the colorant is in detergents and / or cleaning agents, however, typically at some 10 ^{~ 3} to 10 ^{~ 4} wt. -%, based on the total washing and / or cleaning agent.

EXAMPLE:

Silicates, soda, sulphate, citrate, zeolite, carboxymethyl cellulose, Repelotex SRP 4 (ex Rhodia, preparation of polyethylene glycol / polyester, sodium silicoaluminate and sodium sulphate) and the filter dusts and recycling streams (oversize and undersize from screening after granulation / drying) dosed on an anthology and fed from there to an eddy current mill.

The mill working with an air temperature of 38 ⁰ C. The material had after grinding a d ₅₀ of 7 microns, measured in Camsizer Fa. Retsch, and was then used as a shell material for the granulation. The moisture content of the material decreased to about 6.7% by weight, based on the total milled shell material, by the mill drying of about 9% by weight of water.

As core material (d ₅₀ = 0.76 mm), soda was sifted out and used to start the process. Later, in the current process, a granulate ex granulation / drying was screened out as core material, consisting of undersize in a mixture with good grain. For the preparation of 100% by weight of finished product, corresponding to 76.8% by weight of good grain, 17.6% by weight of core material and 109.4% by weight of shell material were fed continuously into the granulation stage, the indication being 100% by weight. -% is based on the finished product, ie on a coated, powdered good grain with all processing components (= finished product). The granulation took place in Lödige ploughshare mixer (KM) at a Froude number of 3 by spatially separate addition of:

2 wt .-% of a 20% aqueous Sokalan solution, wt .-% based on finished product

0.5 wt .-% water glass solution, wt .-% based on finished product

21, 0 wt .-% of a mixture of nonionic surfactant with Na salts of various acids, namely two phosphonic acids, fatty and ABS acid; neutralized with the addition of air

(Foam neutralization) with 4 wt .-% of a 50% sodium hydroxide solution, wt .-% based on

Finished product.

Overall, the balance showed an amount of water supplied during the granulation of about 4.9% by weight. In the fluidized bed about 3.5 wt .-% water have been dried out. The residual amount remains in the product and resulted in a water content of about 8.1% by weight in the coated, powdered finished product,% by weight, based in each case on the finished product.

The granules were then sieved and divided into Gutkorn, nuclear material and oversize and undersize. Screened undersize and oversized grain served as a recycling stream, was metered to flight collection and separation in the filter on a collection tape and fed back from there to the eddy current mill.

In the continuous process, this resulted in a composition of the shell material entering the granulation stage of 55.0% by weight of recycled material and 54.4% by weight of the raw materials mentioned at the beginning (silicates, soda, sulfate, etc.),% by weight on finished product. Part of the screened material / undersize was also returned to the granulation process as core material (d ₅₀ = 0.76 mm). The remaining non-recirculated good grain has then been coated with liquid / suspension and powdering agent. Finally, final powdering and final mixing took place.

The Gutkorn had a d ₅₀ of 0.90 mm (+ 18% compared to the core material) after screening; before screening, the d _{50 was} 0.83 mm (+ 9.2% compared to the core material). The bulk density of the sieved good grain was 610 g / l; the Shape Factor of the sieved Gutkorns at 0.88.

The determination of the solubility of the good grain took place in the so-called L-test. For this purpose, 8 g of substance in 1000 ml of water with a hardness of 16 ° dH at 30 ⁰ C were added and with a propeller stirrer at 800 U / min. Stirred for 1, 5 minutes. The undissolved solids were screened with a sieve with a mesh size of 0.2 mm. The residue was dried to constant weight and weighed, it was 3 wt .-% of the starting material.

Claims

claims

1. A process for the preparation of detergents or cleaners, in which a finer shell material is granulated onto a particulate core material, characterized in that the raw materials to be used in the granulation stage are at least partially guided through a grinding drying plant.

2. The method according to claim 1, characterized in that the granulation mixer at Froude numbers between 2 and 10, preferably between 2.5 and 4, is operated.

3. The method according to claim 1 or 2, characterized in that the product has a diameter d ₅₀ which is at least 5% and at most 66% greater than the diameter d _{50 of} the core material and at least fifteen times the average diameter (d ₅₀ ) of the from a Mahltrocknungsstufe originating shell material.

4. The method according to any one of claims 1-3, characterized in that the grinding drying process in a pipe, impact, pin, vibrating, hammer, air jet or roller mill, preferably in a fluidized air mill, in particular working in a carrier gas Mill is done with rotating grinding plates.

5. The method according to any one of claims 1-4, characterized in that in the mill drying process air at a temperature between 15 and 220 ⁰ C, preferably between 25 and 120 ⁰ C and in particular between 35 and 70 ° C is used.

6. Process according to claims 1-5, characterized in that several, chemically distinguishable granulation aids are added simultaneously or preferably in succession, preferably in the form of solutions, suspensions, dispersions, foams and / or (nano) emulsions.

7. The method according to any one of claims 1-6, characterized in that in the mill-drying step 0.05 to 6 wt .-% of water are removed, based on the shell material.

8. The method according to any one of claims 1-7, characterized in that in a granulation downstream drying step between 0.1 and 6 wt .-% water are removed, based on the granules after drying.

9. The method according to any one of claims 1-8, characterized in that the core material is present in a very uniform particle size distribution, wherein the ratio of d ₅₀ to dgo is at least 0.50.

10. The method according to any one of claims 1-9, characterized in that both screened undersize and oversized grain after the granulation / drying step subjected to a grinding drying process and recycled as part of the shell material in the process.

11. The method according to any one of claims 1-10, characterized in that screened from the product flow, the good and / or undersize and then fed as a core material in the process.

12. The method according to any one of claims 1-11, characterized in that in addition to granulation liquid (s) further hydrophilic and / or lipophilic liquids and / or salts are incorporated in the granulation step.

13. The method according to any one of claims 1-12, characterized in that the Granulierhilfsmittel comprises a liquid containing skin care agents and / or textile care products, in particular silicone oil.

14. The method according to any one of claims 1-13, characterized in that the granulation aid solubility enhancer comprises.

15. The method according to any one of claims 1-14, characterized in that the granulation comprises a liquid of neutralized surfactant and builder acids, preferably having a water content of less than 10 wt .-%, advantageously less than 6 wt .-% based on the granules ,

16. The method according to any one of claims 1-15, characterized in that the granulation comprises a solution of polymeric substances, preferably having a water content of less than 10 wt .-% based on the granules.

17. The method according to any one of claims 1-16, characterized in that the granulation aid comprises at least one foam.

18. The method according to any one of claims 1-17, characterized in that the total granulating a total of less than 12 wt .-% water, based on the granules.

19. The method according to any one of claims 1-18, characterized in that the granulation stage consists of at least one mixer and a fluidized bed.

20. The method according to any one of claims 1-19, characterized in that the granulation stage consists of a fast and a low-speed mixer and a fluidized bed.

21. The method according to any one of claims 1-20, characterized in that a tower method is not part of the method.