EP2004791B1 - Granulés de lessive ou de détergent - Google Patents

Granulés de lessive ou de détergent Download PDF

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Publication number
EP2004791B1
EP2004791B1 EP07726683A EP07726683A EP2004791B1 EP 2004791 B1 EP2004791 B1 EP 2004791B1 EP 07726683 A EP07726683 A EP 07726683A EP 07726683 A EP07726683 A EP 07726683A EP 2004791 B1 EP2004791 B1 EP 2004791B1
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EP
European Patent Office
Prior art keywords
granules
granulation
acid
preferred
oder
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Not-in-force
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EP07726683A
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German (de)
English (en)
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EP2004791A1 (fr
Inventor
Wilfried Rähse
Bernd Larson
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Priority to PL07726683T priority Critical patent/PL2004791T3/pl
Publication of EP2004791A1 publication Critical patent/EP2004791A1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents ; Methods for using cleaning compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents ; Methods for using cleaning compositions
    • C11D11/0082—Special methods for preparing compositions containing mixtures of detergents ; Methods for using cleaning compositions one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets

Definitions

  • 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.
  • the purchase decision is generally based on very different criteria, but above all on the price of the presented goods and their quality.
  • 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.
  • the object of the present invention was to provide aesthetically pleasing granules.
  • the subject matter of the invention 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 Mahltrocknungsstrom wherein 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 15 times the average diameter (d 50 ) of the shell material originating from a mill-drying stage.
  • the mill-drying should advantageously serve to reduce the mean grain diameter and the partial drying of the shell material in question.
  • 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.
  • 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.
  • Nonionic surfactants ethoxylates, APG
  • anionic surfactant acids / pastes anionic surfactant acids / pastes
  • cationic compounds / surfactants e.g.
  • phosphonates e.g., phosphonates, phosphonic acids
  • Sokalan maleic acid acrylic acid copolymer sodium salt (30:70)
  • 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 can finally be treated with zeolite powder and / or shell material.
  • 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.
  • a core material 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 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 mill-drying stage.
  • the average diameter of the products can be adjusted in a controlled manner.
  • 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).
  • 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.
  • 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.
  • 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 advantageously from 2 to 10, more preferably from 2.5 to 8, in particular from 2.5 to 4 in the desired manner from.
  • Froude Zahien particularly beautiful, round granules are obtained.
  • 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.
  • 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 ° C, in particular 35 to 70 ° C, the degree of drying of the shell material can be adjusted specifically.
  • the conveying air may also have a minimum temperature of e.g. 40C, 42C, 44C, 46C, 48C, 50C, 52C, 54C, 56C, 58C or 60C.
  • the conveying air has a maximum temperature of 68 ° C, 66 ° C, 64 ° C or 62 ° C.
  • the conveying air may e.g. 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.
  • a preferred embodiment is to work with several Granulationsangesffenn added at different locations (continuous process) or at different times (batch process).
  • 2, 3, 4 or more granulation aids are used, for example as Granulating agent 1: neutralized acids, eg as 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.
  • 0.05 to 6% by weight, preferably up to 5% by weight, advantageously up to 4% by weight, more preferably up to 3% by weight, of water are removed, based on the shell material 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.
  • 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.
  • 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.
  • 90% of the particle quantity is below the value, ie 10% higher.
  • the ratio d 50 / d 90 approaches the value of 1 at very narrow particle size distributions, or is well below 0.5 for broad distributions.
  • 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.
  • 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 Core incorporated.
  • a granulate obtainable in this way can still be provided with a coating.
  • a conventional mixer / granulator can be used.
  • 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).
  • 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.
  • the granules which can be produced and subsequently coated by the process according to the invention are essentially dust-free.
  • 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.
  • 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
  • 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.
  • the upper limit is even lower, e.g. at a value of preferably 700, 650, 600, 550 or 500 g / L.
  • 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.
  • 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.
  • the lower limit of the surfactant content may also be given a value of e.g.
  • the lower limit may even be at still higher values, e.g. at a value of e.g.
  • 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 .-% are, in each case 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.
  • 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.
  • 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 .-%.
  • the lower limit of the builder content may also be given a value of e.g.
  • the lower limit may even be at still higher values, e.g. at a value of, for example, preferably 35% by weight, 40% by weight, 45% by weight, 50% by weight, 55% by weight or 60% by weight, in each case based on the total granules.
  • 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% by weight, 88% by weight, 89% by weight.
  • the lower limit may even be at even lower values, e.g. at a value of preferably 65% by weight, 60% by weight, 55% by weight, 50% by weight, 45% by weight, 40% by weight, 35% by weight, 30% by weight. % or 25 wt% or even only at a value of 20 wt%; 15 wt .-% or 10 wt .-%, each based on the total granules.
  • 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.
  • 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.
  • 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.
  • 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).
  • 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.
  • 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.
  • the perfume content of the granules 0.1-30 wt .-%, preferably 1-25 wt .-%, advantageously 5-22 wt.%, In particular 10-20 wt .-%.
  • 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.
  • the granules are completely enzyme-free, ie they contain 0% by weight of enzyme, based on the total granules.
  • the granules are bleach-free.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • Mahltrocknungsrea 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.
  • the minimum temperature of the carrier gas may be e.g. advantageously also at 21 ° C, 22 ° C, 23 ° C, 24 ° C, 25 ° C, 26 ° C, 27 ° C, 28 ° C, 29 ° C, 30 ° C, 31 ° C, 32 ° C , 33 ° C, 34 ° C, 36 ° C, 37 ° C, 38 ° C, 39 ° C, 40 ° C, 41 ° C.
  • 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 e.g., air
  • 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.
  • 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.
  • a tower process is not part of the process.
  • the granulation stage consists of at least one mixer and one fluidized bed, then there is a preferred embodiment.
  • the granulation stage consists of a fast and a low-speed mixer and a fluidized bed, so is also a preferred embodiment.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the flowable component which is acted upon for foaming with a gaseous medium, at 20 ° C, a viscosity of 5 to 1500 mPas, preferably from 10 to 1000 mPas and in particular from 50 to 800 mPas.
  • the foaming liquid component may contain nonionic surfactant (s) and / or polymer (s) to promote foaming.
  • a flowable component to be foamed 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.
  • the frothy flowable component may advantageously have temperatures of from 15 to 120 ° C., preferably from 25 to 90 ° C. and in particular from 50 to 75 ° C., before foaming.
  • 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 ° C. and in particular between 30 and 70 ° C.
  • the foam may advantageously have a density below 0.80 gcm -3 , preferably from 0.10 to 0.60 gcm -3, and more preferably from 0.30 to 0.55 gcm -3 .
  • the foam may advantageously have average pore sizes below 10 mm, preferably below 5 mm and in particular below 2 mm.
  • 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 cleaning agents 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.
  • aqueous alkaline component can advantageously also alkali metal hydroxide solutions, 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.
  • 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.
  • the anionic surfactant in acid form it is preferable to use C 8-16 , preferably C 9-13, alkylbenzenesulfonic acids.
  • 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.
  • granulation aids for example liquid nonionic surfactants, polyethylene glycols or other organic solvents
  • granulation liquids for example, salts, water glass.
  • organic solvents with swollen polymers are also possible.
  • 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.
  • 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.
  • 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.
  • 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.
  • the acids e.g. Fatty acids, alkylbenzenesulfonic acids and / or etidronic acid are mixed first and then combined with the alkaline solution.
  • 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.
  • the granulation auxiliary comprises a liquid which contains skin care agents and / or textile care agents, in particular silicone oil.
  • the granulation aid may comprise solubilizer (hydrotrope).
  • solubilizer hydrotropes are e.g. Xylene or cumene sulfonate or other substances such as 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.
  • the (optional) coating is applied without subsequent drying, which corresponds to a preferred embodiment.
  • 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.
  • 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.
  • 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.
  • Low-water means in this context that the coating liquid used contains less than 35 wt .-% water, based on the total coating liquid.
  • 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.
  • the coating liquid may also contain relatively large amounts of water, ie more than preferably 35% by weight, based on the total coating liquid.
  • 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 may even have an even higher water content upper limit, e.g.
  • a melt is applied as (optional) coating, preferably melting of (co) polymers, waxes, esters and / or fats.
  • 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 esters.
  • 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.
  • 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.
  • the optional coating contains lipids and / or silicone oils, which corresponds to a preferred embodiment.
  • the (optional) coating comprises unsaponifiable lipid, preferably selected from free fatty acid, isoprenoid lipids, in particular steroids, carotenoids, monoterpenes etc. and / or tocopherols.
  • the (optional) coating comprises saponifiable lipid, preferably selected from mono-, di-, triacylglycerides, phospholipids (phosphatides), glycolipids, diollipids, waxes and / or sterol esters.
  • the (optional) coating each has at least one unsaponifiable and one saponifiable lipid.
  • the (optional) coating comprises neutral lipid, preferably selected from fatty acids (> C12), mono-, di-, triacylglycerides, sterols, sterol esters, carotenoids, waxes and / or tocopherols.
  • neutral lipid preferably selected from fatty acids (> C12), mono-, di-, triacylglycerides, sterols, sterol esters, carotenoids, waxes and / or tocopherols.
  • the (optional) coating comprises polar lipid, preferably selected from glycerophospholipids, glyceroglycolipids, sphingophospholipids and / or sphingoglycolipids.
  • the (optional) coating has at least one polar and one nonpolar lipid.
  • the (optional) coating contains a silicone oil.
  • 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 ,
  • suspensions ie dispersions of insoluble solid particles with particle sizes down to colloidal dimensions ( ⁇ 10 -6 cm) in liquids, plastic masses or solidified melts.
  • solvent-containing advantageously aqueous suspensions of pulverulent components, preferably of a few ⁇ m diameter, e.g. aqueous suspensions of pigments.
  • 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 .
  • white auxiliaries such as preferably calcium carbonate, talc 3MgO 4SiO 2 ⁇ H 2 O and / or barium sulfate may be included.
  • the (optional) coating lowers the rate of dissolution of the total particles by 5% relative to 20 ° C cold water, i. Accordingly, the coated granules require correspondingly more time to dissolve entirely in 20 ° C cold water, based on dissolving 60 grams of the particles in one liter of tap water in a 2 liter beaker, stirring with a magnetic stirrer / magnetic stirrer (250 ml UPM) at 20 ° C.
  • the reduction of 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%.
  • the complete particle resolution takes twice as long as without coating.
  • 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%.
  • the coated tablet would be dissolved at a value of 500% only after 5 minutes.
  • effervescent or effervescent components are contained in the optionally coated granules.
  • 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%.
  • 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%.
  • the core is designed as such uneven, preferably not spherical or ellipsoidal, but of irregular shape.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the individual particles of this collective n have a density gradient.
  • the particles of the collective ⁇ also have different densities in comparison with each other. This is the case of a heterogeneous individual distribution in a heterogeneous collective.
  • the particles of the collective ⁇ have the same densities in comparison with each other. 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.
  • 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.
  • 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.
  • nonionic surfactants cationic surfactants
  • amphoteric surfactants silicone oil
  • triglycerides Terpene
  • perfume glycerin and / or (co) polymer (solutions) in question.
  • all those substances which are disclosed for the coating of the granulate elsewhere in this description are also suitable.
  • 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.
  • impregnating agents preferably silicone-containing impregnating agents, ie mixtures which advantageously contain different polysiloxanes with condensable groups, which advantageously make water repellency more or less pronounced.
  • agents which serve to hydrophobicize the core or the granules it is preferred to use impregnating agents, preferably silicone-containing impregnating agents, ie mixtures which advantageously contain different polysiloxanes with condensable groups, which advantageously make water repellency more or less pronounced.
  • 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 glutardialdehyde ,
  • hydrophilization is possible, which corresponds to a preferred embodiment.
  • the hydrophilization is carried out with the aid of hydrophilizing agents, e.g. in the form of aqueous. Solutions are applied. 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.
  • agents containing lipids are preferably used.
  • the impregnating agent comprises unsaponifiable lipid, preferably selected from free fatty acids, isoprenoid lipids, in particular steroids, carotenoids, monoterpenes etc. and / or tocopherols.
  • the impregnating agent comprises saponifiable lipid, preferably selected from mono-, di-, triacylglycerides, phospholipids (phosphatides), glycolipids, diollipids, waxes and / or sterol esters.
  • the impregnating agent comprises at least one unsaponifiable and one saponifiable lipid.
  • the impregnating agent comprises neutral lipid, preferably selected from fatty acids (> C12), mono-, di-, triacylglycerides, sterols, sterol esters, carotenoids, waxes and / or tocopherols.
  • neutral lipid preferably selected from fatty acids (> C12), mono-, di-, triacylglycerides, sterols, sterol esters, carotenoids, waxes and / or tocopherols.
  • the impregnating agent comprises polar lipid, preferably selected from glycerophospholipids, glyceroglycolipids, sphingophospholipids and / or sphingoglycolipids.
  • the impregnating agent has at least one polar and one nonpolar lipid.
  • the (optional) coating of the granules can 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 glutardialdehyde.
  • water repellents 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 glutardialdehyde.
  • 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.
  • 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. Polyethylenglykolsorbitanfettklander and comparable substances.
  • solubility of the shell as such can also be manipulated individually, advantageously via the choice of granulation aid.
  • the granulation aid may be more hydrophobic, with the result that the shell dissolves more slowly in an aqueous environment. If the granulating agent is rather hydrophobic, then in the context of this invention in the further description of a simplified "hydrophobically bonded" shell is mentioned.
  • the granulation aid may be more 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 bound "shell is mentioned.
  • the freedom of design of the skilled person are virtually unlimited.
  • 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.
  • the optional coating of the granulates 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.
  • the shell is pH and / or temperature and / or ionic strength sensitive or contains pH and / or temperature and / or ionic strength-sensitive materials.
  • the core is pH and / or temperature and / or ionic strength sensitive or contains pH and / or temperature and / or ionic strength-sensitive materials.
  • 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 concerning 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 regarding pH and / or temperature and / or ionic strength, the shell can thus lose its integrity and dissolve.
  • 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.
  • 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, for example. occur during an automatic laundry process, lose their integrity.
  • 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 fresh water introduced into the machine, preferably in the rinse cycle of the washing process.
  • 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.
  • 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.
  • multi-shell granules in the context of this application can be obtained when a granule obtained is taken as a "core" for one (or more) further Granulationsvorêt.
  • the granules are thus used again as a new core and surrounded with other particles.
  • new particles are applied to the original granules.
  • 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, i. different chemical substances.
  • 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 ..
  • 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 be at a value such as in particular 0.06 mm, 0.07 mm, 0.08 mm, 0.09 mm, 0.1 mm, 0.11 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.
  • 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 4.7 mm, 4.5 mm etc.
  • 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.
  • 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.
  • 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.
  • the particle diameter d 50 of the particles surrounding the core is preferably greater than 2, 3, 4 or 5 ⁇ m.
  • 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 50 of the particles surrounding the core is preferably at least 0.5 , more preferably at least 0.6, in particular at least 0.75.
  • the compositions 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.
  • 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.
  • the optionally coated granules are floatable in water, i. Do not submerge in water or in a wash, but float on the water surface.
  • the granules In order to make the granules floating, it is preferable to adjust their density to values less than 1 g / cm 3 , if necessary.
  • gases in particular air, can be incorporated into the granules.
  • 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.
  • 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.
  • 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 ⁇ m.
  • Grain upper limits are preferably 0.4-250 microns.
  • the thermal conductivity is preferably 0.110-0.156 Wm-1K-1.
  • the internal pressure is preferably about 0.2 bar. At higher shear stress, the hollow spherical shells may preferably burst.
  • 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.
  • 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.
  • the composition according to the invention contains ingredients for the cleaning, care, conditioning and / or after-treatment of textiles.
  • the composition according to the invention contains ingredients for cleaning and / or care of dishes, glasses, cutlery and the like.
  • 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.
  • the softening agents 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
  • 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.
  • 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 remain on this even after completion of the washing process at least partially, this skin-care and / or skin-protecting and / or skin-healing active ingredients are given on contact of the skin with a correspondingly washed textile at least partially from this to the skin and thereby 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.
  • 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.
  • 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 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, wherein the run number a is 0 to 10 wherein R 5 , R 6 , R 7 are each independently hydrogen or an aliphatic or aromatic, straight-chain or branched, saturated or uns
  • 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.
  • fragrance 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 Scents or odoriferous substances which have free hydroxyl groups, regardless of how the molecule is further built up.
  • fragrance esters, ketones, aldehydes designate those fragrances which correspond respectively to free esters, keto or aldehyde This implies that certain molecules, such as salicylic acid for the purposes of this invention For example, they can function both as a fragrance alcohol and as a fragrance ester.
  • 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 agent according to the invention contains one or more skin-care and / or skin-protecting and / or skin-healing active substances.
  • 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 its intact acid mantle providing sufficient protection against microorganisms, germs and pathogens, its buffering capacity and alkali neutralizing capacity being sufficient to ward off the harmful effects of surrounding fluids, providing 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.
  • 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.
  • 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.
  • 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 ,
  • 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.
  • 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 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.
  • 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.
  • the attribute of antiseptic efficacy means an effect that is beneficial to the self-regulatory powers 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.
  • 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.
  • the self-regulatory powers of the skin are sometimes no longer able, even temporarily, to ensure skin health on their own.
  • 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.
  • optionally coated granules of such an embodiment are particularly useful for their purposes when the antiseptic agent 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.
  • an essential oil selected in particular from the group of Angelica fine - Angelica
  • Another advantage of the aforementioned essential oils lies in their particular multifunctionality, which, in addition to the described mild antiseptic activity, results from a multitude 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.
  • the organoleptic properties of these oils are not from the main components, but from the Mau- od. Trace components marked that often go into the hundreds and sometimes synergistically work together.
  • Another advantage associated with the oils mentioned is their harmonious fragrance and scent, which in many cases leads to positive feelings in humans.
  • a corresponding detergent or the laundry washed with this not only supports the natural skin flora of humans, but also helps the human organism to obtain additional benefits of the type just described.
  • tea tree oil is of great advantage for the subject invention.
  • tea tree oil In addition to its considerable germicidal, antiseptic, fungicidal, antiviral, wound-healing, anti-inflammatory, scarring-promoting effect, it has excellent skin tolerance 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.
  • 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.
  • 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, hypericum perforatum, jojoba oil Simondsia chinensis, caraway 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,
  • 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 ⁇ -linolenic acid (GLA), also has an anti-inflammatory, slightly analgesic, healing, nourishing, skin structure improving, preventing the appearance of old age.
  • hemp oil for the purposes of this invention as a result of its high GLA content to play a special role, as In case of disturbed transepidermal water loss, topical treatment with GLA leads to the greatest reduction in 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.
  • 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, more preferably of 0.5% by weight, based on the respective active substance.
  • skin-healing active substances which have a minimum content of 0.1% by weight of GLA, preferably of 0.3% by weight, more preferably of 0.5% by weight, based on the respective active substance.
  • active substances include, for example, black cumin oil, Echiumöl, Trichodesmaöl, evening primrose oil and the blackcurrant seed oil.
  • almond oil 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.
  • 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).
  • 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 the skin.
  • 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.
  • the lactic acid smoothes the skin and supports the detachment of dander.
  • 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-hexanetriol, 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), pyrrolidonecarboxylic acid, sugars and sugar derivatives (for example, fructose, glucose, maltose, maltitol,
  • 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 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.
  • 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 Abpumpvor réellen essentially not from the washing machine and precipitate during the washing process preferably in the course of Abpumpvor réellen on the laundry.
  • 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.
  • 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.
  • 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 Ein Hughessch 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.
  • 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 Ein Hughes redesign 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
  • the optionally coated, contained in the detergent detergent according to the invention are not substantially removed during the washing process in the course of Abpumpvor réellen from the washing machine, but are preferably in the late stages of the washing process, especially in the course of Abpumpvor réellen on the laundry down.
  • 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.
  • 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 determination of the surface curvature is made by an optical measuring method, in which the "shadow cast" of the parts to be examined is determined and converted into a corresponding form factor.
  • the underlying principle for determining the form factor was Gordon Rittenhouse in "A visual method of estimating two-dimensional sphericity" in the Journal of Sedimentary Petrology, Vol. 13, No. 2, pp. 79-81 described.
  • the measurement limits of this optical analysis method are 15 ⁇ m and 90 mm, respectively.
  • the numerical values for d 50 and d 90 are also available via the aforementioned measuring method.
  • 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.
  • 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.
  • 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 conversion 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.
  • detergents and cleaning agents e.g. commercially available detergents and / or cleaners
  • 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.
  • 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.
  • 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.
  • 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).
  • anionic surfactants of the sulfonate and sulfates type can be used.
  • the surfactants of the sulfonate type are preferably C 9-13 -alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as are obtained, for example, from C 12-18 -monoolefins having terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products into consideration.
  • alkanesulfonates which are obtained from C 12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • esters of ⁇ -sulfo fatty acids for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids are suitable.
  • sulfonation of unsaturated fatty acids for example oleic acid, in small amounts, preferably in amounts not above about 2 to 3 wt .-%.
  • ⁇ -sulfofatty acid alkyl esters are preferred which have an alkyl chain with not more than 4 C atoms in the ester group, for example, methyl ester, ethyl ester, propyl ester and butyl ester.
  • methyl esters of ⁇ -sulfo fatty acids (MES), but also their saponified disalts are used.
  • sulfated fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and mixtures thereof, as obtained in the preparation by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol.
  • Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
  • Alk (en) ylsulfates are the alkali metal salts and in particular the sodium salts of the sulfuric monoesters of C 12 -C 18 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half-esters 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.
  • 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 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.
  • 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.
  • C 12 -C 18 fatty acid methyl esters with 10 to 12 EO can be used as surfactants.
  • alkylpolyglycosides are the alkylpolyglycosides (APG).
  • APG alkylpolyglycosides
  • 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 degree of glycosidation 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 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 characterized in particular by their bi- and multi-functionality.
  • 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 + 1 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 ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O 5 yH 2 O are preferred.
  • 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.
  • a useful fine crystalline, synthetic and bound water-containing zeolite is preferably zeolite A and / or P.
  • zeolite P zeolite MAP ® commercial product from Crosfield
  • zeolite X and mixtures of A, X and / or P are particularly preferred.
  • commercially available and preferably usable in the context of the present invention is, for example, a cocrystal of zeolite X and zeolite A.
  • zeolite X (about 80% by weight of zeolite X), which is sold by Condea Augusta SpA under the brand name VEGOBOND AX ® and the formula: nNa 2 O • (1-n) K 2 O • Al 2 O 3 • (2-2.5) SiO 2 • (3.5-5.5) H 2 O, equivalent.
  • 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, in each case based on the anhydrous active substance, for example 1 to 8% by weight or 0 to 5% by weight.
  • the granules which can be prepared according to the invention are free of zeolite.
  • phosphates as builders are 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.
  • 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.
  • 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.
  • 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.
  • citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.
  • 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.
  • 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.
  • 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.
  • 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 ,
  • copolymers are those which preferably have as monomers acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.
  • polymeric aminodicarboxylic acids their salts or their precursors.
  • polyaspartic acids or their salts and derivatives which, in addition to cobuilder properties, also have a bleach-stabilizing action.
  • 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.
  • 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.
  • it is hydrolysis products having average molecular weights in the range of 400 to 500,000 g / mol.
  • 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.
  • DE dextrose equivalent
  • 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 are further suitable co-builders.
  • ethylenediamine-N, N'-disuccinate (EDDS) is preferably used in the form of its sodium or magnesium salts.
  • glycerol disuccinates and glycerol trisuccinates are also preferred in this context.
  • 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.
  • phosphonates are, in particular, hydroxyalkane or aminoalkanephosphonates.
  • hydroxyalkane phosphonates 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.
  • 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.
  • 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.
  • the granules which can be prepared according to the invention can also have acid salts or slightly alkaline salts.
  • Preferred acidifying components here 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.
  • 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.
  • 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 bleaching agents are the diacyl peroxides, e.g. Dibenzoyl.
  • 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 alkylperoxybenzoic acids, but also peroxy- ⁇ -naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ⁇ -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, diperoxysebacic acid, diperoxybrassic acid, the diperoxyphthalic acids, 2-decyldiperoxybutan-1 , 4-di
  • 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 are, 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 into consideration.
  • 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.
  • bleach activators may be included.
  • 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.
  • polyacylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, 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-diisocyanate acetoxy-2,5-dihydrofuran.
  • TAED
  • 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.
  • PAG pentaacetylglucose
  • pentaacetyl fructose pentaacetyl fructose
  • tetraacetylxylose tetraacetylxylose
  • octaacetyl lactose as well as acetylated, optionally N-alkylated glucamine and gluconolactone
  • 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 silicic acid or bistearylethylenediamide.
  • 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.
  • the optionally coated granules are bleach-free.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 from 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 a further advantageous manner 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 less as 10 wt .-%, based on the total mass of the core.
  • a further subject of the invention is the use of the optionally coated, granules according to the invention as enzyme granules, which preferably have an enzyme-free shell and / or an enzyme-free coating.
  • 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, Streptomyceus griseus, Coprinus Cinereus and Humicola insolens as well as from their genetically modified variants enzymatic agents.
  • Bacillus subtilis Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus Cinereus and Humicola insolens
  • subtilisin-type proteases and in particular proteases derived from Bacillus lentus are obtained.
  • 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 lipolylic enzymes of particular interest.
  • 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.
  • 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 entire, optionally coated. Granules.
  • the laundry detergent and / or detergent granules obtainable according to the invention may contain further enzyme stabilizers.
  • the detergent granules and / or detergent 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.
  • 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 ).
  • 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.
  • perfume oils or fragrances individual perfume compounds, for example the synthetic products of the ester type, ethers, aldehydes, ketones, alcohols and hydrocarbons can be used.
  • Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, Linalyl acetate, dimethyl benzyl carbinyl acetate, phenyl ethyl acetate, linalyl benzoate, benzyl formate, ethyl methyl phenylglycinate, allyl cyclohexyl propionate, styrallyl propionate and benzyl salicylate.
  • the ethers include, for example, benzyl ethyl ether, to the aldehydes, for example, the linear alkanals with 8-18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones such as the ionone, ⁇ -isomethylionone and Methylcedrylketon to the alcohols include anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol; the hydrocarbons mainly include the terpenes such as limonene and pinene.
  • fragrance oils may also contain natural fragrance mixtures such as those available from vegetable sources, eg pine, citrus jasmine, patchouly, rose or ylang-ylang oil.
  • perfume oils may also contain natural fragrance mixtures such as those available from vegetable sources, eg pine, citrus jasmine, patchouly, rose or ylang-ylang oil.
  • Muskateller, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon oil, linoleniac oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil are also suitable.
  • the mill worked with an air temperature of 38 ° C. After milling, the material had a d 50 of 7 ⁇ m, measured in the Camsizer from Retsch, and was then used as 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.
  • soda was sifted out and used to start the process.
  • a granulate ex granulation / drying was screened out as core material, consisting of undersize in a mixture with good grain.
  • 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.
  • 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 dosed to flight collection and separation in the filter on a collection tape and fed from there back to the turbulence mill.
  • the Gutkorn showed after screening a d 50 of 0.90 mm (+ 16% compared to the core material) on; prior to screening the d 50 0.83 mm (+ 9.2% compared to the core material) was.
  • the bulk density of the sieved good grain was 610 g / l; the Shape Factor of the sieved Gutkorns at 0.88.

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Claims (15)

  1. Procédé pour la préparation d'agents de lavage ou de nettoyage, dans lequel on dépose sous la forme de granulés, sur une matière particulaire faisant office de partie centrale, une matière plus fine faisant office d'enveloppe, caractérisé en ce que les matières premières à mettre en oeuvre dans l'étape de granulation sont guidées au moins en partie à travers une installation de broyage/séchage et
    le produit présente un diamètre d50 qui est supérieur à concurrence d'au minimum 5 % et d'au maximum 66 % au diamètre d50 de la matière faisant office de partie centrale et représente au moins 15 fois le diamètre moyen (d50) de la matière faisant office d'enveloppe que l'on obtient à partir d'une étape de broyage/séchage.
  2. Procédé selon la revendication 1, caractérisé en ce que le granulateur/mélangeur est entraîné à un nombre de Froude entre 2 et 10, de préférence entre 2,5 et 4.
  3. Procédé selon l'une quelconque des revendications 1 - 2, caractérisé en ce que le processus de broyage/séchage a lieu dans un broyeur tubulaire, dans un broyeur à chocs, dans un broyeur à pointes, dans un broyeur vibrant, dans un broyeur à marteaux, dans un broyeur à jet d'air ou dans un broyeur de type Bowl-Mill, de préférence dans un broyeur à tourbillons, en particulier dans un broyeur travaillant avec un gaz porteur, comprenant des plaques de broyage rotatives.
  4. Procédé selon l'une quelconque des revendications 1 - 3, caractérisé en ce qu'on met en oeuvre, dans le processus de broyage/séchage, de l'air à une température entre 15 et 220 °C, de préférence entre 25 et 120 °C, et en particulier entre 35 et 70 °C.
  5. Procédé selon l'une quelconque des revendications 1 - 4, caractérisé en ce qu'on ajoute de manière simultanée ou de préférence de manière successive plusieurs adjuvants de granulation qui peuvent être distingués du point de vue chimique, de préférence sous la forme de solutions, de suspensions, de dispersions, de mousses et/ou de (nano)émulsions.
  6. Procédé selon l'une quelconque des revendications 1 - 5, caractérisé en ce qu'on élimine, dans l'étape de broyage/séchage, de l'eau à concurrence de 0,05 à 6 % en poids rapportés à la matière faisant office d'enveloppe.
  7. Procédé selon l'une quelconque des revendications 1 - 6, caractérisé en ce que la matière faisant office de partie centrale est présente en une distribution granulométrique la plus uniforme possible dans laquelle le rapport d50 à d90 s'élève à au moins 0,50.
  8. Procédé selon l'une quelconque des revendications 1 - 7, caractérisé en ce que les déclassés, aussi bien trop petits et trop grands séparés par tamisage sont soumis, après l'étape de granulation/séchage à un processus de broyage/séchage et sont renvoyés dans le procédé à titre de partie de la matière faisant office d'enveloppe.
  9. Procédé selon l'une quelconque des revendications 1 - 8, caractérisé en ce que, à partir du courant de produit, les grains acceptables et/ou trop petits sont séparés par tamisage et introduits ensuite dans le procédé à titre de matière faisant office de partie centrale.
  10. Procédé selon l'une quelconque des revendications 1 - 9, caractérisé en ce que, dans l'étape de granulation, on introduit, à côté du/des liquides de granulation, d'autres liquides et/ou sels hydrophiles et/ou lipophiles.
  11. Procédé selon l'une quelconque des revendications 1 - 10, caractérisé en ce que l'adjuvant de granulation comprend un liquide d'acides neutralisés d'agents tensioactifs et de builders, de préférence avec une teneur en eau inférieure à 10 % en poids, de manière avantageuse inférieure à 6 % en poids, rapportés au produit de granulation.
  12. Procédé selon l'une quelconque des revendications 1 - 11, caractérisé en ce que l'adjuvant de granulation comprend une solution de substances polymères, de préférence avec une teneur en eau inférieure à 10 % en poids, rapportés au produit de granulation.
  13. Procédé selon l'une quelconque des revendications 1 - 12, caractérisé en ce que l'adjuvant de granulation comprend au moins une mousse.
  14. Procédé selon l'une quelconque des revendications 1 - 13, caractérisé en ce que l'étape de granulation est constituée par au moins un mélangeur et par un lit fluidisé.
  15. Procédé selon l'une quelconque des revendications 1 - 14, caractérisé en ce que l'étape de granulation est constituée par un mélangeur à rotation rapide et par un mélangeur à rotation lente, ainsi que par un lit fluidisé.
EP07726683A 2006-04-11 2007-03-07 Granulés de lessive ou de détergent Not-in-force EP2004791B1 (fr)

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PL07726683T PL2004791T3 (pl) 2006-04-11 2007-03-07 Granulaty środków piorących lub czyszczących

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DE102006017312A DE102006017312A1 (de) 2006-04-11 2006-04-11 Wasch- oder Reinigungsmittelgranulate
PCT/EP2007/052125 WO2007118733A1 (fr) 2006-04-11 2007-03-07 Granulés de lessive ou de détergent

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EP2004791B1 true EP2004791B1 (fr) 2010-09-29

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DE102009002877A1 (de) 2009-05-06 2010-11-18 Henkel Ag & Co. Kgaa Haarfärbe/wellmittel mit verbesserter Hautverträglichkeit
DE102009002881A1 (de) * 2009-05-06 2010-11-11 Henkel Ag & Co. Kgaa Haar- und kopfhautschonende Shampoos und Conditioner
CN108959742B (zh) * 2018-06-20 2022-12-27 重庆科技学院 大跨越输电塔线体系气动弹性模型设计方法

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DE19524287A1 (de) * 1995-07-06 1997-01-09 Henkel Kgaa Von Staub- und Feinanteilen freie granulare Wasch- und Reinigungsmittel hoher Schüttdichte
DE10125565A1 (de) * 2001-05-25 2002-12-05 Henkel Kgaa Verfahren zur Herstellung von Tensidgranulaten
ES2397226T3 (es) * 2004-11-02 2013-03-05 Henkel Ag & Co. Kgaa Procedimiento para la preparación de granulados / aglomerados para productos de lavado y limpieza

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DE102006017312A1 (de) 2007-10-18
WO2007118733A1 (fr) 2007-10-25
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ATE483013T1 (de) 2010-10-15
PL2004791T3 (pl) 2011-03-31
DE502007005202D1 (de) 2010-11-11

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