WO2007079803A1 - Procédé de production amélioré d'un produit détergent - Google Patents

Procédé de production amélioré d'un produit détergent Download PDF

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Publication number
WO2007079803A1
WO2007079803A1 PCT/EP2006/010357 EP2006010357W WO2007079803A1 WO 2007079803 A1 WO2007079803 A1 WO 2007079803A1 EP 2006010357 W EP2006010357 W EP 2006010357W WO 2007079803 A1 WO2007079803 A1 WO 2007079803A1
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WIPO (PCT)
Prior art keywords
spray
vortex chamber
slurry
nozzle
acid
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PCT/EP2006/010357
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German (de)
English (en)
Inventor
Rene-Andres Artiga Gonzalez
Heike Fleischmann
Stefan Hammelstein
Udo Rupprecht
Detlef Schiwek
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
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Publication of WO2007079803A1 publication Critical patent/WO2007079803A1/fr

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    • 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
    • C11D11/02—Preparation in the form of powder by spray drying
    • 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
    • C11D11/0082—Special methods for preparing compositions containing mixtures of detergents 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
    • B05B1/00—Nozzles, spray heads or other outlets, with or without auxiliary devices such as valves, heating means
    • B05B1/34—Nozzles, spray heads or other outlets, with or without auxiliary devices such as valves, heating means designed to influence the nature of flow of the liquid or other fluent material, e.g. to produce swirl
    • B05B1/3405—Nozzles, spray heads or other outlets, with or without auxiliary devices such as valves, heating means designed to influence the nature of flow of the liquid or other fluent material, e.g. to produce swirl to produce swirl
    • B05B1/341—Nozzles, spray heads or other outlets, with or without auxiliary devices such as valves, heating means designed to influence the nature of flow of the liquid or other fluent material, e.g. to produce swirl to produce swirl before discharging the liquid or other fluent material, e.g. in a swirl chamber upstream the spray outlet
    • B05B1/3421—Nozzles, spray heads or other outlets, with or without auxiliary devices such as valves, heating means designed to influence the nature of flow of the liquid or other fluent material, e.g. to produce swirl to produce swirl before discharging the liquid or other fluent material, e.g. in a swirl chamber upstream the spray outlet with channels emerging substantially tangentially in the swirl chamber
    • B05B1/3426—Nozzles, spray heads or other outlets, with or without auxiliary devices such as valves, heating means designed to influence the nature of flow of the liquid or other fluent material, e.g. to produce swirl to produce swirl before discharging the liquid or other fluent material, e.g. in a swirl chamber upstream the spray outlet with channels emerging substantially tangentially in the swirl chamber the channels emerging in the swirl chamber perpendicularly to the outlet axis

Definitions

  • the present invention relates to an improved manufacturing process for detergents or cleaners, a spray nozzle and the use of a spray nozzle for atomizing washing or cleaning-active substance-containing mixtures.
  • Spray-dried detergents or cleaners are known from the prior art for a long time.
  • a disadvantage of these agents that they usually have a relatively broad particle size range with particle sizes up to 1000 microns, while at the same time dust particles are present with particle sizes below 100 microns.
  • the coarser particles can be formed by agglomeration of the primary particles. They can be identified microscopically as particles with raspberry-like structures. Dust levels are not desirable for the known reasons.
  • spray drying products usually have not only a very non-uniform grain spectrum, and the bulk density is highly dependent on the grain spectrum. Thus, in the past, direct spray-drying products generally had a bulk density of 200 to 400 g / l.
  • Devices for the spray-drying of solvent-containing compositions, in particular water-containing compositions are known from the prior art.
  • Frequently used devices are, for example, spray towers with atomizing nozzles, which are used in particular for liquid educts (solutions, suspensions or melts) to provide a powdery product.
  • the liquid is usually atomized with pressure nozzles and then dried in hot gas in cocurrent or countercurrent. Subsequently, the dry product is separated by cyclones or filters. If a melt is atomized and solidified in cold gas, it is called a prilling tower.
  • Other known spray dryers are disk towers. These are - as well as the nozzle towers - short-term dryers.
  • fluidized bed spray granulators which serve the production of granules in the range of 0.3 mm to several mm from atomizable solutions, suspensions and melts.
  • agglomerating dryers For atomization mostly two-fluid nozzles are used.
  • the product is usually resistant to abrasion and has a relatively high bulk density. The dissolution rate is therefore lower compared to other spray products.
  • Such a granulator can also be used for coating granules, then it is usually operated discontinuously.
  • a lowering of the spray pressure is with the commonly used nozzles, but usually turbulence nozzles, not possible because this, as far as it still comes to the atomization of the preparations, a formation of drops with significantly different sizes result.
  • their dry products also have significantly different sizes and thus a broad range of grain sizes.
  • the object of the invention was to find a way to provide a washing or cleaning agent or a component for this purpose with narrow particle size distribution by a method which does not have these disadvantages.
  • the invention in a first embodiment is therefore a process for the preparation of detergent or cleaning granules, in which a slurry comprising washing or cleaning-active ingredients is sprayed through a Hohlkegeldüse having an inlet opening, a spray opening and a vortex chamber connecting the inlet and the spray opening has, wherein the vortex chamber has a spiral shape.
  • FIG. 1 The shape of a suitable vortex chamber is shown in Figure 1.
  • the illustration is merely a schematic drawing and is intended to illustrate the construction principle of a suitable vortex chamber and to explain the term "cross section of the inlet.”
  • the slurry enters through the recess in the lateral chamber wall.
  • the distance between the two surfaces A and B, which form the entrance of the vortex chamber, at each of the points farthest from the interior of the vortex chamber corresponds to the distance a.
  • the areas A and B are shown in Figure 1 as a line due to the selected perspective. Not shown in the drawing, as can not be seen in the plan view of the vortex chamber, the depth of the vortex chamber. At the widest point of the vortex chamber inlet, the cross section of the inlet opening is calculated from the multiplication of the distance a with the vortex chamber depth.
  • the individual angles, curvatures, distances and areas of the swirl chamber shown in Figure 1 are variable within a wide range, but the geometry of the swirl chamber affects the particle size distribution as well as the flow rate of the product obtained by the atomization of the slurry.
  • the cross-section of the inlet preferably has an area of 5 to 70 mm 2 , preferably 7 to 60 mm 2 , particularly preferably 9 to 50 mm 2 and in particular 11 to 40 mm 2 .
  • the depth of the spiral vortex chamber is preferably from 2.5 mm to 14.0 mm, preferably from 3.0 to 13.0 mm, particularly preferably from 3.5 and 12.0 mm and in particular from 4.0 and 11, 0 mm.
  • the spray opening of the hollow cone nozzle is formed by a preferably circular bore in a plate to be placed on the vortex chamber. With preference, the spray opening has a diameter of 1.0 to 6.0 mm, preferably 1.5 to 5.5 mm, more preferably 2.0 to 5.0 and in particular 2.0 to 4.5 mm ,
  • washing or cleaning agents having a particularly narrow particle size distribution and, in particular, a reduced proportion of excessively fine particles can be produced if the ratio between the depth of the vortex chamber (in mm) and the cross section of the inlet opening (in mm 2 ) is between 1 : 10 and 2: 1, preferably between 1: 8 and 1: 1, more preferably between 1: 6 and 1: 2 and in particular between 1: 4 and 1: 2 amount.
  • a certain range for the ratio between the depth of the vortex chamber and the diameter of the spray opening is maintained.
  • the ratio between the depth of the vortex chamber (in mm) and the diameter of the spray opening (in mm) is between 5: 1 and 1: 2, preferably between 4.5: 1 and 1: 1, 5, more preferably between 4: 1 and 1: 1 and in particular between 3.5: 1 and 1, 5: 1.
  • the ratio between the cross section of the inlet opening (in mm 2 ) and the diameter of the spray opening (in mm) between 1: 1 and 20: 1, preferably between 2: 1 and 17: 1, more preferably between 3: 1 and 14: 1 and especially between 4: 1 and 11: 1.
  • a slurry which contains at least one washing- or cleaning-active substance-containing constituent.
  • This component and optionally other pure or liquid in 20 ° C liquid, pasty or particulate components of the slurries may be dissolved in one or more aqueous or non-aqueous solvent (s), emulsified or dispersed.
  • s aqueous or non-aqueous solvent
  • Substances or substance mixtures which do not contain any solvents should also be encompassed by the term slurry in the context of this application.
  • the slurry in the process according to the invention preferably contains, as solvent, water or a mixture of water with a further, preferably organic, solvent.
  • the proportion of non-aqueous solvents in the slurry is not more than 10% by weight, preferably not more than 5% by weight and in particular not more than 2.5% by weight, based on the slurry.
  • the water content of the slurry is preferably between 10 and 60 wt .-%, preferably between 15 and 55 wt .-% and in particular between 15 and 50 wt .-%.
  • the slurry contains supercritical, liquid carbon dioxide.
  • the term slurry also encompasses melting of a substance or a mixture of substances, as well as dispersions which contain solid or liquid to pasty phases in a melt matrix.
  • the slurry is heated prior to entering the nozzle, which has a particular preference to reduce its viscosity.
  • the slurrytemperatur directly in front of the nozzle between 40 and 95 0 C and in particular between 50 and 95 ° C.
  • the slurry at 50 ° C. preferably has a viscosity (determined according to Brookfield, viscometer LVT-II at 20 rpm, spindle 3) between 100 and 3000 mPas, preferably between 200 and 2800 mPas and in particular between 300 and 2600 mPas on. With particular preference, the viscosity is between 400 and 2600 mPas, more preferably between 500 and 2600 mPas and in particular between 600 and 2600 mPas.
  • highly viscous slurries with viscosities above 2500 mPas, preferably above 3000 mPas, more preferably above 3500 mPas and in particular with at least 3750 mPas are sprayed.
  • the nozzles can be operated at significantly lower pressures while still providing granules having a narrow grain size distribution at a high production rate.
  • the pressure with which the slurry is fed into the nozzle is between 15 and 40 bar, preferably between 17 and 37 bar, more preferably between 19 and 34 bar and in particular between 21 and 31 bar.
  • preferred processes in which the pressure in front of the nozzle is between 15 and 40 bar, preferably between 17 and 37 bar, particularly preferably between 19 and 34 bar and in particular between 21 and 31 bar, have further advantages: It becomes a significantly lower wear on the nozzles, pumps and other slurry aggregates than in known methods observed. Furthermore, these methods, since they enable high production rates to be achieved at low pressure, have considerable energy-saving potential.
  • a higher feed pressure of, for example, 30 to 45 bar and in particular from 35 to 45 bar.
  • the production rate increases due to the increased flow rate through the nozzle.
  • slurries with viscosities above 2000 mPas preferably from 2000 to 4000 mPas and in particular with 3000 to 4000 mPas are atomized at these higher pressures.
  • Another reason to increase the pressure may be the desire for a higher production rate. In these cases, the pressure can also be increased, although the viscosity of the slurries is below 2000 mPas.
  • more than 100 kg of slurry, more preferably more than 250 kg, more preferably more than 350 kg, with particular preference between 350 and 2500 kg and in particular between 450 and 2400 kg of slurry are passed through the nozzle in the inventive process.
  • the corresponding production rates are also achieved when the pressure with which the slurry is introduced into the nozzle is in the range between 15 and 40 bar, preferably between 17 and 37 bar, particularly preferably between 19 and 34 bar and in particular between 21 and 31 bar. This is a particular advantage of the method according to the invention. Such high production rates can not be achieved with the nozzles usually used in the field of detergents or cleaners at low pressures.
  • the detergents or cleaners prepared by means of the inventive method and components thereof are also referred to as granules in the context of this application.
  • granules are obtained whose grain spectrum is distinctly narrower than the grain spectra of products obtained by atomizing slurries by means of nozzles which do not have spiral vortex chambers.
  • a particular advantage of the method is the reduction of the amount of fines formed, which leads to less segregation in the finished products and to a lower dust load during manufacture and use by the consumer.
  • the average particle diameter d 50 of the granules is preferably in the range of 0.2 to 1.2 mm, preferably in the range of 0.3 to 1, 0 mm and in particular between 0.4 and 0.8 mm. In this case or independently thereof, less than 15% by weight, preferably less than 10% by weight and in particular less than 5% by weight, of the granules is less than 0.1 mm.
  • a washing or cleaning agent or a component with a particularly narrow particle size distribution in which preferably less than 15 wt .-%, preferably less than 10 wt .-% of the granules is greater than 1, 6 mm, preferably greater than 1.4 mm and in particular greater than 1.2 mm and with preference less than 15% by weight, preferably less than 10% by weight, of the granules is smaller than 0.4 mm, preferably smaller than 0.3 mm and in particular smaller than 0.2 mm, if, in a preferred embodiment of the inventive method, the ratio between the depth of the vortex chamber (in mm) and the diameter of the spray opening (in mm) between 4: 1 and 1: 1, preferably between 3: 1 and 1: 1 and in particular between 2: 1 and 1: 1, wherein preferably the cross section of the inlet opening has an area of 15 to 40 mm 2 and preferably from 17 to 38 mm 2 .
  • the pressure at which the slurry is fed into the nozzle is from 30 to 45 bar, more preferably from 32 to 44 bar, more preferably from 34 to 43 bar, most preferably from 36 to 42 bar and especially 38 to 42 bar and / or more than 600 kg, preferably more than 800 kg, more preferably more than 1000 kg and in particular more than 1200 kg of slurry are preferably passed through the nozzle per hour.
  • a washing or cleaning agent or a component with a particularly narrow particle size distribution in which preferably less than 15 wt .-%, preferably less than 10 wt .-% of the granules is greater than 1, 0 mm, preferably is greater than 0.8 mm and in particular greater than 0.6 mm, and with preference less than 10 wt .-%, preferably less than 5 wt .-% of the granules is smaller than 0.3 mm, preferably less than 0.2 mm, and in particular smaller than 0.1 mm, can be produced, if in a further preferred embodiment of the method according to the invention, the ratio between the depth of the vortex chamber (in mm) and the diameter of the spray opening (in mm) between 4: 1 and 1: 1, preferably between 3.5: 1 and 1, 5: 1 and in particular between 3: 1 and 2: 1, wherein preferably the cross section of the inlet opening has an area of 10 to 25 mm 2 , preferably 12 to 23
  • the pressure at which the slurry is fed into the nozzle is from 20 to 42 bar, more preferably from 22 to 41 bar, more preferably from 24 to 40 bar, most preferably from 26 to 39 bar and especially 28 to 38 bar and / or more than 300 kg, preferably more than 350 kg, more preferably more than 400 kg and in particular more than 450 kg of slurry are passed through the nozzle per hour.
  • the inventive method allows the provision of granules which flow freely even after storage, do not clump and do not dust.
  • the bulk densities of the granules produced by the method according to the invention can vary within a wide range.
  • the bulk densities of the granules are in a range between 200 g / l and 600 g / l, with a range between 300 g / l and 500 g / l being particularly preferred.
  • Bulk weights in the range of 350 to 450 g / l are again to be regarded as particularly preferred.
  • the resulting granules are spherical or nearly spherical.
  • the granules are also characterized by good Léeeigenschaften.
  • the inventive method is carried out in a spray tower and at least one, preferably at least two and more preferably at least three nozzles are mounted in the upper region of the spray tower.
  • at least four, preferably at least five, and in particular at least six nozzles are mounted at several different heights, preferably at most three different heights of the spray tower.
  • the nozzles are preferably arranged such that the spray cones of the nozzles overlap as little as possible.
  • the spray cone of the nozzle (s) is in a particularly preferred embodiment of the method according to the invention between 40 and 95 °, preferably between 45 and 90 ° and in particular between 50 and 80 °.
  • the spray tower used may optionally be equipped with an integrated fluidized bed.
  • the slurry to be sprayed contains at least one washing or cleaning active ingredient. This is preferably selected from the group of builders, surfactants and polymers.
  • the builders include, in particular, the zeolites, silicates, carbonates, organic cobuilders and, where there are no ecological prejudices against their use, also the phosphates.
  • the finely crystalline, synthetic zeolite containing bound water used is preferably zeolite A and / or P.
  • the zeolite P, zeolite MAP ® (commercially available from Crosfield) is especially preferred.
  • zeolite X and mixtures of A, X and / or P are also suitable, however, are zeolite X and mixtures of A, X and / or P.
  • Commercially available and preferably usable in the context of the present invention is, for example, a cocrystal of zeolite X and zeolite A (about 80% by weight of zeolite X) ), by the formula
  • the zeolite can be used both as a builder in a granular compound, as well as a kind of "powdering" of a granular mixture, preferably a mixture to be pressed, whereby usually both ways to Incorporation of the zeolite into the premix.
  • Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution, measuring method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
  • crystalline layered silicates of general formula NaMSi x O 2x + I ⁇ y H 2 O wherein M is sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1, 9 to 4, wherein particularly preferred values for x are 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20.
  • the crystalline layered silicates of the formula NaMSi x O 2x + 1 • y H 2 O are sold, for example, by the company Clariant GmbH (Germany) under the trade name Na-SKS.
  • silicates Na-SKS-1 (Na 2 Si 22 O 45 .xH 2 O, kenyaite), Na-SKS-2 (Na 2 Si 14 O 29 .xH 2 O, magadiite), Na-SKS -3 (Na 2 Si 8 O 17 • x H 2 O) or Na-SKS-4 (Na 2 Si 4 O 9 • x H 2 O, Makatite).
  • crystalline layer silicates are particularly suitable of the formula NaMSi x O 2x + 1 ⁇ y H 2 O, in which x stands for 2 h.
  • both ⁇ - and ⁇ -sodium disilicates are Na 2 Si 2 O 5 .yH 2 O and furthermore, above all, Na-SKS-5 (Ct-Na 2 Si 2 O 5 ), Na-SKS-7 ( ⁇ -Na 2 Si 2 O 5, natrosilite), Na-SKS-9 (NaHSi 2 O 5 • H 2 O), Na-SKS-10 (NaHSi 2 O 5 • 3 H 2 O, kanemite), Na SKS-11 ( t-Na 2 Si 2 O 5 ) and Na-SKS-13 (NaHSi 2 O 5 ), but especially Na-SKS-6 (5-Na 2 Si 2 O 5 ) 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, which preferably delayed release and have secondary washing properties.
  • the dissolution delay compared with conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying.
  • amorphous is understood to mean that the silicates do not yield sharp X-ray reflections as they are typical for crystalline substances, but at best one or more maxima of the scattered X-radiation, which are several degrees wide of the diffraction angle exhibit, cause.
  • X-ray amorphous silicates are used whose silicate particles produce fuzzy or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of the size of ten to a few hundred nm, with values of up to max. 50 nm and in particular up to max. 20 nm are preferred.
  • Such X-ray amorphous silicates also have a dissolution delay compared to conventional water glasses.
  • particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.
  • phosphates as builders are possible, unless such use should not be avoided for environmental reasons.
  • alkali metal phosphates with particular preference of pentasodium or pentakalium triphosphate (sodium or potassium tripolyphosphate) in the washing and cleaning industry have the greatest importance.
  • Alkali metal phosphates is the summary term for the alkali metal (especially sodium and potassium) salts of various phosphoric acids, in which one can distinguish metaphosphoric acids (HPO 3 ), and orthophosphoric H 3 PO 4 in addition to high molecular weight representatives.
  • the phosphates combine several advantages: they act as alkali carriers, prevent lime deposits on machine parts or lime incrustations in fabrics and also contribute to the cleaning performance.
  • phosphates are the pentasodium triphosphate, Na 5 P 3 Oi 0 (sodium tripolyphosphate) and the corresponding potassium salt pentapotassium triphosphate, K 5 P 3 O 10 (potassium tripolyphosphate).
  • the sodium potassium tri-phosphates are also preferably used according to the invention.
  • alkali carriers are, for example, alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogencarbonates, alkali metal sesquicarbonates, the cited alkali metal silicates, alkali metal silicates and mixtures of the abovementioned substances, preference being given to using alkali metal carbonates, in particular sodium carbonate, sodium bicarbonate or sodium sesquicarbonate for the purposes of this invention.
  • alkali metal carbonates in particular sodium carbonate, sodium bicarbonate or sodium sesquicarbonate for the purposes of this invention.
  • Particularly preferred may be a builder system comprising a mixture of tripolyphosphate and sodium carbonate. Due to their low chemical compatibility with the other ingredients of detergents or cleaners in comparison with other builders, the alkali metal hydroxides are preferably used only in small amounts.
  • Particularly suitable organic co-builders are polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins and 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 the free acid and / or 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.
  • the free acids also typically have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaners.
  • 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 of polymethacrylic acid, for example those having a relative molecular mass of from 500 to 70,000 g / mol.
  • the molecular weights indicated for polymeric polycarboxylates are weight-average molar masses M w of the particular acid form, which were fundamentally determined 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.
  • 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.
  • the (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution.
  • the polymers may also contain allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid as a monomer.
  • 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 have as monomers acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.
  • polymeric aminodicarboxylic acids their salts or their precursors. Particular preference is given to polyaspartic acids or their salts.
  • 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
  • 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.
  • Oxydisuccinates and other derivatives of disuccinates preferably ethylenediamine disuccinate, are further suitable co-builders.
  • Ethylenediamine-N, N'-disuccinate (EDDS) is preferably 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.
  • the group of surfactants includes nonionic, anionic, cationic and amphoteric surfactants.
  • nonionic surfactants it is possible to use all nonionic surfactants known to the person skilled in the art. Low-foaming nonionic surfactants are used as preferred surfactants.
  • Detergents or cleaning agents with particular preference contain nonionic surfactants from the group of alkoxylated alcohols.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in oxo alcohol radicals.
  • EO ethylene oxide
  • alcohol ethoxylates having linear radicals of alcohols of native origin having 12 to 18 carbon atoms, for example coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 moles of EO per mole of alcohol are preferred.
  • the preferred ethoxylated alcohols include, for example, C 12 -i 4 -alcohols with 3 EO or 4 EO, C 9-11 -alkoHo with 7 EO 1 C 13 .is alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12 -is-alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12 - U -AlkOhOl with 3 EO and with 5 EO.
  • the stated degrees of ethoxylation represent statistical averages, which may correspond to a particular product of an integer or a fractional number.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow rank ethoxylates, NRE).
  • nonionic surfactants it is also possible to use fatty alcohols with more than 12 EO. Examples of these are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • nonionic surfactants and alkyl glycosides of the general formula RO (G) x can be used in which R is a primary straight-chain or methyl-branched, especially methyl-branched in the 2-position aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is an arbitrary number between 1 and 10; preferably x is 1.2 to 1.4.
  • nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain.
  • 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.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.
  • surfactants are polyhydroxy fatty acid amides of the formula
  • R is an aliphatic acyl radical having 6 to 22 carbon atoms
  • R 1 is hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms
  • [Z] is a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
  • the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula
  • R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
  • R 1 is a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms
  • R 2 is a linear, branched or cyclic alkyl radical or an aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, wherein C 1-4 -AlkVl- or phenyl radicals are preferred and [Z] is a linear polyhydroxyalkyl radical whose alkyl chain is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or prop - xylated derivatives of this residue.
  • [Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a reduced sugar for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy- or N-aryloxy-substituted compounds can be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
  • combinations of one or more tallow fatty alcohols containing 20 to 30 EO and silicone defoamers are furthermore used.
  • Nonionic surfactants from the group of alkoxylated alcohols particularly preferably from the group of mixed alkoxylated alcohols and in particular from the group of EO / AO / EO nonionic surfactants, or the PO / AO / PO nonionic surfactants, especially the PO / EO / PO nonionic surfactants are particularly preferred.
  • Such PO / EO / PO nonionic surfactants are characterized by good foam control.
  • anionic surfactants for example, those of the sulfonate type and sulfates are used.
  • Suitable surfactants of the sulfonate type are preferably C 9-13 alkyl benzene sulfonates, finsulfonate olefinsulfonates, i.e. mixtures of alkene and hydroxyalkane sulfonates, and the disulfonates obtained, for example, from C 2 -is monoolefins with a terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation obtained.
  • alkanesulfonates which are obtained from C 12 -is-alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • esters of ⁇ -sulfo fatty acids esters of ⁇ -sulfo fatty acids (ester sulfonates), for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.
  • sulfated fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and mixtures thereof, as in the preparation by esterification of a monoglycerol with 1 to 3 mol of fatty acid or in the transesterification of triglycerides with 0.3 to 2 mol Glycerol can be obtained.
  • Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids containing 6 to 22 carbon atoms. Substance atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
  • Alk (en) yl sulfates are the alkali and especially the sodium salts of Schwefelklareschester the C 12 -C 18 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or C 10 -C 2 o Oxo alcohols and those half-esters of secondary alcohols of these chain lengths are preferred. Also preferred are alk (en) ylsulfates of the aforementioned chain length, which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis, which have an analogous decomposition behavior to the adequate compounds based on oleochemical raw materials.
  • 2,3-Alkyl sulfates which can be obtained as commercial products from Shell Oil Company under the name DAN ®, are suitable anionic surfactants.
  • 21 -alcohols such as 2-methyl-branched C 9-11 -AlkOhOIe with an average of 3.5 moles of ethylene oxide (EO) or C 12-18 -FeHaIkOhOIe with 1 to 4 EO, are suitable. They are used in detergents due to their high foaming behavior only in relatively small amounts.
  • Suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • alcohols preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8-18 fatty alcohol residues or mixtures of these.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves constitute nonionic surfactants.
  • Sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred.
  • alk (en) ylsuccinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • 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, soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids.
  • anionic surfactant in addition to the anionic surfactants, including soaps, also includes their acidic precursors, that is, anionic surfactant acids and fatty acids. acids. In the course of the inventive process, these acids are converted into the respective anionic surfactants.
  • the slurry contains anionic surfactants in an amount above 5 wt .-%, and preferably above 6 wt .-%, based on the slurry.
  • the slurry particularly preferably contains fatty acid and / or fatty acid salts, preferably in amounts of from 0.1 to 4% by weight, preferably from 0.2 to 3% by weight, particularly preferably from 0.3 to 2% by weight, based on the slurry.
  • a slurry which contains less than 0.2% by weight of fatty acid and / or fatty acid salts, preferably less than 0.1% by weight and in particular no fatty acid and / or fatty acid salts.
  • the anionic surfactants can be present 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.
  • cationic active substances for example, cationic compounds of the following formulas can be used:
  • Textile softening compounds can be used to care for the textiles and to improve the textile properties such as a softer "avivage” and reduced electrostatic charge (increased wearing comfort) .
  • the active compounds of these formulations are quaternary ammonium compounds having two hydrophobic radicals, such as, for example, the disteryldimethyl ammonium chloride, which, however, due to its insufficient biodegradability, is increasingly being replaced by quaternary ammonium compounds which contain ester groups as biodegradation breakpoints in their hydrophobic residues
  • esterquats having improved biodegradability are obtainable, for example, by mixing mixtures of methyldiethanolamine and or triethanolamine esterified with fatty acids and the reaction products are then quaternized in a manner known per se with alkylating agents material.
  • the group of polymers includes, in particular, the washing or cleaning-active polymers and / or polymers which act as softeners.
  • cationic, anionic and amphoteric polymers can be used in detergents or cleaners in addition to nonionic polymers.
  • “Cationic polymers” for the purposes of the present invention are polymers which carry a positive charge in the polymer molecule, which can be realized, for example, by (alkyl) ammonium groups or other positively charged groups present in the polymer chain quaternized cellulose derivatives, the polysiloxanes with quaternary groups, the cationic guar derivatives, the polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid, the copolymers of vinylpyrrolidone with quaternized derivatives of dialkylaminoacrylate and methacrylate , the vinylpyrrolidone-methoimidazolinium chloride copolymers, the quaternized polyvinyl alcohols or the polymers specified under the INCI names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27.
  • amphoteric polymers also have, in addition to a positively charged group in the polymer chain, also negatively charged groups or monomer units. These groups may be, for example, carboxylic acids, sulfonic acids or phosphonic acids.
  • the detergents or cleaners can contain further ingredients which further improve the performance and / or aesthetic properties of these compositions.
  • Preferred agents contain one or more of the group of electrolytes, pH adjusters, fluorescers, hydrotopes, foam inhibitors, silicone oils, anti redeposition agents, optical brighteners, grayness inhibitors, anti-shrinkage agents, crease inhibitors, dye transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, antistatic agents, ironing aids , Phobic and impregnating agents, swelling and anti-slip agents and UV absorbers.
  • these ingredients are not part of the slurries, but are used in a later process step for the aftertreatment of the granules produced by the inventive method.
  • electrolytes from the group of inorganic salts a wide number of different salts can be used.
  • Preferred cations are the alkali and alkaline earth metals, preferred anions are the halides and sulfates. From a manufacturing point of view, the use of NaCl or MgCl 2 in the washing or cleaning agents is preferred.
  • pH adjusters In order to bring the pH of detergents or cleaners into the desired range, the use of pH adjusters may be indicated. Applicable here are all known acids or alkalis, unless their use prohibits application-related or environmental reasons or for reasons of consumer protection.
  • Suitable foam inhibitors are, inter alia, soaps, oils, fats, paraffins or silicone oils, which may optionally be applied to support materials.
  • Suitable carrier materials are, for example, inorganic salts such as carbonates or sulfates, cellulose derivatives or silicates and mixtures of the abovementioned materials.
  • preferred agents include paraffins, preferably unbranched paraffins (n-paraffins) and / or silicones, preferably linear-polymeric silicones, which are constructed according to the scheme (R 2 SiO) x and are also referred to as silicone oils.
  • silicone oils are usually clear, colorless, neutral, odorless, hydrophobic liquids having a molecular weight between 1000 and 150,000 and viscosities between 10 and 1,000,000 mPa.s.
  • the products made by atomizing the slurry are aftertreated with foam inhibitors.
  • Suitable anti-redeposition agents which are also referred to as soil repellents, are, for example, nonionic cellulose ethers such as methylcellulose and methylhydroxypropylcellulose with a proportion of methoxy groups of 15 to 30% by weight and of hydroxypropyl groups of 1 to 15% by weight, based in each case on the nonionic cellulose ether as well as from the state of Technically known polymers of phthalic acid and / or terephthalic acid or derivatives thereof, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionic modified derivatives thereof. Particularly preferred of these are the sulfonated derivatives of phthalic and terephthalic acid polymers.
  • Optical brighteners can be added to laundry detergents or cleaners to eliminate graying and yellowing of the treated textiles, which draw on the fiber and cause brightening and fake bleaching by turning invisible ultraviolet radiation into visible longer wavelength light convert the absorbed from sunlight ultraviolet light is radiated as pale bluish fluorescence and pure for the yellow shade of the grayed or yellowed laundry white produces Suitable compounds originate for example from the substance classes of 4.4.
  • Grayness inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being rebuilt.
  • Water-soluble colloids of mostly organic nature are suitable for this purpose, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether sulfonic acids or cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
  • water-soluble polyamides containing acidic groups are suitable for this purpose.
  • soluble starch preparations and other than the above-mentioned starch products can be used, for example degraded starch, aldehyde starches and so on. Polyvinylpyrrolidone is also useful.
  • Cellulosic ethers such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose and mixed ethers such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof can furthermore be used as graying inhibitors.
  • synthetic anti-crease agents can be used. These include, for example, synthetic products based on fatty acids, fatty acid esters, fatty acid amides, alkylol esters, -alkylolamides or fatty alcohols, which are usually reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid ester. Phobic and impregnation processes are used to furnish textiles with substances that prevent the deposition of dirt or facilitate its leaching ability.
  • Preferred repellents and impregnating agents are perfluorinated fatty acids, also in the form of their aluminum and zirconium salts, organic silicates, silicones, polyacrylic acid esters with perfluorinated alcohol component or with perfluorinated acyl or sulfonyl radical coupled polymerizable compounds.
  • Antistatic agents may also be included.
  • the antisoiling equipment with repellents and impregnating agents is often classified as an easy-care finish. The penetration of the impregnating agent in the form of solutions or emulsions of the active substances in question can be facilitated by adding wetting agents which reduce the surface tension.
  • a further field of application of repellents and impregnating agents is the water-repellent finish of textiles, tents, tarpaulins, leather and so on, in contrast to the waterproofing, the fabric pores are not closed, so the fabric remains breathable (hydrophobing).
  • the hydrophobizing agents used for hydrophobizing coat textiles, leather, paper, wood and so on with a very thin layer of hydrophobic groups, such as longer alkyl chains or siloxane groups.
  • Suitable hydrophobizing agents are, for example, paraffins, waxes, metal soaps and the like 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, silicones, Tin-organic compounds and glutaric dialdehyde and perfluorinated compounds.
  • the hydrophobized materials do not feel greasy; nevertheless, similar to greasy substances, water droplets emit from them without moistening.
  • silicone-impregnated textiles have a soft feel and are water and dirt repellent; Stains from ink, wine, fruit juices and the like are easier to remove.
  • Antimicrobial agents can be used to combat microorganisms. Depending on the antimicrobial spectrum and mechanism of action, a distinction is made between bacteriostats and bactericides, fungistatics and fungicides and so on. Important substances from these groups are, for example, benzalkonium chlorides, alkylaryl sulfonates, halophenols and phenol mercuriacetate, it also being possible to dispense entirely with these compounds.
  • compositions may contain anti-oxidants.
  • This class of compounds includes, for example, substituted phenols, hydroquinones, catechols and aromatic amines, as well as organic sulfides, polysulfides, dithiocarbamates, phosphites and phosphonates.
  • Antistatic agents increase the surface conductivity and thus allow an improved drainage formed charges.
  • External antistatic agents are generally substances with at least one hydrophilic molecule ligand and give a more or less hygroscopic film on the surfaces. These mostly surface-active antistatic agents can be subdivided into nitrogen-containing (amines, amides, quaternary ammonium compounds), phosphorus-containing (phosphoric acid esters) and sulfur-containing (alkyl sulfonates, alkyl sulfates) antistatic agents.
  • Lauryl (or stearyl) di- methylbenzylammoniumchloride are also suitable as antistatic agents for textiles or as an additive to detergents, with an additional Avivage bin is achieved.
  • Silicone derivatives can be used to improve the water absorbency, rewettability of the treated fabrics, and ease of ironing the treated fabrics. These additionally improve the rinsing out of detergents or cleaning agents by their foam-inhibiting properties.
  • Preferred silicone derivatives are, for example, polydialkyl or alkylaryl siloxanes in which the alkyl groups have one to five carbon atoms and are completely or partially fluorinated.
  • Preferred silicones are polydimethylsiloxanes, which may optionally be derivatized and are then amino-functional or quaternized or have Si-OH, Si-H and / or Si-Cl bonds.
  • Further preferred silicones are the polyalkylene oxide-modified polysiloxanes, ie polysiloxanes which, for example, have polyethylene glycols and the polyalkylene oxide-modified dimethylpolysiloxanes.
  • the granules produced by the inventive method can either be used as a final product or post-treated and / or further processed.
  • the granules are rounded. This can be done in a conventional muller.
  • the rounding time is not longer than 4 minutes, especially not longer than 3.5 minutes. Rounding times of a maximum of 1.5 minutes or less are particularly preferred.
  • rounding a further standardization of the grain spectrum is achieved as any resulting agglomerates are crushed.
  • the granules can also be treated with other ingredients, which may be solid, liquid and / or pasty in nature.
  • an aftertreatment step it is therefore possible to spray the granules with a solid, for example silicic acids, zeolites, carbonates, bicarbonates and / or sulfates, citrates, urea or mixtures thereof, as is well known from the prior art.
  • a solid for example silicic acids, zeolites, carbonates, bicarbonates and / or sulfates, citrates, urea or mixtures thereof.
  • solids in particular bicarbonate and soda, in amounts of up to 15% by weight and in particular in amounts of from 2 to 15% by weight, based in each case on the after-treated product.
  • the granules are aftertreated with nonionic surfactants which may contain, for example, optical brighteners and / or hydrotropes, perfume, a solution of optical brightener and / or foam inhibitors or preparation forms which may contain these ingredients.
  • these ingredients or formulations containing these ingredients are applied to the granules in liquid, molten or pasty form.
  • the granules are post-treated with up to 20 wt .-%, advantageously with 2 to 18 wt .-% and in particular with 5 to 15 wt .-% of active ingredient of the ingredients mentioned. The quantities are in each case based on the aftertreated product.
  • the aftertreatment with the substances mentioned here in a conventional mixer only for example in a 2-wave mixer within a maximum of 1 minute, preferably within 30 seconds and for example within 20 seconds, the time information for Addition and mixing time is done.
  • Such post-treated products may have a bulk density of above 500 g / l, for example from 550 to 700 g / l. It is not surprising to the person skilled in the art that such measures can impair the flowability of the product. Suitable nonionic surfactants have already been described in advance.
  • foam inhibitors such as, for example, foam-inhibiting paraffin oil or foam-inhibiting silicone oil, for example dimethylpolysiloxane.
  • foam inhibitors such as, for example, foam-inhibiting paraffin oil or foam-inhibiting silicone oil, for example dimethylpolysiloxane.
  • foam-inhibiting silicone oil for example dimethylpolysiloxane.
  • the use of mixtures of these agents is possible.
  • solid additives particularly in the above-mentioned foam-inhibiting agents, paraffin waxes, silicas, which may have been rendered hydrophobic in a known manner, and of C 2 - 7 -diamines and C 12 carboxylic acids -22- bisamides derived.
  • Suitable foam-inhibiting paraffin oils which may be present in admixture with paraffin waxes generally represent complex mixtures without a sharp melting point.
  • the melting range is usually determined by differential thermal analysis (DTA) and / or the solidification point. This is the temperature at which the paraffin passes from the liquid to the solid state by slow cooling.
  • Paraffins with less than 17 carbon atoms are not useful in the present invention
  • the proportion in the paraffin oil mixture should therefore be as low as possible and is preferably below the limit that can be significantly measured by conventional analytical methods, for example gas chromatography.
  • paraffins are used, which solidify in the range of 2O 0 C to 70 ° C.
  • paraffin wax mixtures may contain different proportions of liquid paraffin oils.
  • the liquid fraction at 40 ° C. is as high as possible, without already being 100% by weight at this temperature.
  • Preferred paraffin wax mixtures have at 4O 0 C, a liquid content of at least 50 wt .-%, in particular from 55 wt .-% to 80% by weight, and at 60 0 C, a liquid content of at least 90 wt .-%. This has the consequence that the paraffins at temperatures down to at least 7O 0 C, preferably down to at least 6O 0 C are flowable and pumpable.
  • paraffins contain as far as possible no volatile components.
  • Preferred paraffin waxes contain less than 1 wt .-%, in particular less than 0.5 wt .-% at 11O 0 C and atmospheric pressure vaporizable fractions.
  • Paraffins which can be used according to the invention can be obtained, for example, under the trade names Lunaflex® from Guer and Deawax® from DEA Mineralöl AG.
  • the paraffin oils may contain at room temperature solid bisamides derived from saturated fatty acids containing 12 to 22, preferably 14 to 18, carbon atoms and alkylenediamines having 2 to 7 carbon atoms.
  • Suitable fatty acids are lauric, myristic, stearic, arachinic and behenic acids and mixtures thereof, such as are obtainable from natural fats or hardened oils, such as tallow or hydrogenated palm oil.
  • Suitable diamines are, for example, ethylenediamine 1, 3-propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, p-phenylenediamine and toluenediamine.
  • Preferred diamines are ethylenediamine and hexamethylenediamine.
  • Particularly preferred bisamides are bis-myristoyl-ethylenediamine, bispalmitoyl-ethylenediamine, bis-stearoyl-ethylenediamine and mixtures thereof and the corresponding derivatives of hexamethylenediamine.
  • said foam inhibitors may also be included in the direct spray-drying product.
  • the after-treated and optionally rounded product with said ingredients is aftertreated with solids, preferably bicarbonate and / or soda, in particular in amounts of from 2 to 15% by weight, based on the after-treated product.
  • solids preferably bicarbonate and / or soda, in particular in amounts of from 2 to 15% by weight, based on the after-treated product.
  • the aftertreatment with the solids advantageously takes place in a roundabout.
  • the following aftertreatment measures rounding, treatment with liquid to pasty and / or solid ingredients with or without rounding can be a series of post-treated products with good flowability and a high range of bulk density to be obtained.
  • Such post-treated products advantageously have a bulk density of from 380 g / l to 950 g / l and preferably from 580 g / l to 740 g / l.
  • the granules produced by the inventive method and / or the aftertreated products described above can be prepared in a further embodiment of the invention with other ingredients of detergents or cleaning agents, in particular mixed, it being advantageous that components can be admixed the spray drying are not accessible. From the broad state of the art is generally known which ingredients of detergents or cleaners are not accessible to spray drying and which raw materials are usually mixed.
  • detergents or cleaners such as bleaching agents based on per compounds, bleach activators and / or bleach catalysts, enzymes from the class of proteases, lipases and amylases, are carried out; or bacterial strains or fungi, foam inhibitors in optionally granular and / or compounded form, perfumes, temperature-sensitive dyes and the like, which are expediently mixed with the previously dried compositions and optionally post-treated products.
  • detergents or cleaners enzymes can be used. These include in particular proteases, amylases, lipases, hemicellulases, cellulases or oxidoreductases, and preferably mixtures thereof. These enzymes are basically of natural origin; Starting from the natural molecules, improved variants are available for use in detergents and cleaners, which are preferably used accordingly.
  • Detergents or cleaning agents contain enzymes preferably in total amounts of 1 ⁇ 10 -6 to 5 wt .-% based on active protein. The protein concentration can be determined by known methods, for example the BCA method or the biuret method.
  • subtilisin type those of the subtilisin type are preferable.
  • these are the subtilisins BPN 'and Carlsberg and their further developed forms, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase which can no longer be assigned to the subtilisins in the narrower sense, Proteinase K and the proteases TW3 and TW7.
  • amylases which can be used according to the invention are the ⁇ -amylases from Bacillus lichenifor- mis, B. amyloliquefaciens, B. stearothermophilus, Aspergillus niger and A. oryzae, and the further developments of the invention which are improved for use in detergents and cleaners aforementioned amylases.
  • the ⁇ -amylase from Bacillus sp. A 7-7 DSM 12368
  • CTTase cyclodextrin glucanotransferase
  • lipases or cutinases are also usable according to the invention.
  • these include, for example, the lipases originally obtainable from Humicola lanuginosa (Thermomyces lanuginosus) or further developed, in particular those with the amino acid exchange D96L.
  • the cutinases can be used, which were originally isolated from Fusarium solani pisi and Humicola insolens. It is also possible to use lipases, or cutinases, whose initial enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii.
  • Oxidoreductases for example oxidases, oxygenases, catalases, peroxidases, such as halo, chloro, bromo, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) can be used according to the invention to increase the bleaching effect.
  • the enzymes can be used in any form known in the art. These include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, especially in the case of liquid or gel-form detergents, solutions of the enzymes, advantageously as concentrated as possible, sparing in water and / or added with stabilizers.
  • the enzymes may be encapsulated for both the solid and liquid dosage forms, for example by spray-drying or extruding the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are entrapped as in a solidified gel or in such of the core Shell type in which an enzyme-containing core is coated with a water, air and / or chemical impermeable protective layer.
  • additional active ingredients for example stabilizers, emulsifiers, pigments, bleaches or dyes can be applied.
  • Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes.
  • such granules for example by applying polymeric film-forming agent, low in dust and storage stable due to the coating.
  • a protein and / or enzyme can be protected especially during storage against damage such as inactivation, denaturation or disintegration, for example by physical influences, oxidation or proteolytic cleavage.
  • damage such as inactivation, denaturation or disintegration, for example by physical influences, oxidation or proteolytic cleavage.
  • inhibition of proteolysis is particularly preferred, especially if the agents also contain proteases.
  • Detergents may contain stabilizers for this purpose; the provision of such means constitutes a preferred embodiment of the present invention.
  • perfume oils or perfumes which may be used within the scope of the present invention are individual fragrance compounds, for example the synthetic products of the ester type, ethers, aldehydes, ketones, alcohols and hydrocarbons. Preferably, however, mixtures of different fragrances are used, which together produce an attractive fragrance.
  • perfume oils may also contain natural fragrance mixtures such as those available from vegetable sources, for example pine, citrus, jasmine, patchouly, rose or ylang-ylang oil.
  • a fragrance In order to be perceptible, a fragrance must be volatile, whereby besides the nature of the functional groups and the structure of the chemical compound, the molecular weight also plays an important role. For example, most odorants have molecular weights up to about 200 daltons, while molecular weights of 300 daltons and above are more of an exception. Due to the different volatility of fragrances, the smell of one of several fragrances changes. perfume or fragrance during evaporation, whereby the odor impressions are subdivided into "top note”, “middle note” or “middle note” and “base note” (end note or dry out, respectively).
  • the top note of a perfume or fragrance is not only from volatile compounds, while the base note for the most part consists of less volatile, that is adherent fragrances.
  • the base note for the most part consists of less volatile, that is adherent fragrances.
  • more volatile fragrances can be bound to certain fixatives, preventing them from evaporating too quickly.
  • the subsequent classification of the fragrances in "more volatile” or “adherent” fragrances so nothing is said about the olfactory impression and whether the corresponding fragrance is perceived as the head or middle note.
  • the fragrances can be processed directly, but it can also be advantageous to apply the fragrances on carriers that provide a slower fragrance release for long-lasting fragrance.
  • carrier materials for example, cyclodextrins have been proven, the cyclodextrin-perfume complexes can be additionally coated with other excipients.
  • the colorants When choosing the colorant, it must be taken into account that the colorants have a high storage stability and insensitivity to light as well as not too high an affinity for textile surfaces and, in particular, for synthetic fibers. At the same time, it should also be taken into account when choosing suitable colorants that colorants have different stabilities to the oxidation. In general, water-insoluble colorants are more stable to oxidation than water-soluble colorants. Depending on the solubility and thus also on the sensitivity to oxidation, the concentration of the colorant in the detergents or cleaners varies. For highly soluble colorants dyestuff concentrations in the range of some 10 '2 to 10' 3 wt .-% are typically chosen. In the due to their brilliance, particularly preferred, but are less readily water-soluble pigment dyes is the appropriate concentration of the coloring agent in washing or cleaning agents, however, typically a few 10 '3 to 10 "4 wt .-%.
  • Dyeing agents which can be oxidatively destroyed in the washing process and mixtures thereof with suitable blue dyes, so-called blue toners, are preferred. It has proven to be advantageous to use colorants which are soluble in water or at room temperature in liquid organic substances. Suitable examples are anionic colorants, for example anionic nitrosofarbstoffe. bleach
  • the bleaching agents are a particularly preferred washing or cleaning substance.
  • sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Further bleaches that can be used are, for example, peroxypyrophosphates, citrate perhydrates and peroxygenic salts or peracids which yield H 2 O 2 , such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.
  • bleaching agents from the group of organic bleaching agents can also be used.
  • Typical organic bleaches are the diacyl peroxides, such as dibenzoyl peroxide.
  • Other typical organic bleaches are the peroxyacids, examples of which include the alkyl peroxyacids and the aryl peroxyacids.
  • bleaching agent and chlorine or bromine releasing substances can be used.
  • suitable chlorine or bromine-releasing materials are 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.
  • DICA dichloroisocyanuric acid
  • Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydantoin are also suitable.
  • Bleach activators are used in detergents or cleaners, for example, to achieve an improved bleaching effect when cleaning at temperatures of 60 0 C and below.
  • As bleach activators it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic 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-diacetoxy-2 , 5-dihydrofuran, n-methyl-morph
  • bleach activators preferably used in the context of the present application are compounds from the group of cationic nitriles, in particular cationic nitriles of the formula
  • R 1 is -H, -CH 3, a C 2 - 24 alkyl or alkenyl group, a substituted C 2-24 -alkyl or -alkenyl radical having at least one substituent from the group -Cl, -Br, - OH, -NH 2 , -CN, an alkyl or alkenylaryl radical having a C 1-24 -alkyl group, or represents a substituted alkyl- or alkynylaryl radical having a C 1-4 -alkyl group and at least one further substituent on the aromatic ring
  • R 2 and R 3 are independently selected from -CH 2 -CN, -CH 3 , -CH 2 -CH 3 , -CH 2 -CH 2 -CH 3 , -CH (CH 3 ) -CH 3 , -CH 2 - OH, -CH 2 -CH 2 -OH, -CH (OH) -CH 3 , -CH 2 -CH 2 -
  • bleach catalysts can also be used. These substances are bleach-enhancing transition metal salts or transition metal complexes such as Mn, Fe, Co, Ru or Mo-salene 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.
  • Bleach-enhancing transition metal complexes in particular having the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, preferably selected from the group of manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt ( ammin) complexes containing cobalt (acetate) - Complexes of the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, of manganese sulfate are preferably used.
  • complexes of manganese in the oxidation state II, IM, IV or IV which preferably contain one or more macrocyclic ligand (s) with the donor functions N, NR, PR, O and / or S.
  • ligands are used which have nitrogen donor functions.
  • bleach catalyst (s) in the inventive compositions which as macromolecular ligands 1,4,7-trimethyl-1, 4,7-triazacyclononan (Me-TACN), 1, 4,7-triazacyclononane (TACN ), 1, 5,9-trimethyl-1, 5,9-triazacyclododecane (Me-TACD), 2-methyl-1, 4,7-trimethyl-1, 4,7-triazacyclononane (Me / Me-TACN) and or 2-methyl-1, 4,7-triazacyclononane (Me / TACN).
  • macromolecular ligands 1,4,7-trimethyl-1, 4,7-triazacyclononan (Me-TACN), 1, 4,7-triazacyclononane (TACN ), 1, 5,9-trimethyl-1, 5,9-triazacyclododecane (Me-TACD), 2-methyl-1, 4,7-trimethyl-1, 4,7-triazacyclononane (Me / Me-TACN) and or 2-
  • UV absorbers which are absorbed by the treated textiles and improve the light resistance of the fibers.
  • Compounds which have these desired properties are, for example, the compounds which are active by radiationless deactivation and derivatives of benzophenone having substituents in the 2- and / or 4-position.
  • substituted benzotriazoles phenyl-substituted acrylates (cinnamic acid derivatives) in the 3-position, optionally with cyano groups in the 2-position, salicylates, organic Ni complexes and natural substances such as umbelliferone and the endogenous urocanic acid.
  • speckles which stand out from the appearance of the direct and / or after-treated spray-drying products by their color and / or their shape.
  • the speckles may once have a similar to identical grain spectrum as the granules or post-treated granules and the same composition but a different color. It is also possible that the speckles have the same composition as the granules or the aftertreated granules, are not colored, but have a different shape. Ultimately, however, it is preferred that speckles which have the same composition as the granules or the aftertreated granules differ from the latter in color and optionally additionally in their form.
  • speckles are only intended to make the appearance of the finished detergents or cleaning agents even more attractive.
  • the admixed speckles or else other ingredients may for example be spray-dried, agglomerated, granulated, pelletized or extruded.
  • a further subject of the invention is a hollow cone nozzle comprising an inlet opening, a spray opening and a vortex chamber connecting the inlet and the spray opening, which is in the form of a spiral, the cross section of the inlet opening having an area of 20 to 70 mm 2 , preferably 25 to 60 mm 2 , more preferably from 30 to 50 mm 2 and in particular from 35 to 50 mm 2 and the depth of the vortex chamber from 8.0 to 12.0 mm, preferably from 8.4 to 11, 0 mm, particularly preferably from 8.6 to 10.0 mm and in particular from 8.8 to 10.0 mm.
  • the shape of a suitable vortex chamber is shown in Figure 1.
  • the ratio between the depth of the vortex chamber (in mm) and the cross section of the inlet opening (in mm 2 ) of the nozzle is preferably between 1:10 and 2: 1, preferably between 1: 8 and 1: 1, more preferably between 1: 6 and 1: 2, and more preferably between 1: 4 and 1: 2.
  • the spray opening of the nozzle is formed by a preferably circular bore in a plate to be placed on the vortex chamber.
  • the ratio between the depth of the vortex chamber (in mm) and the diameter of the spray opening (in mm) is between 5: 1 and 1: 2, preferably between 4.5: 1 and 1: 1, 5, particularly preferably between 4: 1 and 1: 1 and in particular between 3.5: 1 and 1, 5: 1.
  • the ratio between the cross section of the inlet opening (in mm 2 ) and the diameter of the spray opening (in mm) of the nozzle is calculated to be between 1: 1 and 20: 1, preferably between 2: 1 and 17: 1 preferably between 3: 1 and 14: 1 and in particular between 4: 1 and 11: 1.
  • This nozzle is particularly suitable for atomizing washing or cleaning agent-containing mixtures and is suitable, even if the pressure at which the slurry is passed through the nozzle is low, and preferably between 15 and 40 bar, preferably between 17 and 37 bar, particularly preferred between 19 and 34 bar and in particular between 21 and 31 bar is to achieve high production rates and preferably more than 100 kg of slurry, preferably more than 250 kg, more preferably more than 350 kg, with preference between 350 and 2500 kg and in particular between 450 and spray 2400 kg of slurry per hour.
  • the granules obtained have a narrow grain spectrum with few fines whose particle diameter d 50 is preferably in the range from 0.2 to 1.2 mm, preferably in the range from 0.3 to 1.0 mm and in particular between 0.4 and 0, 8 and / or less than 15 wt .-%, preferably less than 10% by weight and in particular less than 5 wt .-% of the granules is less than 0.1 mm.
  • a third object of the present invention is the use of a hollow cone nozzle, which has an inlet opening, a spray opening and a connecting the inlet and spray opening Swirl chamber with a spiral course, for atomizing washing or cleaning active substance-containing mixtures.
  • nozzle in spray-drying processes has already been described. Also advantageous is the use of a hollow cone nozzle with spiral vortex chamber in a variety of other methods in which wash or cleaning active substance-containing mixtures such as solutions, dispersions, emulsions but also melts are sprayed.
  • the nozzle is preferably used in spray-drying, fluidized-bed granulation, granulation in one or more high-speed, moderate and / or low-speed mixers connected in series and / or in the coating of detergents or a component thereof.
  • a slurry of the following composition having a viscosity of 900 mPas was sprayed through the nozzles indicated in a cylindrical spray tower (height 22.7 m, diameter 3.3 m) sprayed and dried (amount of dry gas 135- 145 m 3 / h, temperature of the drying gas when the gas enters the tower 190 - 204 0 C).
  • 3 nozzles of the same type were used.
  • Zeolite A suspension (about 50% by weight) 37.2% by weight

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

L'invention concerne des procédés de production de granulés détergents selon lesquels une boue contenant des constituants détergents est pulvérisée par une buse à cône creux qui présente un orifice d'entrée, un orifice de pulvérisation et une chambre de turbulence reliant l'orifice d'entrée et l'orifice de pulvérisation. La chambre de turbulence présentant un tracé en spirale. Ces procédés conviennent à la production à basse pression et haut débit de granulés ayant une étroite distribution granulométrique. L'invention concerne enfin des buses à cône creux.
PCT/EP2006/010357 2005-12-29 2006-10-27 Procédé de production amélioré d'un produit détergent WO2007079803A1 (fr)

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DE200510063064 DE102005063064A1 (de) 2005-12-29 2005-12-29 Verbessertes Herstellungsverfahren für Wasch- oder Reinigungsmittel
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DE102014218805A1 (de) * 2014-09-18 2016-03-24 Henkel Ag & Co. Kgaa Verfahren zur Herstellung von sprühgetrockneten Waschmittelpulvern

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE739417C (de) * 1937-10-03 1943-09-25 Henkel & Cie Gmbh Pulverfoermige Perverbindungen enthaltende Waschmittel
EP0252897A2 (fr) * 1986-07-09 1988-01-13 Monsanto Company Formulations de granulés dispersables dans l'eau et leur procédé de préparation
EP0289312A2 (fr) * 1987-04-30 1988-11-02 Unilever Plc Procédé de préparation d'une composition détergente granulaire
DE4204090A1 (de) * 1992-02-12 1993-08-19 Cognis Bio Umwelt Vereinfachtes trocknungsverfahren fuer wertstoffe und wertstoffgemische aus dem bereich der wasch- und reinigungsmittel mit ueberhitztem wasserdampf

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3771728A (en) * 1971-03-17 1973-11-13 F Polnauer Spray nozzles with spiral flow of fluid and method of constructing the same

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE739417C (de) * 1937-10-03 1943-09-25 Henkel & Cie Gmbh Pulverfoermige Perverbindungen enthaltende Waschmittel
EP0252897A2 (fr) * 1986-07-09 1988-01-13 Monsanto Company Formulations de granulés dispersables dans l'eau et leur procédé de préparation
EP0289312A2 (fr) * 1987-04-30 1988-11-02 Unilever Plc Procédé de préparation d'une composition détergente granulaire
DE4204090A1 (de) * 1992-02-12 1993-08-19 Cognis Bio Umwelt Vereinfachtes trocknungsverfahren fuer wertstoffe und wertstoffgemische aus dem bereich der wasch- und reinigungsmittel mit ueberhitztem wasserdampf

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