EP1802733A1 - Particules absorbantes - Google Patents

Particules absorbantes

Info

Publication number
EP1802733A1
EP1802733A1 EP05781858A EP05781858A EP1802733A1 EP 1802733 A1 EP1802733 A1 EP 1802733A1 EP 05781858 A EP05781858 A EP 05781858A EP 05781858 A EP05781858 A EP 05781858A EP 1802733 A1 EP1802733 A1 EP 1802733A1
Authority
EP
European Patent Office
Prior art keywords
particles
weight
acid
drying
preferred
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.)
Granted
Application number
EP05781858A
Other languages
German (de)
English (en)
Other versions
EP1802733B1 (fr
Inventor
Rene-Andres Artiga Gonzalez
Andreas Bauer
Stefan Hammelstein
Jürgen HILSMANN
Wolfgang Lahn
Mario Sturm
Hubert Harth
Ingrid Kraus
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP1802733A1 publication Critical patent/EP1802733A1/fr
Application granted granted Critical
Publication of EP1802733B1 publication Critical patent/EP1802733B1/fr
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0052—Gas evolving or heat producing 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
    • 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
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0034—Fixed on a solid conventional detergent ingredient
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/50—Perfumes
    • C11D3/502—Protected perfumes
    • C11D3/505—Protected perfumes encapsulated or adsorbed on a carrier, e.g. zeolite or clay

Definitions

  • the present invention relates to a process for the production of particles by drying, in particular by spray drying or fluidized bed process, wherein during the Trocknungsprozes ⁇ ses in the material to be dried carbon dioxide is generated. It also relates to particles which can be prepared by such a process and which are aftertreated. It also relates to a surfactant composition which contains such particles and also surfactants and optionally further constituents, and to a process for textile laundering using the detergent composition.
  • Fragrances, essences and aromas which are especially when they are fragrant to humans, summarized under the concept of fragrances, have always been human cultural property and are generally used to produce fragrances or unpleasant odors. Their application today takes place in many everyday life products.
  • the aromas and essences are of considerable importance. These are generally concentrated preparations of odorants or flavors intended to give food a better or more intense smell or taste. By adding flavors and essences, it is therefore possible to further increase the acceptance of the food and stimulants by the consumer.
  • washing and cleaning agents In the textile washing, treatment and aftertreatment, it is therefore very common today to mix the detergents and aftertreatment agents with certain quantities of perfume which are used to treat the washing or rinsing liquor itself, but also the washing or rinsing liquor. textiles to give a pleasant fragrance.
  • the scenting of washing and cleaning and after-treatment agents is an important aspect of the aesthetic product impression and thus an important factor in the consumer decision for or against a particular product.
  • the perfume can either be incorporated directly into the agent or fed in an additional step the washing or rinsing eye. The first way determines a specific product characteristic, while the second way the consumer can decide on different scent variants offered on "his" scent individually, comparable to the choice of an Eau de Toilette or aftershave.
  • Perfume moldings and methods for scenting washing and rinsing eyes are accordingly broadly described in the prior art.
  • DE 41 33 862 (Henkel) discloses tablets which contain carrier materials, fragrances and optionally other ingredients customary in detergents and cleaners, sorbitol and additionally 20 to 70% by weight of a sprinkling system of carbonate and acid being used as carrier material become.
  • These tablets which can be added, for example, to the after-rinse and fabric conditioning cycle in the textile washing in a household washing machine, contain about 3 to 15, preferably 5 to 10,% by weight of perfume. Due to the high explosive content of the tablets, they are sensitive to atmospheric moisture and must be stored appropriately protected.
  • DE 39 11 363 discloses a process for producing a fragrance-enriched washing or rinsing liquor and a perfume excipient serving for this purpose.
  • the additives which are in the form of capsules or tablets, contain the fragrance together with an emulsifier in liquid form (capsules) or bound to fillers and carriers (tablets), with sodium aluminum silicates or cyclodextrins being mentioned as carriers.
  • the perfume content of the capsules or tablets is at least 1 g, the volume of the means being more than 1 cm 3 .
  • Preference is given to tablets or capsules containing more than 2.5 g of fragrance and a volume of at least 5 cm 3 .
  • such tablets or capsules must be provided with a gas-tight and watertight coating layer in order to protect the ingredients. Further details about the preparation and the physical properties of suitable tablets are not contained in this publication.
  • the international application WO 94/25563 (Henkel-Ecolab) describes a process for the preparation of washing and cleaning active moldings using the microwave technique, which operates without high-pressure compression.
  • the moldings produced in this way are characterized by an extremely high dissolution rate or decay rate while breaking strength, without a disintegrant is necessary. At the same time, they are storage-stable and can be stored without additional precautions. It can also be prepared in this way, moldings, the usual for washing and cleaning agent content of perfume oils between 1 and 3 % By weight.
  • Perfume oils are generally volatile and therefore could evaporate already under the influence of microwave irradiation. If higher contents of volatile liquid substances are to be used, a two-component system consisting of a component produced by microwave technology and a component containing the sensitive liquid substances is therefore described.
  • Particulate additives for scenting wash liquors and for use in detergents and cleaners, and processes for their preparation are described in International Patent Applications WO97 / 29176 and WO97 / 29177 (Procter & Gamble). According to the teaching of these documents, porous carrier materials (for example sucrose mixed with zeolite X) are mixed with perfume and finally coated with a coating material (carbohydrates) and brought to the desired particle size distribution.
  • porous carrier materials for example sucrose mixed with zeolite X
  • a coating material carbohydrates
  • German patent application DE 197 35 783 A1 (Henkel) describes high-dose perfume shaped body, the carrier material (ies), 20 to 50 wt .-% fragrance (s) and optionally further customary in detergents and cleaners active ingredients and excipients, wherein the shaped articles, after deduction of the amount of perfume, consist of at least 50% by weight of their weight of fatty acids and fatty acid salts.
  • These perfume moldings are suitable both for the scenting of washing and cleaning agents and for the scenting of textiles in a washing machine.
  • a method for applying fragrances to textile material in a washing machine is described in DE 195 30 999 (Henkel).
  • a fragrance-containing molded article prepared by irradiation with microwaves is used in the rinse cycle of a washing machine.
  • the preparation of the preferably spherical moldings with diameters above 3 mm and bulk densities up to 1100 g / l succeeds according to the teaching of this document by mixing a mixture of predominantly water-soluble carriers, hydrate-viscous substances, optionally surfactants and perfume filled into suitable molds and sintered by means of microwave radiation.
  • the fragrance contents of the molded articles are between 8 and 40% by weight, and starches, silicas, silicates and disilicates, phosphates, zeolites, alkali metal salts of polycarboxylic acids, oxidation products of polyglucosans and polyaspartic acids are used as carriers.
  • An essential condition of the shaped article production method described in this document is that at least partially bound water is present in the mixture, which is sintered into shaped articles with the aid of microwave radiation, i. some of the starting materials are in hydrated form.
  • This object is achieved by a method for producing particles, in which a paste is subjected to drying, characterized in that carbon dioxide is produced in the material to be dried during the drying process.
  • pastes are preferably solid dispersions in liquids with very liquid to very pasty, ie. meant tough consistency.
  • a preferred paste is a slurry, ie a preferably aqueous slurry of solids having a very liquid to pasty or pasty consistency.
  • drying is meant in the broadest sense any technical drying capability with which water and / or other solvents can be removed from the pastes to such an extent that at the end of drying particles, i. particulate solids occur.
  • Solids are substances with a solid outer shape.
  • these particles need not be completely solvent-free and / or anhydrous, for example, they may still contain significant amounts of solvent and / or water, but preferably they have water contents below 30 wt .-%, advantageously below 25 wt .-%, ins ⁇ particular below 20 wt .-%, in each case based on the costs incurred at the end of drying Fest ⁇ material.
  • the water content may also be lower, if desired, for example below 15% by weight or below 10% by weight or below 5% by weight, based in each case on the solid obtained at the end of the drying.
  • the products to be dried are advantageously supplied with heat.
  • the drying can preferably be carried out in cocurrent, countercurrent or crossflow.
  • pressure can be divided into overpressure, normal pressure and vacuum dryers.
  • convection drying the heat is transferred to the material to be dried mainly by hot gases (air or inert gas), which is preferred.
  • hot gases air or inert gas
  • channel, chamber, belt, shaft, fluidized bed and atomizing dryers are used, which is preferred.
  • contact drying which is also preferred, the heat transfer takes place via heat exchanger surfaces.
  • the contact dryers include the roller, tube and cabinet dryers. Eta ⁇ gen-, plate, drum and paddle dryer work on both principles of heat.
  • a very preferred drying method according to the invention is spray-drying. Also preferred for drying are fluidized bed processes.
  • the paste to be processed according to the invention contains substance (s) which release carbon dioxide at elevated temperatures, preferably selected from bicarbonate compounds, citric acid and / or aconitic acid. In the bicarbonate compounds, the sodium bicarbonate is preferred.
  • the paste to be processed according to the invention contains 0 to 40% by weight, preferably 0.1 to 4% by weight, in particular 1 to 3% by weight of citric acid, or 0 to 50% by weight. , preferably 0.1 to 5 wt .-%, in particular 1 to 4 wt .-% of bicarbonate compound, or 0 to 40 wt .-%, preferably 0.1 to 10 wt .-%, in particular 1 to 5 wt % Aconitic acid.
  • drying gas can be used for countercurrent drying or direct current drying. In the so-called countercurrent drying, the drying gas is introduced into the lower part of the tower and directed towards the product stream, while in the DC stream drying the supply of dry gases takes place in the head of the drying tower.
  • the spray drying plant is operated with hot air or hot combustion gases, which are preferably introduced tangentially into the tower, resulting in a certain swirl effect.
  • the first step of a spray-drying process is generally in the production of an aqueous slurry (paste, in particular slurry) of more or less thermally stable ingredients which, under the conditions of spray drying, are generally neither volatilized nor decompose.
  • This paste is then usually transported via pumps in the spray tower and sprayed there in the head of the same usually by nozzles or by virtue of a rapidly rotating Zer ⁇ stubber disc to a fine mist.
  • This spray is dried with a gaseous drying medium such as preferably hot air or an inert gas in cocurrent or countercurrent.
  • a gaseous drying medium such as preferably hot air or an inert gas in cocurrent or countercurrent.
  • the supply of the drying gas is generally operated in direct current from above. For example, around the 250 0 C up to 350 0 C hot air evaporates the adhering water or solvent, so that the other paste components at the tower outlet (temperatures preferably 80-120 0 C) are obtained as a powder.
  • the thus spray-dried powder can now be used directly, it can be aftertreated and it can be mixed with other components, in particular with temperature-labile components, such as in the case of detergents, for example fragrances.
  • the heat of the drying gas whose temperature is preferably> 100 0 C, advantageously> 150 ° C, more preferably> 180 0 C, more preferably> 200 ° C, with a Ober ⁇ limit of 400 0 C, preferably 350 0 C, advantageously of 300 0 C, in particular of 25O 0 C should not be exceeded, causes not only the adhering water or solvent evaporates, but that during drying in the material to be dried advantageously carbon dioxide is generated.
  • the carbon dioxide is released by substances contained in the paste.
  • Substances which have the potential to release carbon dioxide under such conditions are preferably selected from bicarbonate compounds, citric acid and / or aconitic acid.
  • fragrances encompasses the entirety of the fragrances, flavors, essences, perfume oils and perfumes, these terms, in particular the terms fragrances and perfume, being used synonymously in the further course.
  • Perfumes are understood to be i.d.R. alcoholic solutions of suitable fragrances.
  • the direct drying product is capable of receiving larger quantities of perfumes in a subsequent treatment step than usual. Surprisingly, it was found that the flow properties of such scented particles are very good. The flow properties remain very good even with very high perfume loading. The same applies to the mechanical stability. It is surprising that these perfumed particles also have a more persistent scent Have effect, ie the particles smell at least the same scent intensity even longer than herkömm ⁇ Liche (spray) drying products, which were otherwise scented analog.
  • a further advantage of the invention lies in the fact that the fragrance note or perfume note of the particles according to the invention, which has been loaded with fragrances, does not change adversely even during prolonged storage. It is often the case that perfume which is incorporated in a carrier material decomposes at least partially, more or less slowly, in the carrier material. In contrast, this decomposition is at least delayed in a particle according to the invention. Thus, a perfumery stabilizing effect is achieved by the invention. This is especially true when the particles are incorporated into an object, such. B. in a detergent formulation, which by their object property, spielmik, their alkalinity, the stability of perfume is rather detrimental. Here, the perfumery-stabilizing effect has a particularly favorable effect.
  • the subject invention provides even more benefits. It could be found that the particles according to the invention, after being loaded with perfume, lead to a more intense fragrance experience in the consumer with the same perfume charge, for example when compared to conventional particles in whose drying process no carbon dioxide is formed washing is done with a detergent formulation containing the particles of the invention. It has surprisingly been found that the consumer perceives a more intense scent of the gewa ⁇ scrubbing laundry compared to laundry, which was washed with a conventional scented Deter ⁇ gene formulation, even if the contained absolute amount of the perfume was the same.
  • the invention allows a fragrance-enhancing effect that directly affects the particles, as well as objects into which these particles are incorporated, for example, detergent formulations, as well as things such. As textiles, which are treated with the objects (here: detergent formulation).
  • the fragrance impression resulting from the particles according to the invention which were loaded with perfume, indirectly and immediately longer holds.
  • “Immediate” in this context means that the particle according to the invention smells over a longer period of time than an otherwise comparable particle, but during drying no CO 2 was released.
  • “Indirectly” in this context means that objects (eg. B. Detergensformulie ⁇ tion) containing the particles according to the invention smell longer, and even in the appli cation of these objects (eg., Detergent formulation for washing textile) the things treated with it (here: washed textile) smell longer.
  • the invention therefore, a fragrance (impression) with sustained release effect is achieved, with this fragrance-retard effect (ie the temporal extent of the fragrance impression) both on the particles, as on the particles containing objects, such as those with these objects relates to treated things.
  • the carbon dioxide in the (spray) drying material essentially only forms when it is exposed to the hot drying gas stream.
  • the paste is substantially free of carbon dioxide.
  • the drying gas stream may be opposite to the atomized material or, as is preferred, have the same direction of movement as the particles to be dried. He find in accordance with the temperature of the GasMapstroms, in the case of spray drying, when entering the relaxation space at preferably at least 150 ° C, advantageously a temperature of 35O 0 C should be not exceeded but, as previously mentioned.
  • Drying in particular spray drying, has not only been found in the production of detergents, cleaners and care products, but also in the production of a variety of other goods, e.g. of foodstuffs such as dry milk, instant coffee, yeast, egg, fruit juice dry powder or other goods such as wood sugar, tannins, dry blood powder, polyvinyl and polyethylene powder, glue, serums up to pharmaceutical preparations proven.
  • foodstuffs such as dry milk, instant coffee, yeast, egg, fruit juice dry powder or other goods such as wood sugar, tannins, dry blood powder, polyvinyl and polyethylene powder, glue, serums up to pharmaceutical preparations proven.
  • the inventive method is particularly suitable.
  • a very high loading of aromas and essences can advantageously be achieved.
  • a very high loading of essential oils or liquids in particular of a hydrophobic nature, can advantageously be achieved.
  • the process according to the invention is most advantageous with regard to the production of detergents, cleaners and conditioners, so that the paste to be processed according to the invention preferably comprises one or more ingredients which can usually be contained in detergents, cleaners and care agents. Such ingredients will be further described below.
  • the paste to be processed according to the invention comprises ingredients which are customarily contained in foods and stimulants, pharmaceutical preparations or other technical (spray) dried goods.
  • the ingredients in question depend on the intended use of the particles and are familiar to the expert or refer to relevant reference works, such.
  • the aroma can be obtained longer than usual after it has been applied.
  • not only larger amounts of aroma can be introduced without secondary particle properties such as mechanical stability or flowability being impaired, the aroma introduced is also perceptible for a longer time.
  • the paste to be processed according to the invention contains organic carrier material, as is known from the prior art, in particular in connection with detergents and cleaners.
  • the paste to be processed according to the invention contains inorganic carrier material, preferably selected from the group comprising zeolites, sulfates, carbonates, silicates, silicic acid and / or mixtures thereof.
  • inorganic carrier material preferably selected from the group comprising zeolites, sulfates, carbonates, silicates, silicic acid and / or mixtures thereof.
  • Preferred combinations of these carrier materials are the following:
  • the inorganic carrier material contained in the paste is at least 30% by weight, preferably at least 40% by weight, in particular at least 60% by weight, of zeolite, preferably zeolite X, Y, A, P, MAP and / or mixtures thereof, based on the total, contained carrier material.
  • the paste to be processed according to the invention contains both organic and inorganic carrier material.
  • the zeolite which can be used according to the invention is advantageously zeolite A and / or P.
  • the zeolite P used is, for example, zeolite MAP® (commercial product from Crosfield).
  • Y-type zeolite is also preferred.
  • Zeolites which are preferably usable according to the invention, such as those mentioned above, are described further below.
  • Particularly suitable zeolites are faujasite-type zeolites. Together with Zeo ⁇ lithen X and Y, the mineral faujasite belongs to the faujasite types within the zeolite structure group 4, which are characterized by the double-six-membered subunit D6R (Compare Donald W. Breck: "Zeolite Molecular Sieves", John Wiley & Sons, New York, London, Sydney, Toronto, 1974, Page 92).
  • the zeolite structural group 4 also includes the minerals chabazite and gmelinite and also the synthetic zeolites R (chabazite type), S (gmelinite type), L and ZK-5.
  • R chabazite type
  • S gmelinite type
  • L gmelinite type
  • ZK-5 the synthetic zeolites
  • Faujasite-type zeolites are composed of ⁇ -cages linked tetrahedrally via D6R subunits, with the ⁇ -cages resembling the carbon atoms in the diamond.
  • the three-dimensional network of faujasite-type zeolites suitable according to the invention has pores of 2.2 and 7.4 ⁇ , the unit cell additionally contains 8 cavities of about 13 ⁇ diameter and can be replaced by the formula Na 86 [(AIO 2 ) 86 (SiO 2 ) 10 6] ' 264 H 2 O describe.
  • the network of zeolite X contains a void volume of approximately 50%, based on the dehydrated crystal, which represents the largest void space of all known zeolites (zeolite Y: approximately 48% void volume, faujasite: approximately 47% void volume). (All data from: Donald W. Breck: "Zeolite Molecular Sieves", John Wiley & Sons, New York, London, Sydney, Toronto, 1974, pages 145, 176, 177).
  • zeolite type zeolite denotes all three zeolites which form the faujasite subgroup of the zeolite structure group 4.
  • zeolite Y and faujasite and mixtures of these compounds are also suitable according to the invention, the pure zeolite X being preferred.
  • Mixtures or cocrystallizates of faujasite-type zeolites with other zeolites, which need not necessarily belong to the zeolite structure group 4, are also suitable according to the invention, with preferably at least 50% by weight of the faujasite-type zeolites being suitable.
  • the suitable aluminum silicates are commercially available and the methods for their preparation are described in standard monographs.
  • x can take values greater than 0 to 276.
  • These zeolites have pore sizes of 8.0 to 8.4 ⁇ .
  • the zeolite A-LSX described in the European patent application EP-A-816 291 which corresponds to a co-crystallizate of zeolite X and zeolite A and in its anhydrous form has the formula (M 2ZnO + M 1 ⁇ n O) Al 2 O 3 ZSiO 2 , wherein M and M 'may be alkali or Erdal ⁇ kalimetalle and z is a number from 2.1 to 2.6.
  • VEGOBOND AX by the company CONDEA Augusta SpA
  • Y-type zeolites are also commercially available and can be obtained, for example, by the formulas
  • zeolites in which x stands for numbers from greater than 0 to 276. These zeolites have pore sizes of 8.0 ⁇ .
  • the particle sizes of the suitable faujasite-type zeolites are in the range from 0.1 ⁇ m to 100 ⁇ m, preferably from 0.5 ⁇ m to 50 ⁇ m and in particular from 1 ⁇ m to 30 ⁇ m, in each case measured using standard particle size determination methods.
  • silicates in particular amorphous silicates and crystalline phyllosilicates.
  • layered sodium silicates of the general formula NaMSi x O 2x + 1yH 2 O, where M is sodium or hydrogen, x is a number from 1.6 to 4, preferably 1.9 to 4, and y is a number from O is 20 and preferred values for x are 2, 3 or 4.
  • crystalline silicates are preferably subsequently added to the direct or post-treated spray-drying product.
  • Such crystalline layered silicates are described, for example, in European Patent Application EP-AO 164 514.
  • Preferred crystalline layered silicates of the formula given are those in which M is sodium and x is the
  • both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O 5 yH 2 O are preferred.
  • Such compounds are commercially available, for example, under the name SKS® (from Clariant).
  • SKS-6 ® primarily a ⁇ -sodium disilicate having the For ⁇ mel Na 2 Si 2 O 5 .yH 2 O
  • SKS-7 ® is predominantly a beta-sodium disilicate.
  • citric acid or carbonic acid is formed from the ⁇ -sodium disilicate Kanemit NaHSi 2 O 5 yH 2 O, commercially under the names SKS-9 ® and SKS-10 ® (Clariant). It may also be advantageous to use chemical modifications of these phyllosilicates.
  • the alkalinity of the layered silicates can be suitably influenced. Phosphate or carbonate-doped strati licate have in comparison to the ⁇ -sodium disilicate changed crystal morphologies, dissolve faster and show in comparison to ⁇ -sodium disilicate increased calcium binding capacity.
  • phyllosilicates of the general empirical formula x Na 2 O • y SiO 2 • z P 2 O 5 in which the ratio x to y is a number 0.35 to 0.6, the ratio x to z a number of 1.75 to 1200 and the ratio y to z of a number from 4 to 2800 corresponds to that described in the patent application DE-A-196 01 063.
  • the solubility of the layered silicates can also be increased by using particularly finely divided layered silicates.
  • compounds from the crystalline layer silicates with other ingredients can be used.
  • compounds with cellulose derivatives which have advantages in the disintegrating action, as well as compounds with polycarboxylates, for example citric acid, or polymeric polycarboxylates, for example copolymers of acrylic acid, may be mentioned.
  • the preferred support materials also include amorphous sodium silicates having a modulus of Na 2 O: SiO 2 of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2, 6, which are delay-delayed 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.
  • the term "amorphous” is also understood to mean "X-ray amorphous”.
  • the silicates do not yield any sharp X-ray reflections in X-ray diffraction experiments, as are typical for crystalline substances, but at best one or more maxima of the scattered X-radiation, which have a width of several degrees of the diffraction angle. It may be advantageous for the silicate particles to produce washed-out or even sharp diffraction maxima in electron-diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of size 10 to a few hundred nm, with values of up to max. 50 nm and in particular up to max. 20 nm are preferred.
  • Such so-called X-ray-amorphous silicates which likewise have a dissolution delay compared to the conventional water glasses, are described, for example, in German patent application DE-A-44 00 024.
  • Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.
  • Suitable support materials are furthermore phyllosilicates of natural and synthetic origin.
  • Such sheet silicates are known for example from the patent applications DE-B-23 34 899, EP-AO 026 529 and DE-A-35 26 405. Its usability is not limited to any particular composition or structural formula. However, smectites, in particular bentonites, are preferred here.
  • Layer silicates which can be used as carrier material and belong to the group of water-swellable smectites are, for example, montmorillonite, hectorite or saponite.
  • small amounts of iron can be incorporated into the crystal lattice of the phyllosilicates according to the above formulas.
  • the layer silicates may fabric due to their ion-exchanging properties Wasser ⁇ , alkali metal, alkaline earth metal ions, especially Na + and contain Ca 2+.
  • the amount of water of hydration is usually in the range of 8 to 20 wt .-% and is dependent on the swelling state or the type of processing.
  • Useful layered silicates are known, for example, from US Pat. No. 3,966,629, EP-A-026 529 and EP-A-028 432. It is preferred to use sheet silicates which, due to an alkali treatment, are substantially free of calcium ions and strongly coloring iron ions.
  • Particularly preferred support materials are alkali metal carbonates and alkali metal bicarbonates, with sodium and potassium carbonate and in particular sodium carbonate being among the preferred embodiments.
  • Particularly preferred support materials are also the sulfates, preferably alkali metal and Erdal ⁇ kalimetallsulfate, with sodium and magnesium sulfate are clearly preferred.
  • Particularly preferred support materials are also the silicic acids, preferably the precipitated silicic acids, in particular the silica gels (silica gels, silica gels), which are advantageously hydrophobic or hydrophilic.
  • fragrances in the particles produced according to the invention is greatly slower than comparable particles. Even when incorporating the particles according to the invention into strongly alkaline matrices, the fragrances contained in the particle are surprisingly stable. It is easily possible to incorporate the particles according to the invention, which may be loaded with high amounts of fragrances, without incorporating a gas-tight coating layer into other agents, such as, for example, detergents and cleaners. Moreover, since the particles of the invention loaded with fragrances are free-flowing and do not stick together, incorporation into detergents and cleansers or comparable compositions is effortless.
  • the paste to be processed according to the invention may preferably also contain nonionic surfactant, which corresponds to a preferred embodiment of the invention.
  • the nonionic surfactant is selected from the group consisting of the alkoxylated alcohols, the alkylphenol polyglycol ethers, the alkoxylated fatty acid alkyl esters, the polyhydroxy fatty acid amides, the alkyl glycosides, the alkyl polyglucosides, the amine oxides and / or the long-chain alkyl sulfoxides.
  • nonionic surfactants are preferably only present in minor amounts in the direct (spray) dried products.
  • their content can be up to 2 or 3% by weight. be.
  • the directly dried, in particular directly spray-dried, products are even free of nonionic surfactants, ie they contain less than 1% by weight, preferably less than 0.5% by weight and in particular no nonionic at all ⁇ nice surfactant.
  • nonionic surfactants reference is made to the description of the nachbeha ⁇ delten (spray) drying products below.
  • the presence of nonionic surfactant in the paste leads to a further increase in the receptivity of the particles resulting in the process according to the invention.
  • the absorption capacity of the particles is significantly higher when nonionic surfactant is applied to the direct (spray) drying product in a subsequent treatment step.
  • nonionic surfactant is present in the paste, according to a further preferred embodiment of the invention, at least partially alkoxylated alcohol is present as nonionic surfactant, preferably in amounts of at least 40% by weight, advantageously of at least 50% by weight further advantageously at least 60% by weight, most advantageously at least 70% by weight, more preferably at least 80% by weight, in particular at least 90% by weight, in the most advantageous manner in quantities of 100 wt .-%, each based on the total amount of nonionic surfactant contained in the paste, which are advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18, in particular 12 to 18 carbon atoms and preferably average 1 to 12 moles of alkylene oxide, preferably ethylene oxide, per mole of alcohol.
  • the paste contains anionic or cationic surfactant, preferably in small amounts, advantageously in amounts of less than 10 wt .-%, preferably less than 8 wt .-%, in particular less than 5 wt .-%, based on the Paste.
  • anionic or cationic surfactant is able to further increase the perfume-loading capacity of the resulting particles.
  • the resulting particles are still free-flowing and do not stick together.
  • the perfume is stabilized in the particles and a decomposition of the fragrances does not take place or is very stak delayed.
  • Particularly suitable anionic or cationic surfactants are described below.
  • Another object of the invention is a particle which can be produced by an inventive Ver ⁇ , wherein the particles of the direct (spray) drying product is aftertreated.
  • the particles resulting directly from the process according to the invention are referred to as particles of the direct (spray) drying product.
  • Such can be post-treated according to the invention, which is advantageous.
  • the aftertreatment can take place both with solid and with flowable or sprayable substances as well as combined.
  • Under aftertreatment with solids z. B. to understand the dusting of the particles with very fine particulate matter.
  • Post-treatment is also understood to mean the mechanical rounding of the particles.
  • the aftertreatment by rounding represents a preferred measure according to the invention.
  • the rounding of the direct (spray) drying product can be carried out in a conventional milling machine.
  • the rounding time is not longer than 4 minutes, especially not longer than 3.5 minutes. Rounding times of at most 1.5 minutes or less are particularly preferred.
  • the rounding achieves a further standardization of the grain spectrum.
  • the direct (spray) drying product produced according to the invention can advantageously be subjected to (optional) rounding, in particular with nonionic surfactants and perfume or formulations containing these ingredients, preferably with amounts up to 40% by weight of active substance, in particular with amounts of 2 to 35 wt .-% of active substance, in each case based on the aftertreated product, in a conventional manner, preferably in a mixer or optionally a fluidized bed, post-treatment. It is preferred if the direct (spray) drying product is first impregnated with nonionic surfactant and then loaded with perfume. Of course, the direct (spray) drying product can also be immediately loaded with perfume, d. H. the impregnation with nonionic surfactant is omitted. Likewise, the direct (spray) drying product can also be aftertreated with a preparation which is a mixture of nonionic surfactant and perfume and optionally other constituents.
  • the particles produced according to the invention are aftertreated with nonionic surfactants and / or perfume or preparation forms containing these ingredients.
  • the nonionic surfactant is preferably selected from the group consisting of the alkoxylated alcohols, the alkylphenol polyglycol ethers, the alkoxylated fatty acid alkyl esters, the polyhydroxy fatty acid amides, the alkyl glycosides, the alkyl polyglucosides, the amine oxides and / or the long-chain alkyl sulfoxides.
  • the nonionic surfactant used for the aftertreatment comprises alkoxylated alcohol, advantageously comprising ethoxylated, in particular primary, alcohols having preferably 8 to 18, in particular 12 to 18, carbon atoms and preferably on average 1 to 12 moles of alkylene oxide , preferably ethylene oxide, per mole of alcohol.
  • the direct (spray) drying product produced according to the invention may preferably be after the (optional) rounding and / or (optional) aftertreatment with free-flowing or sprayable substances with solids, preferably in amounts of up to 15% by weight, in particular dere in amounts of 2 to 15 wt .-%, each based on the total weight of the aftertreated agent, aftertreat, ie powder.
  • the particles prepared according to the invention are not tacky even if they contain a high degree of loading of perfume or the like, so that powdering can advantageously even be dispensed with altogether.
  • Hydrogen carbonate, carbonate, zeolite, silica, citrate, urea or mixtures thereof, in particular in amounts of from 2 to 15% by weight, based on the total weight of the aftertreated product, can preferably be used as solids for powdering.
  • the aftertreatment can be advantageously carried out in a mixer and / or by means of a macerator.
  • a solid for example silicic acids, zeolites, carbonates, bicarbonates and / or sulfates, citrates, urea or mixtures of 2 or more of the substances mentioned. This can be done either directly after leaving the direct spray-drying product from the tower in a mixer or in the malting machine.
  • the direct (spray) drying product is aftertreated with nonionic surfactants, which can also contain, for example, optical brighteners and / or hydrotropes, as well as with perfume or preparation forms which may contain these ingredients.
  • nonionic surfactants which can also contain, for example, optical brighteners and / or hydrotropes, as well as with perfume or preparation forms which may contain these ingredients.
  • it is first aftertreated with the nonionic surfactants and then with the perfume.
  • these ingredients or formulations containing these ingredients are applied in liquid, molten or pasty form to the direct (spray) drying product.
  • the direct (spray) Trocknungs- products are treated with up to 40 wt .-% of active ingredient of the ingredients mentioned.
  • the quantity stated is related to the aftertreated product. It is preferred that the subsequent treatment with the substances mentioned here take place in a conventional mixer.
  • Such post-treated products may have a bulk density of from 300 to 1000 g / l, preferably from 450 to
  • nonionic surfactant is added to the direct (spray) drying product in the course of the aftertreatment.
  • 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 used in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or contain linear and methyl-branched radicals in the mixture, as they are usually present in Oo xoalkoholresten.
  • alcohol ethoxylates with linear radicals from alcohols of natural origin having 12 to 18 C atoms for example from coconut, palm, palm kernel, tallow or oleyl alcohol, and on average from 2 to 8 EO per mole of alcohol are preferred.
  • the preferred ethoxylated alcohols include, for example, C 12 -C 14 alcohols with 3 EO or 4 EO, C 9 -Cn alcohols with 7 EO, C 13 -C 15 -AlkOhOIe with 3 EO, 5 EO, 7 EO or 8 EO, C 12 -C 18 -alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12 -C 14 -alcohol with 3 EO and Ci 2 -Ci 8 -AlkOhOl with 7 EO.
  • the degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow rank ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples of these are (TaIg) fatty alcohols with 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO.
  • alkoxylated alcohols are very advantageous in order to further maximize the perfume absorption capacity of the particles, to promote the stability of the perfume in the particles and to promote said scent-retard effect and the fragrance-enhancing effect.
  • the nonionic surfactants which are particularly suitable for the aftertreatment are a mixture of at least two different nonionic surfactants, preferably of at least two different alkoxylated, advantageously ethoxylated, in particular primary, alcohols, the distinguishing feature being preferably those with respect to the alkoxylated alcohols in the degree of alkoxylation.
  • this mixture of at least two different nonionic surfactants at least one alkoxylated, preferably ethoxylated alcohol having a degree of alkoxylation of less than 7, advantageously not greater than 6, more advantageously not greater than 5, in particular not greater than 4.5 and at least one further alkoxylated, advantageously ethoxylated alcohol having a degree of alkoxylation of at least 7 before, then it is a further preferred embodiment of the invention.
  • the ratio of lower alkoxylated alcohol to higher alkoxylated alcohol is in the range from 5: 1 to 1: 5, preferably from 4: 1 to 1: 4, advantageously from 3: 1 to 1: 3 , in particular 2: 1 to 1: 2.
  • alkyl glycosides of the general formula RO (G) x in which R is a primary straight-chain or methyl-branched, especially methyl-branched, 2-position aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms and G the symbol is, which represents a glycose unit having 5 or 6 C atoms, preferably glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number from 1 to 10; preferably x is 1, 1 to 1, 4.
  • nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants, in particular together with alkoxylated fatty alcohols and / or alkyl glycosides, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, as described for example in Japanese Patent Application JP 58/217598 or which are preferably prepared according to the method described in International Patent Application WO-A-90/13533.
  • Particularly preferred are C 12 -C 18 fatty acid methyl esters having an average of 3 to 15 EO, insbesonde ⁇ re with an average of 5 to 12 EO.
  • 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, in particular not more than half thereof.
  • alkoxylated alcohol is used as the nonionic surfactant, preferably in amounts of at least 40% by weight, advantageously of at least 50% by weight, more preferably of at least 60% by weight most advantageously at least 70% by weight, more preferably at least 80% by weight, in particular at least 90% by weight, most advantageously in amounts of 100% by weight, based in each case on the total amount Nonionic surfactant, which is added in the course of the aftertreatment.
  • a particle according to the invention contains carrier material, preferably inorganic carrier material, in a total amount of at least 30% by weight, based on the total particle, of perfume ad / absorbed on / in the carrier material, and at least 0, 1 wt .-% of nonionic surfactant, based on the total post-treated particles.
  • the amount of perfume adsorbed in / on the carrier material of a particle according to the invention is at least 1% by weight, preferably at least 5% by weight, advantageously more than 10% by weight, more advantageously more than 15% by weight, more preferably more than 20% by weight, in particular more than 25% by weight, based on the total post-treated particles.
  • additives in particular for the aftertreatment of the products, are foam inhibitors, such as, for example, foam-inhibiting paraffin oil or foam-inhibiting silicone oil, for example dimethylpolysiloxane. The use of mixtures of these agents is possible.
  • Suitable foam-inhibiting paraffin oils which can be present in admixture with paraffin wax are generally complex mixtures without a sharp melting point.
  • the melting range is usually determined by differential thermal analysis (DTA), as described in US Pat "The Analyst” 87 (1962), 420, and / or the solidification point. This is the temperature at which the paraffin passes from the liquid to the solid state by slow cooling.
  • Paraffins having less than 17 carbon atoms are less useful according to the invention, their 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 20 ° C to 7O 0 C.
  • paraffin waxes may contain different proportions of liquid paraffin oils.
  • the liquid fraction at 40 0 C mög ⁇ lichst is high, without be at this temperature already 100%.
  • Preferred specific Paraffinwachsgemi ⁇ have a liquid content of at least 50 wt .-%, particularly from 55 wt .-% to 80 wt .-%, and at 60 0 C a liquid fraction of at least 90 wt .-% at 40 ° C. This has the consequence that the paraffins are flowable and pumpable at temperatures down to at least 70 0 C, preferably down to at least 60 0 C.
  • paraffins contain as far as possible no volatile components.
  • Preferred paraffin waxes contain less than 1 wt .-%, in particular less than 0.5 wt .-% at 110 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 bisamides solid at room temperature which are derived from saturated fatty acids having 12 to 22, preferably 14 to 18, carbon atoms and also alkylenediamines having 2 to 7 carbon atoms.
  • Suitable fatty acids are lauric, myristic, stearic, arachic and behenic acid and mixtures thereof, such as those obtainable from natural fats or hydrogenated oils such as tallow or hydrogenated palm oil.
  • suitable diamines are 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 present in the direct (spray) drying product.
  • a) support material preferably inorganic support material, in amounts of at least 30 wt .-%, advantageously in amounts of 50 to 95 wt .-%, preferably 60 to 90 wt.%
  • b) perfume in amounts of 0.5 to 40 wt. %, preferably from 1 to 35% by weight
  • nonionic surfactant in amounts of from 0.1 to 30% by weight, preferably from 0.5 to 10% by weight, in particular from 1 to 5% by weight
  • the other constituents may advantageously be typical ingredients of detergents and cleaners.
  • Particles which can be prepared according to the invention and are intended in particular for use in or as detergents and cleaners can contain typical ingredients, in particular selected from the group comprising washing, care and / or cleaning active substances such as surfactants, builders, bleaches, bleach activators, Bleach stabilizers, bleach catalysts, enzymes, polymers, cobuilders, alkalizing agents, Acidisersstoff, Antiredeposi- tion agents, silver protectants, colorants, optical brighteners, UV protectants, fabric softeners and / or rinse aid, and optionally contain further ingredients which are described in more detail below ,
  • the described and all other suitable conventional ingredients may be contained directly in the (spray) dried product, but preferably also be applied in the course of a post-treatment on the particles. Likewise, the particles can be mixed together with components containing such and / or other conventional ingredients.
  • the anionic surfactants used are preferably those of the sulfonate and sulfates type.
  • surfactants of the sulfonate type are preferably C 9-13 alkylbenzenesulfonates, olefinsulfona- te, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as example, from C 12-18 monoolefins with terminal or internal double bond Sulfonating with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation obtained, into consideration.
  • alkanesulfonates which are NEN of C 12-i 8 alkanes, for example by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization gewon ⁇ .
  • esters of .alpha.-sulfo fatty acids esters of .alpha.-sulfo fatty acids (ester sulfonates), for example the .alpha.-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.
  • anionic surfactants are sulfated fatty acid glycerol esters.
  • Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and mixtures thereof, as used in the preparation obtained 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 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 degradation behavior to the adequate compounds based on oleochemical raw materials.
  • C 12 -C 16 alkyl sulfates and C 12 - C 15 alkyl sulfates and C 4 -C 15 alkyl sulfates are preferred.
  • 2,3-alkyl sulfates can be obtained as commercial products from Shell Oil Company under the name DAN ®, are suitable anionic surfactants.
  • 2 i-alcohols such as 2-methyl-branched C 9 .n-alcohols having on average 3.5 mol ethylene oxide (EO) or C 12-18 fatty alcohols having 1 to 4 EO, are suitable. Because of their high foaming behavior, they are used only in relatively small amounts, for example in amounts of from 1 to 5% by weight, based on the total agent, in particular cleaning agent, in particular in cleaning agents.
  • alkylsulfosuccinic acid which are also known 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.
  • Preferred sulfosuccinates contain C 8 . 18- fatty alcohol residues or mixtures of these.
  • Particularly preferred sulfosuccinates contain a fatty alcohol radical which is derived from ethoxylated fatty alcohols, which in themselves constitute nonionic surfactants (description below).
  • 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.
  • the content of the agents, preferably detergents and cleaners, which contain the particles according to the invention, in particular the aftertreated (spray) drying products, on the said anionic surfactants is preferably from 2 to 30% by weight and in particular from 5 to 25% by weight. %, with concentrations above 10% by weight and even above 15% by weight preference, in each case based on the total resources.
  • the particles according to the invention as such, in particular the aftertreated (spray) drying product preferably contain only small amounts of anionic surfactant, advantageously less than 10% by weight.
  • soaps may be included.
  • Particularly 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 content of the particles according to the invention, in particular of the aftertreated (spray) drying products on soaps is preferably not more than 3% by weight and in particular from 0.5 to 2.5% by weight, based on the total particles, in particular the nach ⁇ treated (spray) drying product.
  • the anionic surfactants and soaps may be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine. They are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • Anionic surfactants and soaps can also be prepared in situ by introducing into the composition to be dried the anionic surfactant acids and optionally fatty acids, which are then neutralized by the alkali carriers in the (spray) drying composition.
  • builders which act as builders according to the invention, such as zeolites or silicates. In addition to builder-builders, other builders may be included.
  • phosphates in particular pentasodium triphosphate, if appropriate also pyrophosphates and orthophosphates, which act primarily as precipitants for calcium salts. Phosphates are predominantly used in machine dishwashing detergents, but in some cases also in detergents.
  • Alkali metal phosphates is the summary term for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which one can distinguish Metaphosphorkla- ren (HPO 3 ) n and orthophosphoric H 3 PO 4 in addition to high molecular weight representatives.
  • the phosphates combine several advantages: they act as alkali carriers, prevent calcification on machine parts or lime incrustations in fabrics and, moreover, contribute to the cleaning performance.
  • Sodium dihydrogen phosphate, NaH 2 PO 4 exists as a dihydrate (density 1, 91 like '3 , melting point 60 °) and monohydrate (density 2.04 like ' 3 ).
  • Both salts are white powders which are very readily soluble in water and lose the water of crystallization on heating and at 200 ° C into the weak acid diphosphate (sodium hydrogen diphosphate, Na 2 H 2 P 2 O 7 ), at higher temperature in sodium trimetaphosphate (Na 3 P 3 O 9 ) and Maddrell's salt (see below).
  • NaH 2 PO 4 is acidic; It arises when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed.
  • Potassium dihydrogen phosphate (primary or monobasic potassium phosphate, potassium phosphate, KDP), KH 2 PO 4 , is a white salt of density 2.33 "3 , has a melting point 253 ° [Zerset ⁇ tion to form potassium polyphosphate (KPO 3 ) J and is easily soluble in water.
  • Disodium hydrogen phosphate (secondary sodium phosphate), Na 2 HPO 4 , is a colorless, very slightly water-soluble crystalline salt. It exists anhydrous and with 2 mol. (Density 2.066 like “3 , Wasser ⁇ loss at 95 °), 7 mol. (Density 1, 68 like “ 3 , melting point 48 ° with loss of 5 H 2 O) and 12 mol. Water (density 1, 52 like '3 , melting point 35 ° with loss of 5 H 2 O), becomes anhydrous at 100 ° and on more intense heating in the diphosphate Na 4 P 2 O 7 over. Disodium hydrogen phosphate is prepared by neutralization of phosphoric acid with soda solution using phenolphthalein as indicator. Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K 2 HPO 4 , is an amorphous, white salt that is readily soluble in water.
  • Trisodium phosphate is readily soluble in water under alkaline reaction and is prepared by evaporating a solution of exactly 1 mole of disodium phosphate and 1 mole of NaOH.
  • Tripotassium phosphate (tertiary or tribasic potassium phosphate), K 3 PO 4 , is a white, deliquescent, granular powder with a density of 2.56 "3 , has a melting point of 1340 ° and is readily soluble in water with an alkaline reaction.
  • Tripotassium phosphate tertiary or tribasic potassium phosphate
  • K 3 PO 4 Tripotassium phosphate
  • Tetrasodium diphosphate (sodium pyrophosphate), Na 4 P 2 O 7 , exists in anhydrous form (density 2.534 '3 , melting point 988 °, also indicated 880 °) and as decahydrate (density 1, 815-1, 836 like "3 , melting point 94 Both substances are colorless crystals which are soluble in water with an alkaline reaction Na 4 P 2 O 7 is formed on heating disodium phosphate to> 200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dehydrating the solution by spraying.
  • Kali diphosphate potassium pyrophosphate
  • K 4 P 2 O 7 exists in Form of the trihydrate and represents a colorless, hygroscopic powder with a density of 2.33% '3 , which is soluble in water, the pH of the 1% solution at 25 ° being 10.4.
  • Condensation of the NaH 2 PO 4 or of the KH 2 PO 4 gives rise to relatively high molecular weight sodium and potassium phosphates in which cyclic representatives, the sodium or potassium metaphosphates and ketene-type, the sodium or potassium polyphosphates, can be distinguished , In particular, for the latter a variety of names are in use: fused or Glühphosphate, Graham's salt, Kurrolsches and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.
  • n 3
  • 100 g of water dissolve at room temperature about 17 g, at 60 ° about 20 g, at 100 ° around 32 g of the salt water-free salt; after two hours of heating the solution to 100 ° by hydrolysis about 8% orthophosphate and 15% diphosphate.
  • pentasodium triphosphate In the preparation of pentasodium triphosphate, phosphoric acid is reacted with soda solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dehydrated by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentakaliumtriphosphat, K 5 P 3 O 10 (potassium tripolyphosphate), for example, in the form of a 50 wt .-% solution (> 23% P 2 O 5 , 25% K 2 O) in the trade. The potassium polyphosphates are widely used in the washing and cleaning industry. There are also sodium potassium tripolyphosphates which can also be used in the context of the present invention. These arise, for example, when hydrolyzing sodium trimethyl phosphate with KOH:
  • Useful organic builders are, for example, also 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, amino carboxylic acids, nitrilotriacetic acid (NTA), if such use is for ecological reasons not to complain about, as well as mixtures of these.
  • Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, methylglycine diacetic 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 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. 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 from 1000 to 20 000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molecular weights of from 1,000 to 10,000 g / mol, and particularly preferably from 1,200 to 8,000 g / mol, for example 4,500 or 8,000, may again be preferred from this group.
  • Both polyacrylates and copolymers of unsaturated carboxylic acids, monomers containing sulfonic acid groups and optionally other ionic or nonionogenic monomers are particularly preferably used in the compositions according to the invention.
  • the sulfonic acid-containing copolymers will be described in detail below.
  • 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 mass, based on free acids, is in general Common 2000 to 100000 g / mol, preferably 20,000 to 90,000 g / mol and in particular 30,000 to 80,000 g / mol.
  • the content of the direct (spray) drying products of (co) polymeric polycarboxylates is preferably from 0.5 to 20% by weight, in particular from 2 to 20% by weight, with contents of not more than 10% by weight being used for cost reasons. Find favor.
  • the polymers may also contain allylsulfonic acids, such as, for example, allyloxybenzenesulfonic acid and methallylsulfonic acid, as monomer.
  • allylsulfonic acids such as, for example, allyloxybenzenesulfonic acid and methallylsulfonic acid, as monomer.
  • biodegradable polymers of more than two different monomer units for example those which contain as monomers the salts of acrylic acid and of maleic acid and also vinyl alcohol or vinyl alcohol derivatives or the salts of acrylic acid and 2-alkylallyl sulfonic acid as monomers. Derivatives included.
  • copolymers preferably contain acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.
  • polymeric aminodicarboxylic acids their salts or their precursors.
  • polyaspartic acids or their salts and derivatives are particularly preferred.
  • 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 customary measure of the reducing effect of a polysaccharide in comparison with dextrose, which is a DE of Owns 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.
  • a product oxidized to C 6 of the saccharide ring may be particularly advantageous.
  • 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. Suitable quantities are from 3 to 15 wt .-% for zeolite-containing and / or silicate-containing direct (spray) drying products.
  • IDS iminodisuccinates
  • HDIS hydroxyiminodisuccinates
  • 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.
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • 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 agents also contain bleach, it may be preferable to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.
  • all compounds which are capable of forming complexes with alkaline earth ions can be present as co-builders in the particles according to the invention, in particular in the direct (spray) drying products.
  • Graying 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 example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
  • water-soluble, acidic groups containing polyamides are suitable for this purpose.
  • soluble starch preparations and other than the above-mentioned starch products can be used, e.g. degraded starch, aldehyde levels, etc. Also polyvinylpyrrolidone is useful.
  • cellulose ethers such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose and mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof, and also polyvinylpyrrolidone, for example, in amounts of from 0.1 to 5% by weight, based on the used direct (spray) drying products.
  • Suitable plasticizers are, for example, swellable phyllosilicates of the type of corresponding montmorillonites, for example bentonite.
  • the content of water in the direct (spray) drying product is preferably 0 to less than 25 wt .-% and in particular 0.5 to 20 wt .-%, with values of at most 15 wt .-% find special preference. Not included here was the water present on any aluminosilicates, such as zeolite.
  • fragrance 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, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethylmethylphenyl glycinate, allylcyclohexyl propionate, styrallyl propionate and benzyl salicylate.
  • the ethers include, for example, benzyl ethyl ether, to the aldehydes, for example, the linear alkanals with 8-18 C atoms, citral, citronellal, Zitronellyloxyacetaldehyd, cyclamen aldehyde, hydroxycitronellal, Lilial and Bourgeonal, to the ketones such as the ionone, oc-lsomethylionon and methyl cedryl ketone, to the alcohols 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 as are available from vegetable sources, eg pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage, chamomile, clove, meissen, mint, cinnamon, lime, juniper, vetiver, olibanum, galbanum and labdanum, and orange blossom, neroliol, orange peel and sandalwood.
  • the perfume comprises a perfume fixative, preferably in the form of diethyl phthalates, musk (derivatives) and mixtures thereof, the amount of fixative preferably being from 1 to 55% by weight, advantageously from 2 to 50% by weight. %, more preferably 10 to 45 wt .-%, in particular 20 to 40 wt .-% of the total amount of perfume.
  • the particles contain a viscosity of liquids, in particular perfume-increasing agent, preferably PEG (polyethylene glycol), advantageously having a molecular weight of 400 to 2000, wherein the viscosity increasing agent in a preferred manner in amounts of 0.1 to 20 wt .-%, advantageously from 0.15 to 10 wt .-%, more preferably from 0.2 to 5 wt .-%, in particular from 0.25 to 3 wt .-% is contained, based on the particles.
  • PEG polyethylene glycol
  • the added fragrances also include those systems which have a re ⁇ tard effect with respect to the release of fragrance.
  • Such systems can be found in the prior art.
  • These silicic acid esters are characterized, inter alia, by a long-lasting release of fragrance and also cause an extension of the fragrance effect of other fragrances.
  • EP 0 998 911, EP 0 982 313 and EP 0 982 022 of General Electric describe nonvolatile, polymeric, copolymeric or oligomeric siloxanes in which one or more organic siloxanes are present
  • Substituents of be ⁇ voted alcohols, aldehydes, ketones or esters are derived radicals that confer certain advantageous properties both the siloxanes themselves and compositions in which incorporated the corresponding siloxanes, certain. If these alcohols, aldehydes, keto NEN or esters, fragrant compounds such.
  • the direct (spray) drying products and / or the aftertreated products described above can, in a further embodiment of the invention, be treated with further constituents of detergents and cleaners, in particular mixed, it being of advantage that constituents are admixed which are not accessible to (spray) drying. It is generally known from the broad state of the art which ingredients of detergents and cleaners are not available for (spray) drying and which raw materials are usually added.
  • high-temperature-sensitive mixture constituents of detergents and cleaning agents are admixed, such as bleaches based on percompounds, bleach activators and / or bleach catalysts, enzymes, for example from the classes of proteases, lipases, cellulases and / or amylases, or Bacterial strains or fungi, with combinations of 2 or more of the enzyme classes being particularly preferred, foam inhibitors in a possibly granular and / or compounded form, perfumes, temperature-sensitive dyes and the like.
  • enzymes for example from the classes of proteases, lipases, cellulases and / or amylases, or Bacterial strains or fungi, with combinations of 2 or more of the enzyme classes being particularly preferred
  • foam inhibitors in a possibly granular and / or compounded form perfumes, temperature-sensitive dyes and the like.
  • UV absorbers which are applied to the treated textiles and improve the lightfastness of the fibers and / or the lightfastness of other formulation components, can also be added subsequently.
  • UV absorbers are to be understood as meaning organic substances (light protection filters) which are capable of absorbing ultraviolet rays and of releasing the absorbed energy in the form of longer-wave radiation, for example heat.
  • Compounds having these desired properties include, for example, the non-radiative deactivating compounds and derivatives of benzophenone having substituents in the 2- and / or 4-position.
  • 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.
  • 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.
  • Biphe ⁇ nyl- and, above all, stilbene derivatives described, for example in EP 0728749 A and commercially Tinosorb FD ® ® or Tinosorb FR ex Ciba than.
  • 2-phenylbenzimidazole-5-sulfonic acid and its alkali metal, alkaline earth metal, ammonium, alkylammonium, alkanolammonium and glucammonium salts Sulfonic acid derivatives of benzophenones, preferably 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its salts
  • Sulfonic acid derivatives of 3-Benzylidencamphers such as 4- (2-oxo-3-bornylidenemethyl) benzene-sulfonic acid and 2-methyl-5- (2-oxo-3-bomylidene) sulfonic acid and salts thereof.
  • UV-A filter in particular derivatives of benzoylmethane come into question, as example, 1- (4'-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1, 3-dione, 4-tert. Butyl-4'-methoxydibenzoyl- methane (Parsol 1789), 1-phenyl-3- (4'-isopropylphenyl) propane-1,3-dione and enamine compounds, as described in DE 19712033 A1 (BASF).
  • the UV-A and UV-B filters can also be used in mixtures.
  • insoluble photoprotective pigments namely finely dispersed, preferably nano-metal oxides or salts
  • suitable metal oxides are in particular zinc oxide and titanium dioxide and, in addition, oxides of iron, zirconium, silicon, manganese, aluminum and cerium and mixtures thereof.
  • salts silicates (talc), barium sulfate or zinc stearate can be used.
  • the oxides and salts are already used in the form of the pigments for skin-care and skin-protecting emulsions and decorative cosmetics.
  • the particles should have an average diameter of less than 100 nm, preferably from 5 to 50 nm and in particular from 15 to 30 nm.
  • the pigments may have a spherical shape, but it is also possible to use those particles which have an ellipsoidal or otherwise deviating shape from the spherical shape.
  • the pigments can also be surface treated, i. hydrophilicized or hydrophobized. Typical examples are coated titanium dioxides, e.g. Titanium dioxide T 805 (Degussa) or Eusolex® T2000 (Merck). Suitable hydrophobic coating agents are in particular silicones and in particular trialkoxyoctylsilanes or simethicones. Preferably, micronized zinc oxide is used. Further suitable UV photoprotective filters can be found in the review by P.Finkel in S ⁇ FW Journal 122, 543 (1996).
  • the UV absorbers are usually used in amounts of from 0.01% by weight to 5% by weight, preferably from 0.03% by weight to 1% by weight, based on the total resulting agent. In exceptional cases, they may also be present in the direct (spray) drying product.
  • speckles which stand out by their color and / or their shape from the appearance of direct and / or post-treated (spray) drying products.
  • the speckles may once have a similar to identical grain spectrum as the direct and / or post-treated (spray) drying products and diesel ⁇ be composition, but have a different color. It is also possible that the speckles have the same composition as the direct and / or post-treated (spray) drying products, are not stained but have a different shape. Finally, however, it is preferred that speckles having the same composition as the direct and / or post-treated (spray) drying products differ from the latter in color and optionally additionally in their form. In these cases, the speckles are merely intended to make the appearance of the finished detergents and cleaners even more attractive.
  • the speckles have a different chemical composition than the direct and / or post-treated (spray) drying products.
  • certain ingredients for certain purposes such as bleaching or care aspects are included in the final product due to a different color and / or a different shape of the end user.
  • These speckles can not only be spherical to rod-shaped, they can also represent quite different figures.
  • the admixed speckles or else other ingredients can, for example, be spray-dried, agglomerated, granulated, pelletized or extruded.
  • extrusion processes reference is made in particular to the disclosures in European patent EP 0486592 B1 and international patent application WO 98/12299. Since it is an advantage of the direct and / or nacherfindungsdorf post-treated (spray-) drying products that they contain an excellent dissolution rate even at relatively cold water of 30 0 C, it is of course preferred to mix these, such further ingredients and / or raw materials likewise have an excellent dissolution rate. Therefore, in a preferred embodiment of the invention, raw materials which have been prepared according to the disclosure of international patent application WO 99/28433 are admixed to the invention.
  • the present invention is thus in a further embodiment, a living, washing and cleaning agent (detergent composition) or care agent that erfindungs ⁇ contemporary direct (spray) drying product and / or inventively aftertreated product, advantageously in amounts of 0.5 to 99.5 wt .-%, more preferably from 1 to 95 wt .-%, more preferably from 5 to 90 wt .-%, more preferably 10 to 80 wt .-%, preferably 20 to 70 Wt .-% and in particular 30 to 60 wt .-% and other zuge ⁇ mixed ingredients.
  • Another object of the invention is a detergent composition (washing and cleaning agents), comprising:
  • a washing and cleaning agent according to the invention is composed of admixing components and the particles according to the invention.
  • the sodium perborate tetrahydrate and the sodium perborate monohydrate are of particular importance.
  • Other useful bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.
  • detergents and cleaners according to the invention are distinguished by the fact that they contain bleaching agents, preferably sodium percarbonate and / or halogen bleach, in amounts of from 0.5 to 80% by weight, preferably from 2.5 to 70% by weight preferably from 5 to 60 wt .-% and in particular from 10 to 50 wt .-%, each based on the total mass of the composition.
  • bleaching agents preferably sodium percarbonate and / or halogen bleach
  • bleach activators may be present in inventive washing and cleaning agents.
  • bleach activators 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-dioxohexa-hydro-1,3,5-triazine (DADHT) 1 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 acid anhydrides, in particular phthalic acid.
  • Anhydride, acylated polyhydric alcohols especially triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran.
  • bleach catalysts can also be present in detergents and cleaners according to the invention.
  • 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.
  • Suitable enzymes are those from the class of proteases, lipases, amylases, cellulases or de ⁇ ren mixtures in question. Particularly suitable are bacterial strains or fungi, such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus derived enzymatic agents. Preference is given to using proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus.
  • enzyme mixtures for example from protease and amylase or protease and lipase or protease and cellulase or from cellulase and lipase or from protease, amylase and lipase or protease, lipase and cellulase, but in particular cellulase-containing mixtures are of particular interest.
  • Peroxidases or oxidases have also proved suitable in some cases.
  • the enzymes can be adsorbed to carriers and / or embedded in Hüll ⁇ substances to protect them against premature decomposition.
  • the proportion of enzymes, enzyme mixtures or enzyme granules in the detergents and cleaners according to the invention can be, for example, about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight.
  • Detergents according to the invention contain, according to a particularly preferred embodiment, further additives known from the prior art as additives for detergents and cleaners.
  • a preferred group of additives used in the invention are optical brighteners. Can be used here, the usual in detergents optical brightener. Examples of optical brighteners are derivatives of diaminostilbene disulfonic acid or its alkali metal salts. Suitable z. B.
  • salts of 4, 4'-bis (2-anilino-4-morpholino1, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of similar construction which instead of the morpholino group a Diethanol-amino group, a methylamino group, an anilino group or a 2-methoxyethylamino group.
  • brighteners of the type of substituted diphenylstyrene may be present in the detergent compositions according to the invention, eg.
  • alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl or 4- (4-chlorostyryl) 4'- (2 -sulfostyryl-) biphenyl can be used.
  • Disintegration aids preferably a cellulose based disintegration aid, may also be among the relevant ingredients.
  • Well-known disintegration aids are included
  • carbonate / citric acid systems although other organic acids were ⁇ can used.
  • Swelling disintegration aids are, for example, synthetic polymers such as polyvinylpyrrolidone (PVP) or natural polymers or modified natural substances such as cellulose and starch and their derivatives, alginates or casein derivatives. All mentioned disintegration aids can be used according to the invention.
  • PVP polyvinylpyrrolidone
  • compositions may contain antioxidants.
  • antioxidants include 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 of 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 antistatics (amines, amides, quaternary ammonium compounds), phosphorus-containing (phosphoric acid esters) and sulfur-containing (alkyl sulfonates, alkyl sulfates). Lauryl (or stearyl) dimethylbenzylammonium chlorides are also suitable as antistatic agents for textiles or as an additive to detergents, with an additional softening effect being achieved.
  • compositions according to the invention may comprise fabric softeners or softening agents
  • fabric softeners or softening agents Preferred are quaternary ammonium compounds with two hydrophobic radicals, such as For example, the Disteraryldimethylammoni- umchlorid, which, however, due to its insufficient biodegradability increasingly replaced by quaternary ammonium compounds containing ester groups in their hydrophobic residues as predetermined breaking points for biodegradation (Esterquats).
  • the additives comprise softening agents, preferably cationic surfactants, in particular quaternary ammonium compounds.
  • compositions according to the invention are characterized in that they comprise softening agents, preferably cationic surfactant (s), in particular alkylated quaternary ammonium compounds of which at least one alkyl chain is interrupted by an ester group and / or amido group Amounts of from 0.5 to 80% by weight, preferably from 2.5 to 70% by weight, in particular ders preferably from 5 to 60 wt .-% and in particular from 10 to 50 wt .-%, each based on the total mass of the composition contains.
  • softening agents preferably cationic surfactant (s), in particular alkylated quaternary ammonium compounds of which at least one alkyl chain is interrupted by an ester group and / or amido group Amounts of from 0.5 to 80% by weight, preferably from 2.5 to 70% by weight, in particular ders preferably from 5 to 60 wt .-% and in particular from 10 to 50 wt .-%, each based on the total mass of the composition contains.
  • Suitable examples are quaternary ammonium compounds of the formulas (1) and (2),
  • R 1 and R 2 is an acyclic alkyl radical having 12 to 24 carbon atoms
  • R 3 is a saturated C 1 -C 4 alkyl or hydroxyalkyl radical
  • R 4 is either R 1 , R 2 or R 3 or represents an aromatic radical.
  • X denotes either a halide, methosulfate, methophosphate or phosphate ion and mixtures of these Examples of cationic compounds of the formula (1) are didecyldimethylammonium chloride, ditallowdimethylammonium chloride or dihexadecylammonium chloride.
  • compositions according to the invention which are characterized in that they contain a quaternary ammonium compound of the formula (2), are preferred embodiments of the invention. Esterquats are distinguished by excellent biodegradability.
  • R 5 is an aliphatic alkyl radical having 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds
  • R 6 represents H, OH or O (CO) R 8
  • R 7 is unabpatn ⁇ gig of R 6 is H, OH or 0 (CO) R 8, wherein R 8 and R 9 independently of one another each for a liphatischen a- Alkyl radical having 12 to 22 carbon atoms with O, 1, 2 or 3 double bonds, a, b and c may each independently have the value 1, 2 or 3.
  • X " can be either a halide, methosulfate, methophosphate or phosphate ion and mixtures of these.
  • Preferred compounds are those which for R 6 are the group O (CO) R 8 and for R 5 and R 8 are alkyl radicals having from 16 to 18 carbon atoms. particularly preferred are compounds in which R 7 is also OH.
  • Examples of compounds of formula (2) are methyl-N- (2-hydroxyethyl) -N, N-di (talgacyl- oxyethyl) ammonium methosulfate Bis (palmitoyl) ethyl hydroxyethyl methyl ammonium methosulfate or methyl N, N bis (acyloxyethyl) -N- (2-hydroxyethyl) ammonium methosulfate.
  • Quaternized compounds of the formula (2) are used unsaturated alkyl chains, the acyl groups are preferred whose corresponding fatty acids have an iodine value of between 5 and 80, preferably between 10 and 60 and in particular between 15 and 45, and which have a cis / trans isomer ratio (in% by weight). greater than 30:70, preferably greater than 50:50 and especially ere are greater than 70: 30.
  • Commercial examples are by Stepan under the tradename Stepantex ® marketed Methylhydroxyalkyldialkoyloxyalkylammoniummethosulfate or known under Dehyquart ® products from Cognis or known under Rewoquat ® products from Goldschmidt-Witco.
  • Further preferred compounds are the diester quats of the formula (3) which are obtainable under the name Rewoquat® W 222 LM or CR 3099.
  • R 10 and R 11 are each independently an aliphatic radical having 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds.
  • R 12 is H or a saturated alkyl radical having 1 to 4 carbon atoms
  • R 13 and R 14 inde pendent of each other for an aliphatic, saturated or unsaturated alkyl radical having 12 to 18 carbon atoms
  • R 13 alternatively also for O (CO)
  • R 15 where R 15 is an aliphatic, saturated or unsaturated alkyl radical having 12 to 18 carbon atoms
  • Z is an NH group or oxygen
  • d can be integer values between 1 and 4.
  • R 16 , R 17 and R 18 independently represent a C 1-4 alkyl, alkenyl or hydroxyalkyl group
  • R 19 and R 20 each independently represent a C ⁇ - ⁇ ⁇ -alkyl group and e is a number between 0 and 5
  • X " is a suitable anion, preferably a halide, methosulfate, methophosphate or phosphate ion, and mixtures thereof.
  • Agents according to the invention which are characterized in that they contain a quaternary ammonium compound according to formula (5) are particularly preferred ,
  • protonated alkylamine compounds which have plasticizing effect, as well as the non-quaternized, protonated precursors of cationic emulsifiers are suitable.
  • compositions which can be used according to the invention and can be present in the compositions are the quaternized protein hydrolysates.
  • the alkylamidoamines may be in their quaternized or, as shown, their quaternized form.
  • R 21 may be an aliphatic alkyl radical having 12 to 22 carbon atoms with 0, 1, 2 or 3
  • Dop ⁇ pelitatien, f may assume values between 0 and 5.
  • R 22 and R 23 independently of one another each represent H, C 1-4 -alkyl or hydroxyalkyl.
  • Preferred compounds are amines Fett Textreamido- as sold under the name Tego Amid ® S 18 stearyl or available that available under the designation Stepantex ® X 9124 3-tallowamidopropyl trimethylammonium methosulfate nium, which by a good conditioning effect sinhibierende by farbübertragung- Effect as well as specially characterized by their good biodegradability.
  • alkylated quaternary ammonium compounds of which at least one alkyl chain is interrupted by an ester group and / or amido group, in particular N-methyl-N (2 hydroxyethyl) -N, N- (ditalgacyloxyethyl) ammonium methosulfate and / or N-methyl-N (2-hydroxyethyl) -N, N- (palmitoyloxyethyl) ammonium nethanesulfonate.
  • 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.
  • detergents of the invention may contain synthetic crease inhibitors. 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.
  • the agents according to the invention may contain antimicrobial agents.
  • antimicrobial agents Depending on the antimicrobial spectrum and mechanism of action, a distinction is made between bacteriostats and bactericides, fungistatics and fungicides, etc.
  • Important substances from these groups are, for example, benzalkonium chlorides, alkylarylsulfonates, halophenols and phenolmercuric acetate.
  • antimicrobial action and antimicrobial active ingredient have the usual meaning in the context of the teaching according to the invention, which is described, for example, by KH Wallophusser in "Praxis der Sterilisation, Disinfection - Conservation: Germ Identification - Plant Hygiene” (5th Edition - Stuttgart, New York: Thieme All substances described there can be used with antimicrobial action Suitable antimicrobial active substances are preferably selected from the groups of the alcohols, amines, aldehydes, antimicrobial acids or their salts, carboxylic esters, acid amides, phenols , Phenolderi ⁇ vate, diphenyls, diphenylalkanes, urea derivatives, oxygen, nitrogen acetals and formals, benzamidines, isothiazolines, phthalimide derivatives, pyridine derivatives, antimicrobial surface-active compounds, guanidines, antimicrobial amphoteric compounds, quinolines, 1, 2-dibromo-2,4 dicyan
  • the antimicrobial active ingredient may be selected from the group of the compounds mentioned below, where one or more of the compounds mentioned can be used: ethanol, n-propanol, i-propanol, 1,3-butanediol, phenoxyethanol, 1,2-propylene glycol, Glycerol, undecylenic acid, benzoic acid, salicylic acid, dihydracetic acid, o-phenylphenol, N-methylmorpholine-acetonitrile (MMA), 2-benzyl-4-chlorophenol, 2,2'-methylenebis (6-bromo-4 -chlorophenol), 4,4'-dichloro-2'-hydroxydiphenyl ether (dichlosan), 2,4,4'-trichloro-2'-hydroxydiphenyl ether (trichlosan), chlorhexidine, N- (4-chlorophenyl) -N- (3,4-dichlorophenyl) urea, N, N '- (1, 10-decanedi
  • halogenated xylene and cresol derivatives such as p-chloro-meta-cresol or p-chloro-meta-xylene, and natural antimicrobial agents of plant origin (eg from spices or herbs), of animal and microbial origin.
  • antimicrobial surface-active quaternary compounds a natural antimicrobial biological active substance of plant origin and / or a natural antimicrobial agent of animal origin, most preferably at least one natural antimicrobial agent of plant origin from the group comprising caffeine, theobromine and theophylline and essential oils such as eugenol, thymol and geraniol, and / or at least one natural antimicrobial agent of animal origin from the group, comprising enzymes such as protein from milk, lysozyme and lactoperoxidase, and / or at least one antimicrobial surface-active quaternary compound having an ammonium, sulfonium, phosphonium, iodonium or arsonium group, Peroxo compounds and chlorine compounds are used chlorine compounds. Also substances of microbial origin, so-called bacteriocins, can be used.
  • Quaternary ammonium compounds which are suitable antimicrobial agents are, for example, benzalkonium chloride (N-alkyl-N, N-dimethylbenzylammonium chloride, CAS No. 8001-54-5), benzalcon B (mp-dichlorobenzyldimethyl-C 1) alkyl ammonium chloride, CAS No.
  • benzoxonium chloride (benzyldodecyl bis (2-hydroxyethyl) ammonium chloride), cetrimonium bromide (N-hexadecyl-N, N-trimethylammonium bromide, CAS No 57-09-0), Benzetonium chloride (N, N-dimethyl-N- [2- [2- [p- (1,1,3,3-tetramethylbutyl) phenoxy] ethoxy] ethyl] benzylammonium chloride, CAS No. 121-54-0), dialkyldimethylammonium chlorides such as di-n-decyldimethylammonium chloride (CAS No.
  • QACs are the benzalkonium chlorides having C 8 - to C 18 -alkyl radicals, in particular C 12 - to C 12 -alkylbenzyldimethylammonium chloride.
  • Benzalkonium and / or substituted benzalkonium halides are, for example, there are suitable cially available as Barquat ® from Lonza, Marquat® ® from Mason, Variquat ® Witco / Sherex and Hyamine ® company Lonza and Bardac ® from Lonza.
  • antimicrobial agents are N- (3-chloroallyl) hexaminium chloride such as Dowicide ® and Dowi- cil ® from Dow, benzethonium chloride such as Hyamine ® 1622 Rohm & Haas, Methylben- zethoniumchlorid as Hyamine ® 1ox Rohm & Haas and cetylpyridinium chloride, such as cepal chloride from Merrell Labs.
  • N- (3-chloroallyl) hexaminium chloride such as Dowicide ® and Dowi- cil ® from Dow
  • benzethonium chloride such as Hyamine ® 1622 Rohm & Haas
  • Methylben- zethoniumchlorid such as Hyamine ® 1ox Rohm & Haas
  • cetylpyridinium chloride such as cepal chloride from Merrell Labs.
  • the antimicrobial agents are preferably used in agents according to the invention in amounts of from 0.0001% by weight to 1% by weight, preferably from 0.001% by weight to 0.8% by weight, particularly preferably from 0.005% by weight to 0.3 wt .-% and in particular from 0.01 to 0.2 wt .-% used.
  • an agent according to the invention contains those active ingredients which are beneficial to the fiber elasticity, shape retention and tear resistance of the textile fibers.
  • Exposing fibers to a medium or high deformation force for example by stretching the fiber by 80%, may result in untreated fibers in that, if the deformation force ceases, the fiber is not or only partially restored to its original shape returns. Under conversion The fiber can even rip.
  • the consumer desires, of course, textile fibers which do not break or lose their original shape even when exposed to medium or high deformation or stretching forces.
  • active substances are preferably aminosiloxanes, cellulose derivatives, in particular cellulose ethers and carboxylic acid esters.
  • Preferred carboxylic acid esters obey the general formula (7)
  • R 24 is -CO-O - (- CH 2 -CH 2 -O-) g -R 25 , where g is between 0, which is preferred, and 20, where R 25 is a monofunctional hydrocarbon radical of 6-20, preferably 8-18, carbon atoms, and wherein R 24 is a mono-functional hydrocarbon radical containing at least one hydroxy group and at least two carbon atoms, preferably selected from the following radicals:
  • Typical and preferred esters which obey this formula (7) include, but are not limited to, tridecyl salicylate (HO-C 6 H 4 -CO-O- (C 2 H 2 ) 12 -CH 3 ), di- ( C 12 -C 13) -alkylmalate, di- (C tartrate 12 -C 13) alkyl and / or di- (C 12 - C 13) alkyl lactates.
  • tridecyl salicylate HO-C 6 H 4 -CO-O- (C 2 H 2 ) 12 -CH 3
  • di- ( C 12 -C 13) -alkylmalate di- (C tartrate 12 -C 13) alkyl and / or di- (C 12 - C 13) alkyl lactates.
  • the particles according to the invention are at least partially surrounded by a coating, which preferably contains at least one at least partially water-soluble or at least partially water-dispersible component, which is chosen in particular from polyols, carbohydrates, starches, modified Starches, starch hydrolysates, cellulose and cellulose derivatives, natural and synthetic gums, silicates, borates, phosphates, chitin and chitosan, water-soluble polymers, fat components and mixtures thereof.
  • a coating which preferably contains at least one at least partially water-soluble or at least partially water-dispersible component, which is chosen in particular from polyols, carbohydrates, starches, modified Starches, starch hydrolysates, cellulose and cellulose derivatives, natural and synthetic gums, silicates, borates, phosphates, chitin and chitosan, water-soluble polymers, fat components and mixtures thereof.
  • a coating which preferably contains at least one at least partially water-soluble or at least partially water-dispersible component
  • the coating has polycarboxylates.
  • the coating of the particles can be carried out in the manners described in the prior art.
  • the coating material preferably completely encloses the respective particles, albeit a discontinuous coating may be desired.
  • Suitable coating materials are in particular those which are commonly used in connection with detergents and cleaners.
  • Materials which can be used as coating materials in the context of the invention are any inorganic and / or organic substances and / or mixtures of substances, preferably those which are pH, temperature and / or ionic strength-sensitive, so that they depend on a pH value. , Temperature and / or ionic strength change lose their integrity, ie for example, dissolve completely or partially.
  • Particularly preferred as coating materials are polymers and / or copolymers which have film-forming properties and can preferably be used from aqueous dispersion.
  • Organic solvents are for many reasons (flammability, toxicity, etc.) disadvantageous in the production of pH-sensitive coatings.
  • Aqueous dispersions are characterized by a simple handling and the avoidance of all toxicological problems.
  • the decisive factor for the film-forming properties is the glass transition temperature of the film-forming polymer and / or copolymer. Above the glass transition temperature, the polymer or copolymer is elastic, meltable and flowable, while becoming brittle below the glass transition temperature. Only above the glass transition temperature can the polymer be easily processed, as is necessary to form a film coating.
  • the glass transition temperature can be influenced by the addition of low molecular weight substances with softening properties, the so-called plasticizers.
  • plasticizers are all substances which reduce the glass transition temperature of the used, preferably pH-sensitive, polymers and / or copolymers. The polymer can thus be applied at lower temperatures, possibly even at room temperature.
  • plasticizers are citric acid esters (preferably tributyl citrate and / or triethyl citrate), phthalic acid esters (preferably dimethyl phthalate, diethyl phthalate and / or dibutyl phthalate), esters of organic polyalcohols (preferably glycerol triacetate), polyalcohols (preferably glycerol, propylene glycol) and / or polyoxyethylene glycols (preferably polyethylene glycol).
  • the plasticizer is interposed between the polymer chains, thereby increasing the mobility, reducing the interactions and avoiding abrasion and cracks in the film by reducing the brittleness
  • the coating material is a polyacrylate and / or a derivative thereof and / or a corresponding copolymer based on acrylic acid esters or acrylic acids and other monomers.
  • copolymers of acrylamide and acrylic acid and / or derivatives thereof are of advantage for the coating material according to the invention.
  • a further subject of the invention is a process for washing textiles, comprising the step of contacting the textiles with an aqueous medium which contains an effective amount of a washing and cleaning composition (detergent composition) according to the invention.
  • the oil number is a common measure for characterizing the oil absorption capacity of particles.
  • the determination of the oil numbers was carried out according to DIN ISO 787.
  • the slurrytemperatur before the nozzles was about 70 0 C, in the production of the particle B about 120 ° C.
  • the temperature at the inlet (inlet temperature) was about 210 ° C.
  • the gas consumption was about 150-160 m 3 / l.
  • Carboxymethylcellulose sodium salt 2.00% by weight
  • the resulting particles had the following parameters:
  • the resulting particles A had the following parameters: bulk density: 490 g / l oil number: 160 ml / 100 g dso: 0.28 mm
  • Carboxymethylcellulose sodium salt 2.00% by weight
  • the resulting particles B had the following parameters: bulk density: 500 g / l oil absorption: 160 ml / 100g as d: 0.32 mm
  • the particles A and B according to the invention thus had oil numbers which were almost ten percent higher than those of the comparison particles.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Medicinal Preparation (AREA)
  • Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
  • Developing Agents For Electrophotography (AREA)
  • Fats And Perfumes (AREA)
  • Glanulating (AREA)
EP05781858A 2004-10-15 2005-09-08 Particules absorbantes Not-in-force EP1802733B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102004050562A DE102004050562A1 (de) 2004-10-15 2004-10-15 Aufnahmefähige Partikel
PCT/EP2005/009650 WO2006042589A1 (fr) 2004-10-15 2005-09-08 Particules absorbantes

Publications (2)

Publication Number Publication Date
EP1802733A1 true EP1802733A1 (fr) 2007-07-04
EP1802733B1 EP1802733B1 (fr) 2009-01-14

Family

ID=35405811

Family Applications (1)

Application Number Title Priority Date Filing Date
EP05781858A Not-in-force EP1802733B1 (fr) 2004-10-15 2005-09-08 Particules absorbantes

Country Status (6)

Country Link
US (1) US20080293609A1 (fr)
EP (1) EP1802733B1 (fr)
JP (1) JP2008517076A (fr)
AT (1) ATE420942T1 (fr)
DE (2) DE102004050562A1 (fr)
WO (1) WO2006042589A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105143422A (zh) * 2013-04-26 2015-12-09 宝洁公司 具有水可溶胀组分的洗涤剂颗粒

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102006021553A1 (de) * 2006-02-08 2007-08-16 Henkel Kgaa Fluidspeicher
US8043645B2 (en) 2008-07-09 2011-10-25 Starbucks Corporation Method of making beverages with enhanced flavors and aromas
WO2023142099A1 (fr) * 2022-01-30 2023-08-03 The Procter & Gamble Company Procédé de fabrication de particules contenant du parfum

Family Cites Families (30)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3425948A (en) * 1966-01-03 1969-02-04 Wyandotte Chemicals Corp Composition and process for light-weight surfactant products
DE2011445B2 (de) * 1970-03-11 1972-02-17 Chemische Werke Albert, 6202 Wiesbaden-Biebrich Verfahren zur herstellung von natriumtripolyphosphat mit niedrigem schuettgewicht aus thermischer phosphorsaeure
ZA734721B (en) * 1972-07-14 1974-03-27 Procter & Gamble Detergent compositions
GB1455873A (en) * 1973-08-24 1976-11-17 Procter & Gamble Textile-softening detergent compositions
US4115307A (en) * 1974-12-13 1978-09-19 Erco Industries Limited Phosphate composition
US4264464A (en) * 1977-10-06 1981-04-28 Colgate-Palmolive Company High bulk density particulate heavy duty laundry detergent
US4232052A (en) * 1979-03-12 1980-11-04 National Starch And Chemical Corporation Process for powdering high fat foodstuffs
JPS5663818A (en) * 1979-10-31 1981-05-30 Kojiro Takei Manufacture of zeolite molded body
US4311606A (en) * 1980-03-10 1982-01-19 Colgate Palmolive Company Method for manufacture of non-gelling, stable inorganic salt crutcher slurries
CH650017A5 (en) * 1981-10-13 1985-06-28 Colgate Palmolive Co Method for delaying or preventing the formation of a gel in a suspension which can be processed in soap mixers
DE3413571A1 (de) * 1984-04-11 1985-10-24 Hoechst Ag, 6230 Frankfurt Verwendung von kristallinen schichtfoermigen natriumsilikaten zur wasserenthaertung und verfahren zur wasserenthaertung
GB8502032D0 (en) * 1985-01-28 1985-02-27 Unilever Plc Detergent powder
DE3526405A1 (de) * 1985-07-24 1987-02-05 Henkel Kgaa Schichtsilikate mit beschraenktem quellvermoegen, verfahren zu ihrer herstellung und ihre verwendung in wasch- und reinigungsmitteln
JPH068435B2 (ja) * 1987-06-25 1994-02-02 花王株式会社 漂白剤又は漂白剤含有洗浄剤
JPH01224230A (ja) * 1988-03-03 1989-09-07 Sanyo Shikiso Kk 酸化アンチモンを固溶した酸化錫の多孔質状粗粒子
EP0466235B1 (fr) * 1990-07-11 1997-02-05 Quest International B.V. Procédé de préparation de produits détergents parfumés
DE4400024A1 (de) * 1994-01-03 1995-07-06 Henkel Kgaa Silikatische Builder und ihre Verwendung in Wasch- und Reinigungsmitteln sowie Mehrstoffgemische für den Einsatz auf diesem Sachgebiet
GB9414576D0 (en) * 1994-07-19 1994-09-07 Unilever Plc Method for preparing cogranules by compaction
DE4426216A1 (de) * 1994-07-23 1996-01-25 Merck Patent Gmbh Benzyliden-Norcampher-Derivate
DE4426215A1 (de) * 1994-07-23 1996-01-25 Merck Patent Gmbh Ketotricyclo [5.2.1.0] decan-Derivate
DE19528059A1 (de) * 1995-07-31 1997-02-06 Bayer Ag Wasch- und Reinigungsmittel mit Iminodisuccinaten
IT1284078B1 (it) * 1996-06-27 1998-05-08 Condea Augusta Spa Materiale cristallino microporoso, procedimento per la preparazione e uso in composizioni detergenti
CA2310446A1 (fr) * 1997-11-21 1999-06-03 Bernard William Kluesener Compositions detergentes comprenant des activateurs polymeres de mousse, et leur utilisation
DE19855998B4 (de) * 1998-02-17 2006-07-13 H.C. Starck Gmbh Poröse Agglomerate und Verfahren zu deren Herstellung
EP1450941B1 (fr) * 2001-11-22 2007-01-31 Firmenich Sa Microcapsules parfumantes ou aromatisantes contenant un agent ignifugeant
JP4099640B2 (ja) * 2002-03-05 2008-06-11 信越化学工業株式会社 多孔質粒子及びその製造方法
DE10235942B4 (de) * 2002-08-06 2004-12-09 Henkel Kgaa Mittel und Vorrichtung sowie Verfahren zu seiner Herstellung für Wasch-, Reinigungs- oder Pflegemittel
DE60228702D1 (de) * 2002-08-07 2008-10-16 Procter & Gamble Waschmittelzusammensetzung
US7204988B2 (en) * 2003-06-11 2007-04-17 Ultra Biotech Limited Method to prepare compositions comprising yeast treated with electromagnetic energy
DE102004020400A1 (de) * 2004-04-23 2005-11-17 Henkel Kgaa Parfümierte Feststoffe

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2006042589A1 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105143422A (zh) * 2013-04-26 2015-12-09 宝洁公司 具有水可溶胀组分的洗涤剂颗粒
CN105143422B (zh) * 2013-04-26 2018-04-10 宝洁公司 具有水可溶胀组分的洗涤剂颗粒

Also Published As

Publication number Publication date
DE502005006491D1 (de) 2009-03-05
ATE420942T1 (de) 2009-01-15
JP2008517076A (ja) 2008-05-22
EP1802733B1 (fr) 2009-01-14
WO2006042589A1 (fr) 2006-04-27
DE102004050562A1 (de) 2006-05-04
US20080293609A1 (en) 2008-11-27

Similar Documents

Publication Publication Date Title
EP1280878B1 (fr) Utilisation de particules nanoscopiques pour faciliter l'enlevement des salissures
WO2006053615A1 (fr) Combinaison de parfum contenant du 3,7-dimethyloct-6-ene nitrile (citronellyle nitrile) comme substitut de geranonitrile
WO2007028477A1 (fr) Produits de consommation a profils olfactifs variables
WO2008003631A1 (fr) Agent de lavage, de nettoyage et d'entretien
DE102005043189A1 (de) Verbrauchsprodukte mit Duftvielfalt
WO2007054177A1 (fr) Produits de consommation odorants contenant un oxydant
WO2008128826A1 (fr) Particules contenant un matériau photocatalytique
EP2069471A1 (fr) Système de distribution de détergents ou de nettoyants
WO2005105972A1 (fr) Substances solides parfumees
DE102006040103A1 (de) Schmelzgranulate für Wasch- und Reinigungsmittel
DE102014222833A1 (de) Wasch- und Reinigungsmittel mit verbesserter Leistung
EP3497198A1 (fr) Produit de lavage et de nettoyage à efficacité améliorée
WO2005019400A1 (fr) Agents à prise sur la surface de substrats
EP1802733B1 (fr) Particules absorbantes
WO2008116768A1 (fr) Produit anti-acarien
WO2006010390A1 (fr) Particules exemptes de carbonate de sodium presentant des agents tensioactifs non ioniques et/ou des parfums, utilisables dans des agents nettoyants et detergents
DE10235942B4 (de) Mittel und Vorrichtung sowie Verfahren zu seiner Herstellung für Wasch-, Reinigungs- oder Pflegemittel
EP1438383B1 (fr) Procede pour la production des compositions detergentes
DE102008015110A1 (de) Sprühgetrocknete Wasch- oder Reinigungsmittelprodukte
DE102004019752A1 (de) Mittel mit metallisch riechendem Duftstoff geeignet zum Einsatz in Wasch-/Wäschepflege- und Raumbeduftungsmitteln
DE10008306A1 (de) Wasch- und Reinigungsmittel
DE102006031897A1 (de) Wasch-, Reinigungs- und Pflegemittel
EP3041920A1 (fr) Produits détergents d'efficacité améliorée
DE102004017112B4 (de) Verwendung von Pudermittel
DE102005063064A1 (de) Verbessertes Herstellungsverfahren für Wasch- oder Reinigungsmittel

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20070202

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

RIN1 Information on inventor provided before grant (corrected)

Inventor name: HAMMELSTEIN, STEFAN

Inventor name: HILSMANN, JUERGEN

Inventor name: HARTH, HUBERT

Inventor name: KRAUS, INGRID

Inventor name: LAHN, WOLFGANG

Inventor name: STURM, MARIO

Inventor name: BAUER, ANDREAS

Inventor name: ARTIGA GONZALEZ, RENE-ANDRES

17Q First examination report despatched

Effective date: 20070920

RIN1 Information on inventor provided before grant (corrected)

Inventor name: HAMMELSTEIN, STEFAN

Inventor name: KRAUS, INGRID

Inventor name: HARTH, HUBERT

Inventor name: LAHN, WOLFGANG

Inventor name: BAUER, ANDREAS

Inventor name: HILSMANN, JUERGEN

Inventor name: STURM, MARIO

Inventor name: ARTIGA GONZALEZ, RENE-ANDRES

DAX Request for extension of the european patent (deleted)
RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: HENKEL AG & CO. KGAA

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: GERMAN

REF Corresponds to:

Ref document number: 502005006491

Country of ref document: DE

Date of ref document: 20090305

Kind code of ref document: P

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090114

NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090114

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090114

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090425

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090114

REG Reference to a national code

Ref country code: IE

Ref legal event code: FD4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090114

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090514

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090414

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090114

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090615

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090114

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090114

Ref country code: IE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090114

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090114

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090114

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090114

26N No opposition filed

Effective date: 20091015

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090414

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20090903

Year of fee payment: 5

BERE Be: lapsed

Owner name: HENKEL A.G. & CO. KGAA

Effective date: 20090930

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090930

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20090908

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20100531

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090930

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090930

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090415

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090930

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090930

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090908

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090908

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090114

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090908

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090715

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 502005006491

Country of ref document: DE

Effective date: 20110401

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20110401

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090114

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090114