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
  • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
  • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
• • 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
  • C11D17/0047—Detergents in the form of bars or tablets
  • C11D17/0065—Solid detergents containing builders
  • C11D17/0073—Tablets
• • 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
  • C11D3/16—Organic compounds
  • C11D3/20—Organic compounds containing oxygen
  • C11D3/22—Carbohydrates or derivatives thereof
  • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin

Definitions

• the present invention is in the field of disintegration aids for compact Shaped bodies that have washing and cleaning-active properties.
• disintegrant granules for use in washing and cleaning active Shaped bodies such as detergent tablets, dishwasher tablets, Stain-proofing tablets or water softening tablets for household use, in particular for machine use.
• Detergent tablets are widely described in the prior art are becoming increasingly popular with consumers because of the simple dosage.
• Tableted detergents and cleaning agents have a number of powdered detergents Advantages: They are easier to dose and to use and because of their compact size Structure advantages in storage and transportation. Also in the patent literature detergent tablets are therefore comprehensively described.
• a problem, that occurs again and again when using washing and cleaning active moldings, is the too slow rate of disintegration and dissolution of the shaped bodies under conditions of use. Since sufficiently stable, i.e. shape and break resistant molded articles only can be produced by relatively high pressure, there is a strong Compression of the molded parts and resulting in delayed disintegration of the shaped body in the aqueous liquor and thus to a slow release the active substances in the washing or cleaning process.
• wick mechanism With the wick mechanism, water is sucked into the interior of the molded body through the disintegration accelerator and thereby loosens the binding forces between the particles, which also leads to the disintegration of the molded body.
• the repulsion mechanism also differs from this in that the particles released by the water sucked into the pores repel one another by the resulting electrical forces.
• a fundamentally different mechanism is the basis of the "effervescent tablets", which contain active substances or active substance systems which release gaseous substances on contact with water, which cause the shaped body to burst.
• hydrophilizing agents which ensure better wetting of the compressed particles in water and therefore faster disintegration, is known.
• the first group includes, for example, polyethylene glycol sorbitan fatty acid esters, the second Group systems of weak acids and carbonate-containing agents, especially lemon and / or Tartaric acid in combination with bicarbonate or carbonate. But also magnesium peroxide, which releases oxygen with water is used as a disintegrant.
• disintegrants By far the largest group of disintegrants works through swelling and / or wicking effects.
• These agents include, in particular, starches, cellulose and cellulose derivatives, Alginates, dextrans, cross-linked polyvinylpyrrolidones, gelatin, formaldehyde casein, however also typically inorganic substances such as a wide variety of clay minerals (e.g. Bentonite) as well as Aerosil® (silica) and certain ion exchange resins (Amberlit®).
• disintegrants used by drug manufacturing are known here.
• Swellable layered silicates are mentioned as disintegrants such as bentonites, natural substances and natural substance derivatives based on starch and cellulose, alginates and the like, potato starch, methyl cellulose and / or hydroxypropyl cellulose.
• This Disintegrants can be mixed with the granules to be pressed, but also into the to be pressed into granules.
• Disintegrants in detergent or cleaning agent tablets can be advantageous.
• microcrystalline cellulose, sugar such as sorbitol are used here as typical disintegrants also layered silicates, in particular finely divided and swellable layered silicates of the type of Called bentonites and smectites.
• substances contributing to gas formation such as citric acid, Bisulfate, bicarbonate, carbonate and percarbonate are potential disintegrants listed.
• EP-A-0 466 485, EP-A-0 522 766, EP-A-0 711 827, EP-A-0 711 828 and EP-A-0 716 144 describe the production of cleaning-active tablets described, whereby compacted, particulate material with a particle size between 180 and 2000 ⁇ m is used.
• the resulting tablets can be both homogeneous as well as having a heterogeneous structure.
• EP-A-0 522 766 at least the Particles containing surfactants and builders with a solution or dispersion of a binder / disintegrant, especially polyethylene glycol.
• binders / disintegrants are, in turn, those which have already been described and known several times Disintegrants, for example starches and starch derivatives, commercially available cellulose derivatives such as cross-linked and modified cellulose, microcrystalline cellulose fibers, cross-linked polyvinylpyrrolidones, layered silicates etc. Also weak acids such as citric acid or tartaric acid, which in connection with carbonate-containing sources in the Contact with water lead to effervescent effects and according to the Römpp definition the second class of explosives can be used as a coating material.
• a particular problem results from the use of cellulose as a disintegration aid in washing and cleaning active moldings. If the primary particle size is too large the cellulose gives rise to the problem of residue formation on the treated Textiles. In the case of dark textiles in particular, the deposits are comparatively large Cellulose primary particles, which are made in the wash liquor after the disintegration of the molded body the disintegrant compact can be clearly recognized after drying.
• cellulose powders with particle sizes above 150 ⁇ m are usually compacted into granules with a particle size between 0.4 and 2.0 mm and pressed in this form with the other constituents to form washable and cleaning-active moldings.
• the US Pat. No. 4,106,991 describes a granulation process for Production of enzyme granules, in which the wall deposits in the granulator are reduced in which the formation of large particles is caused by a slow growth rate is prevented and the moisture sensitivity of the powder to be granulated is reduced.
• the process uses cellulose fibers, binders, enzymes and Filler and a fluid granulating agent introduced into a granulating device. All Enzyme granules described in US 4,106,991 contain both titanium dioxide and also sodium chloride. Furthermore, the cellulose used also includes primary particle sizes above 100 ⁇ m.
• German Offenlegungsschrift DE-A-2 321 693 describes one for use with Tablet containing optical brighteners suitable for textile detergents and containing 1 up to 25% by weight of microcrystalline to fibrous cellulose.
• the tablets contain also potato starch, Mg or Ca soaps from fatty acids, mineral release agents and if necessary wetting agents.
• the tablets have a short disintegration time cold water.
• the strength properties of the tablets are determined by the cellulose improved so that they also meet the requirements of greater mechanical stress.
• the object of the invention was to provide an auxiliary granulate for to provide washing and cleaning active moldings, on the one hand the residue problem does not have, but on the other hand, in the form of granules in the mixtures to be compressed can be incorporated without losing its effective form.
• the task also existed the invention in a process for the preparation of such disintegrant granules for the To develop incorporation into detergent tablets.
• auxiliary granules Aids and in particular disintegrants understood, which are per se in finely divided powder form and by spray drying, granulating, agglomerating, compacting, pelletizing or Extrusion process were converted into a coarser form. This doesn't just count Disintegrants in granular form, but also, for example, those in co-granulated form.
• particle size and "primary particle size” are used in the context of the present Invention used as synonyms when used to describe cellulose in powder form serve.
• the granules obtained by granulating the cellulose powder have, of course Particle sizes that are larger than the primary particle size of the one used Cellulose powder.
• particle size or “primary particle size” means that the corresponding powders pass completely through a sieve of the specified mesh size and leave less than 1% by weight residue, based on the sieved powder, on the sieve.
• auxiliary granules of the present invention have a number of advantages that they stand out over conventional explosives. So there are backlog problems on laundry which has been washed with detergent tablets which are the inventive Aid granules contained, not to be observed. Also show quantitatively compared to otherwise analog detergent tablets that act as disintegrants Contain cellulose granules from cellulose of primary particle sizes above 150 ⁇ m, better reflectance values, higher degrees of whiteness and an improved "soft grip" of the Laundry.
• the cellulose which is contained as component a) in the auxiliary granules according to the invention, has the formal gross composition (C 6 H 10 O 5 ) n and, formally speaking, is a ⁇ -1,4-polyacetal of cellobiose, which in turn consists of two molecules Glucose is built up.
• Suitable celluloses consist of approximately 500 to 5000 glucose units and consequently have average molecular weights of 50,000 to 500,000.
• a particle size of the cellulose prior to granulation of less than 100 ⁇ m is essential to the invention, primary particle sizes below 70 ⁇ m or below 50 ⁇ m being preferred.
• Cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions can also be used as component a) in the context of the present invention.
• Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxy hydrogen atoms have been substituted.
• celluloses in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as cellulose derivatives.
• the group of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses.
• the cellulose derivatives mentioned are preferably not used alone as component a), but used in a mixture with cellulose.
• the content of these mixtures of cellulose derivatives is preferably below 50% by weight, particularly preferably below 20 % By weight, based on component a).
• Pure component a) is particularly preferred Cellulose used, which is free of cellulose derivatives.
• the auxiliary granules according to the invention contain microcrystalline cellulose and / or Ingredients of washing and cleaning agents in amounts between 5 and 90 wt .-%, based on the auxiliary granulate with the exception of those granules which contain 40% by weight of cellulose (50 ⁇ m Primary particle size), 10% by weight of granules of microcrystalline cellulose (FMC), 28.2% by weight of sodium hydrogen carbonate and 21.8% by weight of anhydrous citric acid. Amounts of these ingredients which are preferably used are in the range from 10 to 70% by weight, with amounts between 20 and 60% by weight and in particular between 30 and 50% by weight are again preferred.
• Microcrystalline cellulose can be used as the sole component b) or as a component of this component.
• This cellulose has primary particle sizes of approx. 5 ⁇ m and was compacted into granules with an average particle size of 200 ⁇ m. These compactates are stable, can be mixed with other substances without disintegrating into the primary particles and are suitable, in turn, with the finely divided cellulose ⁇ component a) ⁇ to form stable auxiliary granules which are stable when mixed with other substances. In this way, it is possible within the scope of the present invention to produce a completely cellulose-based auxiliary granulate which does not have the inherent problem of residues of conventional cellulose disintegrants.
• auxiliary granules disintegrate into the primary particles, as a result of which no cellulose particles with particle sizes greater than 100 ⁇ m remain in the wash liquor.
• ingredients of detergents and cleaning agents ⁇ sole component b) or constituent the same ⁇ can be the aid granules according to the invention
• Detergent and cleaning agent ingredients from the group of builders, bleaches and bleach activators, foam inhibitors and soil-release polymers, the use of Excipients that, in addition to their function of stabilizing the granules with the cellulose, still perform other tasks in the washing and cleaning process, is preferred.
• the ingredients of detergents and cleaning agents used in the invention Aid granules are included from the group of builders, bleaches and Bleach activators, the foam inhibitors and the soil-release polymers selected.
• Preferred components b) from this group are the bleaches and Bleach activators, with auxiliary granules being preferred as components b) 10 to 70, preferably 20 to 60 and in particular 30 to 50% by weight of a bleach or Bleach activator included.
• a preferred auxiliary granulate contains as a component or the sole ingredient of component b) the bleach activator tetraacetylethylenediamine (TAED).
• the auxiliary granules according to the invention preferably have no fines below 0.1 mm and preferably contain a total of only 0 to 5% by weight of particles with particle sizes less than 0.2 mm.
• Preferred granules consist of at least 90% by weight of particles with a size of at least 0.3 mm and at most 2.0 mm.
• components a) and b) are mixed, the cellulose due to the Residue problem must meet the particle size criteria mentioned, while the Component b) is not subject to any restrictions with regard to the particle size.
• the component b) also on particle size ranges less than 1 mm, in particular less than 500 ⁇ m and particularly preferably less than 200 ⁇ m ground.
• the granulation under compacting conditions can, according to all, the expert common procedures are carried out, the most diverse apparatus for Suitable for carrying out the method according to the invention.
• the granulation under compacting Conditions is within the scope of this application with expressions such as granulation, agglomeration, Compacting, extrusion and pelleting equate.
• Suitable as apparatus in which the process according to the invention can be carried out the most diverse types of mixers such as Eirich® mixers the R or RV series (trademark of Maschinenfabrik Gustav Eirich, Hardheim), the Fukae® FS-G mixer (trademark of Fukae Powtech, Kogyo Co., Japan), the Lödige® FM, KM and CB mixers (trademark of Lödige Maschinenbau GmbH, Paderborn) or die Drais® series T or K-T (trademark of Drais-Werke GmbH, Mannheim). More suitable Granulators are pellet presses which are preferred in preferred embodiments Ring die presses are used.
• roller compaction has proven to be particularly preferred in the case of which is the dry premix of components a) and b) by two in opposite directions Sinn rotating rollers compacted into a leaf-shaped cupped by the following Grinding and screening on granules with particle sizes below 2 mm is brought.
• component b) of detergents and cleaning agents The following is a brief description of the ingredients to be used as component b) of detergents and cleaning agents, the substances from the group of builders, the bleach and bleach activator, the foam inhibitors and the soil-release polymers are described one after the other.
• auxiliary granules As builders in the auxiliary granules according to the invention and in the process for Production of these auxiliary granules as the sole component or ingredient of the component b) can be included, in particular silicates, aluminum silicates (in particular Zeolites), carbonates, salts of organic di- and polycarboxylic acids and mixtures of these To name substances.
• silicates aluminum silicates (in particular Zeolites)
• Zeolites aluminum silicates
• carbonates salts of organic di- and polycarboxylic acids and mixtures of these To name substances.
• Suitable crystalline, layered sodium silicates have the general formula NaMSi x O 2x + 1 .H 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4.
• M sodium or hydrogen
• x is a number from 1.9 to 4
• y is a number from 0 to 20 and preferred values for x 2, 3 or 4.
• Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514.
• Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3.
• both ⁇ - and ⁇ -sodium disilicate Na 2 Si 2 O 5 .yH 2 O are preferred, wherein ⁇ -sodium disilicate can be obtained, for example, by the method described in international patent application WO-A-91/08171.
• the delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compaction / compression or by overdrying.
• the term “amorphous” is also understood to mean “X-ray amorphous”.
• silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle.
• it can very well lead to particularly good builder properties if the silicate particles provide washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred.
• Such so-called X-ray amorphous silicates which also have a delay in dissolution compared to conventional water glasses, are described, for example, in German patent application DE-A-44 00 024. Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.
• the finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P.
• zeolite P zeolite MAP® (commercial product from Crosfield) is particularly preferred.
• zeolite X and mixtures of A, X and / or P are also suitable.
• the zeolite can be used as a spray-dried powder or as an undried stabilized suspension which is still moist from its production.
• the zeolite in the event that the zeolite is used as a suspension, it can contain small additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C 12 -C 18 fatty alcohols with 2 to 5 ethylene oxide groups , C 12 -C 14 fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols.
• Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
• phosphates are also used as builder substances possible, provided that such use is not avoided for ecological reasons should be.
• the sodium salts of orthophosphates, pyrophosphates, are particularly suitable and especially the tripolyphosphates.
• Useful organic builders are, for example, those in the form of their sodium salts usable polycarboxylic acids, such as citric acid, adipic acid, succinic acid, glutaric acid, Tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such Use for ecological reasons is not objectionable, 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, sugar acids and mixtures of these.
• bleaching agents which serve as bleaching agents and supply H 2 O 2 in water
• sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
• Further bleaching agents which can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodecanedioic acid.
• bleach activators can be used as the sole component or as an ingredient of Component b) are incorporated.
• bleach activators compounds that are under Perhydrolysis conditions aliphatic peroxocarboxylic acids with preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or optionally substituted perbenzoic acid result, are used.
• Substances containing the O- and / or N-acyl groups are suitable mentioned number of carbon atoms and / or optionally substituted benzoyl groups.
• TAED tetraacety
• Bleaching catalysts can be incorporated into the moldings. Acting on these substances it is bleach-enhancing transition metal salts or transition metal complexes such as for example Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes. Also Mn, Fe, Co, Ru, Lack of revelation, Ti, V and Cu complexes with nitrogenous Tripod ligands as well as Co, Fe, Cu and Ru amine complexes are used as bleaching catalysts usable.
• Suitable foam inhibitors which can be a component of component b), or are used alone as component b), are, for example, soaps of natural or synthetic origin, which have a high proportion of C 18-24 fatty acids.
• Suitable non-surfactant foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica or bistearylethylene diamide. Mixtures of different foam inhibitors are also used with advantages, for example those made of silicones, paraffins or waxes.
• the foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance. Mixtures of paraffins and bistearylethylenediamides are particularly preferred.
• the agents can also be components as component b) or their constituent contain, which have a positive influence on the oil and fat washability from textiles (so-called soil repellents). This effect is particularly evident when a textile is dirty is already several times with a detergent according to the invention, the oil and contains fat-dissolving component, was washed.
• non-ionic cellulose ethers such as methyl cellulose and methylhydroxy-propyl cellulose with a proportion of methoxyl groups from 15 to 30 Wt .-% and of hydroxypropoxyl groups from 1 to 15 wt .-%, each based on the nonionic cellulose ether, and the polymers known from the prior art Phthalic acid and / or terephthalic acid or their derivatives, in particular polymers from ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionically modified derivatives of these.
• CMS carboxymethyl starch
• the invention sees the use of the invention Aid granules for washing and cleaning active moldings as disintegration accelerators in such detergent tablets, in particular detergent tablets, in front.
• the invention thus also relates to shaped articles which are active in washing and cleaning, in particular Detergent tablets, the 1 to 40, preferably 2.5 to 30 and in particular 5 to 20 wt .-% contain an auxiliary granulate according to the invention.
• These shaped articles are made by mixing the auxiliary granulate with the other constituents of the washing and cleaning agent and subsequent shaping pressing receive.
• the moldings can be made in a predetermined spatial shape and size become. Practically all sensibly manageable designs come in as the spatial form Consideration, for example the formation as a board, the rod or bar shape, cubes, Cuboids and corresponding spatial elements with flat side surfaces and in particular cylindrical ones Designs with circular or oval cross-section. This last embodiment captures the presentation form from the tablet to compact cylinder pieces with a ratio of height to diameter above 1.
• the portioned compacts can each be separate individual elements be formed, the predetermined dosage of detergents and / or cleaning agents equivalent. However, it is also possible to form compacts that have a plurality of such mass units connect in a compact, in particular by predetermined breaking points the easy separability of portioned smaller units is provided.
• For the Use of textile detergents in machines of the type common in Europe with horizontal arranged mechanics can form the portioned compacts as tablets, in cylindrical or cuboid shape may be appropriate, with a diameter / height ratio in the range from about 0.5: 2 to 2: 0.5 is preferred.
• Commercial hydraulic presses, eccentric presses or rotary presses are suitable devices, particularly for manufacturing such compacts.
• the spatial shape of another embodiment of the shaped body is in its dimensions Detergent dispenser of commercial household washing machines adapted so that the molded body can be dosed directly into the induction bowl without a dosing aid dissolves during the induction process. It goes without saying that the Detergent tablets easily possible via a dosing aid and within the scope of the present Invention preferred.
• Another preferred shaped body that can be produced has a plate-like or sheet-like shape Structure with alternating thick long and thin short segments, so that individual Segments of this "latch" at the predetermined breaking points, which are the short thin segments display, canceled and can be entered into the machine.
• This principle of the "bar-shaped" molded body detergent can also be used in other geometric shapes, For example, vertical triangles that are only along one side of their sides are interconnected, can be realized.
• the various components do not become one Tablet are pressed, but that shaped bodies are obtained which have several layers, thus have at least two layers. It is also possible that these different Layers have different dissolving speeds. This can be advantageous application properties of the moldings result. If, for example Components are contained in the moldings that have a mutually negative effect, so it is possible to integrate the one component in the more quickly soluble layer and incorporate the other component into a slower soluble layer so that the first Component has already reacted when the second goes into solution.
• the layer structure of the Shaped bodies can be made in a stack-like manner, with an inner dissolving process Layer (s) on the edges of the molded body already takes place when the outer layers are not yet fully resolved, but it can also completely wrap the inner Layer (s) can be reached through the layer (s) lying further out, which leads to prevents premature release of components of the inner layer (s).
• a shaped body consists of at least three layers, i.e. two outer and at least one inner layer, at least a peroxy bleach is contained in one of the inner layers, while in stack-shaped molded body, the two cover layers and the shell-shaped molded body however, the outermost layers are free of peroxy bleach.
• Peroxy bleach and any existing bleach activators and / or enzymes spatially separated from each other in a molded body.
• Such multilayered molded articles have the advantage that they not only have a dispensing chamber or a metering device, which is added to the wash liquor can be used; rather it is in such cases it is also possible to place the molded body in direct contact with the textiles Machine without fear of stains from bleach and the like would.
• the bodies to be coated can be coated, for example, with aqueous Solutions or emulsions are sprayed, or via the process of melt coating get a coating.
• the inventive Moldings contain all the usual components of washing and cleaning agents.
• Auxiliary granules according to the invention are used which determined as component b) Contain ingredients of detergents and cleaning agents, so the further addition these substances can be dispensed with in the production of the shaped body. But it can also be preferred be such constituents of detergents and cleaning agents both as a component b) to be incorporated into the auxiliary granules and also into the shaped body.
• Shaped bodies contain other ingredients that do not have the auxiliary granules be introduced into the molded body.
• washing and cleaning active substances which are incorporated into the moldings, in particular surfactants and enzymes call.
• anionic, nonionic, cationic and / or amphoteric surfactants are used.
• the total surfactant content of the moldings is 5 to 60% by weight, based on the Molded body weight, with surfactant contents above 15% by weight being preferred.
• Anionic surfactants used are, for example, those of the sulfonate and sulfate type.
• the surfactants of the sulfonate type are preferably C 9-13- alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from C 12-18 monoolefins with a terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.
• alkanesulfonates obtained from C 12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
• the esters of ⁇ -sulfofatty acids for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.
• Suitable anionic surfactants are sulfonated fatty acid glycerol esters.
• fatty acid glycerol esters the mono-, di- and triesters and their mixtures are to be understood as they are in the Manufactured by esterification of a monoglycerin with 1 to 3 moles of fatty acid or the transesterification of triglycerides with 0.3 to 2 mol of glycerol can be obtained.
• preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids with 6 up to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, Lauric acid, palmitic acid, stearic acid or behenic acid.
• alk (en) yl sulfates are the alkali and especially the sodium salts of the sulfuric acid half esters of C 12 -C 18 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned, which contain a synthetic, petrochemical-based straight-chain alkyl radical which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials.
• C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates as well as C 14 -C 15 alkyl sulfates are preferred from the point of view of washing technology.
• 2,3-Alkyl sulfates which are produced, for example, according to US Pat. Nos. 3,234,258 or 5,075,041 and can be obtained as commercial products from Shell Oil Company under the name DAN®, are also suitable anionic surfactants.
• the sulfuric acid monoesters of the straight-chain or branched C 7-21 alcohols ethoxylated with 1 to 6 mol of ethylene oxide such as 2-methyl-branched C 9-11 alcohols with an average of 3.5 mol of ethylene oxide (EO) or C 12-18 - Fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight.
• Suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols.
• alcohols preferably fatty alcohols and especially ethoxylated fatty alcohols.
• Preferred sulfosuccinates contain C 8-18 fatty alcohol residues or mixtures thereof.
• Particularly preferred sulfosuccinates contain a fatty alcohol residue, which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below).
• sulfosuccinates the fatty alcohol residues of which are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
• Soaps are particularly suitable as further anionic surfactants.
• Saturated ones are suitable 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 from natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.
• the anionic surfactants including the soaps can be in the form of their sodium, potassium or Ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine, available.
• the anionic surfactants are preferably in the form of their sodium or Potassium salts, especially in the form of the sodium salts.
• the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or can contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
• EO ethylene oxide
• alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred.
• the preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO or 4 EO, C 9-11 alcohol with 7 EO, C 13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C 12-14 alcohol with 3 EO and C 12-18 alcohol with 5 EO.
• the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
• Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
• fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
• alkyl glycosides of the general formula RO (G) x can also be used as further nonionic surfactants, in which R denotes a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, C atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
• the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.
• nonionic surfactants either as the sole nonionic surfactant or used in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters, preferably with 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 described in the international patent application Methods described in WO-A-90/13533.
• nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can be suitable.
• the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half of them.
• Suitable surfactants are polyhydroxy fatty acid amides of the formula (I), in which RCO stands for an aliphatic acyl radical with 6 to 22 carbon atoms, R 1 for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
• the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
• the group of polyhydroxy fatty acid amides also includes compounds of the formula (II) in which R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R 1 represents a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R 2 represents a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, C 1-4 -alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propylated Derivatives of this remainder.
• R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
• R 1 represents a linear, branched or cyclic alkyl radical or an aryl
• [Z] is preferably obtained by reductive amination of a reduced sugar, for example Glucose, fructose, maltose, lactose, galactose, mannose or xylose.
• a reduced sugar for example Glucose, fructose, maltose, lactose, galactose, mannose or xylose.
• the N-alkoxy or N-aryloxy-substituted compounds can then, for example, according to the Teaching of the international application WO-A-95/07331 by reaction with fatty acid methyl esters in the presence of an alkoxide as a catalyst in the desired polyhydroxy fatty acid amides be transferred.
• Enzymes come from the class of proteases, lipases, amylases, cellulases or their mixtures in question. From bacterial strains or fungi, such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus Agents. Proteases of the subtilisin type and in particular are preferred Proteases obtained from Bacillus lentus are used.
• enzyme mixtures for example from protease and amylase or protease and lipase or protease and Cellulase or from cellulase and lipase or from protease, amylase and lipase or protease, Lipase and cellulase, but especially cellulase-containing mixtures of particular Interest.
• Peroxidases or oxidases have also proven to be suitable in some cases.
• the enzymes can be adsorbed on carriers and / or embedded in coating substances to protect them against premature decomposition.
• the proportion of enzymes, enzyme mixtures or enzyme granules in the moldings according to the invention can, for example about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight.
• the moldings can, as optical brighteners, derivatives of diaminostilbenedisulfonic acid or their alkali metal salts. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or similarly constructed Compounds which, instead of the morpholino group, have a diethanolamino group, a methylamino group, carry an anilino group or a 2-methoxyethylamino group.
• Farther brighteners of the substituted diphenylstyryl type may be present, e.g.
• alkali salts 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) -diphenyls.
• Mixtures of the aforementioned brighteners can also be used.
• the invention can also take advantage of the fact that acidifying agents such as citric acid, Tartaric acid or succinic acid, but also acidic salts of inorganic acids ("hydrogen salts"), for example bisulfates, especially in combination with carbonate-containing systems can contribute to the improvement of the disintegration properties of the moldings.
• acidifying agents such as citric acid, Tartaric acid or succinic acid
• hydroogen salts for example bisulfates
• these acidifying agents also coarse-grained, in particular granular form, which have as little dust as possible and in the particle size distribution of those of the auxiliary granules are present.
• the granular acidifying agents can be used, for example, in amounts of 1 to 10 % By weight can be contained in the moldings.
• the moldings according to the invention in particular the previously poorly disintegrating and poorly soluble detergent tablets and bleach tablets have the Use of the auxiliary granulate according to the invention has excellent disintegration properties.
• By compacting the disintegration aid with a detergent ingredient a wider distribution of the auxiliary granules is achieved in the entire molded body.
• the improved disintegration can, for example, take place under critical conditions in a conventional manner Household washing machine (use directly in the washing liquor using a conventional dosing device, Delicates program or colored laundry, washing temperature maximum 40 ° C) or be tested in a beaker at a water temperature of 25 ° C. The implementation the corresponding tests are described in the example section.
• the shaped bodies according to the invention not only completely disintegrate within 10 minutes; the preferred embodiments have disintegration times in the beaker test of less less than 3 minutes, especially less than 2 minutes. Particularly advantageous embodiments even have disintegration times of less than 1 minute. Disintegration times of less than 3 minutes in the beaker test are sufficient to take the detergent tablets or the Washing additive molded body via the induction chamber of conventional household washing machines to be rinsed into the wash liquor.
• a washing process wherein the molded body via the induction device the household washing machine is introduced into the wash liquor.
• the release times of the shaped bodies in the washing machine is preferably less than 8 minutes and especially less than 5 minutes.
• the actual manufacture of the shaped bodies according to the invention is initially carried out by dry mixing of the auxiliary granules with the remaining constituents and subsequent Inform, in particular pressing into tablets, whereby conventional Methods (for example as in the conventional patent literature on tableting) all in the detergent or cleaning agent field, especially as in the above Patent applications and the article "Tabletttechnik: Stand dertechnik", S ⁇ FW-Journal, 122nd year, pp. 1016-1021 (1996)) can be used.
• the Aid granules 1, 2 and 3 according to the invention and comparative examples 4, 5 and 6 prepared, which had a composition according to Table 1.
• the comparative examples either contained an unsuitable component a) (too large Primary particle size, example 4), unsuitable components b) (example 6: additional Bubble system, which is not a common ingredient of detergents and cleaning agents) or no component b) (Example 5)
• the auxiliary granules produced in this way were mixed with other components to form a finished washing and cleaning agent, the base granules being a powder of the following composition: Base granules [% by weight] quantity C 9-13 alkyl benzene sulfonate 15.4 C 13-15 oxo alcohol with 3 to 7 EO 7.9 Soap 1.0 optical brightener 0.2 sodium 13.9 sodium silicate 4.3 Cobuilder H40 4.9 HEDP 0.6 Zeolite A (anhydrous active substance) 25.5 Na perborate monohydrate 18.3 water 8.0
• Cobuilder H 40 is an acrylic acid-maleic acid copolymer from Stockhausen HEDP is the sodium salt of hydroxyethane-1,1-diphosphonic acid
• the mixed detergents and cleaning agents were then in a tablet press pressed into tablets.
• the hardness of the tablets was increased by deforming the tablet measured for fracture, the force acting on the side surfaces of the tablet and the maximum force that the tablet withstood was determined.
• the tablet was placed in a beaker with water (600ml water, temperature 25 ° C) and the time taken for the tablet to completely disintegrate.
• composition of the tablets and the experimental data are shown in Table 3: Detergent tablets [composition in% by weight] tablet Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 aid 5% 4% 10% 4% 4% 8th% base granules 81.25% 82.25% 81.25% 82.25% 82.25% 78.25% enzyme 2.5% 2.5% 2.5% 2.5% 2.5% 2.5% 2.5% TAED 7% 7% 2% 7% 7% 7% foam inhibitor 3.5% 3.5% 3.5% 3.5% 3.5% 3.5% 3.5% 3.5% 3.5% soil release polymer 0.75% 0.75% 0.75% 0.75% 0.75% 0.75% 0.75% tablet hardness 33 N 20 N 30-35 N. 30-35 N. 25 N 25 N tablet disintegration 20 sec 58 sec 5-10 sec 5-10 sec > 5 min > 5 min
• Comparative example 4 shows comparable results both in the tablet hardness and in the disintegration test Values with Examples 1, 2 and 3 according to the invention.
• the following washing tests were carried out:
• the individual detergent tablets were assessed as follows: visual assessment of residue behavior tablet 1 2 3 4 5 6 dried towel 2 2 2 5 bleach dispenser 1 1 1 > 10 > 10 total 3 3 3 6 > 10 > 10
• the shaped bodies 1, 2 and 3 according to the invention show through the use of the finely divided Cellulose combined with very good tablet disintegration (see Table 3) the best residue values.
• the non-inventive example 4 which also has a good decay rate (see Table 3), cuts through the use of cellulose at 150 ⁇ m primary particle size significantly worse: The cellulose residues on the laundry are visually recognizable as annoying residues.

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• 1997
  • 1997-06-03 DE DE19723028A patent/DE19723028A1/de not_active Ceased
  • 1997-06-03 DE DE29724283U patent/DE29724283U1/de not_active Expired - Lifetime
• 1998
  • 1998-05-22 DE DE59811697T patent/DE59811697D1/de not_active Revoked
  • 1998-05-22 JP JP50141299A patent/JP2002502456A/ja active Pending
  • 1998-05-22 EP EP98928312A patent/EP1007616B1/de not_active Revoked
  • 1998-05-22 ES ES98928312T patent/ES2226143T3/es not_active Expired - Lifetime
  • 1998-05-22 SK SK1644-99A patent/SK164499A3/sk unknown
  • 1998-05-22 PL PL98337040A patent/PL337040A1/xx unknown
  • 1998-05-22 CN CN98805695.XA patent/CN1259163A/zh active Pending
  • 1998-05-22 AT AT98928312T patent/ATE271596T1/de not_active IP Right Cessation
  • 1998-05-22 HU HU0003067A patent/HUP0003067A2/hu unknown
  • 1998-05-22 WO PCT/EP1998/003042 patent/WO1998055575A1/de active IP Right Grant
• 1999
  • 1999-11-17 CA CA002290014A patent/CA2290014A1/en not_active Abandoned

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