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
  • C11D3/16—Organic compounds
  • C11D3/20—Organic compounds containing oxygen
  • C11D3/22—Carbohydrates or derivatives thereof
  • C11D3/221—Mono, di- or trisaccharides or derivatives thereof
• • 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
  • 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
  • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
  • C11D17/065—High-density particulate detergent 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
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/20—Organic compounds containing oxygen
  • C11D3/2075—Carboxylic acids-salts thereof
  • C11D3/2086—Hydroxy carboxylic acids-salts thereof

Definitions

• the present invention is in the field of compact molded articles that are washable have cleaning-active properties.
• Such detergent tablets include, for example, detergent tablets for washing textiles, Detergent tablets for automatic dishwashing or hard cleaning Surfaces, bleach tablets for use in washing machines or dishwashers, Water softening tablets or stain tablets.
• the invention relates Detergent tablets that are used to wash textiles in one Household washing machine used and briefly referred to as detergent tablets.
• 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 handle and because of their compact structure Advantages in storage and transport. Also in the patent literature detergent tablets are therefore comprehensively described.
• the delayed Disintegration of the moldings also has the disadvantage that they are customary Detergent tablets not over the induction chamber of household washing machines Let it wash in, as the tablets will not come in quickly enough Secondary particles disintegrate that are small enough to pass from the dispenser into the washing drum to be washed in.
• To provide moldings that are at a given Hardness is characterized by short disintegration times and thus also by the induction bowl Dosing household washing machines was a task of the present Invention.
• Japanese patent application JP 07/286199 describes, in the form of its Derwent abstract, a process for producing detergent tablets by mixing an anionic surfactant with a nonionic surfactant in the presence of at least 10% by weight of water and other detergent ingredients, to give surfactant granules , and pressing these surfactant granules with granular solubilizers with a solubility of at least 20g / 100ml (0 ° C).
• Preferred solubilizers are potassium carbonate, ammonium sulfate, ammonium chloride, sodium benzoate, Na benzenesulfonate, p-toluenesulfonic acid Na, Na xylene sulfonate, NaCl, citric acid, D-glucose, urea and sucrose.
• the solubilizers should be in granular form. None is said in this document about improving the disintegration time of detergent tablets of high hardness or about the ability of the shaped articles to be rinsed into the rinsing chambers of household washing machines.
• European patent application EP 971 023 (Procter & Gamble) claims surfactants Granules containing acetate, especially sodium acetate. This is supposed to the granules become more soluble and detergent tablets into which they are incorporated to give improved solubility.
• acetates have the disadvantage that they are low when touching the molded body with bare hands Release noticeable amounts of acetic acid, which the consumer calls "vinegar smell" is perceived as distracting.
• the fragrance note is used in the tablets Perfume oils are regularly affected by acetate.
• German patent application DE 198 51 441.7 (Henkel KGaA) describes detergent tablets which are notable for their high hardness and short disintegration time. These can be produced if they contain fine-particle sugars, with at least 50% by weight of the sugar particles having particle sizes below 400 ⁇ m. For this purpose, the sugars in the particle size range mentioned are mixed with other components and pressed into detergent tablets.
• sugars are those to be pressed Mixture added as an additive in pure form or detergent tablets not described with their specific problems. None of the above Writings deals with detergent tablets which are sugar and / or contain sugar acids and / or salts of sugar acids in the form of granules, which mainly contains other ingredients. The use of sugar and / or Sugar acids and / or salts of sugar acids in detergent tablets to improve the disintegration times and to enable dosing via the Detergent dispenser of household washing machines is not described in any document or suggested.
• detergent tablets with the aforementioned Have advantages if they contain surfactant granules, which in turn Contain sugar and / or sugar acids and / or salts of sugar acids.
• the invention therefore relates to detergent tablets made of compressed, particulate detergents and cleaning agents containing a surfactant granulate, which contains sugar and / or sugar acids and / or salts of sugar acids.
• sugar in the context of the present invention denotes simple and Multiple sugar, i.e. monosaccharides and oligosaccharides, in which 2 to 6 monosaccharides are linked together like acetals. "Sugar” are within the scope of the present Invention thus monosaccharides, disaccharides, trisaccharides, tetra-, penta- and hexasaccharides.
• Monosaccharides are linear polyhydroxy aldehydes (aldoses) or polyhydroxy ketones (Ketoses). They usually have a chain length of five (pentoses) or six (Hexoses) carbon atoms. Monosaccharides with more (heptoses, octoses etc.) or fewer (tetroses) carbon atoms are relatively rare. Some monosaccharides have a large number of asymmetric carbon atoms. For a hexose with four asymmetric carbon atoms this results in a number of 24 stereoisomers. The orientation of the OH group at the highest numbered asymmetr. C atom in the Fischer projection divides the monosaccharides in D and. L-configured rows.
• Monosaccharides which can be used as sugar in the context of the present invention are, for example the tetroses D (-) - erythrose and D (-) - threose and D (-) - erythrulose, the Pentoses D (-) - ribose, D (-) - ribulose, D (-) - arabinose, D (+) - xylose, D (-) - xylulose as well D (-) - Lyxose and the Hexoses D (+) - Allose, D (+) - Altrose, D (+) - Glucose, D (+) - Mannose, D (-) - Gulose, D (-) - Idose, D (+) - Galactose, D (+) - Talose, D (+) - Psicose, D (-) - Fructose, D (+) - Sorbose and D (-)
• D-glucose D-galactose
• D-mannose D-fructose
• L-arabinose D-xylose
• D-ribose u 2-deoxy-D-ribose.
• Disaccharides are made up of two simple monosaccharide molecules linked by glycosidic bonds (D-glucose, D-fructose, etc.). Is the glycosidic bond between the acetal carbon atoms (1 for aldoses or 2 for ketoses) both monosaccharides, so that the ring shape is fixed in both; that show sugar no mutarotation, do not react with ketone reagents and no longer have a reducing effect (Fehling-negative: trehalose or sucrose type).
• the main disaccharides are sucrose (cane sugar, sucrose), trehalose, lactose (Milk sugar), lactulose, maltose (malt sugar), cellobiose (cellulose breakdown product), Gentobiose, Melibiosis, Turanose and others.
• Trisaccharides are carbohydrates that consist of 3 glycosidically linked monosaccharides are constructed and for which one occasionally also has the incorrect name Trios meets. Trisaccharides are relatively rare in nature, examples are gentianose, Kestose, maltotriose, melecitose, raffinose, and as an example of aminosugar containing trisaccharides streptomycin and validamycin.
• Tetrasaccharides are oligosaccharides with 4 monosaccharide units. Examples of this Compound classes are stachyose, lychnose (galactose-glucose-fructose-galactose) and Secalose (from 4-fructose units).
• Detergent tablets contain glucose and / or sucrose.
• the detergent tablets according to the invention contain the or the Sugar preferably in amounts from 0.1 to 10% by weight, preferably from 0.25 to 5% by weight and in particular from 0.5 to 2.5% by weight, in each case based on the weight of the shaped body.
• the amount of sugar that is contained in the moldings can be about Amount of sugar in the surfactant granules or with a given sugar content in the granules can be controlled via the amount of surfactant granules.
• Sugar acids which can be contained in the surfactant granules within the scope of the present invention are polyhydroxycarboxylic acids which tend to form lactones and which are formed by oxidation of the aldehyde and / or the primary alcohol groups from simple sugars (monosaccharides) to carboxy groups. Mild oxide. the sugar leads to the formation of aldonic acids when the aldehyde to the carboxy group is oxidized. However, if the primary alcohol group is oxidized to the carboxy group, uronic acids are obtained.
• the pentonic acids D (-) - erythronic acid and D (-) - threonic acid and D (-) - erythrulonic acid
• the pentonic acids D (-) - ribonic acid, D (-) - ribulonic acid, D (-) - arabinonic acid, D (+) - xylonic acid, D (-) - xylulonic acid and D (-) - lyxonic acid and the hexonic acids D (+) - allonic acid, D (+) - altronic acid, D (+) - gluconic acid, D (+) - mannonic acid, D (-) - Gulonic acid, D (-) - Idonic acid, D (+) - Galactonic acid, D (+) - Talonic acid, D (+) - Psiconic acid, D (-) - Fructonic acid, D (+) - Sorbonic acid and D (-) - Tagatonic
• the particularly preferred aldonic acids D-gluconic acid, D-galactonic acid, D-mannonic acid, D-fructonic acid, L-arabinonic acid, D-xylonic acid, D-ribonic acid and the like. 2-deoxy-D-ribonic acid.
• uronic acids are in particular D (-) - erythruronic acid and D (-) - threuronic acid as well D (-) - erythruluronic acid, the penturonic acids D (-) - riburonic acid, D (-) - ribuluronic acid, D (-) - arabinuronic acid, D (+) - xyluronic acid, D (-) - xyluluronic acid and D (-) - lyxuronic acid and the hexuronic acids D (+) - alluronic acid, D (+) - altruronic acid, D (+) - glucuronic acid, D (+) - mannuronic acid, D (-) - guluronic acid, D (-) - iduronic acid, D (+) - galacturonic acid, D (+) - taluronic acid, D (+) - psicuronic acid, D (-) - fructuronic acid,
• the particularly preferred uronic acids D-glucuronic acid, D-galacturonic acid, D-mannuronic acid, D-fructuronic acid, L-arabinuronic acid, D-xyluronic acid, D-Riburonic acid u. 2-deoxy-D-riburonic acid.
• ketoaldonic acids which can also be used in the context of the present invention are formed formally by oxidation of a primary OH group of ketoses. Get technical they are obtained by oxidation of a secondary OH group of aldonic acids.
• aldar acids for example threaric acid or erythraric acid (known as tartaric acid), galactaric acid (mucic acid), glucaric acid (a tetrahydroxyadipic acid).
• threaric acid or erythraric acid known as tartaric acid
• galactaric acid mucic acid
• glucaric acid a tetrahydroxyadipic acid
• aldar acids are sugar acids general formula HOOC- (CHOH) n-COOH, especially L-threaric acid [(+) Tartaric acid], erythraric acid [meso-tartaric acid].
• the salts of the preferred acids are also preferred.
• the alkaline earth and alkali metal salts are of the greatest importance; among the latter, the sodium salts are particularly preferred.
• the surfactant granules contain sugar and / or sugar acids and / or salts of sugar acids in amounts of 0.1 to 20 % By weight, preferably from 0.5 to 15% by weight, particularly preferably from 1 to 10% by weight and in particular from 1.5 to 5% by weight, in each case based on the weight of the surfactant granules.
• the surfactant granules naturally contain sugar acids and / or salts of sugar acids Surfactants. These can be from the groups of anionic, nonionic, cationic or amphoteric surfactants, which of course also include mixtures of the above Types of surfactants can be used. Regardless of the type of surfactant used have the surfactant granules in preferred detergent tablets Surfactant contents from 5 to 60% by weight, preferably from 10 to 50% by weight and in particular from 15 to 40% by weight, based in each case on the weight of the surfactant granules.
• Anionic surfactants used are, for example, those of the sulfonate and sulfate type.
• Preferred surfactants of the sulfonate type are 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 an end 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 the production by esterification of a monoglycerin with 1 to 3 moles of fatty acid or obtained in the transesterification of triglycerides with 0.3 to 2 mol of glycerol.
• Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids with 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, Myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
• Alk (en) yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid half esters of C 12 -C 18 fatty alcohols, for example from coconut oil 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, straight-chain alkyl radical prepared on a petrochemical basis and 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 the 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 in particular ethoxylated fatty alcohols.
• alcohols preferably fatty alcohols and in particular ethoxylated fatty alcohols.
• Preferred sulfosuccinates contain C 8-18 fatty alcohol residues or mixtures 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).
• 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 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.
• the anionic surfactants are preferably in the form of their Sodium or potassium salts, especially in the form of the sodium salts.
• detergent tablets are shaped preferred, in which the content of the surfactant granules of anionic surfactants 5 to 45 % By weight, preferably 10 to 40% by weight and in particular 15 to 35% by weight, in each case based on the weight of the surfactant granules.
• preferred surfactant granules have one Content of soap on the 0.2 wt .-%, based on the total weight of the washing and Detergent tablets, exceeds.
• Anionic surfactants to be used with preference the alkylbenzenesulfonates and fatty alcohol sulfates, preferred detergent tablets 2 to 20% by weight, preferably 2.5 to 15% by weight and in particular 5 to 10 wt .-% fatty alcohol sulfate (s), each based on the weight of the Detergent tablets are included.
• 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 may 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 C12-18 alcohol containing 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.
• nonionic surfactants either as the sole nonionic surfactant or in combination with other nonionic surfactants are used are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated Fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl esters.
• alkyl polyglycosides Another class of nonionic surfactants that can be used advantageously are the alkyl polyglycosides (APG).
• Alkyl polyglycosides which can be used satisfy the general formula RO (G) z , in which R denotes a linear or branched, in particular methyl-branched, saturated or unsaturated, aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms and G is the Is symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
• the degree of glycosidation z is between 1.0 and 4.0, preferably between 1.0 and 2.0 and in particular between 1.1 and 1.4.
• Linear alkyl polyglucosides, ie alkyl polyglycosides, in which the polyglycosyl radical is a glucose radical and the alkyl radical is an n-alkyl radical are preferably used.
• the surfactant granules can preferably contain alkyl polyglycosides, with levels of APG over 0.2 wt .-%, based on the entire molded body, are preferred.
• Especially preferred detergent tablets contain APG in amounts of 0.2 to 10% by weight, preferably 0.2 to 5% by weight and in particular 0.5 to 3% by weight.
• 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 ethoxylated fatty alcohols, especially not more than half of it.
• 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 propoxylated Derivatives of this rest.
• 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 by reaction with fatty acid methyl esters in the presence of an alkoxide as a catalyst be converted into the desired polyhydroxy fatty acid amides.
• detergent tablets are preferred in which the Nonionic surfactant content of the surfactant granules 1 to 15% by weight, preferably 2.5 up to 10 wt .-% and in particular 5 to 7.5 wt .-%, each based on the weight of the Granules of surfactant.
• the surfactant granules contain further ingredients of detergents and cleaning agents.
• the So surfactant granules contain builders.
• Other ingredients of washing and Cleaning agents, especially so-called small components such as optical brighteners, Polymers, defoamers, phosphonates, colors and fragrances can be part of the Be surfactant granules.
• the surfactant granules can vary in the laundry detergent and cleaning product tablets Amounts are used.
• Detergent tablets according to the invention the the surfactant granules, which sugar and / or sugar acids and / or salts of sugar acids contains, in amounts of 40 to 95% by weight, preferably 45 to 85% by weight and in particular from 55 to 75% by weight, in each case based on the molding weight, included are preferred.
• Another object of the present invention is a method for producing the Detergent tablets described with advantageous properties, So a process for the production of detergent tablets by Mixing granules containing surfactants with finely divided processing components and subsequent shaping pressing in a manner known per se, in which the surfactant-containing Granules containing sugar and / or sugar acids and / or salts of sugar acids.
• sugar and / or sugar acids are also in the process according to the invention and / or salts of sugar acids in the surfactant granulate advantageously in the range of 0.1 up to 20% by weight, preferably from 0.5 to 15% by weight, particularly preferably from 1 to 10 % By weight and in particular from 1.5 to 5% by weight, in each case based on the weight of the Granular surfactant.
• the surfactant-containing granules are not spray dried, but by a granulation process will be produced.
• a granulation process carried out in a wide variety of mixing granulators and mixing agglomerators press agglomeration processes can also be used, for example. Method, in which the surfactant-containing granules by granulation, agglomeration, press agglomeration or a combination of these methods is therefore preferred.
• the can according to the invention Constituent from the group of sugars and / or sugar acids contained in the granules and / or salts of sugar acids are part of the solid bed, which with the addition is granulated by granulation aids. But it is also possible to find a solution Sugars and / or sugar acids and / or salts of sugar acids in water or in others to use liquids, for example nonionic surfactants, as granulation aids. Of course, it is also possible to use the substances mentioned both as part of the Provide solid bed as well as part of the granulating liquid. It is further possible to granulate a liquid or viscous mass by adding solids. Even with this "reverse" granulation, sugar and / or sugar acids can and / or salts of sugar acids both in the mass to be granulated and in the added solids may be included.
• the granulation can be found in a wide variety of industries in the detergent and cleaning agent industries usually used apparatus can be carried out. For example, it is possible to use the rounders commonly used in pharmacy. In such turntable devices the residence time of the granules is usually less than 20 seconds.
• Conventional mixers and mixing granulators are also suitable for granulation. As Mixers can be both high-intensity mixers ("high-shear mixers") and normal ones Mixers with lower circulation speeds can be used.
• Suitable mixers are, for example, Eirich® mixers of the R or RV series (trademark of the machine factory Gustav Eirich, Hardheim), the Schugi® Flexomix, 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 the Drais® series T or K-T (trademark of Drais-Werke GmbH, Mannheim).
• the dwell times the granules in the mixers are in the range of less than 60 seconds, the Dwell time also depends on the speed of rotation of the mixer. Shorten this the faster the mixer runs, the dwell times accordingly.
• Residence times of the granules in the mixer / rounder are less than one minute, preferably less than 15 seconds.
• dwell times of up to 20 minutes, with dwell times of less than 10 minutes due to the Process economics are preferred.
• Preferred granulation processes for the production of surfactant-containing granules are in mixer granulators performed where some mixer parts or the entire mixer are heated to temperatures that are at least 20 ° C above the temperature that have the substances to be granulated at the beginning of the granulation process. So will Granulated solids that were stored at 20 ° C and at this temperature in the mixer arrive, it is preferred that some or all mixer parts at least one Have a temperature of 40 ° C. Overall, however, a temperature of 120 ° C for the Mixer parts or the entire mixer must not be exceeded. Are only parts of the Mixer heated to the temperatures mentioned, these are preferably the mixer walls or the mixer tools. The former can be heated by a jacket, the latter can be brought to the desired temperature by built-in heating elements.
• non-aqueous granulation aids in particular nonionic surfactants with a melting point in the range of 20 to 50 ° C exhibit.
• the bulk density can be determined by the described preferred granulation process of the surfactant granules, increasing undesirable wall caking on the mixer walls can be significantly reduced.
• the use of such manufactured Surfactant granules in tablettable premixes lead to detergent tablets, which is different from mixtures that are conventionally made Contain granules, characterized by a further reduced disintegration time.
• the surfactant-containing granules are under pressure and compressed under the influence of shear forces and homogenized and then discharged form-giving from the apparatus.
• the most technically significant press agglomeration processes are extrusion, roller compaction, pelleting and tableting.
• Press agglomerating processes containing surfactant-containing granules are extrusion Roll compacting and pelleting.
• the surfactant-containing granules preferably continuously a planetary roller extruder or a 2-shaft extruder or 2-screw extruder with co-rotating or counter-rotating screw guidance fed, its housing and its extruder pelletizing head to the predetermined Extrusion temperature can be heated.
• the premix is under pressure, preferably at least 25 bar with extremely high throughputs, depending on the apparatus used can also lie below, compressed, plasticized, in the form of fine strands through the perforated nozzle plate extruded in the extruder head and finally the extrudate using a rotating Knife knife preferably to approximately spherical to cylindrical granules downsized.
• the hole diameter of the perforated nozzle plate and the strand cut length are matched to the selected granule size.
• this embodiment succeeds in the production of granules of an essentially uniformly predictable Particle size, the absolute particle sizes being the intended one Purpose can be adapted.
• Important embodiments can be seen here the production of uniform granules in the millimeter range, for example in the range from 0.8 to 5 mm and in particular in the range from about 1.0 to 3 mm.
• the length / diameter ratio the chipped primary granules lie in one important embodiment in the range of about 1: 1 to about 3: 1.
• the still plastic primary granulate in a further shaping processing step feed edges present on the crude extrudate are rounded off so that ultimately spherical to approximately spherical extrudate grains can be obtained.
• extrusions / pressings can also be carried out in low-pressure extruders, in the Kahl press or be carried out in the extruder.
• the manufacturing process carried out for the surfactant-containing granules by means of a roller compaction is targeted between two smooth or with depressions rollers of a defined shape are metered in and between the two rollers rolled out under pressure to form a leaf-shaped compact, the so-called Schülpe.
• the rollers exert a high line pressure on the premix and can vary depending on Required to be additionally heated or cooled.
• Preserves when using smooth rollers one has smooth, unstructured cuff bands while using structured Rolls correspondingly structured slugs or individual pellets can be produced can, in which, for example, certain shapes of the later granules or moldings can be specified.
• the cuff band is subsequently knocked off and crushing process broken into smaller pieces and can be done this way processed into granules by further known surface treatment methods further remunerated, especially in an approximately spherical shape can be brought.
• the preparation of the surfactant-containing granules is carried out by means of pelleting.
• the granules containing surfactant are applied to a perforated surface and pressed through the holes by means of a pressure-generating body.
• the surfactant-containing granulate is compressed under pressure, plasticized, pressed through a perforated surface by means of a rotating roller in the form of fine strands and finally comminuted into granules using a knock-off device.
• the most varied configurations of the pressure roller and perforated die are conceivable here.
• the press rolls can also be conical in the plate devices, in the ring-shaped devices dies and press roll (s) can have the same or opposite direction of rotation.
• An apparatus suitable for carrying out the method according to the invention is described, for example, in German laid-open specification DE 38 16 842 (Schlüter GmbH).
• the ring die press disclosed in this document consists of a rotating ring die interspersed with press channels and at least one press roller which is operatively connected to its inner surface and which presses the material supplied to the die space through the press channels into a material discharge.
• the ring die and the press roller can be driven in the same direction, which means that a reduced shear stress and thus a lower temperature increase in the premix can be achieved.
• the surfactant granules containing sugar and / or sugar acids and / or salts of sugar acids then becomes a premix with further processing components mixed, which can then be pressed into detergent tablets.
• the premix to be pressed can be used as preparation components in addition to ingredients already mentioned further ingredients common in detergents and cleaning agents, especially from the group of builders, disintegration aids, bleaches, Bleach activators, enzymes, pH regulators, fragrances, perfume carriers, fluorescent agents, Dyes, foam inhibitors, silicone oils, anti-redeposition agents, optical brighteners, Graying inhibitors, color transfer inhibitors and corrosion inhibitors contain.
• the substances mentioned can also be part or all of them of the surfactant granules.
• builders are the most important ingredients of Detergents and cleaning agents.
• Builders may be included, in particular thus zeolites, silicates, carbonates, organic Cobuilder and - where there are no ecological prejudices against their use - also that Phosphates.
• 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, compacting / 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 deliver 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 amount of zeolite introduced by the surfactant granules P and / or X-type additional zeolite are incorporated into the premix, by adding zeolite as a treatment component.
• the fine crystalline Zeolite containing synthetic and bound water is preferably a zeolite of type A, P, X or Y.
• 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 if such use is not avoided for ecological reasons should be.
• alkali metal phosphates with particular preference for pentasodium or pentapotassium triphosphate (Sodium or potassium tripolyphosphate) in the detergent and cleaning agent industry the greatest importance.
• Alkali metal phosphates is the general term for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which one can distinguish between metaphosphoric acids (HPO 3 ) n and orthophosphoric acid H 3 PO 4 in addition to higher molecular weight representatives.
• the phosphates combine several advantages: They act as alkali carriers, prevent lime deposits on machine parts or lime incrustations in tissues and also contribute to cleaning performance.
• Sodium dihydrogen phosphate, NaH 2 PO 4 exists as a dihydrate (density 1.91 gcm -3 , melting point 60 °) and as a monohydrate (density 2.04 gcm -3 ). Both salts are white, water-soluble powders, which lose water of crystallization when heated and at 200 ° C into the weakly acidic diphosphate (disodium 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 occurs 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 biphosphate, KDP), KH 2 PO 4 , is a white salt with a density of 2.33 gcm -3 , has a melting point of 253 ° [decomposition to form potassium polyphosphate (KPO 3 ) x ] and is light soluble in water.
• Disodium hydrogen phosphate (secondary sodium phosphate), Na 2 HPO 4 , is a colorless, very easily water-soluble crystalline salt. It exists anhydrous and with 2 mol. (Density 2.066 gcm -3 , water loss at 95 °), 7 mol. (Density 1.68 gcm -3 , melting point 48 ° with loss of 5 H 2 O) and 12 mol. Water ( Density 1.52 gcm -3 , melting point 35 ° with loss of 5 H 2 O), becomes anhydrous at 100 ° and changes to the diphosphate Na 4 P 2 O 7 when heated to a greater extent. Disodium hydrogen phosphate is prepared by neutralizing phosphoric acid with soda solution using phenolphthalein as an indicator. Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K 2 HPO 4 , is an amorphous, white salt that is easily soluble in water.
• Trisodium phosphate, tertiary sodium phosphate, Na 3 PO 4 are colorless crystals which, as dodecahydrate, have a density of 1.62 gcm -3 and a melting point of 73-76 ° C (decomposition), as decahydrate (corresponding to 19-20% P 2 O 5 ) have a melting point of 100 ° C and in anhydrous form (corresponding to 39-40% P 2 O 5 ) have a density of 2.536 gcm -3 .
• Trisodium phosphate is readily soluble in water with an alkaline reaction and is produced by evaporating a solution of exactly 1 mol of disodium phosphate and 1 mol of NaOH.
• Tripotassium phosphate (tertiary or triphase potassium phosphate), K 3 PO 4 , is a white, deliquescent, granular powder with a density of 2.56 gcm -3 , has a melting point of 1340 ° and is easily soluble in water with an alkaline reaction. It arises, for example, when heating Thomas slag with coal and potassium sulfate. Despite the higher price, the more easily soluble, therefore highly effective, potassium phosphates are often preferred over corresponding sodium compounds in the cleaning agent industry.
• Tetrasodium diphosphate (sodium pyrophosphate), Na 4 P 2 O 7 , exists in anhydrous form (density 2.534 gcm -3 , melting point 988 °, also given 880 °) and as decahydrate (density 1.815-1.836 gcm -3 , melting point 94 ° with loss of water) .
• Substances are colorless crystals that are soluble in water with an alkaline reaction.
• Na 4 P 2 O 7 is formed by heating disodium phosphate to> 200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dewatering the solution by spraying.
• the decahydrate complexes heavy metal salts and hardness formers and therefore reduces the hardness of the water.
• Potassium diphosphate potassium pyrophosphate
• K 4 P 2 O 7 exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 gcm -3 , which is soluble in water, the pH value being 1% Solution at 25 ° is 10.4.
• Sodium and potassium phosphates in which one can differentiate cyclic representatives, the sodium or potassium metaphosphates and chain-like types, the sodium or potassium polyphosphates. A large number of terms are used in particular for the latter: melt or glow phosphates, Graham's salt, Kurrol's and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.
• pentasodium triphosphate Na 5 P 3 O 10 (sodium tripolyphosphate)
• sodium tripolyphosphate sodium tripolyphosphate
• n 3
• Approx. 17 g of the salt free from water of crystallization dissolve in 100 g of water at room temperature, approx. 20 g at 60 ° and around 32 g at 100 °; After heating the solution at 100 ° for two hours, hydrolysis produces about 8% orthophosphate and 15% diphosphate.
• pentasodium triphosphate In the production of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dewatered by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentapotassium triphosphate, K 5 P 3 O 10 (potassium tripolyphosphate), is commercially available, for example, in the form of a 50% strength by weight solution (> 23% P 2 O 5 , 25% K 2 O). The potassium polyphosphates are widely used in the detergent and cleaning agent industry.
• sodium potassium tripolyphosphates which can also be used in the context of the present invention. These occur, for example, when hydrolyzing sodium trimetaphosphate with KOH: (NaPO 3 ) 3 + 2 KOH ⁇ Na 3 K 2 P 3 O 10 + H 2 O
• these are exactly like sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two can be used; also mixtures of sodium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and Sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium tripolyphosphate can be used according to the invention.
• Organic cobuilders which can be used in the detergent tablets according to the invention in particular polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, Aspartic acid, polyacetals, dextrins, other organic cobuilders (see below) and phosphonates are used. These classes of substances are described below.
• Useful organic builders are, for example, those in the form of their sodium salts usable polycarboxylic acids, such polycarboxylic acids being among polycarboxylic acids can be understood that carry more than one acid function.
• these are citric acid, Adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, Fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if one such use is not objectionable for ecological reasons, as well as mixtures from 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.
• the acids themselves can also be used.
• the acids have a builder effect typically also the property of an acidifying component and serve thus also for setting a lower and milder pH value of washing or Detergents.
• citric acid succinic acid, glutaric acid, Adipic acid, gluconic acid and any mixtures of these.
• Polymeric polycarboxylates are also suitable as builders, for example those Alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a molecular weight of 500 to 70,000 g / mol.
• the molecular weights given for polymeric polycarboxylates are weight-average molecular weights M w of the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), using a UV detector. The measurement was made against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship to the polymers investigated. This information differs significantly from the molecular weight information for which polystyrene sulfonic acids are used as standard. The molecular weights measured against polystyrene sulfonic acids are generally significantly higher than the molecular weights given in this document.
• Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of Have 2000 to 20,000 g / mol. Because of their superior solubility, this can Group in turn the short-chain polyacrylates, the molecular weights from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, preferably his.
• copolymeric polycarboxylates especially those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid.
• the 50 to Contain 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid As special copolymers of acrylic acid with maleic acid have proven suitable, the 50 to Contain 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid.
• Your molecular weight, based on free acids is generally from 2000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol.
• the (co) polymeric polycarboxylates can be either as a powder or as an aqueous solution be used.
• the content of (co) polymeric polycarboxylates in the agents is preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.
• the polymers can also allylsulfonic acids, such as for example, allyloxybenzenesulfonic acid and methallylsulfonic acid, as a monomer.
• allylsulfonic acids such as for example, allyloxybenzenesulfonic acid and methallylsulfonic acid
• biodegradable polymers made from more than two different ones Monomer units, for example those which are salts of acrylic acid as monomers and the maleic acid and vinyl alcohol or vinyl alcohol derivatives or as Monomeric salts of acrylic acid and 2-alkylallylsulfonic acid as well as sugar derivatives contain.
• copolymers are those which preferably contain acrolein as monomers and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.
• further preferred builder substances are polymeric aminodicarboxylic acids, to name their salts or their precursors.
• Polyaspartic acids are particularly preferred or their salts and derivatives, which in addition to cobuilder properties have a bleach-stabilizing effect.
• polyacetals which are obtained by reacting dialdehydes with polyol carboxylic acids, which have 5 to 7 carbon atoms and at least 3 hydroxyl groups can be obtained.
• Preferred polyacetals are made from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from Obtained polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
• Suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates obtained by partial hydrolysis of starches can be.
• the hydrolysis can be carried out according to customary methods, for example acid-catalyzed or enzyme-catalyzed Procedures are carried out. They are preferably hydrolysis products with average molecular weights in the range of 400 to 500000 g / mol.
• DE dextrose equivalent
• Both maltodextrins with a DE between 3 and 20 and dry glucose syrups can be used with a DE between 20 and 37 as well as so-called yellow dextrins and White dextrins with higher molar masses in the range from 2000 to 30000 g / mol.
• the oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.
• An oxidized oligosaccharide is also suitable.
• a product oxidized at C 6 of the saccharide ring can be particularly advantageous.
• Oxydisuccinates and other derivatives of disuccinates are other suitable cobuilders. This is ethylenediamine-N, N'-disuccinate (EDDS) preferably used in the form of its sodium or magnesium salts. Glycerol disuccinates and glycerol trisuccinates are also preferred in this context. Suitable amounts are those containing zeolite and / or silicate Formulations at 3 to 15% by weight.
• organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be in lactone form, and which have at least 4 carbon atoms and at least one hydroxyl group and at most contain two acid groups.
• HEDP 1-hydroxyethane-1,1-diphosphonate
• HEDP 1-hydroxyethane-1,1-diphosphonate
• Aminoalkane phosphonates preferably come from ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologues in question. They are preferably in the form of the neutral sodium salts, e.g. B.
• HEDP is preferably used as the builder from the class of the phosphonates.
• the aminoalkanephosphonates also have a pronounced ability to bind heavy metals. Accordingly, especially if the agents also contain bleach, be preferred to use aminoalkanephosphonates, in particular DTPMP, or To use mixtures of the phosphonates mentioned.
• the amount of builder is usually between 10 and 70 wt .-%, preferably between 15 and 60% by weight and in particular between 20 and 50% by weight.
• the amount of builders used depends on the intended use, so that Bleach tablets may have higher amounts of builders (for example between 20 and 70% by weight, preferably between 25 and 65% by weight and in particular between 30 and 55% by weight), for example detergent tablets (usually 10 to 50 wt .-%, preferably 12.5 to 45 wt .-% and in particular between 17.5 and 37.5% by weight).
• disintegration aids so-called tablet disintegrants
• tablet disintegrants or accelerators of decay are understood as auxiliary substances which are necessary for rapid disintegration of tablets in water or gastric juice and ensure the release of the pharmaceuticals in absorbable form.
• Swelling these substances, which are also called “explosives” due to their effect, enlarge their volume when water enters, whereby on the one hand the volume increases (Swelling), on the other hand, a pressure can be generated via the release of gases which can break the tablet into smaller particles.
• Well-known disintegration tools are, for example, carbonate / citric acid systems, but also other organic ones Acids can be used.
• Swelling disintegration aids are, for example synthetic polymers such as polyvinyl pyrrolidone (PVP) or natural polymers or modified Natural substances such as cellulose and starch and their derivatives, alginates or casein derivatives.
• PVP polyvinyl pyrrolidone
• Natural substances such as cellulose and starch and their derivatives, alginates or casein derivatives.
• Preferred detergent tablets contain 0.5 to 10% by weight, preferably 3 to 8% by weight and in particular 4 to 6% by weight of a disintegration aid, each based on the weight of the molded body.
• Disintegrants based on cellulose are used as preferred disintegrants in the context of the present invention, so that preferred detergent tablets have such a disintegrant based on cellulose in amounts of 0.5 to 10% by weight, preferably 3 to 8% by weight and in particular 4 contain up to 6 wt .-%.
• Pure cellulose 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 is made up of two molecules of glucose. Suitable celluloses consist of approximately 500 to 5000 glucose units and consequently have average molecular weights of 50,000 to 500,000.
• Cellulose-based disintegrants which can be used in the context of the present invention are also cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions.
• 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 disintegrants used on cellulose basis, but used in a mixture with cellulose.
• the salary these mixtures of cellulose derivatives is preferably below 50% by weight, particularly preferably below 20% by weight, based on the disintegrant Cellulose base. Pure is particularly preferred as the disintegrant based on cellulose Cellulose used, which is free of cellulose derivatives.
• microcrystalline cellulose As another disintegrant based on cellulose or as a component of this component microcrystalline cellulose can be used.
• This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions that only attack the amorphous areas (approx. 30% of the total cellulose mass) of the celluloses and dissolve completely, but leave the crystalline areas (approx. 70%) undamaged.
• a subsequent disaggregation of the microfine celluloses resulting from the hydrolysis delivers the microcrystalline celluloses, which have primary particle sizes of approx. 5 ⁇ m and compactible, for example, into granules with an average particle size of 200 ⁇ m are.
• the premix to be pressed has a bulk density has that comes close to the usual compact detergent.
• the premix to be compressed has a bulk density of at least 500 g / l, preferably of at least 600 g / l and in particular above 700 g / l.
• 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 peracid salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.
• Even when using the bleaching agents it is possible to dispense with the use of surfactants and / or builders, so that pure bleach tablets can be produced.
• bleaching agents from the group of organic bleaching agents can also be used.
• Typical organic bleaching agents are the diacyl peroxides, such as dibenzoyl peroxide.
• Other typical organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids.
• Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy- ⁇ -naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ⁇ -phthalimidoxyacidoxy (PAP), )], o-Carboxybenzamidoperoxycapronsäure, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinates, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, Diperocysebacinklare, diperoxybrassylic acid, diperoxyphthalic acids, the 2-decyldiperoxybutane-1, 4-dia
• Chlorine or. Can also be used as bleaching agents in moldings for automatic dishwashing
• Bromine-releasing substances are used.
• appropriate chlorine or bromine releasing materials come, for example, heterocyclic N-bromo- and N-chloramides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, Dibromo isocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with Cations such as potassium and sodium are considered.
• Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydanthoin are also suitable.
• bleach activators can be used in the inventive Detergent tablets are incorporated.
• Can be used as bleach activators Compounds that are aliphatic peroxocarboxylic under perhydrolysis conditions with preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or optionally result in substituted perbenzoic acid can be used.
• Suitable substances are the O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally carry substituted benzoyl groups.
• Multi-acylated alkylenediamines are preferred, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular Tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl or isononanoyloxybenzene sulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular Phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran.
• TAED tetraacet
• bleaching catalysts can be incorporated into the moldings.
• these fabrics are bleach-enhancing transition metal salts or transition metal complexes such as Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes.
• Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing ones Tripod ligands as well as Co, Fe, Cu and Ru amine complexes are used as bleaching catalysts usable.
• Enzymes include, in particular, those from the classes of hydrolases such as proteases, Esterases, lipases or lipolytic enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned in question. All of these hydrolases wear in the laundry to remove stains such as protein, fat or starchy stains and graying. Cellulases and other glycosyl hydrolases can also be removed by removing pilling and microfibrils Color preservation and increase the softness of the textile. For bleaching or Inhibition of color transfer can also be used oxidoreductases.
• hydrolases such as proteases, Esterases, lipases or lipolytic enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned in question. All of these hydrolases wear in the laundry to remove stains such as protein, fat or starchy stains and graying. Cellulases and other glycosyl hydrolases can also be removed
• Bacillus subtilis Especially from bacterial strains or fungi such as Bacillus subtilis, Bacillus are well suited licheniformis, Streptomyceus griseus, Coprinus Cinereus and Humicola insolens as well their genetically modified variants obtained enzymatic active ingredients.
• proteases of the subtilisin type and in particular proteases derived from Bacillus lentus are used.
• enzyme mixtures for example from protease and amylase or protease and lipase or lipolytic enzymes or protease and cellulase or from cellulase and lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytically active enzymes or Protease, lipase or lipolytically active enzymes and cellulase, but especially Protease and / or lipase-containing mixtures or mixtures with lipolytically active Enzymes of special interest.
• lipolytic enzymes are the well-known cutinases. Peroxidases or oxidases have also been found in some Cases proved to be suitable.
• Suitable amylases include in particular alpha amylases, Iso-amylases, pullulanases and pectinases.
• cellulases are preferred Cellobiohydrolases, endoglucanases and glucosidases, also called cellobiases are used, or mixtures of these. Because there are different types of cellulase can distinguish through their CMCase and Avicelase activities, through targeted Mixtures of cellulases to set the desired activities.
• the enzymes can be adsorbed on carriers or embedded in coating substances in order to protect them against premature decomposition.
• the proportion of enzymes, enzyme mixtures or enzyme granules can, for example, about 0.1 to 5 wt .-%, preferably 0.5 to about 4.5% by weight.
• the detergent tablets can also contain components 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, this contains oil and fat-dissolving component, was washed.
• nonionic cellulose ethers such as methyl cellulose and methylhydroxy-propyl cellulose with a proportion of methoxyl groups of 15 to 30 wt .-% and of hydroxypropoxyl groups of 1 to 15 wt .-%, each based on the nonionic cellulose ether, as well as those known from the prior art Polymers of phthalic acid and / or terephthalic acid or their derivatives, in particular Polymers made from ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives of these. Particularly preferred of these are the sulfonated derivatives of phthalic acid and terephthalic acid polymers.
• the moldings can be derivatives of diaminostilbenedisulfonic acid as optical brighteners 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. Brighteners of the substituted diphenylstyryl type may also be present, e.g.
• Dyes and fragrances are the detergent tablets according to the invention added to improve the aesthetic impression of the products and the Consumers in addition to performance a visually and sensory "typical and distinctive" To provide product.
• Individual as perfume oils or fragrances Fragrance compounds e.g. synthetic products of the ester, ether, aldehyde type, Ketones, alcohols and hydrocarbons can be used. Fragrance compounds of the ester type are e.g.
• the ethers include, for example, benzyl ethyl ether, to aldehydes e.g.
• the linear alkanals with 8-18 C atoms citral, citronellal, Citronellyloxyacetaldehyde, Cyclamenaldehyde, Hydroxycitronellal, Lilial and Bourgeonal, to the ketones e.g. the Jonone, ⁇ -isomethyl ionone and methyl cedryl ketone, to the Alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol,
• the hydrocarbons mainly include terpenes such as limonene and Pinene. However, mixtures of different odoriferous substances are preferably used create an appealing fragrance together.
• perfume oils can also be natural Fragrance mixtures contain, as are available from plant sources, e.g. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil.
• Muscatel sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, Juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well Orange blossom oil, neroliol, orange peel oil and sandalwood oil.
• the content of the detergent tablets according to the invention is usually in the range of dyes below 0.01% by weight, while fragrances up to 2% by weight of the total Can make out formulation.
• the fragrances can be incorporated directly into the agents according to the invention but can also be advantageous to apply the fragrances to the carrier, which increase the liability of the perfume on the laundry and by a slower fragrance release for long-lasting fragrance of the textiles.
• Such carrier materials have, for example Cyclodextrins have proven themselves, with the cyclodextrin-perfume complexes additionally can be coated with other auxiliaries.
• the agents can be colored with suitable dyes.
• Preferred dyes the selection of which Specialist poses no difficulty, has a high storage stability and insensitivity compared to the other ingredients of the agents and against light and none pronounced substantivity towards textile fibers so as not to stain them.
• the premix with finely divided surface treatment agents be "powdered". This can affect the nature and physical properties both the premix (storage, pressing) and the finished detergent tablets be an advantage.
• Fine powdering agents are in the stand well-known in the art, mostly zeolites, silicates or other inorganic salts be used.
• the premix is preferred with finely divided zeolite "powdered", with zeolites of the faujasite type being preferred.
• zeolites of the faujasite type As part of the present Invention characterizes the term "faujasite type zeolite" all three zeolites, which form the faujasite subgroup of zeolite structure group 4 (compare Donald W.
• zeolite of the faujasite type with particle sizes below 100 ⁇ m, preferably below 10 ⁇ m and in particular below 5 ⁇ m and at least 0.2% by weight, preferably at least 0.5% by weight and in particular accounts for more than 1% by weight of the premix to be pressed.
• the moldings according to the invention are first produced by dry means Mixing the components, which can be partially or completely pre-granulated, and then Inform, in particular pressing into tablets, whereby conventional Procedure can be used.
• the pre-mix is molded in a so-called die between two stamps compacted into a solid compressed. This process, hereinafter referred to briefly as tableting is divided into four sections: dosage, compression (elastic Deformation), plastic deformation and ejection.
• the premix is introduced into the die, the filling quantity and thus the weight and shape of the resulting molded body through the position of the lower one Stamp and the shape of the press tool can be determined.
• the constant dosage even with high throughputs of shaped bodies, a volumetric flow rate is preferred Dosage of the premix reached.
• the Upper stamp the premix and continues to lower towards the lower stamp. At this compression, the particles of the premix are pressed closer together, whereby the void volume within the filling between the punches is continuous decreases. From a certain position of the upper stamp (and thus from a certain Pressure on the premix) begins the plastic deformation at which the particles flow together and the molded body is formed.
• the phase of elastic Deformation is shortened further and further, so that the resulting shaped body more or may have smaller cavities.
• the Finished molded articles are pressed out of the die by the lower punch and through subsequent transport devices transported away. At this point, it's just that Weight of the molded body finally determined, because the compacts due to physical Processes (stretching, crystallographic effects, cooling etc.) their shape and size can still change.
• Tableting takes place in commercially available tablet presses, which are basically single or Double stamps can be equipped. In the latter case, it is not only the upper stamp used to build up pressure, also the lower stamp moves during the Pressing process towards the upper punch, while the upper punch presses down.
• eccentric tablet presses which the one or more stamps are attached to an eccentric, which in turn on one Axis is mounted with a certain rotational speed. The movement of this Press ram is comparable to the way a conventional four-stroke engine works.
• the pressing can be done with one upper and one lower stamp, but several can also be used Stamp be attached to an eccentric disc, the number of die holes is expanded accordingly.
• the throughputs of eccentric presses vary depending on the type from a few hundred to a maximum of 3000 tablets per hour.
• rotary tablet presses are selected, on which a so-called Matrix table a larger number of matrices is arranged in a circle.
• the number of matrices varies between 6 and 55, depending on the model, with larger matrices also are commercially available.
• Each die on the die table is an upper and lower stamp assigned, with the pressing pressure again being active only through the upper or lower stamp, but can also be built using both stamps.
• the matrix table and the Stamps move around a common vertical axis, the stamp with the help of rail-like curved tracks during the circulation in the positions for filling, Compression, plastic deformation and discharge are brought.
• Rotary presses can also be equipped with two filling shoes to increase throughput be, whereby only a semicircle is run through to produce a tablet got to.
• Several filling shoes are used to produce two- and multi-layer molded articles arranged one behind the other without the slightly pressed first layer in front of the further filling is ejected.
• By appropriate process control are in this way also coated and dot tablets can be produced, which have an onion skin-like structure have, whereby in the case of the point tablets the top of the core or the core layers is not covered and therefore remains visible.
• Rotary tablet presses are also included Single or multiple tools can be equipped, so that, for example, an outer circle with 50 and an inner circle with 35 holes can be used simultaneously for pressing.
• the throughputs of modern rotary tablet presses are over a million tablets per hour.
• Tableting machines suitable for the purposes of the present invention are, for example available from the companies Apparatebau Holzwarth GbR, Asperg, Wilhelm Fette GmbH, Schwarzenbek, Hofer GmbH, Weil, Horn & Noack Pharmatechnik GmbH, Worms, IMAmaschinessysteme GmbH Viersen, KILIAN, Cologne, KOMAGE, Kell am See, KORSCH Pressen AG, Berlin, and Romaco GmbH, Worms.
• Other providers are, for example Dr. Herbert Pete, Vienna (AU), Mapag Maschinenbau AG, Bern (CH), BWI Manesty, Liverpool (GB), I. Holand Ltd., Nottingham (GB), Courtoy N.V., Halle (BE / LU) and Mediopharm Kamnik (SI).
• the hydraulic double-pressure press is particularly suitable HPF 630 from LAEIS, D.
• Tableting tools are for example from the company Adams Tablettierwerkmaschinen, Dresden, Wilhelm Fett GmbH, Schwarzenbek, Klaus Hammer, Solingen, Herber% Söhne GmbH, Hamburg, Hofer GmbH, Weil, Horn & Noack, Pharmatechnik GmbH, Worms, Ritter Pharamatechnik GmbH, Hamburg, Romaco, GmbH, Worms and Notter negligencebau, Tamm available.
• Other providers are e.g. the Senss AG, Reinach (CH) and Medicopharm, Kamnik (SI).
• the moldings can be made in a predetermined spatial shape and a predetermined size become. Practically all sensibly manageable designs come as a spatial form into consideration, for example the formation as a board, the shape of bars or bars, Cubes, cuboids and corresponding room elements with flat side surfaces as well in particular cylindrical configurations with a circular or oval cross section. This last embodiment covers the presentation form from the tablet to 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 corresponds. However, it is also possible to form compacts that have a plurality connect such mass units in a compact, in particular by predetermined The easy separation of portioned smaller units is provided for predetermined breaking points is.
• the formation of the portioned compacts as Tablets, in the shape of a cylinder or cuboid, are expedient, with a diameter / height ratio in the range of about 0.5: 2 to 2: 0.5 is preferred.
• Commercial hydraulic presses, Eccentric presses or rotary presses are suitable devices in particular for the production of such compacts.
• the spatial shape of another embodiment of the shaped body is in its dimensions the induction chamber of commercial household washing machines adapted so that the Shaped bodies can be metered directly into the induction chamber without a metering aid, where it dissolves during the induction process.
• a metering aid where it dissolves during the induction process.
• the detergent tablets are easily possible via a dosing aid and within the present invention preferred.
• Another preferred shaped body that can be produced has a plate or panel-like structure with alternating thick long and thin short segments, so that individual segments of this "bar" at the predetermined breaking points, the short thin Display segments, can be canceled and entered into the machine.
• This Principle of the "bar-shaped" shaped body detergent can also be used in other geometric Shapes, for example vertical triangles, only on one of their Sides are connected alongside one another, can be realized.
• the layer structure of the shaped bodies can be done in a stack-like manner, with one dissolution process the inner layer (s) on the edges of the molded body already takes place, if the outer layers are not yet completely detached, it can also be one complete coating of the inner layer (s) by the outer layer (s) Layer (s) can be achieved, which prevents the premature dissolution of components the inner layer (s).
• a molded body consists of at least three layers, ie two outer and at least one inner layer, wherein at least one of the inner layers contains a peroxy bleach, while in the case of the stacked shaped body, the two outer layers and in the case of the shell-shaped one Shaped bodies, however, the outermost layers are free of peroxy bleach.
• Such multilayer Shaped bodies have the advantage that they do not have only one induction chamber or via a metering device which is added to the wash liquor can be; rather, in such cases it is also possible to direct the molded body To give contact to the textiles in the machine without staining Bleach and the like would be feared.
• the bodies to be coated can be coated with, for example aqueous solutions or emulsions are sprayed, or via the process of Get a coating on the melt coating.
• speckles in addition to the shape and a multi-layer structure also incorporation of colored particles, so-called speckles, into the molded body respectively.
• a white molded body can be colored homogeneously, for example blue, red, green, yellow etc.
• speckles can be colored.
• the amount of color speckles and their Particle size of the remainder of the premix, which forms the shaped body matrix from which the Speckles appear optically be adjusted.
• a tablet mix a grain spectrum of 200 to 1800 ⁇ m, so speckles that are the same or coarser grain spectrum, only above a threshold value of ⁇ 6 % By weight, based on the tabletting mixture, of a homogeneous distribution. Lower amounts then lead to an optically unsightly accumulation of speckles in some shaped body areas, while other areas remain almost unspoiled. To even lower ones Use concentrations of colored particles to achieve a homogeneous impression, it is advisable to reduce the particle size of the colored speckle particles. So in The above example of the tableting mixture in the grain spectrum from 200 to 1800 microns Even with 2 to 3% by weight of colored speckle particles, a homogeneous distribution of the speckles achieved when these particle sizes are between 200 and 800 ⁇ m.
• a layered structure of the moldings can also be visualized.
• This concept can, for example can also be transferred to three-layer tablets in which one layer undyed, the second speckled and the third colored through.
• coloring Layers can also include cores or other sub-areas in core-coated tablets, Toroidal tablets or dotted tablets colored or sprinkled become.
• ⁇ stands for diametral fracture stress (DFS) in Pa
• P is the force in N, which leads to the pressure exerted on the molded body, which causes the molded body to break
• D is the molded body diameter in meters and t the height of the moldings.
• Another object of the present invention is a surfactant-containing granules containing Surfactant (s) and carrier material (a), which additionally sugar and / or sugar acids and / or salts of sugar acids.
• granules containing surfactants preferred, the sugar and / or sugar acids and / or salts of sugar acids in Amounts from 0.1 to 20% by weight, preferably from 0.5 to 15% by weight, particularly preferably from 1 to 10% by weight and in particular from 1.5 to 5% by weight, in each case based on the weight of the surfactant granules.
• sugars and / or sugar acids used in the granules according to the invention and / or salts of sugar acids preference is given to surfactant-containing granules, the saccharides from the group glucose, fructose, sucrose, cellubiosis, maltose, lactose, Contain lactulose, ribose and mixtures thereof, with glucose and / or sucrose are particularly preferred.
• Granules containing surfactants, the sugar acids are further preferred from the group of gluconic acid, ascorbic acid, glucoronic acid, galacturonic acid, 2-oxo-D-gluconic acid, Contain threaric acid, mucic acid, glucaric acid and mixtures thereof, wherein gluconic acid, glucaric acid and / or ascorbic acid are particularly preferred.
• granules containing surfactants are also preferred, which are characterized in that they sugar acid salts from the group of gluconates, ascorbates, glucoronates, galacturonates, 2-oxo-D-gluconates, threarates, mucic acid salts, glucarates and mixtures thereof contain, the alkali metal salts and among these the sodium salts particularly preferred are.
• surfactant granules which have a surfactant content of 5 to 60% by weight, preferably from 10 to 50% by weight and in particular from 15 to 40 % By weight, based in each case on the weight of the surfactant granules.
• Granules containing surfactants the anionic surfactant content of which is preferably 5 to 45% by weight 10 to 40 wt .-% and in particular 15 to 35 wt .-%, each based on the Weight of the surfactant granules, as well as surfactant-containing granules, the content of nonionic surfactants 1 to 15 wt .-%, preferably 2.5 to 10 wt .-% and in particular 5 to 7.5 wt .-%, each based on the weight of the surfactant granules, is particularly preferred.
• Another object of the present invention is the use of sugar and / or sugar acids and / or salts of sugar acids in surfactant-containing granules, the after mixing with finely divided processing components in a manner known per se are pressed into detergent tablets, to improve stability and solubility of detergent tablets. Because of the engagement of sugar and / or sugar acids and / or salts of sugar acids in detergent and cleaning agent granules, which after mixing with other components to wash and Detergent tablets are pressed, the physical properties the molded article can be improved, as the following examples show:
• a tower powder containing surfactants was produced by spray drying and used as the basis for granules containing surfactants were used.
• the tower powder was made with other components (Zeolite, NaOH, anionic surfactant acid, nonionic surfactant, silicate, polymer) in a 50 liter ploughshare mixer granulated by Lödige.
• the granulation approaches according to the invention E1 and E2 each contained 3% by weight sucrose (E1) and sodium gluconate, respectively (E2).
• the granulation batch of the comparative example contained 3% by weight of sodium acetate.
• the quantities of solids and liquids used and the sequence the addition to the mixer is shown in Table 2.
• the granules were in a fluidized bed apparatus Company Glatt dried at a supply air temperature of 60 ° C over a period of 30 minutes. After drying, fine particles ⁇ 0.6 mm and coarse particles> 1.6 mm sieved.
• the surfactant granules E1, E2 and V were then prepared with further components to form a compressible premix, after which the pressing into tablets (diameter: 44 mm, height: 22 mm, weight: 37.5 g) was carried out in a Korsch eccentric press.
• Table 1 shows the composition of the spray-dried tower powder;
• Table 3 shows the composition of the premixes to be pressed (and thus the shaped body).

Landscapes

• Chemical & Material Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Wood Science & Technology (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Emergency Medicine (AREA)
• Molecular Biology (AREA)
• Detergent Compositions (AREA)
• Cosmetics (AREA)

Applications Claiming Priority (2)

Publications (3)

Family

ID=7636872

Family Applications (1)

Country Status (4)

Cited By (7)

Families Citing this family (1)

Citations (7)

Family Cites Families (3)

• 2000
  • 2000-03-29 DE DE10015661A patent/DE10015661A1/de not_active Ceased
• 2001
  • 2001-03-20 EP EP01106884A patent/EP1138756B1/fr not_active Expired - Lifetime
  • 2001-03-20 ES ES01106884T patent/ES2250243T3/es not_active Expired - Lifetime
  • 2001-03-20 AT AT01106884T patent/ATE305962T1/de not_active IP Right Cessation
  • 2001-03-20 DE DE50107588T patent/DE50107588D1/de not_active Expired - Lifetime

Patent Citations (7)

Non-Patent Citations (2)

Also Published As

Similar Documents

Legal Events