EP0985023B1 - Waschmittelformkörper mit verbesserten auflöseeigenschaften - Google Patents
Waschmittelformkörper mit verbesserten auflöseeigenschaften Download PDFInfo
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- EP0985023B1 EP0985023B1 EP98929366A EP98929366A EP0985023B1 EP 0985023 B1 EP0985023 B1 EP 0985023B1 EP 98929366 A EP98929366 A EP 98929366A EP 98929366 A EP98929366 A EP 98929366A EP 0985023 B1 EP0985023 B1 EP 0985023B1
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- EP
- European Patent Office
- Prior art keywords
- detergent
- shaped body
- weight
- acid
- component
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0052—Gas evolving or heat producing compositions
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- 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
- C11D17/0086—Laundry tablets
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/10—Carbonates ; Bicarbonates
-
- 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 compact moldings, the washing and have cleaning-active properties.
- the invention relates to detergent tablets such as detergent tablets, dishwashing tablets, patch salts tablets or water softening tablets for household use, in particular for the machine use.
- Detergent tablets are broadly described in the prior art and enjoy the consumer because of the simple dosage of increasing popularity. Tabletted detergents and cleaners have a number of powdery forms Advantages: They are easier to dose and to handle and have due to their compact Structure Advantages during storage and during transport. Also in the patent literature detergent and cleaner tablets are thus described comprehensively.
- excipients are understood to mean excipients which are suitable for rapid disintegration of tablets in water or gastric juice and for the release of the drugs in resorbable form.
- EP-B-0 396 335 (Beecham Group PLC) discloses chewable tablets which in addition to 1 to 30 wt .-% of an effervescent system from 0.5 to 20 wt .-% citric, Wein, adipic, fumaric or Maleic acid and 0.5 to 30 wt .-% Na, K or Ca (hydrogen) carbonate or sodium glycine additionally 5 to 30 wt .-% of a disintegrating agent such as (modified) cellulose, polyvinylpyrrolidone or starch glycolate.
- a disintegrating agent such as (modified) cellulose, polyvinylpyrrolidone or starch glycolate.
- Combinations of effervescent granules and swelling disintegrants are also known from JP 06 024 959 (BAYER YAKUHIN KK, Derwent Abstract). It describes pharmaceutical compositions in tablet form wherein the active ingredients are mixed with a disintegrator (methylcellulose, carboxymethylcellulose, polyvinyl alcohol, polyvinylpyrrolidone) and partly with disintegrants containing a swelling gel-forming polymer (sodium alginate, carrageenan, polyethylene oxide) and a CO 2 -generating effervescent system to be covered. These tablets are claimed to be sustained release drug carriers despite the use of two disintegration systems. The proposed solutions lead to the desired success in the manufacture of tablets.
- a disintegrator methylcellulose, carboxymethylcellulose, polyvinyl alcohol, polyvinylpyrrolidone
- disintegrants containing a swelling gel-forming polymer sodium alginate, carrageenan, polyethylene oxide
- CO 2 -generating effervescent system to be covered.
- European Patent Application EP-A-0 466 484 (Unilever) describes tablets of compacted particulate detergent which optionally contain other detergent ingredients in addition to surfactant (s) and builder (s), with bulking agents being preferred in the case of binder / disintegrant content are.
- Detergents and cleaning effervescent tablets are described in DE 35 35 516 (Bucher). These tablets contain 2 to 6% by weight of a surfactant, 40 to 60% by weight of bicarbonate, 33 to 53% by weight of a solid organic acid (especially a 2: 3 mixture of citric and tartaric acid), 1, 5 to 2.5 wt .-% polyvinylpyrrolidone and additionally colloidal silica. However, these tablets are not textile detergents, but have as preferred application areas the windscreen washer system of motor vehicles or the Bodenwischzar.
- the object of the invention was to provide a bruseffen Anlagenn
- To provide detergent tablets on the one hand in the application fleet quickly disintegrates and on the other hand, no problems with the formation of residues Causes textiles.
- component a) the contents of the agents at a) or b) are described below briefly referred to as "component a)" or “component b)".
- component in this context as a pure language construction.
- the bubbling system b) may consist of several compounds that are not mandatory must be in the form of a single compound. Rather, the total content is the compounds in question, also in completely different individual raw materials or Compounds may be present, calculated and referred to as “component b)”.
- the swellable, water-insoluble Disintegrationsakusmittel not mandatory in the form of a single compound.
- suitable components a) include, in particular, natural and chemically modified biopolymers which may be selected, for example, from the group of alginates, starches and celluloses.
- component a) is selected from the natural and synthetic polysaccharides and their derivatives.
- These groups include, for example, the pure polysaccharides starch and cellulose, but also the products of esterification or etherification, in which hydroxy-hydrogen atoms were substituted. But also celluloses or starches, in which the hydroxy groups against functional groups that are not bound by an oxygen atom, have been replaced, can be used as polysaccharide derivatives.
- cellulose derivatives Into the group of cellulose derivatives fall, for example, alkali metal celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses, for example, in the group of starch derivatives the carboxymethyl starch (CMS).
- microcrystalline Cellulose be used as swellable, water-soluble Disintegrationstosmittel.
- This cellulose has primary particle sizes of about 5 microns and can, for example, to granules with an average particle size of 200 microns are compacted. Such compactates are stable and can be mixed with other substances mix without decomposing into the primary particles.
- the swellable, water-soluble disintegration aids are not in finely divided Powder form, but by a spray-drying, granulation, Agglomeration, compacting, pelleting or extrusion process into a coarse-grained Shape convicted. These "granulated" disintegration aids not only count Disintegrators in granular, but for example, those in cogranulierter or on others Way of condensed form.
- the component a) used is 1 to 10% by weight, preferably 2 to 7% by weight and in particular 3 to 5% by weight, based on the entire tablet, of a cellulose or of a cellulose derivative.
- the gas-evolving effervescent system ⁇ component b) ⁇ may consist of a single substance which releases a gas on contact with water.
- the gas-releasing effervescent system in turn consists of at least two constituents which react with one another to form gas.
- Preferred components b) consist of alkali metal carbonate and / or bicarbonate and an acidifying agent which is suitable for liberating carbon dioxide from the alkali metal salts in aqueous solution.
- the sodium and potassium salts are for reasons of cost compared to the other salts clearly preferred.
- the relevant pure alkali metal carbonates or bicarbonates be used; Rather, mixtures of different carbonates and bicarbonates be preferred for washing technical interest.
- washing and cleaning agent tablets are as component b) 2 to 20 Wt .-%, preferably 3 to 15 wt .-% and in particular 5 to 10 wt .-% of an alkali metal carbonate or -hydrogencarbonats and 1 to 15, preferably 2 to 12 and in particular 3 to 10% by weight of an acidifying agent, in each case based on the entire molding, used.
- Acidsstoff that release carbon dioxide from the alkali salts in aqueous solution are, for example, boric acid and alkali metal hydrogen sulfates, alkali metal dihydrogen phosphates and other inorganic salts.
- organic Acidifier used, wherein the citric acid is a particularly preferred Acidification agent is.
- the other solid mono, Oligo- and polycarboxylic acids are tartaric acid, succinic acid, Malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and polyacrylic acid.
- Organic sulfonic acids such as sulfamic acid are also usable.
- Sokalan® DCS commercially available and as Acidaimssstoff in the context of the present invention also Preferably used is Sokalan® DCS (trademark of BASF), a mixture of succinic acid (max 31 wt%), glutaric acid (max 50 wt%) and adipic acid (max 33 wt%) Wt .-%).
- washing and cleaning agent tablets in which as acidifying agent in component b) a substance from the group organic di-, tri- and oligocarboxylic acids or mixtures thereof are used.
- the detergent tablets of the present invention preferably contain in addition, other common ingredients in detergents and cleaners from the group surfactants, builders, bleaches, bleach activators, enzymes, optical brighteners, Foam inhibitors, perfumes and dyes. These substances are described in more detail below.
- anionic, nonionic, cationic and / or amphoteric surfactants are used. Preference is given to From an application point of view mixtures of anionic and nonionic surfactants, wherein the proportion of anionic surfactants should be greater than the proportion of nonionic surfactants.
- the total surfactant content of the molded articles is from 5 to 60% by weight, based on the Molded body weight, wherein surfactant contents over 15 wt .-% are preferred.
- anionic surfactants for example, those of the sulfonate type and sulfates are used.
- the surfactants of the sulfonate type are preferably C 9-13 -alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as are obtained, for example, from C 12-18 -monoolefins having terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products into consideration.
- alkanesulfonates which are obtained from C 12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
- esters of ⁇ -sulfo fatty acids for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids are suitable.
- sulfated fatty acid glycerol esters are sulfated fatty acid glycerol esters.
- fatty acid glycerine esters are the mono-, di- and triesters and their mixtures to understand how they in the Preparation by esterification of a monoglycerol with 1 to 3 mol fatty acid or at the transesterification of triglycerides with 0.3 to 2 moles of glycerol can be obtained.
- preferred Sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids with 6 to 22 carbon atoms, for example the caproic acid, caprylic acid, capric acid, myristic acid, Lauric acid, palmitic acid. Stearic acid or behenic acid.
- Alk (en) ylsulfates are the alkali metal salts and in particular the sodium salts of the sulfuric monoesters of C 12 -C 18 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half-esters of secondary alcohols of these chain lengths are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical having an analogous degradation behavior as the adequate compounds based on oleochemical raw materials.
- C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates and C 14 -C 15 alkyl sulfates are preferred.
- 2,3-Alkyl sulfates which are prepared, for example, according to US Pat. Nos. 3,234,258 or 5,075,041 and can be obtained as commercial products of the Shell Oil Company under the name DAN®, are suitable anionic surfactants.
- EO ethylene oxide
- Fatty alcohols with 1 to 4 EO are suitable. Due to their high foaming behavior, they are only used in detergents in relatively small amounts, for example in amounts of from 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 the 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 radicals or mixtures thereof.
- Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which in themselves constitute nonionic surfactants (see description below).
- Sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred.
- alk (en) yl-succinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
- anionic surfactants are particularly soaps into consideration.
- Suitable are saturated Fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular of natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.
- the anionic surfactants including soaps may be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine, 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 on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten.
- alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred.
- the preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO or 4 EO, C 9-11 alcohols 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 of these, 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 means which, for a particular product, may be an integer or a fractional number.
- 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.
- the degree of oligomerization x, the The distribution of monoglycosides and oligoglycosides is any number between 1 and 10; preferably x is 1.2 to 1.4.
- nonionic surfactants used either alone nonionic surfactant or used in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain, in particular Fatty acid methyl esters, as described, for example, in Japanese Patent Application JP 58/217598 are described or preferably according to the in the international patent application 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 alkanolamide may 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.
- polyhydroxy fatty acid amides of the formula (I) wherein RCO is an aliphatic acyl group having 6 to 22 carbon atoms, R 1 is hydrogen, an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl group having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
- the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
- the group of polyhydroxy fatty acid amides also includes compounds of the formula (II) in the R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
- R 1 is a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms
- R 2 is a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having from 1 to 8 carbon atoms, with C 1-4 alkyl or phenyl radicals being preferred
- [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 residue.
- [Z] is preferably obtained by reductive amination of a reduced sugar, for example Glucose, fructose, maltose, lactose, galactose, mannose or xylose.
- a reduced sugar for example Glucose, fructose, maltose, lactose, galactose, mannose or xylose.
- the N-alkoxy or N-aryloxy-substituted compounds can then, for example, according to the International Publication 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.
- builders used in the detergent tablets according to the invention may be contained in particular silicates, aluminum silicates (especially zeolites), Carbonates, salts of organic di- and polycarboxylic acids and mixtures of these substances call.
- Suitable crystalline layered sodium silicates have the general formula NaMSi x O 2x + 1 .H 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4 are.
- Such crystalline sheet 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 is sodium and x assumes the values 2 or 3.
- both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O 5 .yH 2 O are preferred, whereby ⁇ -sodium disilicate can be obtained, for example, by the process described in international patent application WO-A-91/08171.
- amorphous sodium silicates with a Na 2 O: SiO 2 modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which Delayed and have secondary washing properties.
- the dissolution delay compared with conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying.
- the term "amorphous” is also understood to mean "X-ray amorphous”.
- the silicates do not yield sharp X-ray reflections typical of crystalline substances in X-ray diffraction experiments, but at most one or more maxima of the scattered X-rays having a width of several degrees of diffraction angle. However, it may well even lead to particularly good builder properties if the silicate particles provide blurred or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of size 10 to a few hundred nm, values of up to max. 50 nm and in particular up to max. 20 nm are preferred.
- Such so-called X-ray-amorphous silicates which likewise have a dissolution delay compared to the conventional water glasses, are described, for example, in German patent application DE-A-44 00 024. Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.
- the finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P.
- zeolite P zeolite MAP (R) (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 spray-dried powder or else as undried, still moist, stabilized suspension of its preparation.
- the zeolite may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3 wt .-%, based on zeolite, of ethoxylated C 12 -C 18 fatty alcohols having 2 to 5 ethylene oxide groups , C 12 -C 14 fatty alcohols having 4 to 5 ethylene oxide groups or ethoxylated isotridecanols.
- Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution, measuring method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
- phosphates as builders possible, unless such use is avoided for environmental reasons should be.
- Particularly suitable are the sodium salts of orthophosphates, pyrophosphates and in particular 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 environmental 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 thereof. These Salts are used because of their builder properties and are not considered as an ingredient of the effervescent system, especially since the salts are not suitable, for example from Hydrogen carbonates release carbon dioxide.
- sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
- Other useful bleaching agents are, for example, sodium percarbonate.
- bleach activators When washing at temperatures of 60 ° C and below an improved bleaching effect to achieve bleach activators as a sole ingredient or as an ingredient of Component b) are incorporated.
- bleach activators compounds mentioned in U.S. Pat Perhydrolysis conditions aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid be used. Suitable substances are the O- and / or N-acyl groups of bear C-atomic number and / or optionally substituted benzoyl groups.
- TAED te
- Bleaching catalysts are incorporated into the moldings. These substances are it is bleach-enhancing transition metal salts or transition metal complexes such For example, Mn, Fe, Co, Ru or Mo-salene complexes or carbonyl complexes. Also Mn, Fe, Co, Ru, Mo, Ti, V, and Cu complexes with nitrogen-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes are useful as bleach catalysts.
- Suitable foam inhibitors which may be a constituent of component b) or which 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 mixtures thereof with microfine, optionally silanized silica or bistearylethylenediamide. It is also advantageous to use mixtures of various foam inhibitors, for example those of silicones, paraffins or waxes.
- the foam inhibitors are bound to a granular, water-soluble or dispersible carrier substance. In particular, mixtures of paraffins and bistearylethylenediamides are preferred.
- the detergent tablets may also contain components which positively influence the oil and grease washability of textiles (so-called soil repellents). This effect becomes particularly evident when a textile is already soiled previously several times with a detergent according to the invention, this oil and fat dissolving Component contains, was washed.
- nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxyl groups of 15 to 30% by weight and at hydroxypropoxyl groups from 1 to 15 wt .-%, each based on the nonionic Cellulose ethers
- nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxyl groups of 15 to 30% by weight and at hydroxypropoxyl groups from 1 to 15 wt .-%, each based on the nonionic Cellulose ethers
- the known from the prior art polymers of phthalic acid and / or terephthalic acid or its derivatives in particular polymers Ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionically modified derivatives of these.
- Particularly preferred of these are the sulfonated derivatives of phthalic and terephthalic acid polymers.
- Enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof in question. Particularly suitable are bacterial strains or fungi, such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus Agents. Preferably, subtilisin-type proteases and in particular Proteases derived from Bacillus lentus.
- enzyme mixtures for example from protease and amylase or protease and lipase or protease and Cellulase or cellulase and lipase or protease, amylase and lipase or protease, Lipase and cellulase, but especially cellulase-containing mixtures of particular Interest. Peroxidases or oxidases have also proved suitable in some cases.
- the enzymes can be adsorbed on carriers and / or embedded in encapsulating substances be to protect them against premature decomposition.
- the proportion of enzymes, enzyme mixtures or enzyme granules in the moldings of the invention can, for example about 0.1 to 5 wt .-%, preferably 0.1 to about 2 wt .-% amount.
- the moldings can be used as optical brighteners derivatives of Diaminostilbendisulfonklare 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, are a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group.
- brighteners of the substituted diphenylstyrene 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 brightener can be used.
- the particulate premix to be compressed can be used as a pure powder mixture in which the Components a) and b) are present, but it is preferred that individual raw materials be introduced into the premix in pretreated, in particular precompressed form.
- the disintegration aids are preferably in the form of Granules, pellets, compactates or extrudates introduced into the premix.
- certain other ingredients such as surfactants, in the form of beneficial builder-containing particles are introduced into the premix, which by spray drying, Granulation, pelleting, compaction or extrusion can be obtained.
- the particulate detergent composition is compressed at temperatures below 30 ° C and compressive forces below 15 N / cm 2 .
- the actual production of the moldings according to the invention takes place first by the dry mixing of the constituents, which may be pre-granulated in whole or in part, and subsequent informing, in particular pressing into tablets, using conventional methods (for example tableting, as in the conventional patent literature, especially on the Washing or cleaning agent area, in particular as described in the above-mentioned patent applications and the article "tableting: state of the art", S ⁇ FW-Journal, 122th year, pp. 1016-1021 (1996)) can be used.
- the moldings can be made in a predetermined spatial form and predetermined size become.
- a form of space practically all meaningfully manageable flow designs come in Consider, for example, the training as a blackboard, the bar or bar form, cubes, Cuboid and corresponding room elements with flat side surfaces and in particular cylindrical Embodiments with a circular or oval cross-section.
- This last embodiment detects the presentation form of the tablet up to compact Zylinderstükken with a height to diameter ratio above 1.
- the portioned compacts can each as separate individual elements be formed, the predetermined dosage of the detergent and / or detergent equivalent. However, it is also possible to form compacts, which are 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.
- the formation of portioned compacts as tablets, in cylinder or cuboid shape be useful, with a diameter / height ratio in the range from about 0.5: 2 to 2: 0.5 is preferred.
- Commercially available hydraulic presses, eccentric presses or rotary presses are suitable devices, in particular for the production such compacts.
- the spatial form of another embodiment of the moldings is in their dimensions of Ein Titanauer-Teller adapted from commercial household washing machines, so that the moldings can be metered directly into the dispensing chamber without dosing aid, where they are dissolves during the flushing process.
- the moldings can be metered directly into the dispensing chamber without dosing aid, where they are dissolves during the flushing process.
- dosing aid where they are dissolves during the flushing process.
- a use of Detergent tablets via a dosing easily possible and within the scope of the present Invention preferred.
- Another preferred shaped article which can be produced has a plate-like or tabular Structure with alternately thick long and thin short segments, so that individual Segments of this "bar" at the predetermined breaking points, which are the short thin segments can be displayed, canceled and entered into the machine.
- This principle the "bar-shaped" shaped body wash can also be used in other geometric forms, for example, perpendicular triangles, which alongside only one of its sides connected with each other, be realized.
- the various components are not uniform Tablet are pressed, but that moldings are obtained, the several layers, So at least two layers. It is also possible that these different Layers have different dissolution rates. This can be advantageous application properties of the molded articles result.
- Components are contained in the moldings, which influence each other negatively, so it is possible to integrate the one component in the faster soluble layer and to incorporate the other component in a slower soluble layer so that the first Component has already reacted when the second goes into solution.
- the Schichtautbau the Shaped body can be done both stack-like, with a solution process of the inner Layer (s) already takes place at the edges of the shaped body when the outer layers not yet completely solved, but it can also be a complete enclosure of the inner Layer (s) through the respective outer layer (s) are achieved, resulting in preventing the premature dissolution of constituents of the inner layer (s).
- a shaped body consists of at least three layers, so two outer and at least one inner layer, wherein at least in one of the inner layers, a peroxy bleach is contained, while in stack-shaped moldings, the two outer layers and the envelope-shaped molding however, the outermost layers are free of peroxy bleach.
- Peroxy bleach and optionally present bleach activators and / or enzymes spatially separated in a molding of each other.
- Such multilayer moldings have the advantage that they not only via a dispenser or via a metering device, which is added to the wash liquor, can be used; rather, it is in such cases also possible, the molding in direct contact with the textiles in the To give machine without to fear stains caused by bleach and the like would.
- the shaped bodies according to the invention in particular the previously poorly decomposing and poorly soluble detergent tablets and Blleichffenform redesign exhibit by the Content of water-insoluble, swellable disintegration aid and effervescent system ⁇ Components a) and b) ⁇ excellent decay properties.
- This can be, for example in critical conditions in a standard household washing machine (use directly in the wash liquor by means of a conventional metering device, fine wash program or colored laundry, Washing temperature maximum 40 ° C) are tested.
- a washing process is claimed, wherein the shaped body via the Ein Hughesvortechnische the household washing machine in the wash liquor is introduced.
- the dissolution times of the moldings in the washing machine amount preferably less than 8 minutes, and more preferably less than 5 minutes.
- a Another embodiment of the invention claims a washing process in which the shaped body -If necessary with Dosier Vietnamese- is placed directly on the laundry, located in the Drum of a household washing machine is located.
- the molded body advantageously directly, i. be added to the laundry without additional dosing; the use known dosing aids such as bags, sachets, plastic containers or the like is but also easily possible.
- the comparative examples contained either no component a) (Example 3) or no component b) (Example 4), with small amounts of Na 2 CO 3 were used as builder.
- Washing and cleaning agent tablets [% by weight]: Detergent tablets 1 2 3 4 C 9-13 alkyl benzene sulphonate 11.4 10.0 10.6 10.0 C 12-18 fatty alcohol sulfate - 6.6 2.4 6.8 C 12-18 fatty alcohol with 7 EO 5.8 - 4.8 6.2 Soap 0.7 2.1 1.6 1.8 sodium tripolyphosphate - 23.5 - - Zeolite 4A (based on anhydrous substance) 18.5 3.5 20.0 20.0 sodium 18.2 - 18.6 18.6 sodium - 23.0 - - Tetraacetylethylenediamine (TAED) 6.4 3.4 5.8 5.8 Cellulose ⁇ component a) ⁇ 3.4 4.0 - 6.0 Citric acid ⁇ component of component b) ⁇ 3.2 3.5 3.5 - Na 2
- the hardness of the tablets was measured by deformation of the tablet until fracture, wherein the force applied to the side surfaces of the tablet and the maximum force of the tablet withstood, was determined.
- the tablet was placed in a beaker of water (600ml water, temperature 30 ° C) and the time to complete tablet disintegration measured.
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Inorganic Chemistry (AREA)
- Molecular Biology (AREA)
- Emergency Medicine (AREA)
- Detergent Compositions (AREA)
Description
Die genannten Lösungsvorschläge führen bei der Tablettenherstellung von Arzneimitteln zum gewünschten Erfolg. Im Wasch- und Reinigungsmittelbereich tragen sie zwar zu einer Verbesserung der Zerfallseigenschaften von wasch- oder reinigungsaktiven Tabletten bei; jedoch ist die erreichte Verbesserung in vielen Fällen nicht ausreichend. Dies gilt insbesondere dann, wenn der Anteil an klebrigen organischen Substanzen in den Tabletten, beispielsweise an anionischen und/oder nichtionischen Tensiden, steigt. Zusätzlich kann der Einsatz der Zerfallshilfsmittel in wasch- und reinigungsaktiven Formkörpern zu spezifischen Problemen führen, die Arzneimitteln völlig unbekannt sind.
Das gasentwickelnde Brausesystem {Komponente b)} kann aus einer einzigen Substanz bestehen, die bei Kontakt mit Wasser ein Gas freisetzt. Unter diesen Verbindungen ist insbesondere das bereits oben erwähnte Magnesiumperoxid zu nennen, das bei Kontakt mit Wasser Sauerstoff freisetzt. Üblicherweise besteht das gasfreisetzende Sprudelsystem jedoch seinerseits aus mindestens zwei Bestandteilen, die miteinander unter Gasbildung reagieren. Während hier eine Vielzahl von Systemen denk- und ausführbar ist, die beispielsweise Stickstoff, Sauerstoff oder Wasserstoff freisetzen, wird sich das in den erfindungsgemäßen Wasch- und Reinigungsmittelformkörpern eingesetzte Sprudelsystem sowohl anhand ökonomischer als auch anhand ökologischer Gesichtspunkte auswählen lassen. Bevorzugte Komponenten b) bestehen aus Alkalimetallcarbonat und/oder -hydrogencarbonat sowie einem Acidifizierungsmittel, das geeignet ist, aus den Alkalimetallsalzen in wäßrige Lösung Kohlendioxid freizusetzen.
Wasch- und Reingungsmittelformkörper [Gew.-%]: | ||||
Wasch- und Reinigungsmittelformkörper | 1 | 2 | 3 | 4 |
C9-13-Alkylbenzolsulfonat | 11,4 | 10,0 | 10,6 | 10,0 |
C12-18-Fettalkoholsulfat | - | 6,6 | 2,4 | 6,8 |
C12-18-Fettalkohol mit 7 EO | 5,8 | - | 4,8 | 6,2 |
Seife | 0,7 | 2,1 | 1,6 | 1,8 |
Natriumtripolyphosphat | - | 23,5 | - | - |
Zeolith 4A (bezogen auf wasserfreie Substanz) | 18,5 | 3,5 | 20,0 | 20,0 |
Natriumperborat | 18,2 | - | 18,6 | 18,6 |
Natriumpercarbonat | - | 23,0 | - | - |
Tetraacetylethylendiamin (TAED) | 6,4 | 3,4 | 5,8 | 5,8 |
Cellulose {Komponente a)} | 3,4 | 4,0 | - | 6,0 |
Citronensäure {Bestandteil der Komponente b)} | 3,2 | 3,5 | 3,5 | - |
Na2CO3 {Bestandteil der Komponente b)}* | 8,6 | - | 8,1 | 6,3 |
NaHCO3 {Bestandteil der Komponente b)}* | 6,4 | 7,0 | 6,8 | - |
amorphes Natriumsilikat | 3,3 | 2,1 | 3,0 | 3,4 |
Acrylsäure-Maleinsäure-Copolymer | 2,7 | 2,5 | 2,5 | 2,6 |
Enzyme | 2,3 | 4,0 | 2,7 | 2,7 |
Aufheller | 0,2 | 0,2 | 0,2 | 0,2 |
Polyethylenglycol (Molmasse ca. 4000 g/mol) | - | 0,5 | - | - |
Salze / Wasser | Rest | Rest | Rest | Rest |
Waschmitteltabletten [physikalische Daten] | ||||
Tablette | Beisp. 1 | Beisp. 2 | Beisp. 3 | Beisp. 4 |
Tablettenhärte | 33 N | 25 N | 30-35 N | 30-35 N |
Tablettenzerfall | 5-10 sec | 5-10 sec | > 5 min | 3 min |
Rückstand | - | - | 34 g | 12 g |
Claims (10)
- Wasch- und Reinigungsmittelformkörper aus verdichtetem teilchenförmigen Wasch- und Reinigungsmittel, umfassend Tensid(e), Builder sowie gegebenenfalls weitere Wasch- und Reinigungsmittelbestandteile, dadurch gekennzeichnet, daß der Formkörper weiterhina) 1 bis 10 Gew.-% eines oder mehrerer durch einen Sprühtrocknungs-, Granulier-, Agglomerier-, Kompaktier-, Pelletier- oder Extrusionsprozeß in eine grobkörnigere Form überführter, quellfähiger, wasserunlöslicher Desintegrationshilfsmittel undb) 3 bis 60 Gew.-% eines gasentwickelnden Brausesystems
- Wasch- und Reinigungsmittelformkörper nach Anspruch 1, dadurch gekennzeichnet, daß die Komponente a) ausgewählt ist aus den natürlichen und synthetischen Polysacchariden und ihren Derivaten.
- Wasch- und Reinigungsmittelformkörper nach einem der Ansprüche 1 oder 2, dadurch gekennzeichnet, daß die Komponente b) aus Alkalimetallcarbonat und/oder - hydrogencarbonat sowie einem Acidifizierungsmittel, das geeignet ist, aus den Alkalimetallsalzen in wäßriger Lösung Kohlendioxid freizusetzen, besteht.
- Wasch- und Reinigungsmittelformkörper nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß als Komponente a) 1 bis 10 Gew.-%, vorzugsweise 2 bis 7 Gew.-% und insbesondere 3 bis 5 Gew.-%, bezogen auf den gesamten Formkörper, einer Cellulose oder eines Cellulosederivates eingesetzt werden.
- Wasch- und Reinigungsmittelformkörper nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß als Komponente b) 2 bis 20 Gew.-%, vorzugsweise 3 bis 15 Gew.-% und insbesondere 5 bis 10 Gew.-% eines Alkalimetallcarbonats oder -hydrogencarbonats sowie 1 bis 15, vorzugsweise 2 bis 12 und insbesondere 3 bis 10 Gew.% eines Acidifizierungsmittels, jeweils bezogen auf den gesamten Formkörper, eingesetzt werden.
- Wasch- und Reinigungsmittelformkörper nach einem der Ansprüche 3 bis 5, dadurch gekennzeichnet, daß als Acidifizierungsmittel in der Komponente b) ein Stoff aus der Gruppe der organischen Di-, Tri- und Oligocarbonsäuren bzw. Gemische aus diesen eingesetzt werden.
- Verfahren zur Herstellung von Wasch- und Reinigungsmittelformkörpern durch Verpressen eines teilchenförmigen Wasch- und Reinigungsmittels, umfassend Tensid(e), Builder sowie gegebenenfalls weitere Wasch- und Reinigungsmittelbestandteile, dadurch gekennzeichnet, daß das zu verpressende Wasch- und Reinigungsmittel weiterhina) 1 bis 10 Gew.-% eines oder mehrerer durch einen Sprühtrocknungs-, Granulier-, Agglomerier-, Kompaktier-, Pelletier- oder Extrusionsprozeß in eine grobkörnigere Form überführter, quellfähiger, wasserunlöslicher Desintegrationshilfsmittel undb) 3 bis 60 Gew.-% eines gasentwickelnden Brausesystems,
- Verfahren nach Anspruch 7, dadurch gekennzeichnet, daß die teilchenförmige Wasch- und Reinigungsmittelzusammensetzung bei Temperaturen unterhalb von 30°C und Preßkräften unterhalb von 15 N/cm2 verpreßt wird.
- Waschverfahren unter Verwendung eines Formkörpers nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß der Formkörper über die Einspülvorrichtung einer Haushaltswaschmaschine in die Waschflotte eingebracht wird.
- Waschverfahren unter Verwendung eines Formkörpers nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß der Formkörper direkt mit der Wäsche in die Trommel einer Haushaltswaschmaschine eingebracht wird.
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19722832A DE19722832A1 (de) | 1997-05-30 | 1997-05-30 | Waschmittelformkörper mit verbesserten Auflöseeigenschaften |
DE19722832 | 1997-05-30 | ||
PCT/EP1998/003040 WO1998054283A1 (de) | 1997-05-30 | 1998-05-22 | Waschmittelformkörper mit verbesserten auflöseeigenschaften |
CA002289305A CA2289305A1 (en) | 1997-05-30 | 1999-11-10 | Detergent shaped body with enhanced dissolving properties |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0985023A1 EP0985023A1 (de) | 2000-03-15 |
EP0985023B1 true EP0985023B1 (de) | 2005-07-27 |
Family
ID=25681317
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP98929366A Revoked EP0985023B1 (de) | 1997-05-30 | 1998-05-22 | Waschmittelformkörper mit verbesserten auflöseeigenschaften |
Country Status (11)
Country | Link |
---|---|
EP (1) | EP0985023B1 (de) |
JP (1) | JP2002500690A (de) |
CN (1) | CN1257535A (de) |
AT (1) | ATE300606T1 (de) |
CA (1) | CA2289305A1 (de) |
DE (2) | DE19722832A1 (de) |
ES (1) | ES2246070T3 (de) |
HU (1) | HUP0002750A2 (de) |
PL (1) | PL337017A1 (de) |
SK (1) | SK163199A3 (de) |
WO (1) | WO1998054283A1 (de) |
Families Citing this family (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB9821190D0 (en) * | 1998-09-30 | 1998-11-25 | Unilever Plc | Detergent composition |
DE19847283A1 (de) * | 1998-10-14 | 2000-04-20 | Henkel Kgaa | Wasch- und Reinigungsmittelformkörper mit wasserfrei granuliertem Brausesystem |
PT1043391E (pt) * | 1999-03-29 | 2006-12-29 | Dalli Werke Gmbh & Co Kg | Granulado agente de desintegração compactado para corpos moldados prensados, seu fabrico e utilização |
DE19920119A1 (de) * | 1999-05-03 | 2000-11-09 | Henkel Kgaa | Waschverfahren mit Waschmitteltabletten |
JP3352977B2 (ja) | 1999-06-15 | 2002-12-03 | 花王株式会社 | 固形状洗剤 |
EP1090982A1 (de) * | 1999-10-09 | 2001-04-11 | Cognis Deutschland GmbH, Dep. Intellectual Properties | Formkörper mit verbesserter Wasserlöslichkeit |
DE10006306A1 (de) * | 2000-02-12 | 2001-08-23 | Buck Chemie Gmbh | Wirkstoff-Tablette, insbesondere als Reiniger- und/oder Entkalkertablette |
EP1162257B1 (de) * | 2000-06-09 | 2006-02-22 | The Procter & Gamble Company | Verfahren zur Behandlung von Gewebe mit einem Waschmittelformkörper enthaltend ein Ionenaustauscherharz |
DE10126706B4 (de) * | 2001-05-31 | 2008-06-19 | Henkel Kgaa | Handgeschirrspülmittelformkörper mit hohem Tensidgehalt |
CN101892133B (zh) * | 2010-07-22 | 2012-03-21 | 兰州泰坦生物科技有限责任公司 | 去除果蔬农药残留的泡腾片和制备方法及其使用方法 |
CN106190626A (zh) * | 2016-07-25 | 2016-12-07 | 南京尚易环保科技有限公司 | 一种覆膜型衣用片状洗涤剂及其制备方法 |
BR112022022264A2 (pt) * | 2020-05-28 | 2022-12-20 | Unilever Ip Holdings B V | Tablete para formar uma composição para lavagem de louças líquida e método para formar um líquido para lavagem de louças manual |
CN116083178A (zh) * | 2023-03-05 | 2023-05-09 | 余姚市德派日用品有限公司 | 一种地板清洁泡腾片及其制备方法 |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CH313947A (it) * | 1952-09-03 | 1956-05-31 | Pagani & C S A | Detergente sintetico in compresse per uso domestico ed industriale |
CA2040307A1 (en) * | 1991-04-12 | 1992-10-13 | Yogesh Sennik | Effervescent detergent tablets |
ZA916767B (en) * | 1991-08-27 | 1992-09-30 | Marta Florczak Beata | Detergents |
DE19500936A1 (de) * | 1995-01-14 | 1996-07-18 | Weber Rudolf Dipl Ing | Wasserlösliche Waschmittel und Waschhilfsmittel |
-
1997
- 1997-05-30 DE DE19722832A patent/DE19722832A1/de not_active Ceased
-
1998
- 1998-05-22 WO PCT/EP1998/003040 patent/WO1998054283A1/de active IP Right Grant
- 1998-05-22 CN CN98805272.5A patent/CN1257535A/zh active Pending
- 1998-05-22 ES ES98929366T patent/ES2246070T3/es not_active Expired - Lifetime
- 1998-05-22 PL PL98337017A patent/PL337017A1/xx unknown
- 1998-05-22 HU HU0002750A patent/HUP0002750A2/hu unknown
- 1998-05-22 AT AT98929366T patent/ATE300606T1/de not_active IP Right Cessation
- 1998-05-22 JP JP50020999A patent/JP2002500690A/ja active Pending
- 1998-05-22 EP EP98929366A patent/EP0985023B1/de not_active Revoked
- 1998-05-22 DE DE59812964T patent/DE59812964D1/de not_active Revoked
- 1998-05-22 SK SK1631-99A patent/SK163199A3/sk unknown
-
1999
- 1999-11-10 CA CA002289305A patent/CA2289305A1/en not_active Abandoned
Also Published As
Publication number | Publication date |
---|---|
JP2002500690A (ja) | 2002-01-08 |
SK163199A3 (en) | 2000-07-11 |
HUP0002750A2 (hu) | 2000-12-28 |
EP0985023A1 (de) | 2000-03-15 |
PL337017A1 (en) | 2000-07-31 |
ATE300606T1 (de) | 2005-08-15 |
DE19722832A1 (de) | 1998-12-03 |
CN1257535A (zh) | 2000-06-21 |
WO1998054283A1 (de) | 1998-12-03 |
CA2289305A1 (en) | 2001-05-10 |
ES2246070T3 (es) | 2006-02-01 |
DE59812964D1 (de) | 2005-09-01 |
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