EP0595946B1 - Procede de fabrication de produits de lavage a densite apparente elevee et a vitesse de dissolution amelioree - Google Patents
Procede de fabrication de produits de lavage a densite apparente elevee et a vitesse de dissolution amelioree Download PDFInfo
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- EP0595946B1 EP0595946B1 EP92916049A EP92916049A EP0595946B1 EP 0595946 B1 EP0595946 B1 EP 0595946B1 EP 92916049 A EP92916049 A EP 92916049A EP 92916049 A EP92916049 A EP 92916049A EP 0595946 B1 EP0595946 B1 EP 0595946B1
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- liquid
- detergent
- solid
- surfactants
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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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
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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
- C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
- C11D17/065—High-density particulate detergent 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3707—Polyethers, e.g. polyalkyleneoxides
Definitions
- the invention relates to a process for the production of solid washing and cleaning agents which are characterized by an improved dissolving rate, in particular at low temperatures.
- Solid detergents and cleaning agents with a high bulk density i.e. Agents with a bulk density above 500 g / l often have a lower dissolution rate due to their compact shape and the resulting smaller surface area, especially at low temperatures around 15 to 60 ° C, than agents with a comparable composition, but with a bulk density of, for example, only 300 g / l.
- EP 208 534 describes spray-dried granules with improved dissolving behavior. This is achieved in that the aqueous slurry which is spray dried contains polyacrylate and in particular a mixture of polyacrylate, polyethylene glycol and nonionic surfactant.
- the object of the invention was to produce a solid washing and cleaning agent with a high bulk density, which contains conventional ingredients, including ethoxylated alcohols as nonionic surfactants, and which has an improved dissolution rate at temperatures between 15 and 60 ° C.
- the invention accordingly relates to a process for the production of solid detergents and cleaning agents with a high bulk density by combining solid and liquid detergent raw materials with simultaneous or subsequent shaping and, if desired, drying, anionic surfactants, builder substances and alkalizing agents being used as solid constituents, and nonionic surfactants being used as liquid constituents, and in which the liquid nonionic surfactants are used in an intimate mixture with a structure breaker in a weight ratio of liquid nonionic surfactant: structure breaker of 10: 1 to 1: 2 to improve the dissolution behavior and to facilitate incorporation.
- the structure breaker is selected from the group of lower polyalkylene glycols derived from straight-chain or branched glycols having two to six carbon atoms, their sulfates and disulfates, the water-soluble salts of mono- and / or disulfosuccinates of the lower polyalkylene glycols or mixtures of these, addition products from about 20 to 80 moles of ethylene oxide to one mole of an aliphatic alcohol having essentially 8 to 20 carbon atoms, ethoxylated, vicinal internal alkanediols or 1,2-alkanediols with a carbon chain having 8 to 18 carbon atoms and 4 to 15 moles of ethylene oxide per mole of diol , modified nonionic surfactants with a terminal acid group, alkylene glycol monoalkyl ethers of the general formula RO (CH 2 CH 2 O) n H, in which R represents a radical with 2 to 8 carbon atoms and n represents a number from 1 to 8,
- the liquid nonionic surfactants are preferably derived from ethoxylated fatty alcohols with 8 to 20 carbon atoms and an average of 1 to 15 moles of ethylene oxide per mole of alcohol and in particular from primary alcohols with preferably 9 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide per mole of alcohol, in which the alcohol residue may be linear or methyl-branched in the 2-position, or may contain linear and methyl-branched residues in the mixture, as is usually present in oxo alcohol residues.
- linear residues of alcohols of native origin with 12 to 18 carbon atoms such as, for example, coconut oil, tallow oil or oleyl alcohol, are particularly preferred.
- 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 restricted homolog distribution (narrow range ethoxylates, NRE).
- NRE narrow range ethoxylates
- alcohol ethoxylates are preferred which have an average of 2 to 8 ethylene oxide groups.
- the preferred ethoxylated alcohols include, for example, C 9 -C 11 oxo alcohol with 7 EO, C 13 -C 15 oxo alcohol with 3 EO, 5 EO or 7 EO and in particular C 12 -C 14 alcohols with 3 EO or 4 EO, C 12 -C 18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C 12 -C 14 alcohol with 3 EO and C 12 -C 18 alcohol with 5 EO.
- a number of both solid and liquid substances which are hydrophilic, water-soluble or water-dispersible are suitable as structure breakers.
- Suitable are, for example, lower polyalkylene glycols derived from straight-chain or branched glycols having 2 to 6 carbon atoms, preferably polyethylene glycol or polypropylene glycol, and having a relative molecular weight between 200 and 12,000.
- polyethylene glycols with a relative molecular weight of between 200 and 4,000 are preferred, the liquid polyethylene glycols with a relative molecular weight of up to 2,000 and in particular between 200 and 600 having particularly advantageous properties.
- the sulfates and in particular the disulfates of lower polyalkylene glycol ethers are suitable.
- the sulfates and / or disulfates which are derived from polyethylene glycols and Derive polypropylene glycols with a relative molecular mass between 600 and 6000 and in particular between 1,000 and 4,000.
- the disulfates generally originate from polyglycol ethers, such as those which can be caused by the slight traces of water in the alkoxylation of alcoholic components.
- Another group of suitable structure breakers consists of the water-soluble salts of mono- and / or disulfosuccinates of the lower polyalkylene glycol ethers.
- the corresponding polyethylene glycol ether and polypropylene glycol ether compounds are of particular importance, sulfosuccinates and disulfosuccinates of polyglycol ethers having a relative molecular weight between 600 and 6,000, in particular between 1,000 and 4,000, being particularly preferred.
- any salts but preferably the alkali metal salts, in particular the sodium and potassium salts, and ammonium salts and / or salts of organic amines, for example triethanolamine, can be used as structure breakers for the use of the anionically modified polyalkylene glycol ethers.
- the most important salts for practical use are the sodium and potassium salts of the sulfates, disulfates, sulfosuccinates and disulfosuccinates of polyethylene glycol and polypropylene glycol.
- Mixtures of the polyalkylene glycol ethers and their anionically modified derivatives are preferably also used in any mixing ratio.
- a mixture of polyalkylene glycol ether and the sulfosuccinates and / or disulfosuccinates of the polyalkylene glycol ether is preferred.
- a mixture of polyalkylene glycol ether and the corresponding sulfates and / or disulfates and a mixture of polyalkylene glycol ether and the corresponding sulfates and / or disulfates and the corresponding sulfosuccinates and / or sulfodisuccinates are also suitable.
- suitable and preferably used structure breakers are the addition products of about 20 to about 80 moles of ethylene oxide with 1 mole of an aliphatic alcohol having essentially 8 up to 20 carbon atoms, which have long been known ingredients of detergents and cleaning agents.
- the addition products of 20 to 60 mol and in particular of 25 to 45 mol of ethylene oxide with primary alcohols, such as, for example, coconut oil alcohol or tallow fatty alcohol, with oleyl alcohol, with oxo alcohols, or with secondary alcohols with 8 to 18 and preferably 12 to 18 carbon atoms, are particularly important.
- Examples of particularly preferred structure breakers from the group of highly ethoxylated alcohols are tallow fatty alcohol with 30 EO and tallow fatty alcohol with 40 EO. It is also preferred to use mixtures which contain highly ethoxylated alcohols, for example mixtures of tallow fatty alcohol with 40 EO and water or of tallow fatty alcohol with 40 EO and polyethylene glycol with a relative molecular weight between 200 and 2,000.
- Further suitable structure breakers are ethoxylated, vicinal internal alkanediols or 1,2-alkanediols with a carbon chain with 8 to 18 carbon atoms and 4 to 15 moles of ethylene oxide per mole of diol. It is possible for only one of the two OH groups or both OH groups of the alkanediol to be ethoxylated.
- Modified nonionic surfactants with a terminal acid group are also suitable as structure breakers. These are nonionic surfactants, especially fatty alcohols, in which an OH group has been converted into a group with a carboxyl group.
- Nonionic surfactants with a terminal acid group thus include esters or partial esters of a nonionic surfactant with a polycarboxylic acid or a polycarboxylic anhydride.
- acid-terminated nonionic surfactants are the known polyether carboxylic acids and esters or half esters of C 8 -C 18 alcohols with succinic anhydride, maleic anhydride, maleic acid or citric acid.
- alkylene glycol monoalkyl ethers of the general formula RO (CH 2 CH 2 O) n H, in which R represents a radical with 2 to 8 carbon atoms and n represents a number from 1 to 8.
- R represents a radical with 2 to 8 carbon atoms
- n represents a number from 1 to 8.
- additives are ethylene glycol monoethyl ether and diethylene glycol monobutyl ether.
- Water is also a suitable structural breaker in principle.
- the use of water as a structure breaker is less preferred.
- the aim is to keep the free water content in the agents as low as possible in order to achieve the highest possible active ingredient concentrations in the agents.
- anhydrous ingredients for example anhydrous soda or at least partially dewatered zeolite, are often used which are able to bind free water. It is therefore obvious that water is a less suitable structure breaker, since the agents become poorer in water during storage due to the internal drying of the agent, so that the positive effect of the improved dissolving rate after a storage period in use no longer or no longer comes into full effect.
- the liquid nonionic surfactants in particular the ethoxylated fatty alcohols, are used in intimate mixing with the structure breaker.
- This intimate mixing is achieved by producing either a homogeneous solution or a dispersion from the liquid nonionic surfactants used according to the invention and the hydrophilic, water-soluble or water-dispersible structure breakers.
- the additives even in very small amounts, for example around 8% by weight, based on the sum of liquid nonionic surfactant and structure breaker, bring about the desired improvement in the dissolution rate of the finished washing and cleaning agents, so that they preferably have liquid nonionic surfactant in a weight ratio: Structure breakers from 8: 1 to 1: 1.5 can be used.
- liquid nonionic surfactant and structure breaker can be used in all known processes in which washing and cleaning agents with a high bulk density, ie with a bulk density above 500 g / l, preferably above 600 g / l and in particular between 700 and 1000 g / l, and which contain liquid ethoxylated alcohols as nonionic surfactants according to the definition of the invention, are used.
- Examples of such known and preferred processes are granulation processes in which either the ingredients of a washing and cleaning agent or a spray-dried washing and Detergent or a mixture of spray-dried and non-spray-dried ingredients of detergents and cleaning agents is compacted in a high-speed mixer and simultaneously in this mixer or subsequently in another device, for example in a fluidized bed, with which the solution or dispersion according to the invention is applied.
- a method is preferred in which spray-dried and / or non-spray-dried ingredients of detergents and cleaning agents are granulated together with the solution or dispersion used according to the invention, which has been applied to a carrier, in particular to a zeolite-containing carrier.
- a method is preferred, which is described in detail in international patent application WO 91/02047.
- a solid, homogeneous premix is extruded in the form of a strand, with the addition of a plasticizer and / or lubricant, through hole shapes with opening widths of the predetermined granule dimension at high pressures between 25 and 200 bar.
- the strand is cut to the predetermined pellet dimension immediately after exiting the hole shape by means of a cutting device.
- the application of the high working pressure causes the premix to be plasticized during the formation of the granulate and ensures the cutting ability of the freshly extruded strands.
- the premix consists, at least in part, of solid, preferably finely divided, conventional ingredients of detergents and cleaning agents, to which liquid constituents may have been added.
- the solid ingredients can be tower powders obtained by spray drying, but also agglomerates, the mixture components selected in each case as pure substances which are mixed with one another in the finely divided state, and mixtures of these.
- the liquid ingredients are optionally added and then the plasticizer and / or lubricant selected according to the invention is mixed in.
- Preferred plasticizers and / or lubricants are aqueous solutions of polymeric polycarboxylates, as well as highly concentrated anionic surfactant pastes and nonionic surfactants.
- the solutions or dispersions of liquid nonionic surfactants and hydrophilic, water-soluble or water-dispersible structure breakers can either be added to the solid premix as a liquid constituent or as a plasticizer and / or lubricant, or they are part of a solid mixture component of the premix, whereby this solid mixture component consists of a carrier bead to which the solution or dispersion has been applied.
- the addition of the solution or the dispersion according to the invention in liquid form, that is to say not bound to a carrier bead, can be carried out at any point in the process, for example in the preparation of the premix, but also in the processing of the plasticized premix, but before it passes through the hole shape (perforated nozzle plate).
- solutions or dispersions according to the invention are preferably used in the production of washing and cleaning agents by extrusion under high pressure, the weight ratio of liquid nonionic surfactant: structure breaker in the solutions or dispersions being 10: 2 to 1: 1 and in particular 10: 3 to 10: 8 is.
- Kneaders of any configuration for example twin-screw kneaders, can preferably be selected as the homogenizing device.
- the intensive mixing process can in itself lead to a desired temperature increase. Moderately elevated temperatures of, for example, 60 to 70 ° C. are generally not exceeded.
- the premix is preferably fed continuously to a 2-screw kneader (extruder), the housing and the extruder granulation head of which are heated to the predetermined extrusion temperature, for example heated to 40 to 60 ° C.
- the premix is compressed at pressures from 25 to 200 bar, preferably above 30 bar and in particular at pressures from 50 to 180 bar, plasticized, extruded in the form of fine strands through the perforated die plate in the extruder head and finally by means of the extrudate a rotating knives preferably reduced to spherical to cylindrical granules.
- the hole diameter in the perforated nozzle plate and the strand cut length are based on the selected granule dimension.
- the production of granules of an essentially uniformly predeterminable particle size succeeds, and in particular the absolute particle sizes can be adapted to the intended use. In general, particle diameters up to at most 0.8 cm are preferred.
- Important embodiments provide for the production of uniform granules with diameters in the millimeter range, for example in the range from 0.5 to 5 mm and in particular in the range from approximately 0.8 to 3 mm.
- the length / diameter ratio of the chopped-off primary granules is in the range from about 1: 1 to about 3: 1. It is also preferred to feed the still plastic, moist primary granules to a further shaping processing step; edges present on the raw granulate are rounded off, so that ultimately spherical or at least approximately spherical granules can be obtained.
- small amounts of dry powder for example zeolite powder such as zeolite NaA powder, can also be used in this step.
- This shaping can be carried out in standard rounding machines, for example in rounders with a rotating base plate.
- the granules are then preferably fed to a drying step, for example a fluidized bed dryer.
- a drying step for example a fluidized bed dryer.
- extruded granules which contain peroxy compounds as bleaching agents for example perborate monohydrate
- the free water content of the dried granules is preferably up to about 3% by weight, in particular between 0.1 to 1% by weight.
- dry powders are again zeolite-NaA powder, but also precipitated or pyrogenic silica, as are commercially available, for example, as Aerosil (R) or Sipernat (R) (products from Degussa).
- Aerosil (R) or Sipernat (R) products from Degussa.
- Highly concentrated, at least 90% by weight fatty alcohol sulfate powder which essentially, ie at least 90%, consist of particles with a particle size smaller than 100 ⁇ m. Mixtures of zeolite and fatty alcohol sulfate powder are particularly preferred.
- the solid detergents and cleaning agents which are produced by the process according to the invention show an improved dissolution rate at temperatures between 15 and 60 ° C. and in particular between 20 and 45 ° C.
- detergents which contain 20 to 45% by weight of surfactants are preferred.
- Suitable anionic surfactants are, for example, those of the sulfonate and sulfate type.
- Suitable surfactants of the sulfonate type are alkylbenzenesulfonates (C 9 -C 15 alkyl), olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as are obtained, for example, from C 12 -C 18 monoolefins with a terminal and internal double bond by sulfonating with gaseous ones Sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products is considered.
- dialcan sulfonates which are obtainable from C 12 -C 18 alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization or by bisulfite addition to olefins, and in particular the esters of ⁇ -sulfofatty acids (ester sulfonates), for example the ⁇ -sulfonated methyl esters hydrogenated coconut, palm kernel or tallow fatty acids.
- Suitable surfactants of the sulfate type are the sulfuric acid monoesters from primary alcohols of natural and synthetic origin, in particular from fatty alcohols, for example coconut oil alcohols, tallow fatty alcohols, oleyl alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or the C 10 -C 20 oxo alcohols, and those secondary alcohols of this chain length.
- the sulfuric acid monoesters of the alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C 9 -C 11 alcohols with an average of 3.5 mol of ethylene oxide, are also suitable.
- Sulfated fatty acid monoglycerides are also suitable.
- Soaps from natural or synthetic, preferably saturated, fatty acids can also be used.
- Soap mixtures derived from natural fatty acids for example coconut, palm kernel or tallow fatty acids, are particularly suitable.
- Preferred are those which are composed of 50 to 100% of saturated C 12 -C 18 fatty acid soaps and 0 to 50% of oleic acid soaps.
- the anionic surfactants can be in the form of their sodium, potassium and ammonium salts and also as soluble salts of organic bases, such as mono-, di- or triethanolamine.
- the amount of anionic surfactants or anionic surfactant mixtures produced according to the invention is preferably 5 to 40, in particular 8 to 35,% by weight. It is particularly advantageous if the sulfonate and / or sulfate content of the agents is 10 to 35% by weight, in particular 15 to 30% by weight, and the soap content is up to 8% by weight, in particular 0%. 5 to 5% by weight.
- the anionic surfactants can be used in solid form, for example in spray-dried or granulated form, or in liquid to pasty form. Thus, it is preferred to incorporate the anionic surfactants used as plasticizers and / or lubricants in the form of an aqueous surfactant paste.
- the content of the agents in ethoxylated alcohols used according to the invention as nonionic surfactants is preferably 1 to 15% by weight and in particular 2 to 10% by weight.
- the content of the structure breakers used according to the invention inevitably results from this.
- the compositions preferably contain up to 5% by weight, in particular 1 to 3% by weight, of polyethylene glycol with a relative molecular weight between 200 and 1,500.
- the weight ratio of anionic surfactant: nonionic surfactant is preferably at least 1: 1 and in particular 1: 1 to 6: 1, for example 2: 1 to 6: 1.
- nonionic surfactants can also alkylglycosides of the general formula RO- (G) X , in which R is a primary straight-chain or in 2-position methyl-branched aliphatic radical with 8 to 22, preferably 12 to 18 carbon atoms, G is a symbol which represents a glycose unit with 5 or 6 carbon atoms, and the degree of oligomerization x is between 1 and 10, preferably is between 1 and 2 and in particular is significantly smaller than 1.4, for example in amounts of 1 to 10% by weight.
- R is a primary straight-chain or in 2-position methyl-branched aliphatic radical with 8 to 22, preferably 12 to 18 carbon atoms
- G is a symbol which represents a glycose unit with 5 or 6 carbon atoms
- the degree of oligomerization x is between 1 and 10, preferably is between 1 and 2 and in particular is significantly smaller than 1.4, for example in amounts of 1 to 10% by weight.
- Suitable and in particular ecologically harmless builder substances such as finely crystalline, synthetic water-containing zeolites of the NaA type, which have a calcium binding capacity in the range from 100 to 200 mg Ca0 / g (according to the information in DE 24 12 837) are used with preference. Their average particle size is usually in the range from 1 to 10 ⁇ m (measurement method: Coulter Counter, volume distribution).
- the zeolite content of the compositions is generally up to 50% by weight, preferably at least 10% by weight and in particular 20 to 40% by weight, based on the anhydrous substance.
- Zeolite NaA is produced in the form of a water-containing slurry (masterbatch), which is subjected to drying, in particular spray drying, using the processes customary today for the production of textile detergents. It is possible to use the zeolite or at least zeolite fractions in the form of the undried masterbatch or an only partially dried masterbatch.
- builder components which can be used in particular together with the zeolites are (co) polymeric polycarboxylates, such as polyacrylates, polymethacrylates and in particular copolymers of acrylic acid with maleic acid, preferably those from 50% to 10% maleic acid.
- the relative molecular weight of the homopolymers is generally between 1,000 and 100,000, that of the copolymers between 2,000 and 200,000, preferably 50,000 to 120,000, based on free acid.
- a particularly preferred acrylic acid-maleic acid copolymer has a relative molecular weight of 50,000 to 100,000.
- Suitable, albeit less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ethers, in which the proportion the acidity is at least 50%.
- polyacetal carboxylic acids as described, for example, in US Pat. Nos. 4,144,226 and 4,146,495, and polymeric acids which are obtained by polymerizing acrolein and subsequent disproportionation using alkalis and are composed of acrylic acid units and vinyl alcohol units or acrolein units.
- the (co) polymeric polycarboxylates are introduced into the process in solid form or in liquid form, ie in the form of an aqueous solution, preferably in the form of a 30 to 55% strength by weight aqueous solution.
- the content of (co) polymeric polycarboxylates in the agents is preferably up to 10% by weight and in particular 2 to 8% by weight.
- Usable organic builders are, for example, the polycarboxylic acids preferably used in the form of their sodium salts, such as citric acid and nitrilotriacetate (NTA), provided that such use is not objectionable for ecological reasons.
- NTA nitrilotriacetate
- alkali carbonate and alkali silicate especially sodium silicate with a molar ratio Na 2 O: SiO 2 of 1: 1 to 1: 4.0
- the alkalizing agents are preferably introduced into the process in solid form.
- the alkalizing agents at least in part in the form of an aqueous solution, for example in the form of an aqueous alkali silicate solution or a mixture of solid alkali carbonate and an alkali silicate solution.
- the sodium carbonate content of the agents is preferably up to 20% by weight, advantageously between 5 and 15% by weight.
- the sodium silicate content of the agents is generally up to 10% by weight and preferably between 2 and 8% by weight.
- the other detergent ingredients include graying inhibitors (dirt carriers), foam inhibitors, bleaching agents and bleach activators, optical brighteners, enzymes, fabric softening agents, dyes and fragrances as well as neutral salts.
- bleaching agents which can be used are, for example, peroxycarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracid salts or peracids, such as perbenzoates, peroxaphthalates, diperazelaic acid or diperdodecanedioic acid.
- the bleaching agent content of the agents is preferably 5 to 25% by weight and in particular 10 to 20% by weight, with perborate monohydrate being advantageously used.
- bleach activators can be incorporated into the preparations.
- these are N-acyl or O-acyl compounds which form organic peracids with H 2 O 2 , preferably N, N'-tetraacylated diamines, such as N, N, N ', N'-tetraacetylethylenediamine, furthermore carboxylic acid anhydrides and esters of polyols like glucose pentaacetate.
- the bleach activator content of the bleach-containing agents is in the usual range, preferably between 1 and 10% by weight and in particular between 3 and 8% by weight.
- Graying inhibitors have the task of keeping the dirt detached from the fibers suspended in the liquor and thus preventing graying.
- water-soluble colloids of mostly organic nature are suitable, such as, for example, the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
- Water-soluble polyamides containing acidic groups are also suitable for this purpose. Soluble starch preparations and starch products other than those mentioned above can also be used, for example degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone can also be used.
- Carboxymethyl cellulose (sodium salt), methyl cellulose, methyl hydroxyethyl cellulose and mixtures thereof and polyvinylpyrrolidone are preferably used, in particular in amounts of 0.5 to 5% by weight, based on the composition.
- the foaming power of the surfactants can be increased or decreased by combining suitable types of surfactants; a reduction can also be achieved by adding non-surfactant-like organic substances.
- a reduced foaming power, which is desirable when working in machines, is often achieved by combining different types of surfactants, for example sulfates and / or sulfonates with nonionic surfactants and / or with soaps.
- soaps the foam-suppressing effect increases with the degree of saturation and the C number of the fatty acid ester. Soaps of natural and synthetic origin which contain a high proportion of C 18 -C 24 fatty acids are therefore suitable as foam-inhibiting soaps.
- Suitable non-surfactant-like foam inhibitors are organopolysiloxanes and their mixtures with microfine, optionally silanized silica, paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica.
- Bisacylamides derived from C 12 -C 20 alkylamines and C 2 -C 6 dicarboxylic acids can also be used.
- Mixtures of various foam inhibitors are also advantageously used, for example those made from silicones and paraffins or waxes.
- the foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance or are admixed with the plasticizer and / or lubricant.
- the detergents can contain, as optical brighteners, derivatives of diaminostilbenedisulfonic acid or its alkali metal salts.
- derivatives of diaminostilbenedisulfonic acid or its alkali metal salts for example, salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazin-6-yl-amino) -stilbene-2,2'-disulfonic acid or compounds of the same structure are suitable instead of the morpholino group, carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group.
- Brighteners of the substituted 4,4'-distyryl-di-phenyl type may also be present; for example the compound 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl. Mixtures of the aforementioned brighteners can also be used.
- uniformly white granules are obtained if the agents, in addition to the usual optical brighteners, are also present in conventional amounts, for example between 0.1 and 0.5, preferably around 0.1 to 0.3% by weight small quantities, contains, for example, 10 -6 to 10 -3 % by weight, preferably around 10 -5 % by weight, of a blue dye.
- a particularly preferred dye is Tinolux (R) (product name of Ciba-Geigy).
- Enzymes from the class of proteases, lipases and amylases or their mixtures are possible. Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used. The enzyme can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature decomposition.
- the salts of polyphosphonic acids are suitable as stabilizers, in particular for per-compounds and enzymes.
- HEDP 1-hydroxyethane-1,1-diphosphonic acid
- the washing and cleaning agents can be produced uniformly from extrudates which have the above-mentioned ingredients.
- the agents can also be obtained from a mixture of several different granules, of which the extrudates according to the invention form the main component.
- the bleach activator, the enzymes, and colors and fragrances can be subsequently added to the extrudates. It is preferred to use the bleach activator and the enzymes in each case in compacted granular form, for example as extrudates produced separately, which are obtained by means of a kneader of the configuration described above or via a pellet press.
- the premix was plasticized and then extruded at a pressure of 120 bar through the extruder head perforated die plate into fine strands with a diameter of 1.2 mm, which were chopped into approximately spherical granules using a knock-out knife (length / Diameter ratio about 1, hot cutting).
- the resulting warm granules were rounded off for 1 minute in a Marumerizer-type rounding machine and then dried at a supply air temperature of 120 ° C. in a fluidized bed dryer.
- the low-dust product was sieved through a sieve with a mesh size of 1.6 mm. The proportion above 1.6 mm was below 3%.
- the granules obtained had a bulk density of 820 g / l.
- the dissolution rate of the granules was determined using the conductivity measurement method:
- the dissolving time of the granules according to the invention was 2.20 minutes at 20 ° C. and 90% resolution.
- a premix of the same composition as in the example according to the invention was produced, but the ethoxylated alcohols and the polyethylene glycol were not added in a mixture, but separately in succession.
- the premix was extruded, cut, rounded, dried and sieved as in the example according to the invention.
- the bulk density of the granules V1 was about 820 g / l.
- the dissolving time of the granules V1 at 20 ° C. and 90% resolution was 3.77 minutes.
- a premix was prepared which contained the same constituents in the same amounts as in the example according to the invention, with the exception that the additive polyethylene glycol was dispensed with.
- the premix was as in the invention Example extruded, cut, rounded, dried and sieved.
- the bulk density of the granules V2 was about 820 g / l.
- the dissolving time of the Granules V2 was 3.85 minutes at 20 ° C and 90% resolution.
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
Claims (20)
- Procédé de fabrication de produits de lavage et de nettoyage solides, à densité apparente élevée, en réunissant les matières premières solides et liquides des produits de lavage, sous mise en forme simultanée ou postérieure et, éventuellement, séchage, à l'exclusion du séchage par pulvérisation, en utilisant comme constituants solides, des surfactifs anioniques, des substances adjuvantes et des agents d'alcalisation, et comme constituants liquides, des tensioactifs non ioniques, caractérisé en ce que l'on met en oeuvre - afin d'améliorer le comportement de dissolution et de faciliter l'incorporation - les tensioactifs non ioniques liquides en mélange intime avec un casseur de structure, sélectionné parmi le groupe des polyalkyléneglycols inférieurs, qui sont dérivés de glycols à chaîne droite ou ramifiée comportant deux à six atomes de carbone, de leurs sulfates et disulfates, des sels solubles dans l'eau de mono- et/ou des disulfosuccinates de polyalkyléneglycols inférieurs ou de mélanges de ceux-ci, des produits d'addition d'environ 20 à 80 moles d'oxyde d'éthylène à une mole d'un alcool aliphatique comportant essentiellement 8 à 20 atomes de carbone, d'alcanediols ou de 1,2-alcanediols internes, vicinaux, éthoxylés avec une chaîne de carbone comportant 8 à 18 atomes de carbone et 4 à 15 moles d'oxyde d'éthylène par mole de diol, de tensioactifs non ioniques modifiés possédant un groupe acide en fin de chaîne, de monoalkyléthers d'alkylèneglycols de la formule générale RO(CH2CH2On)H, dans laquelle R représente un radical comportant 2 à 8 atomes de carbone et n correspond à un nombre de 1 à 8, et l'eau, dans un rapport pondéral entre le tensioactif non ionique liquide et le casseur de structure de 10:1 à 1:2.
- Procédé selon la revendication 1, caractérisé en ce que le mélange intime entre le tensioactif non ionique liquide et le casseur de structure, en particulier dans le procédé par extrusion, ne contient pas de polycarboxylates (co-)polymères.
- Procédé selon la revendication 1 ou 2, caractérisé en ce que l'on met en oeuvre comme casseur de structure, du polyéthylèneglycol ou du polypropylèneglycol, des sulfates et/ou des disulfates de polyéthylèneglycol ou de polypropylèneglycol, des sulfosuccinates et/ou des disulfosuccinates de polyéthylèneglycol ou de polypropylèneglycol ou des mélanges de ceux-ci.
- Procédé selon une des revendications 1 à 3, caractérisé en ce que l'on met en oeuvre comme casseur de structure, des alcools gras en C8-C18 éthoxylés avec 20 à 60 EO, en particulier avec 25 à 45 EO, de préférence des alcools gras de suif avec 30 et 40 EO.
- Procédé selon une des revendications 1 à 4, caractérisé en ce que l'on met en oeuvre comme tensioactifs non ioniques liquides, des alcools aliphatiques éthoxylés comportant 8 à 20 atomes de carbone et, en moyenne, 1 à 15 moles d'oxyde d'éthylène par mole d'alcool.
- Procédé selon une des revendications 1 à 5, caractérisé en ce que le rapport pondéral entre le tensioactif non ionique liquide et le casseur de structure atteint 8:1 à 1:1,5.
- Procédé selon la revendication 6, caractérisé en ce que l'on met en oeuvre un mélange intime d'alcool éthoxylé et de casseur de structure, dans un rapport pondéral entre l'alcool éthoxylé et le casseur de structure de 10:2 à 1:1, de préférence, de 10:3 à 10:8.
- Procédé selon une des revendications 1 à 7, caractérisé en ce que l'on met en oeuvre les surfactifs anioniques sous forme solide ou liquide à pâteuse.
- Procédé selon une des revendications 1 à 8, caractérisé en ce que l'on met en oeuvre des tensioactifs actifs en quantités de 20 à 45 % en poids, par rapport au produit.
- Procédé selon la revendication 9, caractérisé en ce que l'on met en oeuvre 5 à 40 % en poids, de préférence 8 à 35 % en poids de surfactifs anioniques et 1 à 15 % en poids, de préférence 2 à 10 % en poids, de tensioactifs non ioniques, dans chaque cas par rapport au produit, le rapport pondéral entre le surfactif anionique et le tensioactif non ioniques atteignant de préférence au moins 1:1 et, en particulier 1:1 à 6:1.
- Procédé selon la revendication 9 ou 10, caractérisé en ce que l'on met en oeuvre 0,5 à 5 % en poids de savon, par rapport au produit.
- Procédé selon une des revendications 1 à 11, caractérisé en ce que l'on met en oeuvre comme autres constituants, un agent de blanchiment optique et un colorant bleu.
- Procédé selon une des revendications 1 à 12, caractérisé en ce que l'on met en oeuvre comme autres constituants solides, des agents de blanchiment, de préférence du perborate monohydraté, en quantités de 5 à 25 % en poids par rapport au produit.
- Procédé selon une des revendications 1 à 13, caractérisé en ce que l'on met en oeuvre comme autres constituants, des polycarboxylates (co-)polymères sous forme solide ou liquide.
- Procédé selon une des revendications 1 à 14, caractérisé en ce que l'on procède à la réunion et à la mise en forme selon un procédé, dans lequel un prémélange homogène solide est comprimé en boudins à des pressions comprises entre 25 et 200 bars, sous adjonction d'un plastifiant et/ou d'un lubrifiant, à des pressions élevées, comprises entre 25 et 200 bars, via des moules perforés avec des largeurs d'ouverture de la dimension de granulé prédéterminée, et en ce que le boudin est découpé à la dimension de granulé prédéterminée, directement après la sortie du moule perforé, au moyen d'un dispositif de coupe.
- Procédé selon la revendication 15, caractérisé en ce que l'activateur de blanchiment, les enzymes ainsi que les colorants et les matières odoriférantes sont ajoutés postérieurement par mélange aux produits d'extrusion.
- Procédé selon la revendication 16, caractérisé en ce que l'on met en oeuvre l'activateur de blanchiment et les enzymes, sous forme compactée, comme produits d'extrusion fabriqués séparément chacun, qui sont obtenus à l'aide d'un malaxeur ou d'une pastilleuse.
- Procédé selon une des revendications 1 à 14, caractérisé en ce que l'on procède à la réunion et à la mise en forme selon un procédé, dans lequel soit les constituants d'un produit de lavage et de nettoyage, soit un produit de lavage et de nettoyage séché par pulvérisation, ou un mélange de constituants séchés et non séchés par pulvérisation de produits de lavage et de nettoyage sont compactés dans un malaxeur à grande vitesse, et chargés du mélange intime du tensioactif non ionique et du casseur de structure, simultanément dans ce mélangeur ou à la suite de celui-ci dans un autre dispositif.
- Procédé selon une des revendications 1 à 14, caractérisé en ce que l'on procède à la réunion et à la mise en forme selon un procédé, dans lequel les constituants séchés et non séchés par pulvérisation des produits de lavage et de nettoyage sont granulés conjointement avec la solution ou la dispersion de tensioactif non ionique et de casseur de structure, qui a été appliquée sur un support, de préférence sur un support contenant de la zéolithe.
- Procédé selon une des revendications 1 à 19, caractérisé en ce que l'on ajuste une densité apparente des produits de lavage et de nettoyage entre 600 et 1000 g/l.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4124701A DE4124701A1 (de) | 1991-07-25 | 1991-07-25 | Verfahren zur herstellung fester wasch- und reinigungsmittel mit hohem schuettgewicht und verbesserter loesegeschwindigkeit |
DE4124701 | 1991-07-25 | ||
PCT/EP1992/001616 WO1993002176A1 (fr) | 1991-07-25 | 1992-07-16 | Procede de fabrication de produits de lavage a densite apparente elevee et a vitesse de dissolution amelioree |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0595946A1 EP0595946A1 (fr) | 1994-05-11 |
EP0595946B1 true EP0595946B1 (fr) | 1997-03-12 |
Family
ID=6437010
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP92916049A Expired - Lifetime EP0595946B1 (fr) | 1991-07-25 | 1992-07-16 | Procede de fabrication de produits de lavage a densite apparente elevee et a vitesse de dissolution amelioree |
Country Status (6)
Country | Link |
---|---|
EP (1) | EP0595946B1 (fr) |
JP (1) | JPH06509369A (fr) |
AT (1) | ATE150084T1 (fr) |
DE (2) | DE4124701A1 (fr) |
ES (1) | ES2098520T3 (fr) |
WO (1) | WO1993002176A1 (fr) |
Families Citing this family (47)
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EP0660873B2 (fr) † | 1992-09-01 | 2006-05-31 | The Procter & Gamble Company | Detergent en poudre de haute densite |
GB9300311D0 (en) * | 1993-01-08 | 1993-03-03 | Unilever Plc | Detergent powders and process for preparing them |
DE4303211C2 (de) * | 1993-02-04 | 1996-05-15 | Henkel Kgaa | Anionische Tenside mit verbesserter Löslichkeit |
DE4303176C2 (de) * | 1993-02-04 | 1997-07-31 | Henkel Kgaa | Feste Wasch-, Spül- und Reinigungsmittel |
DE4303448A1 (de) * | 1993-02-05 | 1994-08-11 | Henkel Kgaa | Gerüststoff für Wasch- oder Reinigungsmittel |
DE4319666A1 (de) * | 1993-06-14 | 1994-12-15 | Henkel Kgaa | Verfahren zur Herstellung fester Wasch- oder Reinigungsmittel mit hohem Schüttgewicht und verbesserter Rheologie |
DE4325500A1 (de) * | 1993-07-29 | 1995-02-02 | Henkel Kgaa | Verfahren zur Herstellung wasch- oder reinigungsaktiver Extrudate |
US5733862A (en) * | 1993-08-27 | 1998-03-31 | The Procter & Gamble Company | Process for making a high density detergent composition from a sufactant paste containing a non-aqueous binder |
DE4403323A1 (de) * | 1993-09-23 | 1995-08-10 | Henkel Kgaa | Extrudierte Wasch- oder Reinigungsmittel mit verbesserten Löseeigenschaften |
ES2364774T3 (es) * | 1994-02-24 | 2011-09-14 | HENKEL AG & CO. KGAA | Enzimas mejoradas y detergentes que las contienen. |
ATE512226T1 (de) | 1994-02-24 | 2011-06-15 | Henkel Ag & Co Kgaa | Verbesserte enzyme und detergentien damit |
DE4415362A1 (de) * | 1994-05-02 | 1995-11-09 | Henkel Kgaa | Verfahren zur Herstellung silikatischer Buildergranulate mit erhöhtem Schüttgewicht |
DE4415369C1 (de) * | 1994-05-02 | 1995-08-31 | Henkel Kgaa | Heterogene Tensidgranulate |
DE19501269A1 (de) | 1995-01-18 | 1996-07-25 | Henkel Kgaa | Amorphes Alkalisilikat-Compound |
DE19525378A1 (de) * | 1995-07-12 | 1997-01-16 | Henkel Kgaa | Amorphes Alkalisilicat-Compound |
DE19533790A1 (de) * | 1995-09-13 | 1997-03-20 | Henkel Kgaa | Verfahren zur Herstellung eines amorphen Alkalisilikats mit Imprägnierung |
DE19620364A1 (de) * | 1996-05-22 | 1997-11-27 | Basf Ag | Verwendung von mindestens dreiwertigen Alkoholen und deren Alkoxylierungsprodukten zur Erhöhung der Lösegeschwindigkeit von teilchenförmigen Waschmittelformulierungen in Wasser |
DE19624415A1 (de) * | 1996-06-19 | 1998-01-02 | Henkel Kgaa | Verfahren zur Herstellung von festen Wasch- oder Reinigungsmitteln |
DE19624416A1 (de) * | 1996-06-19 | 1998-01-02 | Henkel Kgaa | Verfahren zur Herstellung von festen Wasch- oder Reinigungsmitteln |
DE19638599A1 (de) * | 1996-09-20 | 1998-03-26 | Henkel Kgaa | Verfahren zur Herstellung eines teilchenförmigen Wasch- oder Reinigungsmittels |
WO1999013045A1 (fr) * | 1997-09-11 | 1999-03-18 | Henkel Kommanditgesellschaft Auf Aktien | Procede pour la production de detergents particulaires |
ES2162337T3 (es) * | 1996-11-18 | 2001-12-16 | Basf Ag | Alcoholes polivalentes y sus productos de alcoxilado en agentes de lavado en forma de particulas para el aumento de la velocidad de disolucion. |
DE19648014C2 (de) * | 1996-11-20 | 2002-09-19 | Cognis Deutschland Gmbh | Wasserfreie Tensidgemische |
DE19850223A1 (de) | 1998-10-31 | 2000-05-04 | Clariant Gmbh | Wasch- und Reinigungsmittel enthaltend alkoxylierte Fettsäurealkylester |
US6818606B1 (en) | 1999-06-16 | 2004-11-16 | Kao Corporation | Article for use in washing in sheet form |
US6610752B1 (en) | 1999-10-09 | 2003-08-26 | Cognis Deutschland Gmbh | Defoamer granules and processes for producing the same |
DE19953792A1 (de) | 1999-11-09 | 2001-05-17 | Cognis Deutschland Gmbh | Waschmitteltabletten |
DE19956802A1 (de) | 1999-11-25 | 2001-06-13 | Cognis Deutschland Gmbh | Waschmitteltabletten |
DE19962883A1 (de) | 1999-12-24 | 2001-07-12 | Cognis Deutschland Gmbh | Waschmitteltabletten |
DE10013763A1 (de) * | 2000-03-20 | 2001-10-18 | Henkel Kgaa | Verwendung von Duftalkoholalkoxylaten in Wasch- und Reinigungsmitteln und kosmetischen Zubereitungen |
DE10031619A1 (de) | 2000-06-29 | 2002-01-10 | Cognis Deutschland Gmbh | Tensidgranulate mit verbesserter Auflösegeschwindigkeit |
DE10044472A1 (de) | 2000-09-08 | 2002-03-21 | Cognis Deutschland Gmbh | Waschmittel |
DE10044471A1 (de) | 2000-09-08 | 2002-03-21 | Cognis Deutschland Gmbh | Waschmittel |
GB2367830A (en) * | 2000-10-12 | 2002-04-17 | Procter & Gamble | Process for preparing tablets |
GB0030669D0 (en) | 2000-12-15 | 2001-01-31 | Unilever Plc | Detergent compositions |
GB0030671D0 (en) | 2000-12-15 | 2001-01-31 | Unilever Plc | Detergent compositions |
DE10137925A1 (de) | 2001-08-07 | 2003-02-20 | Cognis Deutschland Gmbh | Geminitenside und Polyethylenglycol |
GB0124307D0 (en) | 2001-10-10 | 2001-11-28 | Unilever Plc | Detergent compositions |
GB0124308D0 (en) | 2001-10-10 | 2001-11-28 | Unilever Plc | Detergent compositions |
DE10242222A1 (de) * | 2002-09-12 | 2004-03-25 | Henkel Kgaa | Unter Druck kompaktiertes Wasch- oder Reinigungsmittel |
WO2004041982A1 (fr) | 2002-11-04 | 2004-05-21 | Unilever Plc | Composition de detergent de lessive |
EP1690922A1 (fr) * | 2005-02-11 | 2006-08-16 | The Procter & Gamble Company | Composition détergente solide |
DE102006021553A1 (de) | 2006-02-08 | 2007-08-16 | Henkel Kgaa | Fluidspeicher |
JP2009084525A (ja) * | 2007-10-03 | 2009-04-23 | Kao Corp | 洗浄剤組成物 |
AU2010240944B2 (en) | 2009-04-24 | 2013-01-10 | Unilever Plc | Manufacture of high active detergent particles |
DE102015002877A1 (de) | 2015-03-09 | 2016-09-15 | Henkel Ag & Co. Kgaa | Granulares Wasch- oder Reinigungsmittel mit verbesserter Lösegeschwindigkeit |
JP7095864B2 (ja) * | 2018-04-27 | 2022-07-05 | 株式会社ニイタカ | コーヒーマシン用タブレット洗浄剤及びコーヒーマシン用タブレット洗浄剤の製造方法 |
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US3849327A (en) * | 1971-11-30 | 1974-11-19 | Colgate Palmolive Co | Manufacture of free-flowing particulate heavy duty synthetic detergent composition containing nonionic detergent and anti-redeposition agent |
US3925224A (en) * | 1973-04-17 | 1975-12-09 | Church & Dwight Co Inc | Detergent additive composition |
CA1293421C (fr) * | 1985-07-09 | 1991-12-24 | Mark Edward Cushman | Compositions detergentes granulaires, sechees par pulverisation, a base de surfactif non ionique, de polyethylene glycol et de polyacrylate |
DE3812530A1 (de) * | 1988-04-15 | 1989-10-26 | Henkel Kgaa | Verfahren zur erhoehung der dichte spruehgetrockneter, phosphatreduzierter waschmittel |
CA2017922C (fr) * | 1989-06-09 | 1995-07-11 | Frank Joseph Mueller | Preparation de granules detergentes a haut pouvoir nettoyant au moyen d'un systeme de neutralisation continue |
JPH05500076A (ja) * | 1989-08-09 | 1993-01-14 | ヘンケル・コマンディットゲゼルシャフト・アウフ・アクチェン | 洗剤中で使用する高密度顆粒の製造方法 |
-
1991
- 1991-07-25 DE DE4124701A patent/DE4124701A1/de not_active Ceased
-
1992
- 1992-07-16 WO PCT/EP1992/001616 patent/WO1993002176A1/fr active IP Right Grant
- 1992-07-16 EP EP92916049A patent/EP0595946B1/fr not_active Expired - Lifetime
- 1992-07-16 DE DE59208196T patent/DE59208196D1/de not_active Expired - Fee Related
- 1992-07-16 JP JP5502585A patent/JPH06509369A/ja active Pending
- 1992-07-16 ES ES92916049T patent/ES2098520T3/es not_active Expired - Lifetime
- 1992-07-16 AT AT92916049T patent/ATE150084T1/de not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
ATE150084T1 (de) | 1997-03-15 |
DE59208196D1 (de) | 1997-04-17 |
DE4124701A1 (de) | 1993-01-28 |
JPH06509369A (ja) | 1994-10-20 |
WO1993002176A1 (fr) | 1993-02-04 |
ES2098520T3 (es) | 1997-05-01 |
EP0595946A1 (fr) | 1994-05-11 |
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