EP0845028B1 - Procede de production d'un silicate alcalin amorphe soumis a une impregnation - Google Patents

Procede de production d'un silicate alcalin amorphe soumis a une impregnation Download PDF

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Publication number
EP0845028B1
EP0845028B1 EP96928415A EP96928415A EP0845028B1 EP 0845028 B1 EP0845028 B1 EP 0845028B1 EP 96928415 A EP96928415 A EP 96928415A EP 96928415 A EP96928415 A EP 96928415A EP 0845028 B1 EP0845028 B1 EP 0845028B1
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Prior art keywords
weight
silicate
dried
spray
alkali metal
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English (en)
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EP0845028A1 (fr
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Rene-Andres Artiga Gonzalez
Kathrin Schnepp
Manfred Greger
Katrin Burmeister
Peter Sandkühler
Volker Bauer
Adolf Wiche
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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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
    • C11D3/08—Silicates
    • 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

Definitions

  • the invention relates to a process for the production of free-flowing amorphous alkali silicates by spray drying, the alkali silicate then impregnated with ingredients from washing or cleaning agents is, as well as the use of such impregnated alkali silicates in detergents or cleaning agents.
  • Alkali silicates in granular form with higher bulk densities can according to the teaching of European patent application EP-A-0 526 978, whereby an alkali silicate solution with a solids content between 30 and introduces 53% by weight into a heated drum, one in the longitudinal axis Shaft with a variety of close to the inner surface of the drum Arms rotates, the drum wall having a temperature between 150 and 200 ° C and the drying process by a fed into the drum Supported gas with a temperature between 175 and about 250 ° C becomes. According to this process, a product is obtained, the middle one Particle size is in the range between 0.2 and 2 mm. A preferred one Drying gas is heated air.
  • European patent application EP-A-0 542 131 describes a process in which a product which is completely soluble in water at room temperature and has a bulk density of between 500 and 1200 g / l is obtained. Drying is preferably carried out using heated air.
  • a cylindrical dryer with a heated wall 160 to 200 ° C.
  • a rotor with blade-shaped blades rotates at such a speed that the silicate solution has a solids content of between 40 and 60% by weight pseudoplastic mass with a free water content between 5 and 12 wt .-% arises. Drying is supported by a hot air stream (220 to 260 ° C).
  • the unpublished international patent application WO 95/33684 also describes a water-soluble, amorphous and granular alkali silicate, which is similar to that described in EP-A-0 526 978 is produced, but contains silicic acid.
  • amorphous is meant "X-ray amorphous”. This means that the alkali silicates at X-ray diffraction images do not provide sharp reflections, but at most one or more broad maxima, the width of which is several degree units of the diffraction angle is. However, this does not mean that in electron diffraction experiments areas are found that are sharp Provide electron diffraction reflections. This is to be interpreted as meaning that Substance microcrystalline areas in the order of magnitude up to approx. 20 nm (max. 50 nm).
  • Granular amorphous sodium silicates which by spray drying aqueous Water glass solutions, subsequent grinding and subsequent compacting and Rounding can be obtained with additional removal of water from the ground material, are the contents of US Pat. Nos. 3,912,649, 3,956,467, 3,838,193 and 3,879,527.
  • the water content of the products obtained is at about 18 to 20 wt .-% with bulk weights well above 500 g / l.
  • EP-A-0 561 656 and EP-A-0 488 868 are known. These are compounds of alkali silicates with certain Q distributions and alkali carbonates.
  • the older, unpublished German patent application P 44 46 363.4 describes an amorphous alkali silicate with secondary washing power and a molar ratio of M 2 O: SiO 2 between 1: 1.5 and 1: 3.3, which is impregnated with ingredients of washing or cleaning agents and has a bulk density of 300 g / l.
  • the silicate carrier grain to be impregnated is preferably in granular form and / or as a compound with alkali carbonates and can be produced by spray drying, granulation and / or compacting, for example roller compaction.
  • the silicate is impregnated with surfactants and in particular with nonionic surfactants. By absorbing the impregnating agent, the flowability of the silicate material is reduced, but this can be restored if the impregnated material is subsequently treated with an aqueous solution.
  • the object of the invention was therefore to develop a method spray-dried amorphous silicates are produced that - even if they do not contain any additional alkali carbonates included - impregnated without a serious loss of free-flowing properties can be.
  • Sodium and / or potassium silicate are particularly suitable here. Sodium silicates are preferred for economic reasons. However, if, for reasons of application technology, a particularly high dissolution rate in water is important, it is advisable to replace sodium at least partially with potassium.
  • the composition of the alkali silicate can be chosen so that the silicate has a potassium content, calculated as K 2 O, of up to 5% by weight.
  • Preferred alkali silicates are in granular form and / or as a compound with alkali carbonate, preferably sodium and / or potassium carbonate, and / or have a bulk density between 300 and 1200 g / l, in particular from 350 to 800 g / l.
  • the water content of these preferably used amorphous alkali silicates or the compounds containing the amorphous alkali silicates is advantageously between 10 and 22% by weight, in particular between 12 and 20% by weight. Water contents of 14 to 18% by weight can be particularly preferred.
  • amorphous alkali silicates of the specified module also commercially available granular silicates or Carbonate-silicate compounds, suitable starting materials in the sense of this invention are.
  • These silicates can themselves be spray dried, Granulation and / or compacting, for example by roller compacting have been produced if such manufacture of the silicate Starting products also do not always make sense as these products must be dissolved again in an aqueous batch.
  • the aqueous batch to be spray-dried essentially contains the aforementioned Alkali silicates as active substance, it being particularly preferred that a slurry is made that does not contain alkali carbonates or alkali carbonates only in weight ratios of alkali silicate (based on anhydrous Active substance): Contains alkali carbonate from 3: 1 to 20: 1.
  • Embodiments of the invention are spray-dried compounds (a) prepared which 65 to 95 wt .-%, preferably 70 to 90 wt .-% alkali silicate (based on anhydrous active substance), 0 to 15% by weight, preferably 2 to 10% by weight of alkali carbonate and 5 to 22% by weight, preferably Contain 10 to 20 wt .-% and in particular 12 to 18 wt .-% water.
  • a prepared which 65 to 95 wt .-%, preferably 70 to 90 wt .-% alkali silicate (based on anhydrous active substance), 0 to 15% by weight, preferably 2 to 10% by weight of alkali carbonate and 5 to 22% by weight, preferably Contain 10 to 20 wt .-% and in particular 12 to 18 wt .-% water.
  • ingredients in particular ingredients of washing or cleaning agents incorporated become.
  • Their content is based on the spray-dried silicate product of process stage (a), preferably 0.5 to 20 % By weight and in particular 1 to 15% by weight.
  • It can be, for example surfactants, especially anionic surfactants such as alkylbenzenesulfonates, Alkyl sulfates, 2,3-alkyl sulfates, alkyl ether sulfates and soaps, however also about neutral salts like sodium or potassium sulfates, about graying inhibitors or nonionic surfactants such as alkyl polyglycosides or optionally alkoxylated Act polyhydroxy fatty acid esters.
  • anionic surfactants such as alkylbenzenesulfonates, Alkyl sulfates, 2,3-alkyl sulfates, alkyl ether sulfates and soaps, however also about neutral salts like sodium or potassium sulfates, about graying inhibitors
  • anionic surfactants in the spray-dried slurry and / or organic cobuilders preferably in amounts of 1 to 15 % By weight, based on the spray-dried silicate product of the process stage (a) used.
  • Organic cobuilders that can be used are, for example, those optionally shown in Form of their sodium salts used polycarboxylic acids, such as citric acid, Adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, Nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, as well as mixtures of this.
  • Preferred salts are the salts of polycarboxylic acids such as citric acid, Adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.
  • Suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches.
  • the hydrolysis can be carried out by customary processes, for example acid-catalyzed or enzyme-catalyzed. They are preferably hydrolysis products with average molecular weights in the range from 400 to 500,000.
  • DE dextrose equivalent
  • Both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher molar masses in the range from 2000 to 30000 can be used.
  • a preferred dextrin is described in British patent application 94 19 091.
  • the oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.
  • Such dextrins and processes for their preparation are known, for example, from European patent applications EP-A-0 232 202, EP-A-0 427 349, EP-A-0472 042 and EP-A-0 542 496 and international patent applications WO-A- 92/18542, WO-A-93/08251, WO-A-94/28030, WO-A-95/07303, WO-A-95/12619 and WO-A-95/20608.
  • a product oxidized at C 6 of the saccharide ring can be particularly advantageous.
  • Suitable cobuilders are oxydisuccinates and other derivatives of Disuccinates, preferably ethylenediamine disuccinate. Particularly preferred in this context are also glycerol disuccinates and glycerol trisuccinates, such as, for example, in US Pat. No. 4 524 009, US 4,639,325, in European patent application EP-A-0 150 930 and Japanese patent application JP 93/339896. Suitable Amounts used are those containing zeolite and / or silicate Formulations at 3 to 15% by weight.
  • organic cobuilders are, for example, acetylated Hydroxycarboxylic acids or their salts, which optionally also in Lactone form can be present and which have at least 4 carbon atoms and contain at least one hydroxy group and a maximum of two acid groups.
  • Such cobuilders are described, for example, in international WO-A-95/20029 described.
  • Suitable builder substances are oxidation products of carboxyl-containing ones Polyglucosans and / or their water-soluble salts, such as for example in international patent application WO-A-93/08251 be described or their production, for example, in the international Patent application WO-A-93/16110 is described. Also suitable are also oxidized oligosaccharides according to the older German patent application P 196 00 018.1.
  • polymeric polycarboxylates are particularly preferred, for example the sodium salts of polyacrylic acid or polymethacrylic acid, for example those with a molecular weight of 800 to 150,000 (based on acid).
  • Suitable copolymeric polycarboxylates are in particular those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid. Copolymers have proven particularly suitable of acrylic acid with maleic acid, the 50 to 90 wt .-% acrylic acid and contain 50 to 10% by weight of maleic acid.
  • Your molecular weight, based on free acids is generally 5000 to 200000, preferably 10,000 to 120,000 and especially 50,000 to 100,000.
  • biodegradable terpolymers are also preferred, for example those which according to DE-A-43 00 772 as monomers salts of acrylic acid and the maleic acid and vinyl alcohol or vinyl alcohol derivatives or according to DE-C-42 21 381 as monomer salts of acrylic acid and 2-alkylallylsulfonic acid as well as sugar derivatives.
  • Other preferred copolymers are those in the German patent applications DE 43 03 320 and DE 44 17 734 are described and as monomers preferably acrolein and Have acrylic acid / acrylic acid salts or vinyl acetate.
  • spray-dried products In contrast to granular products of equivalent composition, spray-dried products usually have a relatively low absorption capacity for ingredients of detergents or cleaning agents which are liquid to waxy at the usual processing temperatures because of the sintered surface of the spray-dried beads. So that such ingredients can be applied to the spray-dried beads, their surface structure must first be destroyed or the surface increased accordingly.
  • the spray-dried silicate products (a) are preferably impregnated in amounts of from 3 to 15% by weight and in particular from 5 to 12% by weight, based in each case on the impregnated and possibly finally dried silicate product.
  • Suitable impregnating agents are, for example, surfactants, silicone and / or paraffin-based foam inhibitors or textile-softening compounds such as cationic surfactants.
  • Particularly preferred impregnating agents are again nonionic surfactants, for example alkoxylated, preferably ethoxylated and / or ethoxylated and propoxylated, aliphatic C 8 -C 22 alcohols. These include in particular primary alcohols with preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be methyl-branched linearly or preferably in the 2-position or contain linear and methyl-branched radicals in the mixture can, as is usually present in oxo alcohol residues.
  • nonionic surfactants for example alkoxylated, preferably ethoxylated and / or ethoxylated and propoxylated, aliphatic C 8 -C 22 alcohols. These include in particular primary alcohols with preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be methyl-branche
  • alcohol ethoxylates with linear residues from alcohols of native origin with 12 to 18 carbon atoms for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are also preferred.
  • the preferred ethoxylated alcohols include, for example, C 12 -C 14 alcohols with 3 EO or 4 EO, C 9 -C 11 alcohol with 7 EO, C 13 -C 15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12 -C 18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C 12 -C 14 alcohol with 3 EO and C 12 -C 18 alcohol with 5 EO.
  • the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • nonionic surfactants usually specified below, which are usually used in washing or cleaning agents, are also suitable in principle.
  • Impregnating agent in the form of an aqueous dispersion and in particular in Form is applied as an emulsion.
  • the invention an emulsion of a nonionic surfactant and an aqueous solution of an organic cobuilder.
  • organic cobuilders are particularly suitable for the above however, the (co) polymeric polycarboxylates mentioned are preferred, which advantageously in amounts of 1 to 10 wt .-%, especially in Quantities of 4 to 10% by weight, based on the impregnated and possibly final dried silicate product.
  • the watery Solutions generally contain 10 to 45% by weight of the (co) polymers Polycarboxylates; Concentrated solutions are also conceivable.
  • the amount of water used can vary depending on the one used Impregnation agent and also depending on the water content of the spray-dried silicate product (a) is a critical factor represent; water is therefore preferably not used in the impregnation in amounts above 20% by weight, based on the impregnated and not final dried product used.
  • the water content of the finished silicate products is preferably not above 22 and in particular not above 18% by weight. So if through the water content of the spray-dried product and the after-treatment with the aqueous dispersion a water content above the above Limits in the product is reached in a preferred embodiment the invention a final drying of the first two process steps connected, this drying advantageously in a continuous process is involved.
  • the impregnation step (b) can be carried out, for example, in such a way that first the aqueous dispersion and preferably the aqueous dispersion of nonionic surfactant and organic cobuilder by intensive mixing of the nonionic surfactant and an aqueous solution of the organic water-soluble cobuilder or the nonionic surfactant, the organic Cobuilders and water is made.
  • the actual impregnation process can, however, be carried out in conventional mixers / granulators of the high-speed mixer type, for example a CB30 (R) recycler from Lödige, Germany, a Flexomix (R) from Schugi, Germany, or a Fukae GS30 mixer also take place in slower running mixers, for example ploughshare mixers from Lödige, in a conventional manner.
  • a CB30 (R) recycler from Lödige, Germany a Flexomix (R) from Schugi, Germany
  • Fukae GS30 mixer also take place in slower running mixers, for example ploughshare mixers from Lödige, in a conventional manner.
  • the process step (b) not only submitted the silicate product (a).
  • a spray-dried silicate Product (a) and at least one other solid, powdery or granular product which is a single raw material or a compound from at least 2 different raw materials, together in the process step (b) be impregnated.
  • an alkali (bi) carbonate containing compound which also contains organic cobuilders of the type described above, to use.
  • Compounds of this type are particularly preferred here, which more than 40 wt .-% organic cobuilders and 10 to 40 wt .-% Contain alkali carbonates.
  • mixtures of nonionic surfactants preferably ethoxylated C 12 -C 18 alcohols, and aqueous solutions of organic cobuilders in weight ratios of 3: 1 to 1: 3, in particular 2: 1 to 1: 2 used.
  • a spray-dried silicate product (a) with 10 to 30 parts by weight of an aqueous dispersion containing nonionic surfactants and organic cobuilders or 60 to 80 parts by weight of one spray-dried silicate product (a) and 5 to 20 parts by weight of at least one further solid powdery or granular product are impregnated with 10 to 30 parts by weight of an aqueous dispersion containing nonionic surfactants and organic cobuilders.
  • drying preferably in a fluidized bed, carried out.
  • the bulk density of the silicate products produced according to the invention is generally between 200 and 600 g / l and can be compacted Measures of a known type, for example by roller compaction or extrusion, can be further increased.
  • the particle size distribution (sieve analysis) is generally so pronounced that no dust particles (particles with a diameter below 0.1 mm) can be obtained and preferably 60 to 100% by weight of the particles, in particular 80 to 100% by weight of the Particles with a particle diameter of at least 0.2 mm and a maximum of 0.8 mm.
  • the silicatic ones produced according to the invention can Products obtained after process step (b) or (c) for further increase in bulk density aftertreated with finely divided dry powders become.
  • the dry powder used for 100 parts by weight of the silicate product are zeolite, silicas, salts of Fatty acids such as calcium stearate, but also bleach activators and fine particles Alkyl sulfates, or mixtures of zeolite or silica with at least another of the powders mentioned.
  • the amorphous and impregnated alkali silicates produced according to the invention can be used as an additive component in powdery to granular washing or cleaning agents or as a component in the manufacture of the granular Detergents or cleaning agents, preferably for granulation and / or compacting can be used.
  • Such washing or cleaning agents can have a bulk density between 300 and 1200 g / l, preferably from 500 to 1000 g / l, have and contain those prepared according to the invention impregnated silicates preferably in amounts of 5 to 50 % By weight, in particular in amounts of 10 to 40% by weight.
  • Your manufacture can by any of the known processes such as mixing, spray drying, granulating, Compacting such as roller compaction and extrusion take place.
  • Suitable are in particular those processes in which several sub-components, for example spray-dried components and granulated and / or extruded components are mixed together. It is also there possible that further spray-dried or granulated components subsequently in processing, for example with nonionic surfactants, in particular ethoxylated fatty alcohols, applied by the usual methods become. Especially in granulation and extrusion processes it is preferred to form any anionic surfactants present a spray-dried, granulated or extruded compound either subsequently as an admixture component in the process or as an additive use other granules.
  • Suitable surface modifiers are known from the prior art.
  • Particularly preferred embodiments of the invention are extruded Detergents or cleaning agents with a bulk density above 600 g / l, which anionic and optionally nonionic surfactants and a Amorphous and impregnated alkali silicate of those produced according to the invention Type contained in the extrudate.
  • This extruded washing or Detergent is based on the known extrusion processes, in particular refer to European patent 486 592.
  • the strand after exiting the hole shape by means of a Cutting device tailored to the specific granule dimension as well the plastic and possibly still moist extrudate to another shaping processing step and then dried, the impregnated alkali silicates produced according to the invention be used in the premix.
  • the finished washing or cleaning agents can be in addition to those according to the invention prepared impregnated alkali silicates the following Contain ingredients.
  • surfactants especially anionic surfactants and, if appropriate nonionic surfactants, but also cationic, amphoteric or zwitterionic surfactants.
  • Preferred anionic surfactants of the sulfonate type are C 9 -C 13 alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates, and disulfonates such as are obtained, for example, from C 12 -C 18 monoolefins with an end or internal double bond by sulfonating with gaseous Sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products is considered.
  • alkanesulfonates obtained from C 12 -C 18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • esters of ⁇ -sulfofatty acids are also suitable, for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.
  • suitable anionic surfactants are the ⁇ -sulfofatty acids obtainable by ester cleavage of the ⁇ -sulfofatty acid alkyl esters or their di-salts.
  • the mono-salts of the ⁇ -sulfofatty acid alkyl esters are obtained in their industrial production as an aqueous mixture with limited amounts of di-salts.
  • the disalt content of such surfactants is usually below 50% by weight of the anionic surfactant mixture, for example up to about 30% by weight.
  • Suitable anionic surfactants are sulfonated fatty acid glycerol esters, which Represent mono-, di- and triesters as well as their mixtures, as in the preparation by esterification by a monoglycerol with 1 to 3 mol Fatty acid or in the transesterification of triglycerides with 0.3 to 2 mol Glycerin can be obtained.
  • Suitable surfactants of the sulfate type are the sulfuric acid monoesters from primary alcohols of natural and synthetic origin.
  • the alk (en) yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid half esters of C 12 -C 18 alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred.
  • alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials.
  • C 16 -C 18 alk (en) yl sulfates are particularly preferred from the point of view of washing technology. It can also be particularly advantageous, and particularly advantageous for machine washing agents, to use C 16 -C 18 -alk (en) yl sulfates in combination with lower melting anionic surfactants and in particular with those anionic surfactants which have a lower Krafft point and relatively low ones Washing temperatures of, for example, room temperature to 40 ° C.
  • the compositions therefore contain mixtures of short-chain and long-chain fatty alkyl sulfates, preferably mixtures of C 12 -C 14 alkyl sulfates or C 12 -C 18 alkyl sulfates with C 16 -C 18 alkyl sulfates and in particular C 12 -C 16 -Alkyl sulfates with C 16 -C 18 -alkyl sulfates.
  • saturated alkyl sulfates but also unsaturated alkenyl sulfates with an alkenyl chain length of preferably C 16 to C 22 are used.
  • 2,3-alkyl sulfates which, for example, according to the US patents 3,234,258 or 5,075,041 are manufactured and sold as commercial products Shell Oil Company under the name DAN can be obtained Anionic surfactants.
  • the sulfuric acid monoesters of the straight-chain or branched C 7 -C 21 alcohols ethoxylated with 1 to 6 mol ethylene oxide such as 2-methyl-branched C 9 -C 11 alcohols with an average of 3.5 mol ethylene oxide (EO) or C 12 - C 18 fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are used in detergents only in relatively small amounts, for example in amounts of 1 to 5% by weight.
  • Preferred anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which represent monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8 to C 18 alcohol residues or mixtures thereof.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below).
  • alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • the agents can also be soaps, preferably in amounts of 0.2 to 5% by weight.
  • Saturated ones are suitable Fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, Stearic acid, hydrogenated erucic acid and behenic acid, and in particular from natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.
  • the anionic surfactants and soaps can be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, Di- or triethanolamine.
  • the anionic are preferably located Surfactants in the form of their sodium or potassium salts, especially in the form of Sodium salts.
  • detergents or cleaning agents especially preferred extruded washing or cleaning agents, which contain 10 to 30% by weight of anionic surfactants.
  • anionic surfactants preferably at least 3% by weight and in particular at least 5% % By weight of sulfate surfactants.
  • sulfate surfactants in the means - based on the total anionic surfactants - at least 15 wt .-%, in particular 20 to 100 wt .-% sulfate surfactants.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (E0) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred.
  • the preferred ethoxylated alcohols include, for example, C 12 -C 14 alcohols with 3 EO or 4 EO, C 9 -C 11 alcohol with 7 E0, C 13 -C 15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12 -C 18 alcohols with 3 E0, 5 E0 or 7 E0 and mixtures thereof, such as mixtures of C 12 -C 14 alcohol with 3 E0 and C 12 -C 18 alcohol with 5 EO.
  • the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • non-ionic surfactants that either as the sole nonionic surfactant or in combination with others nonionic surfactants, especially together with alkoxylated Fatty alcohols used are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl ester, as for example in the Japanese patent application JP 58/217598 are described or which are preferably according to the in the international patent application WO-A-90/13533 become.
  • alkyl glycosides of the general formula RO (G) x can also be used as further nonionic surfactants, in which R denotes a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, C atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10.
  • nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may be suitable.
  • the amount of this nonionic Surfactants are preferably no more than that of the ethoxylated ones Fatty alcohols, especially not more than half of them.
  • Suitable surfactants are polyhydroxy fatty acid amides of the formula (I), in the R 2 CO for an aliphatic acyl radical having 6 to 22 carbon atoms, R 3 for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups stands.
  • the polyhydroxy fatty acid amides are known substances that usually 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 can be obtained.
  • the polyhydroxy fatty acid amides are preferably derived from reducing sugars with 5 or 6 carbon atoms, especially from Glucose.
  • Nonionic surfactants are preferred in the agents according to the invention in amounts of 0.5 to 15% by weight, in particular in amounts of 2 to 10 % By weight.
  • the agents also contain additional builder substances and cobuilders.
  • the latter include primarily the ingredients already mentioned above, for example polycarboxylates and polymeric polycarboxylates.
  • cobuilders are preferably in the compositions in amounts of 2 to 20 % By weight and in particular from 5 to 15% by weight.
  • the synthetic zeolite used is preferably finely crystalline and contains bound water.
  • Zeolite A for example, but also zeolite X and zeolite P and mixtures of A, X and / or P are suitable.
  • the zeolite can be used as a spray-dried powder or as an undried stabilized suspension which is still moist from its production.
  • the zeolite may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C 12 -C 18 fatty alcohols with 2 to 5 ethylene oxide groups , C 12 -C 14 fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols. It is also possible to use zeolite suspensions and zeolite powder. Suitable zeolite powders have an average particle size of less than 10 ⁇ m (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
  • washing or Detergent 0 to 16% by weight zeolite (based on anhydrous active substance) and 10 to 40% by weight of an impregnated fabricated according to the invention Alkali silicate, in particular it should be ensured that the finished agent at least 15 wt .-% of these builder substances mentioned having.
  • the washing or cleaning agent therefore 0 to 5 wt .-% zeolite (based on anhydrous Active substance) and 15 to 40 wt .-% of a prepared according to the invention impregnated alkali silicate or 10 to 30 wt .-% zeolite (based on anhydrous active substance) and 15 to 40 wt .-% of an invention manufactured zeolite. It is possible that the zeolite is not only co-extruded, but that the zeolite is partially or wholly subsequently, i.e. after the extrusion step into the detergent or cleaning agent is introduced. Washing or washing are particularly preferred Detergents that contain an extrudate that is inside the extrudate grain is free of zeolite.
  • Crystalline layered silicates can also be used as substitutes for the zeolite and / or conventional phosphates are used. However, it is preferred that phosphates only in small amounts, in particular up to a maximum 10% by weight, are contained in the washing or cleaning agents.
  • Such crystalline layered silicates are described, for example, in European patent application EP-AO 164 514.
  • Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3.
  • both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O 5 .yH 2 O are preferred.
  • these crystalline layered silicates are preferably contained in the extrudates according to the invention only in amounts of not more than 10% by weight, in particular less than 8% by weight, advantageously not more than 5% by weight.
  • the agents can also contain components which and grease washability from textiles positively. This effect becomes particularly clear when a textile that is already soiled is soiled previously several times with a detergent according to the invention that this oil and contains fat-dissolving component, is washed.
  • nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion on methoxyl groups from 15 to 30% by weight and on hydroxypropoxyl groups from 1 to 15% by weight, based in each case on the nonionic cellulose ether, as well as the polymers of phthalic acid known from the prior art and / or terephthalic acid or its derivatives, in particular Polymers made from ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives of this.
  • nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion on methoxyl groups from 15 to 30% by weight and on hydroxypropoxyl groups from 1 to 15% by weight, based in each case on the nonionic cellulose ether, as well as the polymers of phthalic acid known from the prior art and / or terephthalic acid or its derivatives, in particular Polymers made from
  • the agents can also contain components which have solubility especially the heavy granules.
  • Such components and the introduction of such components for example in international patent application WO-A-93/02176 and in German patent application DE 42 03 031.
  • Ingredients include in particular fatty alcohols with 20 to 80 Moles of ethylene oxide per mole of fatty alcohol, for example tallow fatty alcohol with 30 EO and tallow fatty alcohol with 40 EO, but also fatty alcohols with 14 EO as well Polyethylene glycols with a molecular weight between 200 and 2000.
  • bleaching agents which can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracid salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.
  • 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.
  • Percarbonate is also preferred as an ingredient. However, percarbonate is preferably not co-extruded, but optionally mixed in subsequently.
  • 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, p- (alkanoyloxy) benzenesulfonates, furthermore caprolactam derivatives, carboxylic acid anhydrides and esters of polyols such as Glucose pentaacetate.
  • bleach activators are acetylated mixtures of sorbitol and mannitol, as for example in the European patent application EP-A-0 525 239.
  • the content of bleach Bleach activators are preferably in the usual range between 1 and 10% by weight and in particular between 3 and 8% by weight.
  • Particularly preferred bleach activators are N, N, N ', N'-tetraacetylethylene diamine (TAED), 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine (DADHT) and acetylated sorbitol-mannitol mixtures (SORMAN).
  • Suitable foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C 18 -C 24 fatty acids.
  • Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bistearylethylenediamide. Mixtures of various foam inhibitors are also used with advantages, for example those made of silicones, paraffins or waxes.
  • the foam inhibitors, in particular silicone and / or paraffin-containing foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance. Mixtures of paraffins and bistearylethylenediamides are particularly preferred.
  • Bacterial strains or fungi such as Bacillus are particularly suitable subtilis, Bacillus licheniformis, Streptomyces griseus and Humicola insolens obtained enzymatic active ingredients.
  • Proteases are preferred of the subtilisin type and especially proteases derived from Bacillus lentus won, used.
  • enzyme mixtures for example from protease and amylase or protease and lipase or lipolytic Enzymes or protease and cellulase or from cellulase and lipase or lipolytically active enzymes or from protease, amylase and lipase or lipolytically active enzymes or protease, lipase or lipolytic acting enzymes and cellulase, but especially protease and / or Mixtures containing lipase or mixtures with lipolytically active enzymes of special interest.
  • lipolytically active Enzymes are the well-known cutinases. Also peroxidases or oxidases have proven to be suitable in some cases.
  • amylases include in particular ⁇ -amylases, iso-amylases, pullulanases and pectinases.
  • Cellobiohydrolases, endoglucanases are preferably used as cellulases and ⁇ -glucosidases, which are also called cellobiases, or mixtures used from these. Because the different cellulase types can distinguish by their CMCase and Avicelase activities targeted mixtures of the cellulases set the desired activities become.
  • the enzymes can be adsorbed on carrier substances and / or in coating substances embedded to protect them against premature decomposition.
  • the amount the enzymes, enzyme mixtures or enzyme granules can for example about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight.
  • the salts of polyphosphonic acids come as stabilizers, in particular 1-hydroxyethane-1,1-diphosphonic acid (HEDP), diethylenetriaminepentamethylenephosphonic acid (DETPMP) or ethylenediaminetetramethylenephosphonic acid in Consideration.
  • HEDP 1-hydroxyethane-1,1-diphosphonic acid
  • DETPMP diethylenetriaminepentamethylenephosphonic acid
  • ethylenediaminetetramethylenephosphonic acid in Consideration.
  • the agents can also contain further enzyme stabilizers.
  • enzyme stabilizers For example, 0.5 to 1% by weight sodium formate can be used. It is also possible to use proteases which are stabilized with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme.
  • boron compounds for example boric acid, boron oxide, borax and other alkali metal borates, such as the salts of orthoboric acid (H 3 BO 3 ), metaboric acid (HBO 2 ) and pyrobic acid (tetraboric acid H 2 B 4 O 7 ), is particularly advantageous.
  • Graying inhibitors have the task of detaching from the fiber Keep dirt suspended in the fleet and prevent graying.
  • Water-soluble colloids of mostly organic nature are suitable for this, for example the water-soluble salts of polymeric carboxylic acids, Glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids Starch or the cellulose or salts of acidic sulfuric acid esters Cellulose or starch. Also water-soluble containing acidic groups Polyamides are suitable for this purpose.
  • soluble ones Use starch preparations and other starch products than those mentioned above, e.g. degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone is also useful.
  • cellulose ethers such as carboxymethyl cellulose are preferred (Na salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers, such as Methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and their mixtures, and polyvinylpyrrolidone, for example in amounts of 0.1 to 5% by weight, based on the composition.
  • the agents can, as optical brighteners, derivatives of diaminostilbenedisulfonic acid or their alkali metal salts. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or similarly constructed connections that instead the morpholino group is a diethanolamino group, a methylamino group, carry an anilino group or a 2-methoxyethylamino group. Brighteners of the substituted diphenylstyryl type may also be present be, e.g.
  • Example 1 was repeated with 75 parts by weight of a spray-dried sodium disilicate (water content 15% by weight) and 10 parts by weight of a Sokalan CPS (R) powder. The trickle behavior was 9%.
  • Example 2 was repeated with 15 parts by weight of an emulsion of 10 parts by weight of C 12 -C 18 fatty alcohol with 7 EO and 5 parts by weight of water.
  • the trickle behavior was 8%.
  • Example 1 (according to the invention)
  • Comparative Example 4 Comparative Example 4 was repeated, except that 9.5 parts by weight of C 12 -C 18 fatty alcohol with 7 EO and 15.8 parts by weight of a 30% by weight aqueous Sokalan CP5 (R) solution in the form a premixed emulsion was used in a high-speed mixer (the second granulation stage was omitted) and finally dried in a fluidized bed.
  • the trickle behavior was 68%.

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Claims (16)

  1. Procédé de production d'un silicate de métal alcalin amorphe sous forme de particules, présentant un rapport molaire M2O:SiO2 (M = métal alcalin) compris entre 1:1,5 et 1:3,3, caractérisé en ce que
    a) une préparation aqueuse, renfermant comme substance active, essentiellement un silicate de métal alcalin amorphe de la composition spécifiée, est séchée par pulvérisation et ensuite
    b) imprégnée d'une dispersion aqueuse de constituants de produits de lavage ou de nettoyage, un des constituants de cette dispersion étant un coadjuvant organique, et
    c) le cas échéant, séchée.
  2. Procédé selon la revendication 1, caractérisé en ce qu'on l'on prépare une préparation aqueuse, qui ne renferme pas de carbonates de métal alcalin ou seulement en proportions pondérales entre le silicate de métal alcalin (par rapport à la substance anhydre) et le carbonate de métal alcalin de 3:1 à 20:1.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce que l'on prépare un compound silicatique séché par pulvérisation (a), qui contient 65 à 95 % en poids, de préférence 70 à 90 % en poids de silicate de métal alcalin (par rapport à la substance active anhydre), 0 à 15 % en poids, de préférence 2 à 10 % en poids de carbonate de métal alcalin, ainsi que 5 à 22 % en poids, de préférence 10 à 20 % en poids, et en particulier 12 à 18 % en poids d'eau.
  4. Procédé selon une des revendications 1 à 3, caractérisé en ce que l'on incorpore dans la préparation à sécher par pulvérisation, d'autres constituants, en particulier des constituants de produits de lavage ou de nettoyage, dont la concentration, par rapport au produit silicatique séché par pulvérisation de l'étape de procédé (a), atteint de préférence 0,5 à 20 % en poids.
  5. Procédé selon une des revendications 1 à 4, caractérisé en ce que sont mis en oeuvre dans la préparation à sécher par pulvérisation, des surfactifs anioniques et/ou des coadjuvants organiques, de préférence en proportions de 1 à 15 % en poids par rapport au produit silicatique séché par pulvérisation de l'étape de procédé (a).
  6. Procédé selon une des revendications 1 à 5, caractérisé en ce que, dans l'étape de procédé (b), les produits silicatiques séchés par pulvérisation sont imprégnés d'une dispersion aqueuse de constituants de produits de lavage ou de nettoyage en concentrations de 3 à 15 % en poids et en particulier, de 5 à 12 % en poids, dans chaque cas par rapport au produit silicatique imprégné et, le cas échéant, ayant encore fait l'objet d'un séchage terminal.
  7. Procédé selon une des revendications 1 à 6, caractérisé en ce que l'on met en oeuvre comme dispersion aqueuse, une émulsion constituée d'un tensioactif non ionique et d'une solution aqueuse d'un coadjuvant organique.
  8. Procédé selon une des revendications 1 à 7, caractérisé en ce qu'un produit silicatique séché par pulvérisation (a) et au moins un autre produit solide, pulvérulent ou granulaire, qui est une matière première individuelle ou un compound constitué d'au moins 2 matières de départ différentes, sont imprégnés conjointement au cours de l'étape (b) de procédé.
  9. Procédé selon la revendication 8, caractérisé en ce que l'on met en oeuvre comme autre compound, un compound qui renferme du carbonate de métal alcalin et des coadjuvants organiques.
  10. Procédé selon la revendication 8 ou 9, caractérisé en ce que 60 à 80 parties en poids du produit silicatique séché par pulvérisation (a) et 5 à 20 parties en poids d'au moins un autre produit solide, pulvérulent ou granulaire sont imprégnés conjointement selon l'étape de procédé (b).
  11. Procédé selon une des revendications 1 à 10, caractérisé en ce que sont mis en oeuvre comme dispersion aqueuse, des mélanges de tensioactifs non ioniques, de préférence d'alcools en C12-C18 éthoxylés et de solutions aqueuses de coadjuvants organiques en rapports pondéraux de 3:1 à 1:3, en particulier de 2:1 à 1:2.
  12. Procédé selon la revendication 11, caractérisé en ce que 60 à 90 parties en poids d'un produit silicatique séché par pulvérisation (a) sont imprégnées avec 10 à 30 parties en poids d'une dispersion aqueuse, renfermant des tensioactifs non ioniques et des coadjuvants organiques, ou 60 à 80 parties en poids d'un produit silicatique séché par pulvérisation (a) et 5 à 20 parties en poids d'un autre produit solide, pulvérulent ou granulaire avec 10 à 30 parties en poids d'une dispersion aqueuse, renfermant des tensioactifs non ioniques et des coadjuvants organiques.
  13. Procédé selon une des revendications 1 à 12, caractérisé en ce que l'on procède à un séchage terminal, au cas où la teneur en eau cumulée du silicate séché par pulvérisation et de la dispersion aqueuse après les deux premières étapes de procédé, est supérieure à 22 % en poids, de préférence supérieure à 18 % en poids.
  14. Procédé selon une des revendications 1 à 13, caractérisé en ce que le produit silicatique, qui est obtenu après l'étape de procédé (b) ou (c) fait l'objet d'un traitement postérieur avec des poudres sèches en fines particules afin d'accroítre encore la densité en vrac.
  15. Procédé selon la revendication 14, caractérisé en ce que l'on met en oeuvre 1 à 5 parties en poids de la poudre sèche pour 100 parties en poids du produit silicatique.
  16. Utilisation d'un silicate de métal alcalin amorphe en fines particules, qui a été produit selon une des revendications 1 à 15, comme composant d'addition par mélangeage de produits de lavage ou de nettoyage.
EP96928415A 1995-08-15 1996-08-06 Procede de production d'un silicate alcalin amorphe soumis a une impregnation Expired - Lifetime EP0845028B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19529908A DE19529908A1 (de) 1995-08-15 1995-08-15 Verfahren zur Herstellung eines amorphen Alkalisilikats mit Imprägnierung
DE19529908 1995-08-15
PCT/EP1996/003466 WO1997007194A1 (fr) 1995-08-15 1996-08-06 Procede de production d'un silicate alcalin amorphe soumis a une impregnation

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EP0845028A1 EP0845028A1 (fr) 1998-06-03
EP0845028B1 true EP0845028B1 (fr) 2000-01-05

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JP (1) JPH11510844A (fr)
KR (1) KR19990036368A (fr)
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DE (2) DE19529908A1 (fr)
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US7226899B2 (en) 2003-12-23 2007-06-05 Kimberly - Clark Worldwide, Inc. Fibrous matrix of synthetic detergents

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DE19533790A1 (de) † 1995-09-13 1997-03-20 Henkel Kgaa Verfahren zur Herstellung eines amorphen Alkalisilikats mit Imprägnierung
DE19700775A1 (de) * 1997-01-13 1998-07-16 Henkel Kgaa Verfahren zur Herstellung aniontensidhaltiger wasch- und reinigungsaktiver Tensidgranulate
DE19710156A1 (de) * 1997-03-12 1998-09-17 Henkel Ecolab Gmbh & Co Ohg Granuliertes Waschmittel

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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
US3920586A (en) * 1972-10-16 1975-11-18 Procter & Gamble Detergent compositions
AU660101B2 (en) * 1992-08-07 1995-06-08 Colgate-Palmolive Company, The Heavy duty laundry detergent compositions of reduced dye transfer properties
DE4446363A1 (de) * 1994-12-23 1996-06-27 Henkel Kgaa Amorphes Alkalisilikat mit Imprägnierung
DE19501269A1 (de) * 1995-01-18 1996-07-25 Henkel Kgaa Amorphes Alkalisilikat-Compound

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7226899B2 (en) 2003-12-23 2007-06-05 Kimberly - Clark Worldwide, Inc. Fibrous matrix of synthetic detergents

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HUP9802376A2 (hu) 1999-01-28
EP0845028A1 (fr) 1998-06-03
DE59604128D1 (de) 2000-02-10
DE19529908A1 (de) 1997-02-20
ES2142603T3 (es) 2000-04-16
KR19990036368A (ko) 1999-05-25
WO1997007194A1 (fr) 1997-02-27
JPH11510844A (ja) 1999-09-21
ATE188505T1 (de) 2000-01-15
PL324634A1 (en) 1998-06-08

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