EP0859827B2 - Verfahren zur herstellung eines amorphen alkalisilikats mit imprägnierung - Google Patents

Verfahren zur herstellung eines amorphen alkalisilikats mit imprägnierung Download PDF

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Publication number
EP0859827B2
EP0859827B2 EP96931031A EP96931031A EP0859827B2 EP 0859827 B2 EP0859827 B2 EP 0859827B2 EP 96931031 A EP96931031 A EP 96931031A EP 96931031 A EP96931031 A EP 96931031A EP 0859827 B2 EP0859827 B2 EP 0859827B2
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Prior art keywords
weight
spray
dried
silicate
alkali metal
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English (en)
French (fr)
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EP0859827A1 (de
EP0859827B1 (de
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Rene-Andres Artiga Gonzalez
Hubert Freese
Manfred Greger
Kathrin Schnepp
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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • 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

Definitions

  • the invention relates to a process for the preparation of free-flowing amorphous alkali metal silicates by spray drying, wherein the alkali metal silicate is subsequently impregnated with ingredients of detergents or cleaners.
  • Alkali silicates in granular form with higher bulk densities can be obtained according to the teachings of European Patent Application EP-A-0 526 978, wherein an alkali silicate solution having a solids content between 30 and 53 wt .-% in a heated drum brings, in the longitudinal axis a shaft having a plurality of arms reaching close to the inner surface of the drum rotates, the drum wall having a temperature between 150 and 200 ° C, and the drying process being assisted by a gas fed into the drum at a temperature between 175 and about 250 ° C , According to this method, a product is obtained whose average particle size is in the range between 0.2 and 2 mm. A preferred drying gas is heated air.
  • European Patent Application EP-A-0 542131 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.
  • the 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 with a solids content between 40 and 60 wt pseudoplastic mass having a free water content between 5 and 12 wt .-% is formed. Drying is assisted by a hot air flow (220 to 260 ° C).
  • German patent application DE-A-4419745 also describes a water-soluble, amorphous and granular alkali metal silicate, which is prepared in a similar manner as described in EP-A-0 526 978, but is siliceous.
  • amorphous is meant "X-ray amorphous”. This means that the alkali metal silicates do not give sharp reflections in X-ray diffraction recordings, but at best one or more broad maxima whose width is several degrees of the diffraction angle. However, this does not exclude the possibility of finding areas in electron diffraction experiments that yield sharp electron diffraction reflections. This is to be interpreted as meaning that the substance has microcrystalline regions in the order of up to about 20 nm (max 50 nm).
  • Granular amorphous sodium silicates which are obtained by spray-drying aqueous waterglass solutions, followed by milling and subsequent compacting and rounding with additional dehydration of the ground material are the content 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 about 18 to 20 wt .-% at bulk densities well above 500 g / l.
  • alkali silicates with secondary washing ability are known from European patent applications EP-A-0 561 656 and EP-A-0 488 868. These are compounds of alkali silicates with certain Q distributions and alkali carbonates.
  • granular detergents are described, which are composed of 2 granules.
  • the base granules are an anionic surfactant-containing spray-dried granules, in addition, the detergent contains a Sillkatgranulat on the nonionic surfactants are absorbed.
  • the silicate granules can be prepared from aqueous slurries, preferred granules being obtained by flash drying of the silicate slurries.
  • the older, not previously published German patent application DE-A-44 46 363 describes an amorphous alkali metal silicate with secondary washing power and a molar ratio of M 2 O: SiO 2 between 1: 1.5 and 1: 3.3, which with ingredients of washing or Cleaning agent is impregnated 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 metal carbonates and can be prepared by spray drying, granulation and / or compaction, for example roll compaction.
  • the silicate is impregnated with surfactants and in particular with nonionic surfactants. The inclusion of the impregnating agent reduces the flowability of the silicate material, but this can be restored if the impregnated material is subsequently treated with an aqueous solution.
  • the object of the invention was to develop a method in the use of which spray-dried amorphous silicates are prepared which, even if they do not contain additionally used alkali metal carbonates contained in the spray-to-dry approach - can be impregnated without a serious loss of flowability.
  • M alkali metal
  • sodium and / or potassium silicate come into consideration.
  • the sodium silicates are preferred.
  • the composition of the alkali silylate may be selected such that the sillate has a potassium content, calculated as K 2 O, of up to 5% by weight.
  • amorphous alkali metal silicates of the specified module in addition to the known water glasses so also commercially available granular silicates or carbonate-Slilkat compounds, suitable starting materials for the purposes of this invention.
  • These silicates may have been prepared by spray drying, granulation and / or compaction, for example by roll compaction, even if such preparation of the starting silicate products is not always meaningful, since these products must be redissolved in an aqueous mixture.
  • the aqueous mixture to be spray-dried essentially contains the said alkali metal silicates as the active substance, and it is particularly preferred to prepare a slurry which does not contain alkali metal carbonates or alkali carbonates in weight ratio alkali metal silicate (based on anhydrous active substance): alkali carbonate of 3: 1 to 20: 1 ,
  • spray-dried silicate compounds (a) are prepared which contain 55 to 95% by weight, preferably 60 to 90% by weight, of alkali metal silicate (based on anhydrous active substance), 0 to 15% by weight, preferably 2 to 10 wt .-% alkali carbonate and 5 to 22 wt .-%, preferably 10 to 20 wt .-% and in particular at least 15 wt .-% water.
  • ingredients of detergents or cleaning agents can be incorporated.
  • Their content is, based on the spray-dried silicate product of process step (a), preferably 0.5 to 20 wt .-% and in particular 1 to 15 wt .-%.
  • anionic surfactants such as alkylbenzenesulfonates, alkyl sulfates, 2,3-alkyl sulfates, alkyl ether sulfates and soaps, but also neutral salts such as sodium or potassium sulfates, graying inhibitors or nonionic surfactants such as alkyl polyglycosides or optionally alkoxylated polyhydroxy fatty acid esters .
  • anionic surfactants and / or organic cobuilders preferably in amounts of from 1 to 15% by weight, based on the spray-dried silicate product of process step (a), are used in the spray-to-be-dried slurry.
  • Spray-dried products in contrast to granular products of equivalent composition usually due to the sintered surface of the spray-dried beads by a relatively low capacity for liquid at the usual processing temperatures liquid to waxy ingredients of detergents.
  • liquid to waxy ingredients of detergents In order for such ingredients to be applied to these spray-dried beads, their surface structure must first be destroyed or the surface area correspondingly increased.
  • the spray-dried silicatic products (a) with amounts of 3 to 40 wt .-% and in particular from 5 to 35 wt .-%, each based on the impregnated and possibly still finally dried silicate product, an aqueous dispersion of ingredients of Wash or cleaning agents impregnated.
  • Suitable impregnating agents are, for example, surfactants, foam inhibitors based on silicone and / or paraffin, or fabric softening compounds such as cationic surfactants. Particularly preferred are surfactants and foam inhibitors. Particularly preferred impregnating agents here are again nonionic surfactants, for example alkoxylated, preferably ethoxylated and / or ethoxylated and propoxylated aliphatic C 8 -C 22 -alcohols.
  • alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or contain linear and methyl-branched radicals in the mixture can, as they are usually present in Oxoalkoholresten.
  • EO ethylene oxide
  • alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 C atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 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 of these, 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 means which, for a particular product, may be an integer or a fractional number.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants, especially together with alkoxylated fatty alcohols, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the Alkyl chain, in particular fatty acid methyl esters, as described for example in Japanese Patent Application JP 58/217598 or which are preferably prepared according to the method described in International Patent Application WO-A-90/13533.
  • nonionic surfactants and alkyl glycosides of the general formula RO (G) x can be used in which R is a primary straight-chain or methyl-branched, especially in the 2-position methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10.
  • the stated nonionic surfactants may be used alone or in admixture with the other nonionic surfactants mentioned or else in combination with other non-water-soluble organic constituents, advantageously also using the said alkoxylated fatty alcohols as alkoxylated fatty alcohols as well as said alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters become.
  • the silicate products preferably contain 70 to 90% by weight of amorphous silicates, 0.1 to 2% by weight of foam-inhibiting oils and / or waxes based on silicone and / or paraffin and the remainder water.
  • these silicatic products may also contain other ingredients, for example anionic surfactants, in particular alkylbenzenesulfonates and / or alkyl sulfates, and / or cobuilders, in particular (polymeric) polycarboxylates, and / or phosphonates.
  • the content of these further ingredients is preferably below 20% by weight, in particular below 15% by weight, with particular preference even below 10% by weight.
  • spray-dried silicate products which are impregnated with organic ingredients of detergents or cleaners only have sufficient flowability if the impregnation agent is applied in the form of an aqueous dispersion and in particular in the form of an emulsion.
  • an emulsion of one or more nonionic surfactants and an aqueous solution of one or more inorganic salts is used.
  • a dispersion of nonionic surfactants with water alone is not sufficient to achieve a satisfactory flowability of the products.
  • dispersions are used which comprise aqueous solutions of inorganic salts. It is believed that the use of the aqueous salt solution, the viscosity of the dispersion is increased accordingly, so that an improved flowability of the finished product is effected.
  • salt solutions of silicates, carbonates, bicarbonates and / or sulfates are used in the aqueous dispersion.
  • silicates and (bi-) carbonates are particularly preferably used, sulfates are used only in smaller quantities.
  • the content of sulfate based on the total dispersion, preferably only 2 to 10 wt .-%. while the content of the dispersion of silicate and / or (bi-) carbonate may well be up to 40 or even 50 wt .-%.
  • a silicate product is used which has either served as starting material for process step (a) or was obtained as spray-dried product according to process step (a).
  • a solution of the spray-dried product (a) in water preferably in amounts of 10 to 40 wt .-% and in particular in amounts of 15 to 35 wt .-%, each based on the total Dispersion is used.
  • the water content of the dispersions is preferably in a range of 10 to 40 wt .-%, in particular from 15 to 35 wt .-%.
  • Preferably used dispersions preferably have at least 40 wt .-% and in particular 50 to 85 wt .-% of dispersed organic ingredients of detergents or cleaners.
  • water depending on the impregnating agent used and also depending on the water content of the spray-dried silicate product (a), may be a critical factor with regard to the flowability of the finished product; Therefore, water is preferably not used in amounts above 20% by weight, based on the impregnated and not finally dried product, in the impregnation.
  • the water content of the finished silicate products is preferably not above 22 and in particular not above 20 wt .-%.
  • a final drying is connected to the first two process steps, this drying advantageously in a continuous Process is involved.
  • the impregnation step (b) can be carried out, for example, by first mixing the aqueous dispersion and preferably the aqueous dispersion of nonionic surfactant and aqueous inorganic salt solution by thoroughly mixing the nonionic surfactant and the aqueous solution or nonionic surfactant, inorganic solid salt and Water is produced.
  • the invention provides here that 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 of at least 2 different raw materials, are impregnated together in process step (b). It has proved to be particularly advantageous to use as a further compound a Alkalicarbonat Anlagens compound, which also contains organic cobuilders of the type described above. Preferably, 60 to 80 parts by weight of the spray-dried silicate product (a) and 5 to 20 parts by weight of at least one other solid powdery or granular product are impregnated together according to process step (b).
  • the invention provides that the product obtained according to process step (b) is aftertreated with a further liquid preparation form before drying, which may be carried out conclusively.
  • a spray-dried silicate product (a) are impregnated first with 5 to 38 parts by weight of an aqueous dispersion (b) and then with 2 to 15 parts by weight of another liquid preparation, preferably an aqueous solution of organic Cobulldem, aftertreated.
  • organic cobuilder solutions preferably have at least 20% by weight of solids, preferably 25 to 50% by weight of solids, in order not to excessively increase the water content in the silicate product.
  • the maximum water content should not exceed 22% by weight and especially not more than 20% by weight, if no drying is to be connected.
  • Such a process is therefore particularly suitable when either in process step (b) a dispersion is used, the high levels, for example more than 50 wt .-%, of organic dispersed ingredient and / or small amounts, for example less than 20 wt .-%, water or if only relatively small amounts of the aqueous dispersion, for example less than 25 wt .-% and in particular significantly less than 20 wt .-%, in each case based on the finished and not finally dried product used.
  • a drying preferably in a fluidized bed, carried out. This is preferably carried out directly after the above-described process steps without prior storage of the silicate product. Drying is then preferably carried out if the water content after the first two process steps and the further aftertreatment optionally carried out as the sum of the spray-dried silicate, the aqueous dispersion and optionally the aqueous preparation form from the after-treatment above 22 wt .-%, in particular above 20 wt .-% is.
  • the bulk density of the silicate products prepared according to the invention is generally between 300 and 650 g / l and can be further increased by compacting measures of known type, for example by roll compacting or extrusion.
  • the particle size distribution (sieve analysis) is generally so pronounced that no dust contents (particles with a diameter below 0, mm) are obtained and preferably 60 to 100 wt .-% of the particles, in particular 80 to 100 wt .-% of the particles has a particle diameter of at least 0.2 mm and not more than 1.6 mm.
  • the silicate products prepared according to the invention obtained after process step (b), a further aftertreatment or (c) can be further finely divided to increase the bulk density Dry powders are post-treated.
  • dry powders are zeolite, silicas, salts of fatty acids, such as calcium stearate, but also bleach activators and finely divided alkyl sulfates, or mixtures of zeolite or silica with at least one other of said powders.
  • the amorphous and impregnated alkali metal silicates prepared according to the invention can be used as admixing components in pulverulent to granular detergents or as constituents in the preparation of granular detergents or cleaners, preferably in granulation and / or compaction.
  • Such detergents or cleaners may have a bulk density of between 300 and 1200 g / l, preferably of 500 to 1000 g / l, and preferably contain the impregnated silicates prepared according to the invention in amounts of from 5 to 50% by weight, in particular in amounts of 10 to 40% by weight.
  • They can be prepared by any of the known methods such as mixing, spray drying, granulation, compacting such as roll compaction and extrusion.
  • Particularly suitable are those processes in which several subcomponents, for example spray-dried components and granulated and / or extruded components, are mixed together. It is also possible that further spray-dried or granulated components are subsequently applied in the treatment, for example, with nonionic surfactants, in particular ethoxylated fatty alcohols, according to the usual methods.
  • nonionic surfactants in particular ethoxylated fatty alcohols
  • Suitable surface modifiers are known from the prior art.
  • suitable finely divided zeolites, silicic acids, amorphous silicates, fatty acids or fatty acid salts for example calcium stearate, but especially mixtures of zeolite and silica, in particular in the weight ratio of zeolite to silica of at least 1: 1, or zeolite and calcium stearate particularly preferred.
  • Particularly preferred embodiments of the invention are extruded detergents or cleaners having a bulk density above 600 g / l which contain anionic and optionally nonionic surfactants and an amorphous and impregnated alkali metal silicate of the type according to the invention in the extrudate.
  • the particulate alkali metal silicates prepared according to the invention may serve once as an admixing component, as in other preparation processes, but it is particularly preferred to incorporate these alkali metal silicates into the premix to be extruded and to carry out coextrusion of these silicates.
  • the finished detergents or cleaners may contain the following ingredients in addition to the impregnated alkali metal silicates prepared according to the invention.
  • the following list also contains more specific descriptions for some of the ingredients found in the silicatic additives of this invention.
  • surfactants especially anionic surfactants and optionally nonionic surfactants, but also cationic, amphoteric or zwitterionic surfactants.
  • Preferred anionic surfactants of the sulfonate type are C 9 -C 13 -alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as those obtained, for example, from C 12 -C 18 -monoolefins having terminal or internal double bonds by sulfonation with gaseous Sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation obtained.
  • alkanesulfonates which are obtained from C 12 -C 18 -alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • esters of ⁇ -sulfo fatty acids esters of ⁇ -sulfo fatty acids (ester sulfonates), for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.
  • anionic surfactants are the ⁇ -sulfofatty acids or their di-salts obtainable by ester cleavage of the ⁇ -sulfofatty acid alkyl esters.
  • the mono-salts of the ⁇ -sulfofatty acid alkyl esters are obtained during their industrial production as an aqueous mixture with limited amounts of di-salts.
  • the disalt content of such surfactants is usually less than 50% by weight. of the anionic surfactant mixture, for example up to about 30% by weight.
  • sulfated fatty acid glycerol esters which are mono-, di- and triesters and mixtures thereof, as in the preparation by esterification by a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 mol Glycerol can be obtained.
  • Suitable surfactants of the sulfate type are the sulfuric acid monoesters of primary alcohols of natural and synthetic origin.
  • alk (en) ylsulfates are the alkali metal salts and, in particular, the sodium salts of the sulfuric monoesters 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) ylsulfates of said chain length which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials.
  • C 16 -C 18 alk (en) ylsulfates are particularly preferred. It may also be of particular advantage and in particular for automatic detergents of advantage, C 16 -C 18 -Alk (en) ylsulfate in combination with lower melting anionic surfactants and in particular with those anionic surfactants having a lower Krafft point and at relatively low Washing temperatures of for example room temperature to 40 ° C show a low tendency to crystallize, use.
  • the compositions therefore comprise 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.
  • not only saturated alkyl sulfates, but also unsaturated alkenyl sulfates having an alkenyl chain length of preferably C 16 to C 22 are used.
  • mixtures of saturated sulfonated fatty alcohols predominantly composed of C 16 and unsaturated sulfonated fatty alcohols consisting predominantly of C 18 for example those derived from solid or liquid fatty alcohol mixtures of the type HD-Ocenol (R) (commercial product of the Applicant)
  • Weight ratios of alkyl sulfates to alkenyl sulfates of from 10: 1 to 1: 2 and in particular from about 5: 1 to 1: 1 are preferred.
  • 2,3-Alkyl sulfates which are prepared, for example, according to US Pat. Nos. 3,234,258 or 5,075,041 and can be obtained as commercial products of Shell Oil Company under the name DAN (R) , are suitable anionic surfactants.
  • sulfuric acid monoesters of 1 to 6 moles of ethylene oxide ethoxylated straight chain or branched C 7 -C 21 alcohols such as 2-methyl branched C 9 -C 11 alcohols with an average of 3.5 moles of ethylene oxide (EO) or C 12 -C 18 - Fatty alcohols with 1 to 4 EO are suitable. They are used in detergents due to their high foaming behavior only in relatively small amounts, for example in amounts of 1 to 5 wt .-%.
  • Preferred anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic esters and the 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 of these.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which in themselves constitute nonionic surfactants (see description below).
  • Sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred.
  • alk (en) yl-succinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • compositions may also contain soaps, preferably in amounts of from 0.2 to 5% by weight.
  • soaps preferably in amounts of from 0.2 to 5% by weight.
  • saturated fatty acid soaps such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular of natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.
  • the anionic surfactants and soaps may be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases such as mono-, di- or triethanolamine.
  • the anionic surfactants are preferably present in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • washing or cleaning agents in particular extruded detergents or cleaners, which contain 10 to 30% by weight of anionic surfactants are preferred.
  • at least 3% by weight and especially at least 5% by weight of sulfatic surfactants are preferred.
  • the detergents contain - based on the anionic surfactants in total - at least 15% by weight, in particular from 20 to 100% by weight, of sulphatic surfactants.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten.
  • EO ethylene oxide
  • the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten.
  • 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 of these, 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 means which, for a particular product, may be an integer or a fractional number.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.
  • Suitable surfactants are polyhydroxy fatty acid amides of the formula (I) in R 2 CO is an aliphatic acyl radical having 6 to 22 carbon atoms, R 3 is hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups stands.
  • the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • the polyhydroxy fatty acid amides are preferably derived from reducing sugars having 5 or 6 carbon atoms, in particular from glucose.
  • Nonionic surfactants are present in the compositions according to the invention preferably in amounts of from 0.5 to 15% by weight, in particular in amounts of from 2 to 10% by weight.
  • the agents may also contain additional builders and cobuilders.
  • additional builders and cobuilders include in the first place the ingredients already mentioned above, for example polycarboxylates and polymeric polycarboxylates.
  • co-builders are preferably present in the compositions in amounts of from 2 to 20% by weight and in particular from 5 to 15% by weight.
  • customary builders such as phosphates, zeolites and crystalline phyllosilicates may be included in the compositions.
  • the synthetic zeolite used is preferably finely crystalline and contains bound water. Suitable zeolite A, for example, but also zeolite X and zeolite P and mixtures of A, X and / or P.
  • the zeolite can be used as a spray-dried powder or as undried, still moist from their preparation, stabilized suspension used.
  • the zeolite may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3 wt .-%, based on zeolite, of ethoxylated C 12 -C 18 fatty alcohols having 2 to 5 ethylene oxide groups , C 12 -C 14 fatty alcohols having 4 to 5 ethylene oxide groups or ethoxylated isotridecanols.
  • nonionic surfactants for example 1 to 3 wt .-%, based on zeolite, of ethoxylated C 12 -C 18 fatty alcohols having 2 to 5 ethylene oxide groups , C 12 -C 14 fatty alcohols having 4 to 5 ethylene oxide groups or ethoxylated isotridecanols.
  • zeolite suspensions and zeolite powder have an average particle size of less than 10 ⁇ m (volume distribution, measuring method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound
  • washing or cleaning agents contain 0 to 16% by weight of zeolite (based on anhydrous active substance) and 10 to 40% by weight of an impregnated alkali metal silicate prepared according to the invention, wherein it should be ensured in particular that the finished composition is at least 15 wt .-% of these builders mentioned.
  • the washing or cleaning agents therefore contain 0 to 5 wt .-% zeolite (based on anhydrous active substance) and 15 to 40 wt .-% of an impregnated alkali silicate-containing additive according to the invention or 10 to 30 wt .-% zeolite (Based on anhydrous active substance) and 15 to 40 wt .-% of a silicate-containing additive according to the invention prepared.
  • the zeolite is not only coextruded, but that the zeolite is partially or completely subsequently, so introduced after the extrusion step in the detergent or cleaning agent. Particular preference is given to washing or Detergents containing an extrudate which is free of zeolite inside the extrudate grain.
  • zeolite and crystalline phyllosilicates and / or conventional phosphates can be used.
  • phosphates are present only in small amounts, in particular up to a maximum of 10 wt .-%, in the washing or cleaning agents.
  • Such crystalline sheet silicates are described, for example, in European Patent Application EP-A-0 164 514.
  • Preferred crystalline layered silicates of the formula given are those in which M is sodium and x assumes the values 2 or 3.
  • both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O 5 .yH 2 O are preferred.
  • these crystalline sheet 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.
  • Useful organic cobuilders are, for example, the polycarboxylic acids preferably used in the form of their sodium salts, 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, and mixtures thereof
  • Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof.
  • polymeric polycarboxylates for example the sodium salts of polyacrylic acid or polymethacrylic acid, for example those having a relative molecular weight of 800 to 150,000 (based on acid).
  • Suitable copolymeric polycarboxylates are, in particular, those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
  • Their molecular weight relative to free acids is generally from 5000 to 200,000, preferably from 10,000 to 120,000 and in particular from 50,000 to 100,000.
  • biodegradable terpolymers for example those which are salts according to DE-A-43 00 772 as monomers of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or according to DE-C-42 21 381 as monomers of the salts of acrylic acid and 2-Alkylallylsuffonklare and sugar derivatives.
  • Further preferred copolymers are those which are described in the German patent applications DE 43 03 320 and DE 44 17 734 and preferably have as monomers acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.
  • compositions may also contain components that positively affect oil and grease washout from fabrics. This effect is particularly evident when a textile is soiled, which has been previously washed several times with a detergent according to the invention containing this oil and fat dissolving component.
  • the preferred oil and fat dissolving components include, for example, nonionic cellulose ethers such as methylcellulose and methylhydroxypropylcellulose with a proportion of methoxyl groups of 15 to 30 wt .-% and hydroxypropoxyl groups of 1 to 15 wt .-%, each based on the nonionic Cellulose ethers, as well as the known from the prior art polymers of phthalic acid and / or terephthalic acid or derivatives thereof, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionic modified derivatives thereof.
  • compositions may also contain ingredients which further enhance the solubility, particularly of the heavy granules.
  • ingredients which further enhance the solubility, particularly of the heavy granules.
  • Such components and the introduction of such components are described for example in International Patent Application WO-A-93/02176 and in German Patent Application DE 42 03 031.
  • the preferred ingredients include in particular fatty alcohols with 20 to 80 moles of ethylene oxide per mole of fatty alcohol, such as tallow fatty alcohol with 30 EO and tallow fatty alcohol with 40 EO, but also fatty alcohols with 14 EO and polyethylene glycols having a molecular weight between 200 and 2000.
  • bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -containing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid or diperdodecanedioic acid.
  • the content of the bleaching agents is preferably from 5 to 25% by weight and in particular from 10 to 20% by weight, it being advantageous to use perborate monohydrate.
  • Percarbonate is also preferred as a constituent. However, percarbonate is preferably not coextruded, but optionally added later.
  • bleach activators can be incorporated into the preparations.
  • N-acyl or O-acyl compounds which form organic peracids with H 2 O 2 , preferably N, N'-tetraacylated diamines, p- (alkanoyloxy) benzenesulfonates, furthermore carboxylic acid anhydrides and esters of polyols, such as glucose pentaacetate.
  • bleach activators are acetylated mixtures of sorbitol and mannitol, as described, for example, in European Patent Application EP-A-0 525 239.
  • the content of bleach-activating agents in bleach activators is in the usual range, preferably between 1 and 10% by weight, and in particular between 3 and 8% by weight.
  • Particularly preferred bleach activators are N, N, N ', N'-tetraacetylethylenediamine (TAED), 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine (DADHT) and acetylated sorbitol-mannitol mixtures (SORMAN).
  • 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 foam inhibitors are, for example, organopolysiloxanes and mixtures thereof with microfine, optionally silanized silica and paraffins, waxes, microcrystalline waxes and mixtures thereof with silanated silica or bistearylethylenediamide. It is also advantageous to use mixtures of different foam inhibitors, for example those of silicones, paraffins or waxes.
  • foam inhibitors in particular silicone- and / or paraffin-containing foam inhibitors, are preferably bound to a granular, water-soluble or dispersible carrier substance.
  • a granular, water-soluble or dispersible carrier substance In particular, mixtures of paraffins and bistearylethylenediamides are preferred.
  • Suitable enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof. Particularly suitable are enzymatic agents obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus and Humicola insolens. Preferably, subtilisin-type proteases and in particular proteases derived from Bacillus lentus are used.
  • Enzyme mixtures for example from protease and amylase or protease and lipase or protease and cellulase or from cellulase and lipase or from protease, amylase and lipase or protease, lipase and cellulase, but in particular protease- and / or lipase-containing mixtures are of particular interest , Peroxidases or oxidases have also proved suitable in some cases.
  • the enzymes may be adsorbed to carriers and / or embedded in encapsulants to protect against premature degradation.
  • the proportion of enzymes, enzyme mixtures or enzyme granules may be, for example, about 0.1 to 5 wt .-%, preferably 0.1 to about 2 wt .-%.
  • Suitable stabilizers are the salts of polyphosphonic acids, in particular 1-hydroxyethane-1,1-diphosphonic acid (HEDP), diethylenetriaminepentamethylenephosphonic acid (DETPMP) or ethylenediamine tetramethylenephosphonic acid.
  • HEDP 1-hydroxyethane-1,1-diphosphonic acid
  • DETPMP diethylenetriaminepentamethylenephosphonic acid
  • ethylenediamine tetramethylenephosphonic acid ethylenediamine tetramethylenephosphonic acid.
  • the agents may also contain other enzyme stabilizers.
  • enzyme stabilizers For example, 0.5 to 1 wt .-% sodium formate can be used.
  • 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 pyroboric acid (tetraboric acid H 2 B 4 O 7 ).
  • Graying inhibitors have the task of keeping suspended from the fiber debris suspended in the fleet and thus to prevent graying.
  • Water-soluble colloids of mostly organic nature are suitable for this purpose, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or of cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
  • water-soluble polyamides containing acidic groups are suitable for this purpose.
  • soluble starch preparations and other than the above-mentioned starch products can be used, e.g. degraded starch, aldehyde levels, etc. Also polyvinylpyrrolidone is useful.
  • cellulose ethers such as carboxymethylcellulose (sodium salt), methylcellulose, hydroxyalkylcellulose and mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof, and polyvinylpyrrolidone, for example, in amounts of from 0.1 to 5% by weight, based on the compositions, used.
  • the agents may contain as optical brighteners derivatives of Diaminostilbendisulfonklare or their alkali metal salts. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or similarly constructed compounds which, instead of the morpholino group, a diethanolamino group , a methylamino group, an anilino group or a 2-methoxyethylamino group. Furthermore, brighteners of the type of substituted diphenylstyrene may be present, e.g.
  • silicate granules submitted, however, after mixing with the nonionic surfactant alone no longer free-flowing (not measurable!) And already so sticky to breiförmig that further exposure to the aqueous solution could not be performed.
  • Example 1 was carried out with 83 parts by weight of a spray-dried silicate granules having the composition specified in Example 1 with 10 parts by weight of an aqueous dispersion of 72 wt.% C 12 -C 18 -alcohol with 7 EO, 24 wt .-%. Water and 4 wt .-% sodium sulfate repeated. Subsequently, a post-treatment with 7 parts by weight of a 30 wt .-% aqueous solution of Sokalan CP5 (R) (copolymeric sodium salt of acrylic acid and maleic acid, commercial product of BASF, Federal Republic of Germany). The bulk density was 468 g / l. The trickle behavior was 79%.
  • silicate granules For comparison, 83 parts by weight of the specified spray-dried silicate granules were mixed with 10 parts by weight of C 12 -C 18 -alcohol with 7 EO. However, the silicate granules after mixing with the nonionic surfactant alone no longer free-flowing (not measurable!) And already so sticky to breiförmig that a further application of the aqueous Sokalan solution could not be performed.

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EP96931031A 1995-09-13 1996-09-05 Verfahren zur herstellung eines amorphen alkalisilikats mit imprägnierung Expired - Lifetime EP0859827B2 (de)

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PCT/EP1996/003905 WO1997010325A1 (de) 1995-09-13 1996-09-05 Verfahren zur herstellung eines amorphen alkalisilikats mit imprägnierung

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Römpp Lexikon der Chemie, Band 3, Seite 1956 (1990) †
Römpp Lexikon der Chemie, Band 5, Seite 4017 (1992) †
Römpp lexikon der Chemie, Band 6, Seite 4498 (1992) †

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DE59607182D1 (de) 2001-08-02
WO1997010325A1 (de) 1997-03-20
PL324860A1 (en) 1998-06-22
DE19533790A1 (de) 1997-03-20
EP0859827A1 (de) 1998-08-26
ES2160254T3 (es) 2001-11-01
ES2160254T5 (es) 2007-03-01
JP3889810B2 (ja) 2007-03-07
HUP9900372A3 (en) 2001-11-28
SK32098A3 (en) 1998-08-05
KR19990036403A (ko) 1999-05-25
KR100416832B1 (ko) 2004-07-22
ATE202597T1 (de) 2001-07-15
US5958864A (en) 1999-09-28
JPH11512463A (ja) 1999-10-26
HUP9900372A2 (hu) 1999-05-28
EP0859827B1 (de) 2001-06-27

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