EP0859827A1 - Procede de production d'un silicate alcalin amorphe avec impregnation - Google Patents

Procede de production d'un silicate alcalin amorphe avec impregnation

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Publication number
EP0859827A1
EP0859827A1 EP96931031A EP96931031A EP0859827A1 EP 0859827 A1 EP0859827 A1 EP 0859827A1 EP 96931031 A EP96931031 A EP 96931031A EP 96931031 A EP96931031 A EP 96931031A EP 0859827 A1 EP0859827 A1 EP 0859827A1
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EP
European Patent Office
Prior art keywords
weight
silicate
spray
dried
water
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP96931031A
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German (de)
English (en)
Other versions
EP0859827B1 (fr
EP0859827B2 (fr
Inventor
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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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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 production of free-flowing amorphous alkali silicates by spray drying, the alkali silicate subsequently being impregnated with ingredients of washing or cleaning agents, and to the use of such impregnated alkali silicates in washing or cleaning agents.
  • Alkali silicates in granular form with higher bulk densities can be obtained according to the teaching of European patent application EP-A-0526978, an alkali silicate solution with a solids content of between 30 and 53% by weight being introduced into a heated drum with a shaft in its longitudinal axis with a plurality of arms extending close to the inner surface of the drum rotates, the drum wall having a temperature between 150 and 200 ° C and the drying process by a gas fed into the drum with a temperature between 175 and about 250 ° C is supported. This process gives a product 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-0 542 131 describes a process in which a product which is completely soluble in water at room temperature and has a bulk density between 500 and 1200 g / l is obtained.
  • the drying is preferably done using heated air.
  • a cylindrical dryer with a heated wall 160 to 200 ° C.
  • a rotor with scoop-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).
  • Granular amorphous sodium silicates which are obtained by spray drying aqueous water glass solutions, subsequent grinding and subsequent compacting and rounding 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 approximately 18 to 20% by weight with bulk weights significantly 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 488868. These are compounds of alkali silicates with certain Q distributions and alkali carbonates.
  • the older, not prepublished German patent application P 4443363.4 describes an amorphous alkali silicate with secondary washing power and a molar ratio of M2 ⁇ : Si ⁇ 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 / 1.
  • 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 process in the use of which spray-dried amorphous silicates are produced which - even if they do not contain any alkali metal carbonates additionally used in the spray-dried batch - can be impregnated without a serious loss of free-flowing properties.
  • a) is an aqueous one Approach containing, as active substance, essentially an amorphous alkali silicate of the specified composition, spray-dried and then b) impregnated with an aqueous dispersion of ingredients of detergents or cleaners, at least one organic ingredient of detergents or cleaners in water or is dispersed in an aque
  • Sodium and / or potassium silicate are particularly suitable here. Sodium silicates are preferred for economic reasons. If, however, value is placed on a particularly high rate of dissolution in water for technical reasons, it is advisable to at least partially replace sodium with potassium.
  • the composition of the alkali silicate can be selected so that the silicate has a potassium content, calculated as K2O, of up to 5% by weight.
  • amorphous alkali silicates of the module indicated in addition to the known water glasses, that is to say commercially available granular silicates or carbonate-silicate compounds, are suitable starting materials for the purposes of this invention.
  • These silicates can themselves have been produced by spray drying, granulation and / or compacting, for example by roller compaction, if such a preparation of the silicate starting products is not always expedient, since these products have to be dissolved again in an aqueous batch.
  • the aqueous batch to be spray-dried essentially contains the alkali silicates mentioned as the active substance, it being particularly preferred that a slurry is prepared which contains no alkali carbonates or alkali metal carbonates only in weight ratios of alkali silicate (based on anhydrous active substance): alkali metal carbonate from 3: 1 to 20 : 1 contains.
  • spray-dried silicate compounds (a) are prepared which contain 55 to 95% by weight, preferably 60 to 90% by weight alkali silicate (based on anhydrous active substance), 0 to 15% by weight, preferably contain 2 to 10% by weight of alkali carbonate and 5 to 22% by weight, preferably 10 to 20% by weight and in particular at least 15% by weight of water.
  • ingredients of detergents or cleaning agents can also be incorporated into the batch to be spray-dried.
  • Their content is preferably 0.5 to 20% by weight and in particular 1 to 15% by weight.
  • surfactants especially anionic surfactants such as alkylbenzenesulfonates, alkyl sulfates, 2,3-alkyl sulfates, alkyl ether sulfates and soaps, but also about neutral salts such as sodium or potassium sulfates, graying inhibitors or nonionic surfactants such as alkyl polyglycosides or possibly alk ⁇ act oxylated polyhydroxy fatty acid esters.
  • anionic sides and / or organic cobuilders are added to the spray-dried slurry, preferably in amounts of 1 to 15% by weight, based on the spray-dried silicate product Process stage (a) used.
  • 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, owing to 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 area increased accordingly.
  • the spray-dried silicate products (a) are preferably used in amounts of 3 to 40% by weight and in particular of 5 to 35% by weight, based in each case on the impregnated and possibly finally dried silicate product, of an aqueous solution Dispersion of ingredients from washing or cleaning agents impregnated.
  • Suitable impregnating agents are, for example, surfactants, foam inhibitors based on silicone and / or paraffin, or textile-softening compounds such as cationic surfactants. Tenides and foam inhibitors are particularly preferred. Particularly preferred impregnating agents are again nonionic surfactants, for example alkoxylated, preferably ethoxylated and / or ethoxylated and propoxylated, aliphatic C ⁇ -C22 alcohols.
  • 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 linear and methyl-branched radicals in the Can contain mixture, as they are usually present in oxo alcohol residues.
  • EO ethylene oxide
  • alcohol ethoxylates with linear residues from alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol are also average 2 to 8 EO per mole of alcohol is preferred.
  • Preferred ethoxylated alcohols include, for example, Ci2-Ci4 * alcohols with 3 EO or 4 EO, Cg-C j i-alcohol with 7 EO, Ci3-Ci5 alcohols containing 3 EO, 5 EO, 7 EO or 8 EO, Ci2 -Ci8 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of Ci2 ⁇ Ci4 alcohol with 3 EO and Ci2-Ci8 alcohol with 5 EO.
  • the degrees of ethoxylation given represent statistical mean values which can be an integer or a fraction for a special 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 of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • Another class of preferably used nonionic surfactants, which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, in particular together with alkoxylated fatty alcohols, 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 esters, as described, for example, in Japanese patent application JP 58/217598 or which are preferably prepared by the process described in international patent application WO-A-90/13533.
  • alkyl glycosides of the general formula R0 (G) x can also be used as further nonionic surfactants, in which R is a primary straight-chain or methyl-branched, in particular in the 2-position methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 ° C.
  • -Atoms means 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.
  • the nonionic surfactants mentioned can be used alone or in a mixture with the other nonionic surfactants mentioned, or also in combination with other non-water-soluble organic constituents, the organic dispersion constituent advantageously also the alkoxylated fatty alcohols mentioned, preferably, in addition to the alkoxylated fatty alcohols ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters are used.
  • 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 rest water.
  • these silicate products can also have further ingredients, for example anionic surfactants, in particular alkylbenzenesulfonates and / or alkylsulfates, 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 constituents of detergents or cleaning agents only have sufficient flowability when the impregnating 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 water or 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 which contain aqueous solutions of inorganic salts. It is assumed that the viscosity of the dispersion is correspondingly increased by the use of the aqueous salt solution, so that the finished product has improved free-flowing properties.
  • dispersions of nonionic surfactant and water are also sufficient.
  • the person skilled in the art can determine by means of a simple test (checking the pourability) whether he should use an aqueous salt solution in the dispersion or whether water is the only one inorganic component of the dispersion is sufficient.
  • a dispersion is used which, as the organic ingredient of detergents or cleaning agents, uses ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters of the type specified, but does not contain salt solutions as an inorganic constituent but only water.
  • salt solutions in particular of silicates, carbonates, bicarbonates and / or sulfates, are preferably used in the aqueous dispersion.
  • Silicates and (bi-) carbonates are used with particular preference, sulfates are only used in smaller amounts.
  • the sulfate content, based on the total dispersion, is preferably only 2 to 10% by weight, while the dispersion content of silicate and / or (bi-) carbonate is also up to 40 or even 50% % By weight.
  • a silicate product is used which either served as the starting material for process step (a) or was obtained as a spray-dried product according to process step (a). It is particularly advantageous if a solution of the spray-dried product (a) in water in the aqueous dispersion, preferably in amounts of 10 to 40% by weight and in particular in amounts of 15 to 35% by weight, based in each case the entire dispersion is used.
  • the water content of the dispersions is preferably in a range from 10 to 40% by weight, in particular from 15 to 35% by weight.
  • Dispersions used with preference preferably have at least 40% by weight and in particular 50 to 85% by weight of dispersed organic constituents of detergents or cleaning agents.
  • water is preferably not impregnated in amounts above 20 wt .-%, based on the impregnated and not finally dried product used.
  • the water content of the finished silicate products is preferably not above 22 and in particular not above 20% by weight.
  • a final drying is connected to the first two process steps, with this drying is advantageously integrated into a continuous process.
  • 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 water or aqueous inorganic salt solution by intensive mixing of the nonionic surfactant and water or the aqueous solution or the non-ionic surfactant, inorganic solid salt and water.
  • the actual impregnation process can be carried out in conventional mixers / granulators of the high-speed mixer type, for example a CB3 ⁇ (R) recycler from Lödige, Federal Republic of Germany, a Flexomix (R) from Schugi, Federal Republic of Germany, or a Fukae GS30 mixer , but also in slower-running mixers, for example ploughshare mixers from Lödige, in a conventional manner.
  • CB3 ⁇ (R) recycler from Lödige, Federal Republic of Germany
  • Flexomix R
  • Fukae GS30 mixer Fukae GS30 mixer
  • the invention provides here that a spray-dried silica product (a) and at least one further solid, powdered or granular product, which is a single raw material or a compound of at least 2 different raw materials, together in process step (b) be impregnated. It has proven to be particularly advantageous to use an alkali carbonate-containing compound as a further 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 impregnated further solid powdery or granular product 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 any drying is carried out if necessary.
  • a spray-dried silicate product (a) are first impregnated with 5 to 38 parts by weight of an aqueous dispersion (b) and then with 2 to 15 parts by weight of another liquid Form of preparation, preferably an aqueous solution of organic cobuilders, aftertreated.
  • Organic cobuilder solutions of this type preferably have at least 20% by weight of solids, preferably 25 to 50% by weight of solids, in order not to increase the water content in the silicate product too much.
  • the maximum water content should preferably not exceed 22% by weight and in particular not exceed 20% by weight if no drying is to be connected.
  • a method of this type is particularly useful when either a process is used in process step (b) which contains large amounts, for example more than 50% by weight, of organic dispersed ingredient and / or small amounts, for example less than 20% by weight, water or if only relatively small amounts of the aqueous dispersion, for example less than 25% by weight and in particular significantly less than 20% by weight, in each case based on the finished and not finally dried product, be used.
  • drying preferably in a fluidized bed, is carried out. This is preferably carried out directly after the process steps described above without prior storage of the silicate product. Drying is preferably carried out when the water content after the first two process steps and the further treatment which may have been carried out as a sum of the spray-dried silicate, the aqueous dispersion and, if appropriate, the aqueous preparation form from the aftertreatment is above 22% by weight, in particular above 20% by weight.
  • the bulk density of the silicate products produced according to the invention is generally between 300 and 650 g / l and can be further increased by compacting measures of a known type, for example by roller compaction or extrusion.
  • the particle size distribution (sieve analysis) is generally so pronounced that no dust particles (part
  • the silicate products produced according to the invention which are obtained after process step (b), a further aftertreatment or (c), can be aftertreated with finely divided dry powders to further increase the bulk density.
  • finely divided dry powders in particular 1 to 5 parts by weight of the dry powder are used per 100 parts by weight of the silicatic product.
  • 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 silicic acid with at least one other of the powders mentioned.
  • the amorphous and impregnated alkali silicates produced according to the invention can be used as admixing components in powdery to granular detergents or cleaning agents or as a constituent in the production of the granular washing or cleaning agents, preferably in the granulation and / or compacting.
  • Such detergents or cleaners can have a bulk density between 300 and 1200 g / 1, preferably from 500 to 1000 g / 1, and preferably contain the impregnated silicates produced in accordance with the invention in amounts of 5 to 50% by weight, in particular in amounts of 10 to 40% by weight.
  • They can be produced by any of the known processes such as mixing, spray drying, granulation, compacting such as roller compaction and extrusion.
  • Suitable surface modifiers are known from the prior art.
  • Particularly preferred embodiments of the invention are extruded washing or cleaning agents with a bulk density above 600 g / l, which contain anionic and optionally nonionic surfactants and an amorphous and impregnated alkali silicate of the type produced according to the invention in the extrudate.
  • the particulate alkali silicates produced according to the invention can be used once - as with others - 13 -
  • Production process - serve as an admixture component, but it is particularly preferred to incorporate these alkali silicates into the premix to be extruded and to carry out a coextrusion of these silicates.
  • the finished washing or cleaning agents can contain the following ingredients in addition to the impregnated alkali silicates produced according to the invention.
  • the following list also contains more detailed descriptions of some of the ingredients found in the silica additives produced according to the invention.
  • surfactants above all anionic surfactants and, if appropriate, nonionic surfactants, but also cationic, amphoteric or zwitterionic surfactants.
  • Preferred anionic surfactants of the sulfonate type are Cg-Ci3-alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from Ci2-Ci8 mono-olefins with an end or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.
  • alkanesulfonates which are obtained from C 2 -C 8 -alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • esters of ⁇ -sulfo fatty acids for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.
  • 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 already in their industrial production as an aqueous mixture with limited amounts of di-salts.
  • the salt 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 are mono-, di- and triesters and their mixtures, as they are produced by esterification by a monoglycerol with 1 to 3 mol of fatty acid or in the transesterification of triglycerides with 0.3 to 2. mol Glycerin can be obtained.
  • Suitable sulfate-type surfactants are the sulfuric acid monoesters from primary alcohols of natural and synthetic origin.
  • alk (en) yl sulfates the alkali and in particular the sodium salts of the sulfuric acid semiesters of the Ci2-Ci8 * alcohols are obtained, for example, from coconut fatty alcohol, taig fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ⁇ o-C2 ⁇ 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.
  • C15-C18-alk (en) yl sulfates are particularly preferred for reasons of washing technology. It can also be particularly advantageous, and particularly advantageous for machine washing agents, to use Ci6-Ci8-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 Ci2-Ci4-alkyl sulfates or Ci2-Ci8-alkyl sulfates with Cia-Cis-alkyl sulfates and in particular Ci2-Ci6-alkyl sulfates with Ciss-Ci ⁇ Alkyl sulfates.
  • Ci2-Ci4-alkyl sulfates or Ci2-Ci8-alkyl sulfates with Cia-Cis-alkyl sulfates and in particular Ci2-Ci6-alkyl sulfates with Ciss-Ci ⁇ Alkyl sulfates.
  • Ci2-Ci6-alkyl sulfates with Ciss-Ci ⁇ Alkyl sulfates.
  • 2,3-Alkyl sulfates which are produced, for example, according to US Pat. Nos. 3,234,258 or 5,075,041 and can be obtained as commercial products from the Shell Oil Company under the name DANC), are also suitable anionic surfactants.
  • the sulfuric acid monoesters of the straight-chain or branched C7-C2i alcohols ethoxylated with 1 to 6 moles of ethylene oxide such as 2-methyl-branched Cg-Cji alcohols with an average of 3.5 moles of ethylene oxide (EO) or Ci2-C ⁇ -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 are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain CQ to Cj8 alcohol residues or mixtures thereof.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols which, viewed in isolation, are nonionic surfactants (for a description, see below).
  • sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution are particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof. In addition to the anionic surfactants, the agents can also contain soaps, preferably in amounts of 0.2 to 5% by weight.
  • Saturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids.
  • the anionic surfactants and soaps can be present in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • the anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • washing or cleaning agents in particular extruded washing or cleaning agents, which contain 10 to 30% by weight of anionic surfactants are preferred.
  • at least 3% by weight and in particular at least 5% by weight of sulfate surfactants are preferred.
  • the compositions — based on the anionic surfactants as a whole — contain at least 15% by weight, in particular 20 to 100% by weight, of 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 has a methyl or linear branching, preferably in the 2-position may be 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 E0 per mole of alcohol are particularly preferred.
  • the preferred ethoxylated alcohols include, for example, Ci2-Ci4 alcohols with 3 E0 or 4 E0, Cg-Cu alcohol with 7 E0, Ci3-Ci5 alcohols with 3 E0, 5 E0, 7 E0 or 8 E0, Ci2-Ci8- Alcohols with 3 E0, 5 E0 or 7 E0 and mixtures of these, such as mixtures of C12-Ci4 alcohol with 3 E0 and C ⁇ 2-Ci8 alcohol with 5 E0.
  • the degrees of ethoxylation given represent statistical mean values for a special product can 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 of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • Nonionic surfactants of the amine oxide type for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable.
  • the amount of these non-ionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them.
  • Suitable surfactants are polyhydroxy fatty acid amides of the formula (I),
  • R 2 CO is an aliphatic acyl radical having 6 to 22 carbon atoms
  • R ** is hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms
  • [Z] is a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
  • the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • the polyhydroxy fatty acid amides are preferably derived from reducing sugars with 5 or 6 carbon atoms, in particular from glucose.
  • Nonionic surfactants are contained in the agents according to the invention preferably in amounts of 0.5 to 15% by weight, in particular in amounts of 2 to 10% by weight.
  • the agents can also contain further, additional builder substances and cobuilders.
  • additional builder substances and cobuilders primarily include the ingredients already mentioned, for example polycarboxylates and polymeric polycarboxylates.
  • cobuilders are contained in the compositions preferably in amounts of 2 to 20% by weight and in particular 5 to 15% by weight.
  • the synthetic zeolite used is preferably finely crystalline and contains bound water. Suitable are, for example, zeolite A, 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 an undried stabilized suspension which is still moist from its production.
  • the zeolite in the event that the zeolite is used as a suspension, it can contain small additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C12-Ci8 "fatty alcohols with 2 to 5 ethylene oxide groups , Ci2 * -Ci4 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.
  • detergents 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 silicate produced according to the invention, it being particularly important to ensure that the finished agent has at least 15% by weight of these builder substances mentioned.
  • the washing or cleaning agents therefore contain 0 to 5% by weight of zeolite (based on water-free active substance) and 15 to 40% by weight of an impregnated alkali metal additive prepared according to the invention or 10 to 30% by weight .-% zeolite (based on anhydrous active substance) and 15 to 40 wt .-% of a silicate-containing additive produced according to the invention.
  • the zeolite not only to be coextruded, but for the zeolite to be introduced into the washing or cleaning agent partially or completely subsequently, that is to say after the extrusion step. Washing or cleaning agents which contain an extrudate which is free of zeolite in the interior of the extrudate grain are particularly preferred.
  • Crystalline phyllosilicates and / or conventional phosphates can also be used as substitutes for the zeolite.
  • the detergents or cleaning agents contain only small amounts, in particular up to 10% by weight, of phosphates.
  • Crystalline layered silicates are, in particular, crystalline, layered sodium silicates of the general formula NaMSi x ⁇ 2 ⁇ + ⁇ * yH2 ⁇ , where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values are suitable for x 2, 3 or 4.
  • Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514.
  • Preferred crystalline layered silicates of the formula given are those in which M is sodium and x is 2 or 3.
  • both ⁇ - and S ' sodium disilicate Na2Si2 ⁇ 5 * yH2 ⁇ 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.
  • Usable 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), provided that 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.
  • polymeric polycarboxylates for example the sodium salts of polyacrylic acid or polymethacrylic acid, for example those with 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 relative molecular mass, based on free acids is generally 5,000 to 200,000, preferably 10,000 to 120,000 and in particular 50,000 to 100,000.
  • biodegradable terpolymers for example those which according to DE-A 4300772 as monomeric salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or according to DE-C-4221 381 as monomeric salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives.
  • Other preferred copolymers are those which are described in German patent applications DE 43 03 320 and DE 44 17734 and which preferably contain acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.
  • the agents can also contain components which have a positive effect on the ability to wash off fat and fat from textiles. This effect is particularly evident when a textile is soiled that has already been washed several times beforehand with a detergent according to the invention which contains this oil and fat-dissolving component.
  • the preferred oil- and fat-dissolving components include, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxyl groups of 15 to 30% by weight and of hydroxypropoxyl groups of 1 to 15% by weight, in each case based on the nonionic cellulose ether, and also the polymers of phthalic acid and / or terephthalic acid or their derivatives known from the prior art, in particular polymers of ethylene terephthalates and / or Polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives thereof.
  • nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxyl groups of 15 to 30% by weight and of hydroxypropoxyl groups of 1 to 15% by weight, in each case based on the nonionic cellulose ether
  • the agents can also contain constituents which further improve the solubility, particularly of the heavy granules.
  • constituents which further improve 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 03031.
  • the components preferably used include in particular fatty alcohols with 20 to 80 moles of ethylene oxide per mole of fatty alcohol, for example tallow alcohol with 30 E0 and tallow alcohol with 40 E0, but also fatty alcohols with 14 E0 and polyethylene glycols with a relative molecular weight between 200 and 2000.
  • bleaching agents which can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and peracid salts or peracids providing H2O2, such as perbenzoates, peroxophthalates, diperazelaic acid or diperdodecanedioic acid.
  • the bleaching agent content of the agents is preferably 5 to 25% by weight and in particular 10 to 20% by weight, with perborate monohydrate being advantageously used.
  • Percarbonate is also preferred as an ingredient. However, percarbonate is preferably not coextruded but, if necessary, mixed in subsequently.
  • bleach activators can be incorporated into the preparations.
  • these are N-acyl or O-acyl compounds which form organic peracids with H2O2, 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 are described, for example, in European patent application EP-A-0 525 239.
  • the content of bleach activators in the bleach-containing agents is in the usual range, preferably between 1 and 10% by weight and in particular between 3 and 8% by weight.
  • 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 Mixes (SORMAN).
  • Suitable foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of Ci8 ⁇ C24 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 different foam inhibitors are also used with advantages, e.g. those made of silicone, 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.
  • Suitable enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof. Enzymes obtained from bacterial strains or fungi, such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus and Humicola insolens, are particularly suitable. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used.
  • Enzyme mixtures for example of protease and amylase or protease and lipase or protease and cellulase or of cellulase and lipase or of protease, amylase and lipase or protease, lipase and cellulase, but especially protease- and / or lipase-containing mixtures of of special interest.
  • Peroxidases or oxidases have also proven to be suitable in some cases.
  • the enzymes can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature decomposition.
  • the proportion of the enzymes, enzyme mixtures or enzyme granules can be, for example, about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight.
  • the salts of polyphosphonic acids in particular 1-hydroxyethane-l, 1-diphosphonic acid (HEDP), diethylenetriaminepentamethylenephosphonic acid (DETPMP) or ethylenediaminetetramethylenephosphonic acid, are suitable as stabilizers.
  • 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 (H3BO3), metaboric acid (HBO2) and pyroboric acid (tetraboric acid H2B4O7), is particularly advantageous.
  • Graying inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing 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 of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
  • Water-soluble polyamides containing acidic groups are also suitable for this purpose. Soluble starch preparations and starch products other than those mentioned above can also be used, e.g. degraded starch, aldehyde starches, etc.
  • Polyvinylpyrrolidone can also be used.
  • cellulose ethers such as carboxymethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers, such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof, and polyvinylpyrrolidone, for example in amounts of 0.1 to 5% by weight, based on the detergent, are preferred used.
  • the agents can contain derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. Suitable are, for example, salts of 4,4'-bis (2-an ⁇ lino-4-morpholino-l, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of the same structure which contain an replace the morpholino group with a diethanolamino group, a methyl amino group, an anilino group or a 2-methoxyethylamino group.
  • Brighteners of the substituted diphenylstyryl type may also be present, for example the alkali metal salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4th -chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) diphenyl. Mixtures of the aforementioned brighteners can also be used.
  • Example 1 was mixed with 83 parts by weight of a spray-dried silicate granules with the composition indicated in Example 1 with 10 parts by weight of an aqueous dispersion of 72 wt .-% Ci2-CI8 -A lkohol m ⁇ t 7 E0, 24 wt .-% Water and 4 wt .-% sodium sulfate repeated. This was followed by an aftertreatment with 7 parts by weight of a 30% by weight aqueous solution of Sokalan CP ⁇ ( R ) (copolymeric sodium salt of acrylic acid and maleic acid, commercial product from BASF, Federal Republic of Germany). The bulk density was 468 g / l. The giant behavior was 79%.
  • Sokalan CP ⁇ R
  • each of the powder funnels according to Examples 1 to 3 according to the invention was filled into a powder funnel which was initially closed at its outlet opening, and then the outlet time of the silicate products compared to dry sea sand was measured.
  • the discharge time of the dry sea sand after opening the discharge opening (13 seconds) was set to 100%.

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
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Abstract

L'invention a pour objet de produire des silicates amorphes séchés par pulvérisation et de les imprégner, dans les conditions habituelles de traitement, de substances liquides à cireuses de produits de lavage ou de nettoyage, sans réduction considérable de la coulabilité. A cet effet, l'invention propose un procédé selon lequel on procède a) au séchage par pulvérisation d'une solution initiale aqueuse, renfermant comme substance active principalement un silicate alcalin amorphe de composition molaire M2O: SiO2 (M = métal alcalin) dont le rapport molaire est compris entre 1:1,5 et 1:3,3 et ensuite b) à l'imprégnation de la solution initiale par une dispersion aqueuse de substances de produits de lavage ou de nettoyage dans de l'eau, au moins une substance organique de produits de lavage ou de nettoyage étant en dispersion dans l'eau ou dans une solution aqueuse, et enfin c) à un éventuel séchage.
EP96931031A 1995-09-13 1996-09-05 Procede de production d'un silicate alcalin amorphe avec impregnation Expired - Lifetime EP0859827B2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19533790A DE19533790A1 (de) 1995-09-13 1995-09-13 Verfahren zur Herstellung eines amorphen Alkalisilikats mit Imprägnierung
DE19533790 1995-09-13
PCT/EP1996/003905 WO1997010325A1 (fr) 1995-09-13 1996-09-05 Procede de production d'un silicate alcalin amorphe avec impregnation

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EP0859827A1 true EP0859827A1 (fr) 1998-08-26
EP0859827B1 EP0859827B1 (fr) 2001-06-27
EP0859827B2 EP0859827B2 (fr) 2006-06-07

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DE (2) DE19533790A1 (fr)
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ATE202597T1 (de) 2001-07-15
JP3889810B2 (ja) 2007-03-07
DE59607182D1 (de) 2001-08-02
US5958864A (en) 1999-09-28
WO1997010325A1 (fr) 1997-03-20
EP0859827B1 (fr) 2001-06-27
DE19533790A1 (de) 1997-03-20
KR19990036403A (ko) 1999-05-25
KR100416832B1 (ko) 2004-07-22
ES2160254T5 (es) 2007-03-01
HUP9900372A2 (hu) 1999-05-28
JPH11512463A (ja) 1999-10-26
EP0859827B2 (fr) 2006-06-07
ES2160254T3 (es) 2001-11-01
PL324860A1 (en) 1998-06-22
HUP9900372A3 (en) 2001-11-28
SK32098A3 (en) 1998-08-05

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