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
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/02—Inorganic compounds ; Elemental compounds
  • C11D3/04—Water-soluble compounds
  • C11D3/08—Silicates
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties

Definitions

• the invention relates to a process for the production of free-flowing amorphous alkali silicates by spray drying, the alkali silicate 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 rotates with a plurality of arms close to the inner surface of the drum, the drum wall having a temperature between 150 and 200 ° C and the drying process by means of a gas fed into the drum with a temperature between 175 and about 250 ° C is supported. According to this process, 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-0 542 131 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).
• the unpublished international patent application WO 95/33684 also describes a water-soluble, amorphous and granular alkali silicate, which is prepared in a similar manner to that described in EP-A-0 526 978, but contains silicic acid.
• amorphous means "X-ray amorphous”. This means that the alkali silicates do not provide sharp reflections in X-ray diffraction recordings, but at most one or more broad maxima, the width of which is several degree units of the diffraction angle. However, this does not rule out the possibility that areas are found in electron diffraction experiments which give sharp electron diffraction reflections. This is to be interpreted in such a way that the substance has microcrystalline areas of a size up to approximately 20 nm (max. 50 nm).
• 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 millbase, 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 power are known from European patent applications EP-A-0 561 656 and EP-A-0488868. These are compounds of alkali silicates with certain Q distributions and alkali carbonates.
• the older, unpublished German patent application P 4446363.4 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 which spray-dried amorphous silicates are produced which, even if they do not contain any additional alkali metal carbonates, can be impregnated without a serious loss of free-flowing properties.
• 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.
• Preferred alkali silicates are in granular form and / or as a compound with alkali carbonate, preferably sodium and / or potassium carbonate, and / or have a bulk density between 300 and 1200 g / 1, in particular from 350 to 800 g / 1.
• the water content of these preferably used amorphous alkali silicates or of the compounds which contain the amorphous alkali silicates is advantageously between 10 and 22% by weight, in particular between 12 and 20% by weight. Water contents of 14 to 18% by weight can be particularly preferred.
• amorphous alkali silicates of the specified module including commercially available granular silicates or carbonate-silicate compounds, are suitable starting materials in the sense 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 also not always expedient, since these products are dissolved again in an aqueous batch have to.
• 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 compounds (a) are produced which contain 65 to 95% by weight, preferably 70 to 90% by weight of alkali metal isate (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 12 to 18% by weight of water.
• ingredients of detergents or cleaning agents can also be incorporated into the batch to be spray-dried.
• Their content, based on the spray-dried silicate product of process step (a), 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 neutral salts such as sodium or potassium sulfates, graying inhibitors or nonionic surfactants such as Act alkyl polyglycosides or optionally alk ⁇ oxylated polyhydroxy fatty acid esters.
• anionic surfactants and / or organic cobuilders are used in the slurry to be spray-dried, preferably in amounts of 1 to 15% by weight, based on the spray-dried silicate product of process stage (a).
• Usable organic cobuilders are, for example, the polycarboxylic acids optionally used in the form of their sodium salts, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, amino carboxylic acids, nitrilotriacetic acid (NTA), provided that such use is not objectionable for ecological reasons, and mixtures from these.
• Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.
• dextrins for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches.
• the hydrolysis can be carried out by customary, for example acid or enzyme-catalyzed, processes. They are preferably hydrolysis products with average molecular weights in the range from 400 to 500,000.
• This is a polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30, is preferred, DE being a customary measure of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100 .
• DE dextrose equivalent
• Both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher molar masses in the range from 2000 to 30000 can be used.
• a preferred dextrin is described in British patent application 94 19 091.
• the oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.
• Such dextrins and processes for their preparation are known, for example, from European patent applications EP-A-0232202, EP-A-0427349, EP-A-0472042 and EP-A-0 542 496 and international patent applications W0-A-92/18542, W0 A-93/08251, W0-A-94/28030, W0-A-95/07303, W0-A-95/12619 and W0-A-95/20608 are known.
• a product oxidized to C ⁇ of the saccharide ring can be particularly advantageous.
• Suitable cobuilders are oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate. Also particularly preferred in this context are glycerol disuccinates and glycerol trisuccinates, as described, for example, in US Pat. Nos. 4,524,009, 4,639,325, European Patent Application EP-A-0 150 930 and Japanese Patent Application JP 93/339896 to be discribed. Suitable amounts used in formulations containing zeolite and / or silicate are 3 to 15% by weight.
• organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may also be in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.
• Such cobuilders are described, for example, in international WO-A-95/20029.
• oxidation products of carboxyl-containing polyglucosans and / or their water-soluble salts such as they are described, for example, in the international patent application W0-A-93/08251 or their production is described, for example, in the international patent application W0-A-93/16110.
• Oxidized oligosaccharides according to the older German patent application P 19600018.1 are also suitable.
• 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 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 weight, 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 are also particularly preferred, for example those which, according to DE-A-4300772, are salts of monomers acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives or according to DE-C-4221 381 as monomers salts of acrylic acid and 2-alkylallyl sulfonic acid and sugar derivatives.
• Further preferred copolymers are those which are described in German patent applications DE 43 03 320 and DE 44 17 734 and which preferably contain acrolein and acrylic acid / acrylic acid salts or vinyl acetate as monomers.
• 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 wax-like at the usual processing temperatures because of the sintered surface of the spray-dried beads. So that such ingredients can be applied to the spray-dried beads, their surface structure must first be destroyed or the surface area enlarged accordingly.
• the spray-dried silicate products (a) are preferably impregnated in amounts of from 3 to 15% by weight and in particular from 5 to 12% by weight, based in each case on the impregnated and possibly finally dried silicate product.
• Impregnating agents are suitable, for example, surfactants, foam inhibitors based on silicone and / or paraffin, or textile-softening compounds such as cationic surfactants.
• Particularly preferred impregnating agents are again nonionic surfactants, for example alkoxylated, preferably ethoxylated and / or ethoxylated and propoxylated, aliphatic C8-C22 alcohols. These include in particular primary alcohols with 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 methyl-branched linearly or preferably in the 2-position or linear and methyl-branched May contain residues in the mixture, as they are usually present in oxo alcohol residues.
• nonionic surfactants for example alkoxylated, preferably ethoxylated and / or ethoxylated and propoxylated, aliphatic C8-C22 alcohols. These include in particular primary alcohols with 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 methyl-branched linearly
• 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, and an average of 2 to 8 EO per mole of alcohol are preferred.
• the preferred ethoxylated alcohols include, for example, Ci2-Ci4 alcohols with 3 EO or 4 EO, Cg-Cn alcohol with 7 EO, Ci3-Ci5 alcohols with 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 broken number for a specific product.
• Preferred alcohol ethoxylates have a narrowed homolog distribution (narrow range ethoxylates, NRE).
• NRE narrow range ethoxylates
• 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 usually specified below, which are usually used in washing or cleaning agents, are also suitable in principle.
• spray-dried silicate products which are impregnated with detergent or cleaning agent ingredients can only have sufficient flowability if the impregnating agent is applied in the form of an aqueous dispersion and in particular in the form of an emulsion.
• an emulsion of a nonionic surfactant and an aqueous solution of an organic cobuilder is used.
• the above-mentioned are particularly suitable as organic cobuilders, in particular
• preference is given to the (co) polymeric polycarboxylates mentioned which are advantageously in amounts of 1 to 10% by weight, in particular in amounts of 4 to 10% by weight, based on the impregnated and, if appropriate, finally dried silicate Product.
• the aqueous solutions generally contain 10 to 45% by weight of the (co) polymeric polycarboxylates; Concentrated solutions are also conceivable.
• the amount of water used can be a critical factor depending on the impregnating agent used and also on the water content of the spray-dried silicate product (a); water is therefore preferably not used in the impregnation in amounts above 20% by weight, based on the impregnated and not finally dried product.
• the water content of the finished silicate products is preferably not above 22 and in particular not above 18% 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 organic cobuilder by intensive mixing of the nonionic surfactant and an aqueous solution of the organic water-soluble cobuilder or the nonionic surfactant, of the organic cobuilder and water is produced.
• 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.
• a silicate product (a) is introduced in process step (b).
• an alkali (bi) carbonate-containing compound as a further compound, which also contains organic cobuilders of the type described above.
• Compounds which contain more than 40% by weight of organic cobuilders and 10 to 40% by weight of alkali metal carbonates are particularly preferred.
• 60 to 80 parts by weight of the spray-dried silicate product (a) and 5 to 20 parts by weight of at least one further solid powdery or granular product are impregnated together in accordance with process step (b).
• mixtures of nonionic surfactants preferably ethoxylated Ci2-Ci8 alcohols, and aqueous solutions of organic co-builders in weight ratios of 3: 1 to 1: 3, in particular 2: 1 to 1: 2 used.
• a spray-dried silicate product (a) with 10 to 30 parts by weight of an aqueous dispersion containing nonionic surfactants and organic cobuilders or 60 to 80 parts by weight of one spray-dried silicate product (a) and 5 to 20 parts by weight of at least one further solid powdery or granular product are impregnated with 10 to 30 parts by weight of an aqueous dispersion containing nonionic surfactants and organic cobuilders.
• drying preferably in a fluidized bed, is carried out.
• the bulk density of the silicate products produced according to the invention is generally between 200 and 600 g / l and can be achieved by known compacting measures, for example by roller compaction or extrusion, can be further increased.
• the particle size distribution (sieve analysis) is generally so pronounced that no dust particles (particles with a diameter below 0.1 mm) are obtained and preferably 60 to 100% by weight of the particles, in particular 80 to 100% by weight .-% of the particles have a particle diameter of at least 0.2 mm and at most 0.8 mm.
• the silicate products produced according to the invention which are obtained after process step (b) or (c), can be post-treated 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 for 100 parts by weight of the silicate 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 cleaning agents 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 according to the invention in amounts of 5 to 50% by weight 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.
• extruded detergents or cleaning agents reference is made to the known methods for extrusion, in particular to European Patent 486592.
• a solid and free-flowing premix is extruded in the form of strands at pressures of up to 200 bar, the extrudate is cut to the specific granulate dimension after exiting the hole shape by means of a cutting device, and the plastic and possibly still moist extrudate is fed to a further shaping processing step and then fed dried, the impregnated alkali silicates produced according to the invention being used in the premix.
• the finished washing or cleaning agents can contain the following ingredients in addition to the impregnated alkali silicates 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, i.e. Mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as are obtained, for example, from C 1 -C 8 -mono-olefins with a terminal 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 Ci2-Ci8-alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
• esters of ⁇ -sulfo fatty acids esters of ⁇ -sulfo fatty acids (ester sulfonates), e.g. the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.
• anionic surfactants are the ⁇ -sulfo fatty acids or their di-salts obtainable by ester cleavage of the ⁇ -sulfo fatty acid alkyl esters.
• the mono-salts of the ⁇ -sulfofatty acid alkyl esters are obtained as aqueous mixtures with limited amounts of di-salts even during their industrial production.
• the disalt content of such surfactants is usually below 50% by weight of the anionic surfactant mixture, for example up to about 30% by weight.
• Suitable anionic surfactants are sulfonated fatty acid glycerol esters, which 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 Moles of glycerol 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 especially the sodium salts of the sulfuric acid half-esters of the Ci2-Ci8 ⁇ alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or di e J s 9 s Halbester secondary alcohols of this chain length.
• 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 Cjo-Ci ⁇ -alkyl sulfates and in particular Ci2-Ci6-alkyl sulfates with Ciö -Ciss-alkyl sulfates.
• not only saturated alkyl sulfates but also unsaturated alkenyl sulfates with an alkenyl chain length of preferably CJ ⁇ to C22 are used.
• 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 DAN, are also suitable anionic surfactants.
• the sulfuric acid monoesters of the straight-chain or branched C7-C21 alcohols ethoxylated with 1 to 6 moles of ethylene oxide such as 2-Me- Methyl-branched Cg-Cn alcohols with an average of 3.5 moles of ethylene oxide (EO) or Ci2-Ci8 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 Cis alcohol residues or mixtures thereof.
• Particularly preferred succinosuccinates 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 the fatty alcohol residues of which 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.
• compositions 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 from natural fatty acids, e.g. Coconut, palm kernel or taig fatty acids, derived soap mixtures.
• 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.
• anionic surfactants preferably at least 3% by weight and in particular at least 5% % By weight of sulfate surfactants.
• 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 (EO) per mole of alcohol in which the alcohol radical has a methyl or linear branching 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.
• the preferred ethoxylated alcohols include, for example, Ci2-Ci4 alcohols with 3 EO or 4 EO, Cg-Cn alcohol with 7 EO, Ci3-Ci5 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C ⁇ 2-Ci8- Alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C12-Cj4 alcohol with 3 EO and Ci2-Ci8 alcohol with 5 EO.
• the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
• Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
• fatty alcohols with more than 12 EO can also be used. Examples of this are tallow fatty alcohol with 14 EO, 25 EO, 30 E0 or 40 E0.
• 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.
• nonionic surfactants of the amine oxide type for example N-coco-alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide. and the fatty acid alkanolamides may 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 ⁇ CO for an aliphatic acyl radical with 6 to 22 carbon atoms
• R3 for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms
• [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 is up 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. With regard to the processes for their production, reference is made to US Pat. Nos. 1,985,424, 2,016,962 and 2,703,798 and international patent application WO-A-92/06984.
• the polyhydroxy fatty acid amides are preferably derived from reducing sugars with 5 or 6 carbon atoms, especially from the 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 include primarily 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 minor additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C12-cis fatty alcohols having 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 anhydrous active substance) and 15 to 40% by weight of an impregnated alkali metal silicate produced according to the invention or 10 to 30% by weight. % Zeolite (based on anhydrous active substance) and 15 to 40% by weight of a zeolite produced according to the invention. It is possible for 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 extruded 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.
• 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 fr-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.
• the agents can also contain components which have a positive influence on the oil and fat washability from textiles. This effect becomes particularly clear 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 methoxy groups of 15 to 30% by weight and of hydroxypropoxyl groups of 1 to 15% by weight.
• nonionic cellulose ether based in each case on the nonionic cellulose ether, and 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 anionic and / or nonionic modified derivatives. of these.
• 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 4203031.
• 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 that can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H2O2-providing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic 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.
• bleach activators can be incorporated into the preparations.
• N-acyl or O-acyl compounds which form organic peracids with H2O2, preferably N, N'-tetraacylated diamines, p- (alkanoyloxy) benzenesulfonates, furthermore caprolactam derivatives, carboxylic acid anhydrides and esters of polyols such as glucose pentaacetate .
• bleach activators are acetylated mixtures of sorbitol and mannitol, as are described, for example, in European patent application EP-A-0525239.
• the bleach activator content of the bleach-containing agents is in the usual range, preferably between 1 and 10% by weight and in particular between 3 and 8% by weight.
• Particularly preferred bleach activators are N, N, N'.N'-tetraacetylethylene diamine (TAED), 1,5-diacetyl-2,4-dioxo-hexahydro-1,5,5-triazine (DADHT) and acetylated sorbitol mannitol Mixes (SORMAN).
• Suitable foam inhibitors are, for example, soaps are natural or synthetic origin which have a high content of acids CI8-C24 ⁇ fatty ä.
• Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally signed silica, and also paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bistearylethylenediamide. Mixtures of various foam inhibitors are also used with advantages, for example those made of silicones, paraffins or waxes.
• the foam inhibitors, in particular silicone and / or paraffin-containing foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance. Mixtures of paraffins and bistearylethylenediamides are particularly preferred.
• Particularly suitable enzymes are those from the class of hydrolases, such as proteases, lipases or lipolytically active enzymes, amylases, cellulases or mixtures thereof. Oxireductases are also suitable. Enzymatic active ingredients obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus and Humicola are particularly well suited. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used.
• enzyme mixtures for example from protease and amylase or protease and lipase or lipolytically active enzymes or protease and cellulase or from cellulase and lipase or lipolytically active enzymes or from protease, amylase and lipase or lipolytically active enzymes or protease, lipase or lipolytically active enzymes and cellulase, but especially protease- and / or lipase-containing mixtures or mixtures with lipolytically active enzymes of particular interest.
• Known cutinases are examples of such lipolytically active enzymes.
• Peroxidases or oxidases have also proven to be suitable in some cases.
• Suitable amylases include, in particular, ⁇ -amylases, iso-amylases, pullulanases and pectinases.
• Cellobiohydrolases, endoglucanases and ⁇ -glucosidases, which are also called cellobiases, or mixtures thereof are preferably used as cellulases. Since the different cellulase types differ in their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases.
• 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 are suitable as stabilizers.
• HEDP l-hydroxyethane-l, l-diphosphonic acid
• DETPMP diethylenetriaminepentamethylenephosphonic acid
• ethylenediaminetetramethylenephosphonic acid are suitable as stabilizers.
• the agents can also contain further enzyme stabilizers.
• further enzyme stabilizers For example, 0.5 to 1% by weight sodium formate can be used. It is also possible to use proteases with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the ? 3
• 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 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 or 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 also polyvinylpyrrolidone, for example in amounts of 0.1 to 5% by weight , based on the funds used.
• the agents can contain derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. Suitable are, for example, salts of 4,4'-bis (2-anilino-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 methylamino group, an anilino group or a 2-methoxyethylamino group.
• Brighteners of the substituted diphenylstyryl type may also be present, for example the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) diphenyl. Mixtures of the aforementioned brighteners can also be used. Examples
• Example 1 was repeated with 75 parts by weight of a spray-dried sodium disilicate (water content 15% by weight) and 10 parts by weight of a Sokalan CP ⁇ ( R ) powder.
• the trickle behavior was 9%.
• Example 2 was repeated with 15 parts by weight of an emulsion of 10 parts by weight of Ci2-Ci8 fatty alcohol with 7 E0 and 5 parts by weight of water. The trickle behavior was 8%.
• Comparative example 4 was repeated, except that 9.5 parts by weight of Ci2-Ci8 fatty alcohol with 7 EO and 15.8 parts by weight of a 30% by weight aqueous Sokalan CP5 ( R ) solution in the form a premixed emulsion was used in a high-speed mixer (the second granulation stage was omitted) and finally dried in a fluidized bed.
• the trickle behavior was 68%.

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• Oil, Petroleum & Natural Gas (AREA)
• Wood Science & Technology (AREA)
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• Inorganic Chemistry (AREA)
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• 1995
  • 1995-08-15 DE DE19529908A patent/DE19529908A1/de not_active Withdrawn
• 1996
  • 1996-08-06 HU HU9802376A patent/HUP9802376A3/hu unknown
  • 1996-08-06 EP EP96928415A patent/EP0845028B1/de not_active Expired - Lifetime
  • 1996-08-06 KR KR1019980701036A patent/KR19990036368A/ko not_active Application Discontinuation
  • 1996-08-06 JP JP9508899A patent/JPH11510844A/ja active Pending
  • 1996-08-06 ES ES96928415T patent/ES2142603T3/es not_active Expired - Lifetime
  • 1996-08-06 PL PL96324634A patent/PL324634A1/xx unknown
  • 1996-08-06 AT AT96928415T patent/ATE188505T1/de not_active IP Right Cessation
  • 1996-08-06 DE DE59604128T patent/DE59604128D1/de not_active Expired - Lifetime
  • 1996-08-06 WO PCT/EP1996/003466 patent/WO1997007194A1/de not_active Application Discontinuation

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