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
  • C11D3/12—Water-insoluble compounds
  • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
  • C11D3/1246—Silicates, e.g. diatomaceous earth
  • C11D3/128—Aluminium silicates, e.g. zeolites
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/66—Non-ionic compounds
  • C11D1/83—Mixtures of non-ionic with anionic compounds
• • 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
  • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
  • C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
• • 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
  • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
  • C11D11/04—Special methods for preparing compositions containing mixtures of detergents by chemical means, e.g. by sulfonating in the presence of other compounding ingredients followed by neutralising
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
  • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
  • C11D17/065—High-density particulate detergent compositions
• • 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
  • C11D3/12—Water-insoluble compounds
  • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
  • C11D3/1246—Silicates, e.g. diatomaceous earth
  • C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
  • C11D3/1273—Crystalline layered silicates of type NaMeSixO2x+1YH2O
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/02—Anionic compounds
  • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
  • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/66—Non-ionic compounds
  • C11D1/72—Ethers of polyoxyalkylene glycols

Definitions

• the invention relates to a method for producing a storable and free-flowing granulate of detergents and cleaning agents containing anionic surfactants with a bulk density above 600 g / l as well as washing and washing agents containing anionic and nonionic surfactants Cleaning supplies.
• Patent step EP 0 642 576 B1 describes a two-stage process for the production of Granules known.
• the use of zeolites or Phosphates are described as builder substances. Phosphates are used as builders from environmental biology Reasons used less preferred. Even the absence of zeolites is preferred as builder components because of their poor solubility.
• WO 93/23520 From the teaching of WO 93/23520 is a process for the preparation of anionic surfactants Detergents and cleaning agents known. Here, a neutralizate that contains anionic surfactants is prepared separately. This then becomes a solid or placed in a mixer added to a solid mixture and granulated in the same mixer. By teaching this document will cause excessive heat buildup due to the neutralization reaction avoided. However, the choice of the solids proves disadvantageous with this procedure. Either builders from the zeolite or phosphate groups are not omitted or it is the commercially available crystalline alkali silicates, optionally in combination with alkali carbonates. By applying the neutralization medium to the Solid and the granulation in the same mixer, however, becomes a poorly pourable Received product.
• the object of the invention is therefore to provide a method that the above Does not have disadvantages. It is said to be a process for producing a granulate of detergents and cleaning agents that are made available by the inventive Process steps neither glued nor greased, to water-insoluble ones Zeolites and phosphates as builder components can be dispensed with, however Detergent and cleaning agent, based on anionic surfactants, with excellent properties of the detergent and delayed release speed of the builder components.
• the invention relates to a process for producing a storable and free-flowing granulate of detergents and cleaning agents containing anionic surfactants with a bulk density above 600 g / l, characterized in that firstly (a) at least one completely neutralized neutralizate containing at least one anionic surfactant acid a non-ionic surfactant and sodium hydroxide solution are produced, (b) this is applied to a water-soluble silicate builder to produce a precursor, (c) is mixed with other customary detergent constituents and finally (d) is granulated with a granulating liquid, the preparation of the precursor and the granules are produced spatially separated and continuously.
• the process is carried out continuously according to the invention.
• at least two mixers connected in series.
• the primary product is in the first mixer manufactured, i.e. the neutralisate, which in turn is produced separately, is there on the silicate builder applied.
• the other solids and / or liquids become the preliminary product added and the granulation step carried out.
• the following, if applicable Powdering with flow improvers takes place either in the discharge zone of the second mixer or separately in a downstream third mixer.
• a so-called Schugi mixer is preferred as the third mixer for this purpose.
• a method which provides that the silicate builders (the preliminary product) treated with neutralized material are first coated with further substances.
• Suitable coating substances are water-soluble detergent components which are sprayed in the form of their aqueous solution onto the silicate builder treated with neutralized material (fluidized bed coating). Excess water is evaporated during this application process. This is preferably achieved with disilicate and / or polycarboxylate solutions, for example in a fluid bed dryer from Glatt, Aeromatic or Escher-Wyss.
• the preliminary product is powdered with flow improvers. Wessalith and / or precipitated silicas are particularly suitable for this.
• the neutralisates can be prepared in a stirred tank or in all conventional, customary ones Mixers are made and carried out separately.
• concentrated sodium hydroxide solution is used.
• the concentrated sodium hydroxide solution contains between 30 and 60% by weight sodium hydroxide, preferably between 45 and 55% by weight.
• the anionic surfactant acid (s) is (are) usually specified and the sodium hydroxide solution as Neutralization medium added. A reverse procedure is also possible.
• the nonionic surfactant component (s) given the anionic surfactants added in their acid form and finally the neutralization was carried out with concentrated sodium hydroxide solution.
• the three components of the neutralizate are continuous and synchronous introduced in the mixing process.
• the neutralizate contains one or more anionic surfactants between 10 and 99% by weight, one or more non-ionic surfactants between 1 and 90 wt .-% (each based on the neutralizate) and the lowest possible water content.
• the usable water content depends on the type and amount of nonionic surfactant used. The water content should be determined in any case so that after the neutralization of the anionic surfactant a liquid phase is retained.
• the anionic surfactant-containing mixtures prepared according to this preferred embodiment are preferably at temperatures between 5 and 20 ° C, in particular between 8 and 15 ° C, flowable and pumpable.
• the known sulfonates and sulfates and soaps made from preferably natural fatty acids or fatty acid mixtures are suitable as anionic surfactants.
• sulfo fatty acids and fatty acids are preferably converted into their anionic surfactants.
• the use of saturated and unsaturated fatty acids with C 8 -C 18 chain lengths in the form of their mixtures and / or the ⁇ -sulfofatty acids of saturated C 8 -C 18 fatty acids is preferred.
• olefin sulfonic acids ie mixtures of alkene and hydroxyalkanesulfonic acids, and the sulfonic acids obtained, for example, from C 12 -C 18 monoolefins having an end and internal double bond by sulfonating with gaseous sulfur trioxide, are suitable as anionic surfactants in their acid form of the sulfonic acid type Consideration.
• alkanesulfonic acids which are obtainable from C 12 -C 18 alkanes by sulfochlorination and sulfoxidation and by subsequent hydrolysis or by bisulfite addition to olefins, and in particular the esters of ⁇ -sulfofatty acids, e.g. B. the ⁇ -sulfonated methyl ester of hydrogenated coconut, palm kernel, or tallow fatty acids.
• Suitable alkyl sulfuric acids are the sulfuric acid monoesters from primary alcohols of natural and synthetic origin, especially from fatty alcohols, e.g. B.
• coconut fatty alcohols coconut fatty alcohols, tallow fatty alcohols, oleyl alcohol, lauryl, myristyl, palmityl or stearyl alcohol, or the C 10 -C 20 oxo alcohols, and those secondary alcohols of this chain length.
• anionic surfactants mentioned in their acid form for example fatty acid and alkylbenzenesulfonic acid or fatty acid and sulfofatty acids of saturated and / or unsaturated fatty acids or sulfofatty acid alkyl esters of saturated and / or unsaturated fatty acids. It is particularly advantageous if the fatty acids are first added to the ethoxylated nonionic surfactant and then the further sulfonated anionic surfactants in their acid form.
• the neutralizate used is made from alkylbenzenesulfonic acid, sodium hydroxide solution and at least one nonionic surfactant.
• Alkylbenzenesulfonic acids having a C 9 -C 15 alkyl group are particularly preferred.
• the neutralizate is composed of alkylbenzenesulfonic acid, Sodium hydroxide solution and non-ionic surfactants from the group of ethoxylated nonionic surfactants manufactured.
• the ethoxylated nonionic surfactants are derived from primary alcohols with preferably 9 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide per mole of alcohol, in which the alcohol radical can be linear or methyl-branched in the 2-position or can contain linear and methyl-branched radicals in the mixture , as they are usually present in oxo alcohol residues.
• linear residues of alcohols of native origin with 12 to 18 carbon atoms are preferred, such as. B. coconut oil, tallow fat or oleyl alcohol.
• 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).
• alcohol ethoxylates are preferred which have an average of 2 to 8 ethylene oxide groups.
• the preferred ethoxylated alcohols include, for example, C 9 -C 11 oxo alcohol with 7 EO, C 13 -C 15 oxo alcohol with 3 EO, 5 EO, 7 EO or 8 EO and in particular C 12 -C 14 alcohols with 3 EO or 4 EO, C 12 -C 18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C 12 -C 14 alcohol with 3 EO and C 12 -C 18 alcohol with 5 EO.
• This mixture of anionic surfactant in acid form and ethoxylated nonionic surfactants can be combined in one broad weight ratio, preferably in a weight ratio of anionic surfactant in acid form to ethoxylated nonionic surfactant from 1: 0.5 to 1:30, in particular up to 1:20 become.
• Mixtures are advantageously used in the case of complete neutralization used in which the weight ratio of anionic surfactant in acid form to ethoxylated nonionic surfactant is less than 1, preferably 1: 2 to 1:20 and in particular less than 1: 5.
• the metering takes place with the mixer and knife ring running.
• Suitable mixers are e.g. Eirich mixer the R and RV series, manufactured by the Gustav Eirich machine factory, Hardheim, Germany, the Fukae FS-G mixer, manufactured by the Fukae Powtech Kogyo Co., Japan, the Lödige FM, KM and CB mixers, manufactured by Lödige Maschinenbau GmbH, Paderborn, Germany, or the Drais series T or K-T by Drais Maschinene GmbH, Mannheim, Germany.
• the neutralisate preferably introduced into the mixer via nozzles. The addition can also - if also less preferred - manually, for example by pouring.
• Granular sodium and / or potassium silicates obtained by spray drying, compaction and grinding with a molar SiO 2 : M 2 O ratio of preferably 2.0 to 3.0, in particular sodium silicates with a certain water content, are used as silicate builder components.
• the water content is preferably between 15 and 22% by weight. Only granular silicates are used in the context of the invention. In particular, the use of alkali carbonates is dispensed with.
• Granular silicates selected from the commercially available granular Britesil (R) disilicates (commercial products from AKZO-PQ Silica) of the type H20 (module 2.0), H20 Plus (module 2.0) and H24 (module 2, 4), which are suitable as substitutes for zeolites and / or crystalline layered disilicates.
• the detergents and cleaning agents produced in accordance with the process contain at least 15% by weight, in particular 30 to 60% by weight, based on the total detergent or cleaning agent formulation, of these granular silicates.
• These water-soluble amorphous, granular silicates are particularly preferred over ground water glass. Compared to water glass, they show a significantly delayed dissolving behavior. This means that the alkali silicates mentioned also do justice to their builder effect, but without leaving behind insoluble washing or cleaning residues.
• the builder treated with neutralized at least one further anionic surfactant component and / or one soap component added alongside other typical detergent components.
• Preferred surfactants here are surfactants of the sulfonate type, particularly preferably C 9 -C 13 -alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates of the type obtained, for example, from C 12 -C 18 monoolefins with terminal or internal Double bond obtained by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.
• alkanesulfonates obtained from C 12 -C 18 alkanes for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization, are also suitable.
• Preferred anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which represent monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
• Preferred sulfosuccinates contain C 8 -C 18 fatty alcohol residues or mixtures thereof.
• Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which are nonionic surfactants in themselves.
• sulfosuccinates the fatty alcohol residues of which are derived from ethoxylated fatty alcohols with a restricted homolog distribution, are particularly preferred.
• esters of ⁇ -sulfo fatty acids e.g. the ⁇ -sulfonated Methyl ester of hydrogenated coconut, palm kernel or tallow fatty acids.
• alk (en) yl sulfates the alkali and in particular the sodium salts of the sulfuric acid half-esters of the C 12 -C 18 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred.
• alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials.
• C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates and C 14 -C 15 alkyl sulfates are particularly preferred from the point of view of washing technology.
• 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 (R) , are also suitable anionic surfactants.
• the sulfuric acid monoesters of the alcohols ethoxylated with 1 to 6 mol of ethylene oxide such as 2-methyl-branched C 9 -C 11 alcohols with an average of 3.5 mol of ethylene oxide, are also suitable.
• the anionic surfactants can be in the form of their sodium, potassium or ammonium salts as well as soluble salts of organic bases, such as mono-, di- or triethanolamine.
• the anionic surfactants are in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
• the anionic surfactants are preferably used in amounts of 3 to 25% by weight, in particular in Quantities of 10 to 20% by weight, based in each case on the sum of the constituents used, used. However, their content can also exceed 15% by weight.
• Preferred Anionic surfactants are fatty alkyl sulfates, alkyl benzene sulfonates, sulfosuccinates and mixtures from these, such as mixtures of fatty alkyl sulfates and sulfosuccinates or fatty alkyl sulfates and fatty alkyl benzene sulfates, especially in combination with soap. It is special preferred that at least a portion of the sulfonate and / or sulfate surfactants not as fixed Component, but used in liquid form as part of the granulating liquid becomes.
• Suitable surfactants are soaps, either alone or in combination with the anionic surfactants mentioned.
• Saturated fatty acid soaps such as salts of myristic, lauric, palmitic or stearic acid, are particularly suitable.
• Unsaturated fatty acids derived, for example, from oleic acid are also suitable.
• Fatty acid mixtures which can be extracted from natural resources, for example coconut, palm kernel or tallow fatty acids, are also suitable.
• those soap mixtures are preferred which are composed of 50 to 100% by weight of saturated C 12 -C 18 fatty acid soaps.
• the soaps are preferably present in amounts of 0.5 to 8% by weight.
• detergents and cleaning agents are, for example organic cobuilders, graying inhibitors, such as anionic and / or non-ionic Cellulose derivatives, especially carboxymethyl cellulose (CMC) and / or methyl cellulose (MC), and polyvinyl pyrrolidone (PVP) or foam inhibitors such as silicones or paraffin oils on granular carriers and fatty alkyl phosphoric acid esters.
• graying inhibitors such as anionic and / or non-ionic Cellulose derivatives, especially carboxymethyl cellulose (CMC) and / or methyl cellulose (MC)
• PVP polyvinyl pyrrolidone
• foam inhibitors such as silicones or paraffin oils on granular carriers and fatty alkyl phosphoric acid esters.
• Useful organic builders are, for example, those in the form of their sodium salts usable polycarboxylic acids, such as citric acid, adipic acid, succinic acid, glutaric acid, Tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if one such use is not objectionable for ecological reasons, as well as 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.
• the acids themselves can also be used.
• the acids have a builder effect typically also the property of an acidifying component and serve thus also for setting a lower and milder pH of washing or Detergents.
• citric acid succinic acid, glutaric acid, adipic acid, To name gluconic acid and any mixtures of these.
• Suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches.
• the hydrolysis can be carried out by customary processes, for example acid-catalyzed or enzyme-catalyzed. They are preferably hydrolysis products with average molecular weights in the range from 400 to 500,000.
• DE dextrose equivalent
• Both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher molar masses in the range from 2000 to 30000 can be used.
• a preferred dextrin is described in British patent application 94 19 091.
• the oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.
• Such oxidized dextrins and processes for their preparation are known, for example, from European patent applications EP-A-0 232 202, EP-A-0 427 349, EP-A-0 472 042 and EP-A-0 542 496 as well as international patent applications WO- A-92/18542, WO-A-93/08251, WO-A-94/28030, WO-A-95/07303, WO-A-95/12619 and WO-A-95/20608.
• a product oxidized at C 6 of the saccharide ring can be particularly advantageous.
• organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be in lactone form, and which have at least 4 carbon atoms and at least one hydroxyl group and at most contain two acid groups.
• Such cobuilders are used, for example, in the international Patent application WO-A-95/20029.
• Suitable polymeric polycarboxylates are, for example, the sodium salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight from 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 have been found to be particularly suitable Maleic acid proven to be 50 to 90% by weight acrylic acid and 50 to 10% by weight Maleic acid contain.
• Their relative molecular weight, based on free acids is in general 5000 to 200000, preferably 10000 to 120000 and in particular 50000 to 100000. Also homopolymeric salts of acrylic acid with relative molecular weights between about 2000 and about 15,000, especially between 4,000 and 10,000, are suitable.
• the (co) polymeric polycarboxylates can be either as a powder or as an aqueous solution are used, 20 to 55% by weight aqueous solutions being preferred.
• Polymers composed of more than two different monomer units are also particularly preferred, for example those which, according to DE-A-43 00 772, are monomers as salts acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives or according to DE-C-42 21 381 as monomer salts of acrylic acid and 2-alkylallylsulfonic acid as well as sugar derivatives.
• copolymers are those described in German patent applications DE-A-43 03 320 and DE-A-44 17 734 are described and preferably as monomers Have acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.
• Suitable builder substances are oxidation products of carboxyl-containing ones Polyglucosans and / or their water-soluble salts, such as those used in the international Patent application WO-A-93/08251 can be described or their preparation is described, for example, in international patent application WO-A-93/16110. Oxidized oligosaccharides according to the earlier German patent application are also suitable P 196 00 018.1.
• polymeric aminodicarboxylic acids their To name salts or their precursors.
• Polyaspartic acids are particularly preferred or their salts and derivatives, of which in German patent application P 195 40 086.0 discloses that in addition to cobuilder properties, it also has a have a bleach-stabilizing effect.
• polyacetals which are obtained by reacting dialdehydes with polyol carboxylic acids, which have 5 to 7 carbon atoms and at least 3 hydroxyl groups have, for example, as in European patent application EP-A-0 280 223 described, can be obtained.
• Preferred polyacetals are made from dialdehydes such as Glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
• the other granular components include, for example, compact ones Bleach or bleach activator granules, enzyme granules, foam inhibitor granules, preferably concentrated foam inhibitor granules and granular carriers for color and Fragrances.
• bleach activators for example, with H 2 O 2 which form organic peracids N-acyl or O-acyl compounds, preferably N, N'-tetraacylated diamines, also carboxylic anhydrides and esters of polyols such as glucose pentaacetate.
• the bleach activators contain bleach activators in the usual range, preferably between 1 and 10% by weight and in particular between 2 and 8% by weight.
• Particularly preferred bleach activators are N, N, N ', N'-tetraacetylethylenediamine (TAED) and 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine (DADHT).
• Enzymes come from the class of proteases, lipases, amylases, cellulases or their mixtures in question.
• Bacterial strains or are particularly well suited Fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are enzymatic Active ingredients.
• Proteases of the subtilisin type and in particular are preferred Proteases obtained from Bacillus lentus are used. Your share can about 0.2 to about 2% by weight.
• the enzymes can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature decomposition.
• stabilizers in particular for per-compounds and enzymes are the salts of polyphosphonic acids, especially 1-hydroxyethane-1,1-diphosphonic acid (HEDP) into consideration.
• HEDP 1-hydroxyethane-1,1-diphosphonic acid
• Suitable foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C 18 -C 24 fatty acids.
• Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica. Mixtures of various foam inhibitors, for example those made of silicones, paraffins or waxes, are also advantageously used.
• Bleaching agents can be added to the preliminary product as further typical detergent components become.
• perborates and / or percarbonates are used as bleaching agents.
• Sodium perborate tetrahydrate and sodium perborate monohydrate are preferably used.
• sodium percarbonates are preferably used.
• peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracid salts or peracids for example perbenzoates and / or peroxaphthalates.
• the proportion of the bleaching agents, based on the finished product is 5 to 25% by weight, in particular 10 to 20% by weight.
• the bleaching agents are added to the treated builder in addition to the other usual detergent components mentioned above to produce the precursor. If appropriate, the bleaching agents can also be added in whole or in part in a preparation step downstream of the granulation.
• the intermediate or through Coating "and / or powder-treated preliminary product is mixed in the second mixer with other common detergent raw materials and granulated with the addition of liquid (s).
• liquid s
• polycarboxylate solution as granulation liquid is preferred.
• a mixture of optical brighteners and polycarboxylate solution is added as the granulation liquid in the granulation step.
• Derivatives of diaminostilbenedisulfonic acid or its alkali metal salts are suitable as optical brighteners. Suitable are, for example, salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazin-6-yl-amino) stilbene-2,2'-disulfonic acid or compounds of the same structure which are used instead of Morpholino group carry a diethanolamino group, a methylamino group, anilino group or a 2-methoxyethylamino group.
• Brighteners of the substituted 4,4'-distyryl-di-phenyl type may also be present, for example the compound 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl. Mixtures of the aforementioned brighteners can also be used. Particularly uniform white granules are obtained if, in addition to the usual brighteners, the agents are used in customary amounts, for example between 10 -6 to 10 -3 % by weight, preferably between 0.1 and 0.3% by weight, even small amounts. contains, for example, 10 -6 to 10 -3 % by weight, preferably around 10 -5 % by weight, of a blue dye.
• a particularly preferred dye is Tinolux ® (a product of Ciba-Geigy).
• the granulation is carried out in the form of mixing, pressing or roller granulation Mixers, extruders or roller presses familiar to those skilled in the art.
• the granulation however, it is particularly preferably carried out in a mixer / granulator.
• a suitable mixer e.g. Eirich mixers of the R and RV series, manufactured by the machine factory Gustav Eirich, Hardheim, Germany, the Fukae FS-G mixer, manufactured by the Fukae Powtech Kogyo Co., Japan, the Lödige FM, KM and CB mixers, manufactured by the Lödige Maschinenbau GmbH, Paderborn, Germany, or the Drais series T or K-T, produced by Drais Maschinene GmbH, Mannheim, Germany.
• Intensive mixer too Company IMCATEC Germany
• the usual one needed for granulation Residence time in these mixers is in the range of one minute to approximately 10 minutes.
• the granulate produced according to the invention is under Using flow improvers, powdered and dried at the end of the granulation.
• Amorphous and / or crystalline aluminum silicates are particularly preferred as flow improvers as well as silicas.
• Zeolite A and / or X is among the aluminum silicates and / or P, for example Wessalith P® (commercial product from Degussa, Germany), and particularly preferred among the silicas Sipernat®.
• the flow improver are usually mixed into the granulate. Your share, based on the finished product, is between 0.5 and 8% by weight.
• a proportion of the silicas is particularly preferred between 0.5 and 3% by weight and / or a proportion of the zeolites between 1.5 and 7.5 % By weight.
• the intermediate typically contains between 0 and 10% by weight nonionic surfactant, of 40 up to 65% by weight disilicate, from 5 to 15% by weight ABS, from 2 to 10% by weight flow improver, from 0 to 20% by weight of polycarboxylate and water.
• the drying step is carried out in the fluidized bed, especially at supply air temperatures below of 180 ° C.
• Products manufactured in accordance with the invention have a Bulk density of more than 600 g / l.
• the granules produced according to the invention are pourable and pourable, non-sticky and almost dust-free.
• the granular detergents and cleaning agents, produced according to the invention preferably contain between 3 and 12% by weight, in particular between 3 and 6% by weight nonionic surfactants, 10 to 60% by weight, in particular between 30 and 60% by weight Alkali silicates as a solid and 10 to 35 wt .-%, in particular between 15 and 35% by weight of anionic surfactants.
• the granules produced according to the invention have one Bulk density above 600 g / l, preferably between 700 and 1000 g / l.
• the granules with a weight ratio of FAS: ABS of about 3.3: 1 were easy to pour and had a bulk density of 810 g / l.
• the granules obtained were also free-flowing and had a bulk density of 920 g / l.
• This granulate was produced in One-step process ", ie this processing was carried out in the same mixer without separating preliminary product production and granulation.
• the recipe for the mixture used in the present comparative example and the raw materials, compounds and granulating liquids used correspond to the recipe and the starting materials of Example 1.

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• 1997
  • 1997-07-24 DE DE19731890A patent/DE19731890A1/de not_active Withdrawn
• 1998
  • 1998-07-15 AT AT98113138T patent/ATE241005T1/de not_active IP Right Cessation
  • 1998-07-15 ES ES98113138T patent/ES2200240T3/es not_active Expired - Lifetime
  • 1998-07-15 EP EP98113138A patent/EP0893492B1/fr not_active Expired - Lifetime
  • 1998-07-15 DE DE59808416T patent/DE59808416D1/de not_active Expired - Lifetime

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