WO1993005133A1

WO1993005133A1 - Washing and/or cleaning process

Info

Publication number: WO1993005133A1
Application number: PCT/EP1992/001934
Authority: WO
Inventors: Christian Block; Hans Dolhaine; Johannes Hachgenei; Gerald Schreiber; Jörg Poethkow; Horst Upadek
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 1991-08-30
Filing date: 1992-08-22
Publication date: 1993-03-18
Also published as: DE4128826A1

Abstract

A washing and/or cleaning process should counteract the formation of incrustations without the use of substances that prevent or delay the deposit of calcium carbonate on hard surfaces or textile fabrics, for example polymer polycarboxylates. According to the invention, the formation of calcium carbonate in amounts that exceed the solubility product of calcium carbonate at temperatures between 15 and 95 °C is reduced or avoided by delaying the supply of alkali carbonate to the washing, rinsing and cleaning preparation. For that purpose, the alkali carbonate is added later on to the preparation or a treated alkali carbonate is used whose speed of dissolution at temperatures between 15 and 95 °C is slower than that of untreated alkali carbonate.

Description

'Washing and / or cleaning processes'

The invention relates to a method for washing and / or cleaning, new agents ₄ which are used in this method, and methods for producing the new agents.

It is generally known that in washing and / or cleaning processes, a detergent, dishwashing detergent or cleaning agent with conventional ingredients, which also include alkali carbonates, is added to water with a hardness above 0 ° d. Incrustations caused by the formation of poorly soluble calcium carbonate. Nowadays, agents are used in washing and / or cleaning processes which contain builder substances, the task of which, inter alia, is to counteract the formation of calcium carbonate and thus the formation of incrustations. One of the most modern and most important builder substances of modern times are the aluminosilicates, in particular zeolite such as zeolite NaA in detergent quality. A disadvantage of these zeolites is, however, that in washing and / or cleaning processes in which agents are used which contain both zeolite and alkali carbonate, the formation of the sparingly soluble calcium carbonate from alkali carbonate and the hardness-forming agent of the water takes place faster than the cation exchange through the builder substance zeolite. In order to avoid disruptive incrustations, it is therefore necessary to add further compounds, for example polymeric polycarboxylates, to the agents used in the washing and / or cleaning processes, which are intended to prevent the calcium carbonate formed from settling on hard surfaces or textile fabrics ¬ beats.

The object of the invention was to provide a washing and / or cleaning process in which washing, rinsing or cleaning agents coexist usual ingredients, and in which the formation of incrustations is counteracted without relying on the use of substances which prevent or delay the deposition of calcium carbonate on hard surfaces or textile fabrics, for example polymeric polycarboxylates . A further task was to provide alkali carbonates in a new form of supply which can be used in the washing and / or cleaning processes according to the invention or in the washing, rinsing or cleaning agents used there.

The invention accordingly relates in a first embodiment to a washing and / or cleaning process, the formation of incrustations being reduced when using a washing, rinsing or cleaning agent with conventional ingredients in that the formation of alkali carbonate to water with a hardness above 0 ° d caused formation of calcium carbonate in the amounts that exceed the solubility product of calcium carbonate at temperatures between 15 and 95 ° C, reduced or avoided by the alkali carbonate of washing, rinsing or Cleaning fleet is made available with a time delay.

The alkali carbonate is preferably made available to the washing, rinsing or cleaning liquor with a time delay such that in the first minute, in particular in the first 2 minutes and with particular advantage in the first 10 minutes, for example after 3, 4, 5 or 6 minutes, after adding the washing, rinsing or cleaning agent to the liquor, 10 to 100% by weight, preferably 20 to 100% by weight and in particular 30 to 80% by weight, less alkali carbonate, based on the total amount of alkali carbonate is made available when this is the case with the same total amount of alkali carbonate which is introduced via a conventional alkali carbonate-containing agent with a customary composition. In a preferred embodiment, the alkali carbonate can be made available with a time delay in that a treated alkali carbonate, which was obtained by modifying an untreated alkali carbonate and has a lower dissolution rate in water at temperatures between 15 and 95 ° C. than the untreated alkali carbonate, has separately with a Washing, rinsing or cleaning agent is introduced into the washing and / or cleaning liquor or as part of a washing, rinsing or cleaning agent in the washing and / or cleaning liquor. In a further preferred embodiment, the alkali carbonate is made available with a time delay in that the addition of a treated or untreated alkali carbonate to the washing, rinsing or cleaning liquor is 1 to 5 minutes, preferably 2 to 3 minutes, after the addition of a wash -, Flushing or cleaning agent that does not contain alkali carbonate takes place.

In the context of this disclosure, an “untreated alkali carbonate” is understood to mean a commercially available alkali carbonate which serves as the starting material for the production of the “treated alkali carbonate”. Examples of these commercially available alkali carbonates are both light and compacted, powdery or granular alkali carbonates with a bulk density between 300 and 1 200 g / 1 and roller-compacted alkali carbonates in Schülpen-For. These untreated alkali carbonates can be obtained, for example, from Matthes & Weber, Federal Republic of Germany, Sodawerk Bernburg GmbH, Federal Republic of Germany, or Deutsche Solvay-Werke GmbH. A sodium carbonate, in particular a water-containing or anhydrous granulated or crystallized sodium carbonate with a bulk density between 500 and 1200 g / 1, with particular advantage between 800 and 1000 g / 1, is preferably used as the untreated alkali carbonate, the latter at least 85% by weight. -% consists of particles with a diameter between 200 and 2,000 microns and a maximum of 5 wt .-% of particles with a diameter smaller than 200 microns.

In a further embodiment, the invention relates to the treated alkali metal carbonate, which has a lower dissolution rate in water than the untreated alkali metal carbonate at temperatures between 15 and 95 ° C. A treated alkali carbonate is preferred, which is obtained by melting the untreated alkali carbonate and then grinding the cooled melt, a maximum of 10% by weight of the ground particles having a diameter of less than 0.8 mm and in particular at least 90% by weight. of the ground particles have a diameter between 0.8 and 2 mm. In particular, however, a treated alkali metal carbonate is preferred which contains untreated or treated alkali metal carbonate or which is obtained by melting the untreated alkali metal carbonate and then grinding the cooled melt and is partially or completely coated. The effect of a lower dissolution rate in water of the treated alkali metal carbonate compared to the untreated alkali metal carbonate already occurs when only small parts of the entire surface of the untreated alkali metal carbonate are coated. Advantageously, however, 10 to 100%, preferably 30 to 100% and in particular 50 to 100% of the entire surface of the untreated alkali carbonate are coated. The coating substance can accordingly be used in a very variable weight ratio of coating substance: alkali carbonate. Preferably, treated, coated alkali carbonate contains 0.5 to 90% by weight, in particular 1 to 50% by weight and particularly advantageously 2 to 25% by weight, based in each case on the untreated alkali carbonate, of coating substance.

In a preferred embodiment, the treated alkali carbonates contain coating substances which are anionic surfactants in their acid form. Suitable anionic surfactants in their acid form are, for example, those of the organically derivatized sulfonic and sulfuric acid type. As derivatives of sulfonic acid type are preferably alkyl aryl sulfonic acids, especially Cg-Cj _j -alkylbenzenesulfonic, Cg-Cis-alkyl sulfonic acids, mono- or polyunsaturated C 8 -C 22 Alky1ensulfonsäuren, more particularly sondere monoethylenically unsaturated C8-C22 Alkylensulfonsäuren, and sulphonic acids of mono- and / or polycarboxylic acids, especially α-sulfo fatty acids and sulfosuccinic acid.

Suitable organic derivatives of the sulfuric acid type are the sulfuric acid monoesters from primary alcohols of natural and synthetic origin (alkylsulfuric acids), that is to say from C 16 -C 12 alcohols, in particular from fatty alcohols, for example from coconut fatty alcohols, tallow fatty alcohols, oleyl alcohol , Lauryl, myristyl, palmityl or stearyl alcohol, or the Cιo-C2θ-0 * oalkoholen, and those of secondary alcohols of this chain length. The sulfuric acid monoesters of the alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl-branched Cg-Cn- Alcohols with an average of 3.5 moles of ethylene oxide per mole of alcohol are suitable. Fatty acid monoglyceride sulfuric acids are also suitable.

Other anionic surfactants in their acid form are fatty acids from natural or synthetic, preferably saturated or ethylenically unsaturated C8-C28 fatty acids or mixtures thereof. Natural fatty acid mixtures are particularly suitable, for example coconut, palm kernel or tallow fatty acids. Preference is given to those which are composed of 50 to 100% of saturated C 12-18 fatty acids and 0 to 50% by weight of oleic acids. Longer-chain fatty acids with 15 to 24 carbon atoms, optionally in a mixture with shorter-chain fatty acids with 8 to 10 carbon atoms, are particularly preferred. Particularly preferred fatty acids are stearic acid and isostearic acid or mixtures thereof.

Other suitable anionic surfactants in their acid form are the fluorinated or perfluorinated derivatives of the sulfuric acid derivatives, sulfonic acid derivatives and fatty acids mentioned.

The treated alkali carbonate preferably contains anionic surfactants in their acid form in an amount of 0.5 to 50% by weight, based on the untreated alkali carbonate. In particular, the treated alkali metal carbonates contain organic derivatives of sulfuric acid and sulfonic acid, for example Cs-Ci8-alkylsulfuric acid and Cg-C ^ -alkylbenzenesulfonic acid, in amounts of

1 to 20 wt .-%, based on the sum of untreated alkali carbonate and anionic surfactant in acid form. The content of fatty acids or fatty acid mixtures in the treated alkali metal carbonates is preferably 1 to 15% by weight and in particular 2 to 10% by weight, in each case based on the untreated alkali carbonate, it being particularly advantageous if the treated alkali metal carbonates as coating substances are a mixture from fatty acids or a fatty acid mixture and organic derivatives of sulfuric acids or sulfonic acids, for example

2 to 5 wt .-% Ci2-Ci8 fatty acids or fatty acid mixture and 5 to 15 wt .-% Ci2-Ci8-alkyl sulfuric acid or Cg-C ^ alkylbenzenesulfonic acid, each based on the untreated alkali carbonate. In particular, however, treated alkali carbonates are preferred which contain a mixture of fatty acid or one as coating substances Fatty acid mixture and alkali silicates, for example a mixture of 2 to 15% by weight of fatty acid or fatty acid mixture and 2 to 10% by weight of amorphous alkali silicate.

The coating of the untreated alkali carbonate with anionic surfactants in their acid form can be carried out in all customary mixing and / or granulating devices. Temperatures between room temperature and 150 ° C., for example up to 100 ° C. and in particular between 40 and 80 ° C., are preferably used. In the cases in which treated alkali carbonate is produced by coating untreated alkali carbonate with fatty acid or a fatty acid mixture, it is particularly advantageous if the coating of the untreated alkali carbonate is carried out at temperatures above the melting point of the fatty acid or the fatty acid mixture.

Other suitable coating substances are known, non-surfactant-like foam inhibitors, for example silicones, preferably organopolysiloxanes, and their mixtures with microfine, optionally silanized silica, paraffins or waxes. In particular, linear or branched dimethylpolysiloxanes, which advantageously contain a relative molecular mass between 1,000 and 100,000, are preferred. Branched dimethylpolysiloxanes which have carboxylate groups in the side chains have particularly advantageous properties. The silicones are used alone or in a mixture, in particular in a mixture with other coating substances. The content of silicones in the treated alkali carbonates is preferably 0.1 to 5% by weight, based on the sum of untreated alkali carbonate and coating substances. The untreated alkali carbonate is coated with silicones as described above, preferably at temperatures between 40 and 150 ° C.

Other suitable coating substances are solids from the group calcium stearate, microwaxes, for example a micropowder, which is available under the name Hoechst-Wachs Cv ^R ) from Hoechst AG, Federal Republic of Germany, amorphous and crystalline alkali silicates, zeolite, in particular zeolite NaA in detergent quality , and natural or synthetic layered silicates, especially sectites and bentonites. Finely divided solids are preferably used as the coating substance, which consist of at least 90% of particles with a diameter below 40 μm. The alkali silicates are preferably amorphous alkali silicates with a molar ratio M2O to SiO 2 of 1: 2.0 to 1: 4.5 and in particular of 1: 2.3 to 1: 4.0, where M is preferably sodium or potassium. The coating substance preferably consists of one or more of the fine-particle solids mentioned and of mixtures of the fine-particle solids with other coating substances. The content of coating substances of finely divided solids in the treated alkali metal carbonates is preferably 0.5 to 90% by weight, based on the untreated alkali metal carbonate. Calcium stearate is advantageously up to 8% by weight, in particular up to 5% by weight and particularly advantageously between 1 and 2% by weight, and microwaxes in amounts between 1 and 20% by weight, in particular between 2 and 10 % By weight used, in each case based on the untreated alkali carbonate. Alkali silicates, preferably sodium silicates, on the other hand, are advantageously used in amounts between 1 and 90% by weight, in particular between 3 and 80% by weight, based in each case on the untreated alkali carbonate.

The coating of the untreated alkali carbonate with the above-mentioned, preferably finely divided solids is preferably carried out in conventional mixing, pouring and granulating devices in a dry mixing process. It is particularly preferred that the untreated alkali carbonate with the finely divided, preferably only moderately water-soluble to water-insoluble solids at room temperature to slightly elevated temperatures which are below the melting temperature of the coating substance and preferably do not exceed 60 ° C, in particular 40 ° C, is mixed dry. In a further embodiment, in which micro waxes are used as the coating substance, it is particularly preferred that after the dry mixing at room temperature to slightly elevated temperatures, the temperature for solidifying the core shell with the core to a temperature above the melting point of the coating substance is increased, the temperature preferably being below 150 ° C. and in particular below 100 ° C. Coating substances which consist of dispersions of nonionic surfactants and moderately water-soluble to water-insoluble solids are particularly advantageous. Suitable nonionic surfactants include adducts of 1 to 80 moles of ethylene oxide (E0) with 1 mole of an aliphatic compound having essentially 8 to 20 carbon atoms from the group of alcohols, carboxylic acids, fatty amines, carboxamides or alkanesulfonamides. The addition products of 2 to 20 moles, in particular of 2 to 8 moles of ethylene oxide, to primary alcohols, such as, for example, to the addition products of 3, 5 or 7 E0 to coconut or tallow fatty alcohols, to oleyl alcohol, to oxo alcohols, or to secondary alcohols, are particularly important Alcohols with 8 to 18, preferably 12 to 18 carbon atoms, and mixtures of these. 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 restricted homolog distribution (narrow range ethoxylates, nre). Other nonionic surfactants that can be used are alkyl glycosides of the general formula R-0- (G) _x , in which R is a primary straight-chain or aliphatic radical which is methyl-branched in the 2-position and has 8 to 22, preferably 12 to 18, carbon atoms, and G is a symbol , which stands for a glycose unit with 5 or 6 carbon atoms, and the degree of oligomerization x is between 1 and 10, preferably between 1 and 2 and in particular is significantly less than 1.4, for example in amounts of 1 to 10 wt. -%, are used. The preferred solids include synthetic and natural aluminosilicates, for example zeolite, in particular zeolite NaA in detergent quality. Further preferred aluminosilicates are layered silicates, especially smectites and bentonites. The weight ratio of nonionic surfactant: solid in the dispersions is preferably 10: 1 to 1: 5 and in particular 5: 1 to 1: 1. In a further preferred embodiment, treated alkali metal carbonates contain coating substances, the mixtures of dispersions from moderately water-soluble to water-insoluble represent solids in nonionic surfactants with anionic surfactants in acid form. The content of the treated alkali carbonates in coating substances from dispersions of moderately water-soluble to water-insoluble solids in nonionic surfactants is preferably 0.5 to 25% by weight and in particular 1 to 15% by weight, in each case based on the untreated Alkali carbonate. The coating of the untreated alkali carbonate with dispersions of moderately water-soluble to water-insoluble solids in nonionic surfactants is preferably carried out like the coating of the untreated alkali carbonate with anionic surfactants in their acid form. Temperatures from 40 to 100 ° C. and in particular from 60 to 80 ° C. are particularly preferred.

In a further embodiment, the invention relates to a method for producing a treated alkali carbonate, the coating being carried out with an aqueous solution or an aqueous dispersion of the coating substances. The coating is preferably carried out with an aqueous solution of an alkali silicate with a molar ratio M2O to SiO 2 of 1: 2.0 to 1: 4.5, where M stands for sodium or potassium. In particular, it is preferred that the coating be carried out with an aqueous solution of a sodium silicate with a molar ratio of 1: 2.3 to 1: 4.0. A 10 to 60% strength by weight solution of an alkali silicate is advantageously sprayed onto the untreated alkali carbonate at elevated temperatures, in particular at temperatures between 80 and 140 ° C., in a mixer or granulator, in a warm air stream or in a fluidized bed. The process can be carried out in conventional mixers, for example of the Lödige, Schugi or Eirich type, or in conventional fluidized bed devices.

In a further embodiment, the invention relates to a solid washing, rinsing and / or cleaning agent which contains a treated alkali carbonate. Preference is given to agents, in particular heavy powder with a bulk density between 600 and 1 100 g / 1, the treated alkali carbonate, preferably sodium carbonate, in amounts of 1 to 20% by weight, preferably in amounts of 3 to 15% by weight and in particular in amounts of 5 to 10 wt .-%, based on the detergent, as well as other usual ingredients of detergents, dishwashing detergents or cleaning agents. The agents can be produced using the known granulation and extrusion methods and by mixing several base powders or base granules. For example, the agents can be obtained by adding an agent without alkali carbonate, Drying, granulating or extruding methods was produced, the treated alkali carbonate is dry mixed.

The other usual ingredients of washing, spraying or cleaning agents include, in particular, surfactants such as anionic surfactants, nonionic surfactants, amphoteric surfactants or cationic surfactants. Anionic and nonionic surfactants are particularly preferred.

Suitable anionic surfactants are, for example, those of the sulfonate and sulfate type. The surfactants of the sulfonate type are alkylbenzenesulfonates (Cg-Ci5-alkyl), olefin sulfonates, ie. H. Mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as those obtained, for example, from Ci2 "Ci8 monoolefins with terminal and internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products, are also suitable. Dialkane sulfonates are also suitable which are obtainable from Ci2-Ci8-Al anen by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization or by bisulfite addition to olefins, and in particular the esters of α-sulfofatty acids (ester sulfonates), for example the α-sulfonated ones Methyl ester of hydrogenated coconut, palm kernel or tallow fatty acids.

Suitable surfactants of the sulfate type are the sulfuric acid monoesters from primary alcohols of natural and synthetic origin, that is to say from fatty alcohols, for example coconut oil alcohols, tallow fatty alcohols, oleyl alcohol, lauryl, myristyl, palmityl or stearyl alcohol, or the Cιo 20 ~ 0 ^% alcohols, and those of secondary alcohols of this chain length. The sulfuric acid monoesters of the alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl-branched Cg-Cn alcohols with an average of 3.5 mol of ethylene oxide, are also suitable. Sulfated fatty acid monoglycerides are also suitable.

Soaps from natural or synthetic, preferably saturated, fatty acids can also be used. Soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids, are particularly suitable. Preferred are those which are 50 to 100% saturated Ci2-Ci8 fatty acid soaps and 0 to 50% composed of oleic acid soaps.

The anionic surfactants can be in the form of their sodium, potassium and ammonium salts and also as soluble salts of organic bases, such as mono-, di- or triethanolamine. The detergent content according to the invention of anionic surfactants or of anionic surfactant mixtures is preferably 5 to 40, in particular 8 to 35,% by weight. It is particularly advantageous if the content of sulfonates and / or sulfates in the compositions is 10 to 35% by weight, in particular 15 to 30% by weight, and the soap content is up to 8% by weight. , in particular 0.5 to 5 wt .-%.

Particularly suitable nonionic surfactants are those which can also be used as a coating substance. The content of the agents in ethoxylated alcohols preferably used as nonionic surfactants is preferably 1 to 10% by weight and in particular 2 to 8% by weight.

Weakly acidic, neutral or alkaline-reacting soluble and / or insoluble components which are able to precipitate or bind calcium ions in a complex manner are suitable as organic and inorganic builders. Suitable and, in particular, ecologically harmless builder substances, such as finely crystalline, synthetic water-containing zeolites of the NaA type, which have a calcium binding capacity in the range from 100 to 200 mg CaO / g, are preferably used. Their average particle size is usually in the range from 1 to 10 μm (measurement method: Coulter Counter, volume distribution). The zeolite content of the compositions is generally up to 60% by weight, preferably at least 10% by weight and in particular 20 to 55% by weight, based on the anhydrous substance.

Other builder components which can be used together with the zeolites are (co) polymeric polycarboxylates, such as polyacrylates, polyethacrylates and in particular copolymers of acrylic acid with maleic acid, preferably those from 50% to 10% maleic acid. The relative molecular weight of the homopolymers is generally between 1,000 and 100,000, that of the copolymers between 2,000 and 200,000, preferably 50,000 to 120,000, based on free acid. A particularly added acrylic acid-maleic acid copolymer has a relative molecular weight of 50,000 to 100,000. Suitable, albeit less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ether, in which the proportion of acid is at least 50%. Also useful are polyacetal carboxylic acids, as described, for example, in US Pat. Nos. 4,144,226 and 4,146,495, and polymeric acids which are obtained by polymerizing acrolein and subsequent disproportionation using alkalis and are composed of acrylic acid units and vinyl alcohol units or acrolein units. The content of (co) polymeric polycarboxylates in the agents can be, for example, up to 10% by weight, preferably 2 to 8% by weight. A particularly preferred embodiment of the invention provides, however, that the washing and / or cleaning agents are free of (co) polymeric polycarboxylates.

Usable organic builders are, for example, the polycarboxylic acids preferably used in the form of their sodium salts, such as citric acid and nitrilotriacetic acid (NTA), provided that such use is not objectionable for ecological reasons.

Other suitable ingredients of the agents are inorganic alkalizing agents such as silicates; In particular, alkali silicate, especially sodium silicate with a molar ratio Na2Ö: S θ2 of 1: 1 to 1: 4.5, is used. The content of sodium silicate in the compositions is generally up to 10% by weight and preferably between 2 and 8% by weight.

Other common detergent, dishwashing or cleaning agent components include graying inhibitors (dirt carriers), foam inhibitors, bleaching agents and bleach activators, optical brighteners, enzymes, textile-softening substances, colorants and fragrances, and neutral salts.

Among the compounds which provide H2O2 in water and which serve as bleaching agents, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further bleaching agents that can be used are, for example, peroxycarbonate, peroxypyrophosphates, citrate perhydrates and H2O2-providing peracid salts or peracids, such as perbenzoates, Peroxaphthalates, 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.

In order to achieve an improved bleaching effect when washing at temperatures of 60 ° C. and below, bleach activators can be incorporated into the preparations. Examples of these are N-acyl or O-acyl compounds which form organic peracids with H2O2, preferably N, N'-tetraacylated diamines, such as N, N, N ', N'-tetraacetylethylene diamine, furthermore carboxylic acid anhydrides and esters of polyols such as glucose pentaacetate. 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.

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, such as, 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, for example degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone can also be used. Carboxymethyl cellulose (sodium salt), methyl cellulose, methyl hydroxyethyl cellulose and mixtures thereof, and polyvinyl pyrrolidone are preferably used, for example in amounts of 0.1 to 5% by weight, based on the composition.

The foaming power of the surfactants can be increased or decreased by combining suitable types of surfactants; a reduction can also be achieved by adding non-surfactant-like organic substances. A reduced foaming power, which is desirable when working in machines, is often achieved by combining different types of surfactants, for example sulfates and / or sulfonates with nonionic surfactants and / or with soaps. In the case of soaps, the foam-suppressing effect increases with the degree of saturation and the C number of the fatty acid residue. Soaps of natural and synthetic origin which contain a high proportion of Cχ8-C24 fatty acids are therefore suitable as foam-inhibiting soaps. Suitable non-surfactant foam inhibitors are the organopolysiloxanes already mentioned as coating substances and their mixtures with microfine, optionally silanized silica, paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica. Mixtures of various foam inhibitors are also used with advantage, for example those composed of silicones and paraffins or waxes. The foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance.

The detergents can contain, as optical brighteners, derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. For example, salts of 4,4'-bis (2-anilino-4-morpholino-l, 3,5-triazin-6-yl-amino) -stilbene-2,2'-disulfonic acid or compounds of the same structure are suitable which, instead of the morpholino group, carry a diethanola ino group, a methylamino group, an 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.

Enzymes from the class of proteases, lipases, cellulases and amylases or mixtures thereof are possible. Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Strepto yces griseus are particularly suitable. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used. The enzymes can be adsorbed on carriers and / or embedded in shell substances in order to protect them against premature decomposition.

The salts of polyphosphonic acids, in particular l-hydroxyethane-l, l-diphosphonic acid (HEDP), are suitable as stabilizers, in particular for per-compounds and enzymes. Examples

A compressed calcined soda (V-soda) with a bulk density of approximately 900 g / l was used as the untreated alkali carbonate, 0.1% by weight of the particles having a diameter above 2 mm and 2% by weight of the particles having a diameter below 0.2 mm (commercial product from Matthes & Weber, Federal Republic of Germany).

This untreated alkali carbonate was - as listed in Examples 1 to 5 - converted into a treated alkali carbonate. The treated alkali carbonate provided the carbonate ions with a time delay in comparison to the untreated alkali carbonate, ie the dissolution rate of the treated alkali carbonates was less than the dissolution rate of the untreated alkali carbonate. The dissolving speed of the alkali carbonate samples was determined by means of conductivity measurements. For this purpose, 0.5 g of the untreated alkali carbonate or an amount of treated alkali carbonate, which contained 0.5 g of untreated alkali carbonate, was dissolved or suspended in 100 ml of deionized water with stirring at room temperature and the conductivity of the solution or suspension was carried out with the aid of a guide ¬ ability measuring cell determined as a function of time. Since the conductivity of soda solutions up to a concentration range of 10 g / 1 is approximately linearly proportional to the concentration of the solution, the proportion of dissolved soda can be determined directly from the ratio of final conductivity to conductivity at a defined point in time. These proportions are listed in Table 1.

The conductivity measurements showed a good correlation to the results of the gravimetric carbonate determination (flash filtration, drying, weighing). However, contributions of the coating material to the conductivity were neglected: When calculating the values given in Table 1, it was assumed that the conductivity is caused exclusively by the carbonate ions. However, this only applies exactly to the untreated V-soda. For the examples 1.1. until 5.2. can the in values given in Table 1 are to be regarded as maximum limit values for the proportion of dissolved sodium carbonate.

Table 2 lists the reduced formation of calcium carbonate in a zeolite / treated alkali carbonate system. The formation of calcium carbonate as a competitive reaction between calcium ion exchange and calcium carbonate precipitation was determined as follows:

2 g of zeolite NaA in powder form, calculated as the anhydrous active substance, and 1 g of untreated alkali carbonate (V-soda) or the amount of treated alkali carbonate, which contained 1 g of V-soda, in 1 1 of a CaCl 2 solution with a hardness of 30 ° d (corresponds to 300 mg CaO) suspended at room temperature. The suspension was stirred for 10 minutes and then filtered. The filter cake was washed free of carbonate with a dilute sodium hydroxide solution which had been prepared from distilled water and sodium hydroxide and had a pH of about 9, was dried at 120 ° C. for 20 hours, weighed and the carbonate content (calculated) determined as calcium carbonate) microanalytically. For this purpose, the dried filter cake was mixed with a dilute 10% by weight sulfuric acid. The resulting carbon dioxide was passed into an aqueous, 25% by weight, weighed potassium hydroxide solution, weighed back and converted to precipitated calcium carbonate.

example 1

The treated alkali carbonates 1.1. and 1.2. manufactured:

1.1. Treated alkali carbonate, consisting of 100 parts by weight of V-soda and 8.1 parts by weight of a 1: 1 mixture of Cs-Cio-fatty acid and stearic acid

1.2. Treated alkali carbonate, consisting of 100 parts by weight of V-soda and 8.1 parts by weight of a 1: 1 mixture of stearic acid and iso-stearic acid. For this purpose, 100 parts by weight of V-soda were mixed with 8.1 parts by weight of the specified melted fatty acids at 120 ° C. in a Lödige mixer for 20 minutes.

Example 2

The treated alkali carbonates 2.1., 2.2. and 2.3. manufactured:

2.1. Treated alkali carbonate, consisting of 100 parts by weight of V soda and

1 part by weight of calcium stearate

2.2. Treated alkali carbonate, consisting of 100 parts by weight of V soda and

2 parts by weight of calcium stearate

2.3. Treated alkali carbonate, consisting of 100 parts by weight of V-soda and 5 parts by weight of calcium stearate.

For this purpose, 100 parts by weight of V-soda were mixed with the stated amounts of calcium stearate in a Turbula mixer. The shaking times were 10 minutes.

Example 3

The treated alkali carbonates 3.1. and 3.2. manufactured:

3.1. Treated alkali carbonate, consisting of 100 parts by weight of V soda and 2 parts by weight of Hoechst wax C ( ^R ) (micropowder)

3.2. Treated alkali carbonate, consisting of 100 parts by weight of V soda and 5 parts by weight of Hoechst wax C ( ^R ) (micropowder).

The preparation was carried out as described in Example 2. Example 4

The treated alkali carbonates 4.1., 4.2., 4.3 »and 4.4. manufactured:

4.1. Treated alkali carbonate, consisting of 100 parts by weight of V-soda and 4.2 parts by weight of a sodium silicate with a molar ratio Na2θ: Siθ2 of 1: 2.0.

4.2. Treated alkali carbonate, consisting of 100 parts by weight of V-soda and 7 parts by weight of a sodium silicate with a molar ratio Na2θ: Siθ2 of 1: 3.4

4.3. Treated alkali carbonate, consisting of 100 parts by weight of V-soda and 5 parts by weight of a sodium silicate with a molar ratio Na2θ: Siθ2 of 1: 4.0

4.4. Treated alkali carbonate, consisting of 100 parts by weight of V-soda and 10 parts by weight of a sodium silicate with a molar ratio Na2θ: Siθ2 of 1: 4.0.

For this purpose, 100 parts by weight of V-soda were sprayed in a Lödige mixer with a 30% by weight water glass solution of the type specified and dried at 120 ° C. for 2 hours.

Example 5

The treated alkali carbonates 5.1. and 5.2. manufactured:

5.1. Treated alkali carbonate, consisting of 100 parts by weight of V soda, 7.5 parts by weight of a sodium silicate with a molar ratio a θ: S θ2 of 1: 2.0 and 10 parts by weight of a 1: 1 mixture from Cδ-Cin fatty acid and stearic acid

5.2. Treated alkali carbonate, consisting of 100 parts by weight of V-soda, 4 parts by weight of a sodium silicate with a molar ratio Na2θ: Siθ2 of 1: 2.0 and 5.5 parts by weight of stearic acid. For this purpose, 100 parts by weight of V-soda were sprayed in a Lödige mixer with a 30% by weight waterglass solution of the type specified, as in Example 4, and dried at 120.degree. The dried alkali carbonate was then treated as described in Example 1 with the fatty acid or the fatty acid mixture.

Table 1: proportions of dissolved sodium carbonate in% by weight (maximum values are given in 1.1. To 5.2.)

Table 2: Calcium carbonate content in the filter cake

CaCÜ3 content in the filter cake in wt.

V soda 10.4

First, a suspension of zeolite NaA powder and CaCl2 solution was prepared as stated above. The untreated alkali carbonate (V-soda) was added 2 minutes later. The rest of the procedure was carried out as indicated above.

Claims

Patent claims

1. Washing and / or cleaning process, the formation of incrustations being reduced when using a washing, rinsing or cleaning agent with customary ingredients, characterized in that the water caused by the addition of alkali carbonate with a hardness above 0 ° d The formation of calcium carbonate in amounts which exceed the solubility product of calcium carbonate at temperatures between 15 and 95 ° C. is reduced or avoided by making the alkali carbonate available to the washing, rinsing or cleaning liquor with a time delay.

2. The method according to claim 1, characterized in that in the first minute, preferably in the first 2 minutes and in particular in the first 10 minutes, for example after 3, 4, 5 or 6 minutes, after the addition of washing, rinsing or detergent to the liquor 10 to 100 wt .-%, preferably 20 to 100 wt .-% and in particular 30 to 80 wt .-% less alkali carbonate, based on the total amount of alkali carbonate, is made available than with an alkali carbonate-containing agent usual composition.

3. The method according to claim 1 or 2, characterized in that a washing, rinsing or cleaning agent is used which contains a be¬ treated alkali metal carbonate, which has a lower dissolving speed in water at temperatures between 15 and 95 ° C than untreated ¬ tes has alkali carbonate.

4. The method according to claim 1 or 2, characterized in that the addition of a treated or untreated alkali carbonate to the washing, rinsing or cleaning liquor 1 to 5 minutes, preferably 2 to 3 minutes, after the addition of a washing, rinsing or cleaning ¬ means that contains no alkali carbonate takes place.

5. The method according to claim 3 or 4, characterized in that as untreated alkali carbonate sodium carbonate, preferably water-containing or anhydrous, granulated or crystallized sodium carbonate with a bulk density between 500 to 1 200 g / 1, preferably between 800 and 1 000 g / 1, the latter consisting of at least 85% by weight of particles with a diameter between 200 and 2,000 μm and a maximum of 5% by weight of particles with a diameter of less than 200 μm.

6. Treated alkali carbonate, which has a lower dissolution rate in water than the untreated alkali carbonate at temperatures between 15 and 95 ° C. and is obtained by melting the untreated alkali carbonate and then grinding the cooled melt, with a maximum of 10% by weight of the ground particles have a diameter of less than 0.8 mm and in particular at least 90% by weight of the ground particles have a diameter of between 0.8 and 2 mm.

7. Treated alkali carbonate, which has a lower dissolving rate in water than the untreated alkali carbonate at temperatures between 15 and 95 ° C., the alkali carbonate being partially or completely coated.

8. Treated alkali carbonate according to claim 7, characterized in that it is 0.5 to 90 wt .-%, preferably 1 to 50 wt .-% and in particular 2 to 25 wt .-%, each based on the untreated alkali carbonate , contains coating substance.

9. Treated alkali carbonate according to one of claims 7 or 8, characterized in that the coating substances are anionic surfactants in their acid form.

10. Treated alkali carbonate according to claim 9, characterized in that the coating substances fatty acids, preferably saturated or ethylenically unsaturated C8-C28 fatty acids or mixtures thereof, Cg-Ci3-alkylbenzenesulfonic acids, C8-Cχ8-alkylsulfonic acids, preferably monoethylenically unsaturated C8-C22 ~ alkylene sulfonic acids , C8 ~ Ci8-alkyl sulfuric acids, α-sulfofatty acids, sulfosuccinic acid or fluorinated or perfluorinated derivatives of these acids.

11. Treated alkali carbonate according to one of claims 7 or 8, characterized in that the coating substances contain silicones, preferably linear or branched dimethylpolysiloxanes, in particular with a relative molecular weight between 1,000 and 100,000, which alone or in a mixture with other coating substances be used.

12. Treated alkali carbonate according to one of claims 7 or 8, characterized in that the coating substance is one or more solids from the group of calcium stearate, the microwaxes, alkali silicates, zeolites and phyllosilicates.

13. Treated alkali carbonate according to claim 12, characterized in that the coating substances are dispersions of moderately water-soluble to water-insoluble solids, preferably zeolite and layered silicates, in nonionic surfactants.

14. A method for producing a treated alkali metal carbonate according to one of claims 8 to 11 or 13, characterized in that the coating of the untreated alkali metal carbonate is carried out at temperatures between room temperature and 150 ° C, for example up to 100 ° C and in particular between 40 and 80 ° C becomes.

15. The method according to claim 14, characterized in that fatty acid or a fatty acid mixture is used as the coating substance and the coating of the untreated alkali carbonate is carried out at temperatures above the melting point of the fatty acid or the fatty acid mixture.

16. A method for producing a treated alkali carbonate according to claim 12, characterized in that the untreated alkali carbonate with finely divided, preferably only moderately water-soluble bis water-insoluble solids at room temperature to slightly elevated temperatures, which are below the melting temperature of the coating substance and preferably do not exceed 40 ° C., are mixed dry.

17. The method according to claim 16, characterized in that after the dry mixing, the temperature for solidifying the core shell with the core is raised to a temperature above the melting point of the Umschlag¬ substance, the temperature preferably below 150 ° C and in particular below 100 ° C lies.

18. A process for the preparation of a treated alkali carbonate according to one of claims 7 to 13, characterized in that the coating is carried out with an aqueous solution or an aqueous dispersion of the coating substances.

19. A method for producing a treated alkali carbonate according to claim 18, characterized in that a 10 to 60 wt .-% aqueous solution of an alkali silicate, which preferably has a molar ratio of 2O: SiO 2, where M is sodium or potassium, in particular Na 2 O. : SiO2, from 1: 2.0 to 1: 4.5, in particular from 1: 2.3 to 1: 4.0, is sprayed onto the untreated alkali carbonate, the spraying preferably being carried out at elevated temperatures , especially at temperatures between 80 and 140 ° C, in a mixer, a fluidized bed or in a warm air stream.

20. Washing, rinsing and / or cleaning agent containing a treated alkali carbonate according to one of claims 6 to 13.

21. Detergent according to claim 20, characterized in that it contains detergent-grade zeolite, preferably zeolite NaA in amounts of 10 to 60% by weight, in particular in amounts of 20 to 55% by weight, based on the detergent, of treated alkali metal carbonate Amounts of 1 to 20% by weight, preferably in amounts of 3 to 15% by weight and in particular in amounts of 5 to 10% by weight, based on the detergent, and also contain other conventional detergent ingredients, but this is free of (co) polymeric polycarboxylates.