DE2141280A1 - Tetrasodium edta particles coated with fatty acids - - for use in bleaching and washing compsns - Google Patents

Abstract

Release of tetrasodium EDTA in aq. bleaching or washing baths is delayed, or rapidly effected only at elevated temps. at which the per components of the bath becomes active, by coating at least partly its granules or agglomerates with a mixt. of fatty acids melting at 35-80 degrees C (pref. 40-70 degrees C). Inactivation of EDTA is prevented. EDTA forms complexes with heavy metals, esp. Fe and Cu, which catalytically decompose H2O2 and, hence, must be inactivated in the form of a complex with EDTA.

Description

"For use in bleaches and detergents containing active oxygen certain enveloped ethylenediamine tetraacetate containing Mftivsauerstoff Bleaching and washing liquors are often salts of ethylenediaminetetraacetic acid added to prevent heavy metal ions, especially iron or copper ions, to binuen and thus to prevent catalytic decomposition of the hydrogen peroxide. In internal, not pre-published investigations it was found that ethylenediaminetetraacetic acid Salts in bleaching and washing liquors containing active oxygen are gradually inactivated so that their complexing effect and thus the protection of the hydrogen peroxide subsides more and more before decomposition.

The invention relates to use in solid, active oxygen-containing Bleaches and detergents bestixamtes tetrasodium ethylenediamine tetraacetate, its Particles in a fatty acid or mixture of fatty acids at the freezing point 35-80 ° C., preferably 40-70 ° C., are encased. The products according to the invention consist of about 5 - 50, preferably about 10 - 30% by weight of fatty acids and to about 50-95, preferably about 70-90% by weight of tetrasodium ethylenediamine tetraacetate.

The invention achieves that the encased material in the Case of use is only released when the temperature rises and in solution goes; it is therefore protected from inactivation at the beginning of the bleaching process. By choosing non-fatty acids with lower Q of the higher melts respectively.

Melting areas are in your hand, almost ten perature determine at which the encased material should go into solution. This goes without saying also dependent on the degree of envelope; this will be discussed further below.

The solvent to be coated with fatty acids according to the invention, ethylenediamine tetraacetate, hereinafter referred to as "EDTA" for the sake of simplicity, is in the most varied Qualities and grain sizes in trade. According to the invention, fine-powder to Process granular, if necessary pre-granulated goods. The mean particle size of the EDTA used as the starting material can, for example, be in the range from 0.03 - 2, preferably from 0.07 to 1.5 mm. In the starting material, if necessary, in Larger quantities of finer constituents present are expediently removed.

The fatty acids used as shell materials can be chemically more uniform Be natural, such as fatty acids with 10-22, preferably 12-18, carbon atoms per molecule; But it can also be industrially obtained fatty acid mixtures, for example those with freezing points in the range of 30-85, preferably 40-70 OC. The freezing point can be determined, for example, using the Shukoff method (Berl-Lunge: "hemisch-technical investigation methods", 4th volume 1933, page 417) determine.

The most varied of these are suitable for wrapping the EDTA with fatty acids Procedure; in all cases the solid, finely powdered to granulated EDTA is with brought together the fatty acids present in the liquid state, if necessary divided into individual particles in order to then solidify the fatty acids.

The fatty acids can be melted or in suitable organic solvents be drawn. Although in principle all organic substances that are inert towards EDTA are used Solvents for fatty acids can be used, it is recommended to be incombustible and - if possible use physiologically harmless solvents. Find such solvents among the halogenated hydrocarbons, especially among the fluorinated ones and / or halogenated hydrocarbons with 1-3 carbon atoms. Used with preference one methylene chloride, 1,1, 1-trichloroethane, 1,1, 2-Trichloräthyl.en; the physiological less harmless solvents chloroform, carbon tetrachloride, perchlorethylene and tetrachloroethane can be used with appropriate precautions.

The process according to the invention can be used, for example, in all apparatus perform in which the pourable EDTA to be enveloped is preferably moved over Surfaces that are trickled away and there with the melted or in solvents dissolved fatty acids is sprayed. Such methods can be, for example in inclined rotating plates, so-called granulating plates, or in inclined ones performing rotating drums.

The melted or dissolved in organic solvents are sprayed Fatty acids on the moving EDTA; forms when the two components meet a layer of fatty acid forms on the surface of the EDTA. Then you let them freeze, by cooling the product or by passing over the evaporation of the solvent accelerated by inert gases.

To encase the EDTA z. B. the well-known vortex turbulence, in which the powdery to granular EDTA is brought into a fluidized bed by means of a stream of inert gas is transferred, d'3s one then with the melted or dissolved in solvents Fatty acids sprayed. The spray jet can be directed onto the fluidized bed from above; man but can also use the spray jet, expediently with the aid of a gas in which Let the fluidized bed arise itself. In any case, the whirled up EDTA comes in close contact with the fatty acids used for coating. You have the one you want Amount of fatty acids applied, then the EDTA is aftertreated in the manner described above.

Two further process variants for the production of an encased EDTA are also suitable for processing a dust-fine starting material, its grain size may be wholly or partially below the limits given above. After that, will the EDTA is converted into a suspension with molten fatty acids, which is then after is divided into fine particles in a known method. By cooling the Particles you get the smeared product.

One of these methods of breaking the suspension into fine particles may consist of atomizing the suspension and the atomized particles using gases, especially air, to cool eu and thus to solidify the fatty acids bring.

The second variant of the method is to use the suspension suitable apparatus, for example with the aid of screw presses, in strands of any shape and preferably small cross-section to transfer and this To freeze strands. This process variant is expediently at carried out at a temperature at which some of the fatty acids are already solidified Condition exists, but the mass is still soft enough to be in such a To have equipment processed. The one from the mouthpiece of such an extruder exiting strands, the diameter of which e. B. in the range of 0.1-2, preferably 0.2 - 1.5 mm can break into pieces after solidification of different lengths. If you use a mouthpiece with a rotating knife mechanism, then this cuts the emerging strands into pieces always the same length, and one obtains a more uniform one with regard to the particle dimensions Were. These products are also expediently solidified by cooling.

The wrapped products that then arise. own one at room temperature Satisfactory shelf life, which can be improved by using the products after the treatment with fatty acids additionally with a layer of solid, preferably inorganic materials. As such, it is expedient to use substances which do not interfere in the bleach bath, such as B. the inorganic to be enumerated below Structural substances or the water-insoluble stabilizers for per compounds. Microcrystalline silica can also be applied for this purpose. For example If you mix the freshly sprayed with fatty acids EDTA particles in which the Fatty acids do not need to be completely solidified with the finely powdered, materials intended to form the surface layer.

With the help of the method according to the invention it is easily possible Manufacture products that have a degree of coating of at least 50% by weight at 20 OC exhibit. "Degree of coating" is understood to mean that percentage amount of EDTA which does not dissolve in the water after 20 minutes of exposure to water. The determination the degree of coverage is described in the examples. Of course leaves the degree of coverage can also be determined at other temperatures, for example at 40 or 60 0C. It is by no means necessary that the products according to the invention are completely encased. For example, if you put products with a degree of coating of only about 50 26 at 40 0c, then you already reach at Temperatures up to 40 0C trapping the heavy metal ions; becomes the existing EDTA inactivated over time, so the encased EDTA becomes with increasing Temperature further material delivered so that during the whole bleaching and Washing process there is enough EDTA available to bind the heavy metal ions.

The invention further relates to the use of the invention encased EDTA in bleaches and detergents containing peroxo compounds.

Such agents are, for example, aqueous ones containing H 2 O 2 Solutions to understand, where the H202 of itself solid, in aqueous solution H202 supplying peroxo compounds. These aqueous solutions can be customary Contain additives, especially substances such as those in bleaching liquors for textiles and are mostly present in particular in bleaching additives for washing liquors.

As bleaching agents in which the EDTA encased according to the invention is present can be, but are also solid, preferably powdery bleaching agents or detergents to understand. These funds have the following composition, for example: 3 - 95, preferably 15-93% by weight in aqueous solution of peroxo compounds providing H202 and optionally activators and / or stabilizers for these peroxo compounds, 0.05-5, preferably 0.15-5% by weight of EDTA in encased form, the Quantities refer to the non-encased EDTS, 5 - 97, preferably 7 - 85% by weight of other common ingredients of such agents.

Other common ingredients include, for example, surfactants, alkaline or neutrally reacting, complex-forming or non-complex-forming structural substances, Dirt carriers, anti-corrosive agents, antimicrobial substances, brighteners, Enzymes, perfume, dyes.

The EDTA encased according to the invention is preferably used in bleaching Pre-wash or detergents, the composition of which is generally in the range of the following formulation is: 5 - 40, preferably 7 - 30 wt. of a surfactant component, Containing at least one surfactant of the sulfonate, sulfate, soap and Xor type Nonionics and possibly one or more of the following substances: O - 10, preferably 0.5-8% by weight foam stabilizers, 0-10, preferably 0.5-8% by weight non-surfactant foam inhibitors, 5-50, preferably 10-35% by weight in Peroxo compounds delivering H2O2 in aqueous solution and, if necessary, activators and / or stabilizers for these peroxo compounds, 0.05-5, preferably -0.15 - 3 wt .-% EDTA in the form encased according to the invention, the amounts given refer to the non-enveloped EDTA., 10 - 92, preferably 30 - 70 wt. alkaline or neutrally reacting, complex-forming and / or non-complex-forming framework punches, the amount of the alkaline to neutrally reacting builder substances preferably 0.5 to 7 times and in particular 1 to 5 times the total surfactant component matters O - 20, preferably 2 - 15% by weight of other detergent ingredients, such as B. textile softeners, erosion inhibitors, antimicrobial substances, Dirt carriers, brighteners, enzymes, perfume, dyes and water.

The use of the invention is of particular practical importance encased EDTA in low-foam detergents, which are used in washing machines, in particular in drum washing machines. The surfactant component of such Laundry detergent usually has the following composition: 15 - 99, preferably 35 - 90 % By weight of sulfonates and / or sulfates with preferably 8-18 carbon atoms in the hydrophobic residue, 10-60, preferably 10-50% by weight of nonionics, and optionally one or more of the following substances: 5-70, preferably 10-60% by weight soap, 0-10, preferably 0.5-8% by weight of foam stabilizers, 0-10, preferably 0.5-8% by weight not Surfactant-like foam inhibitors, but the foaming capacity of the surfactant component either through the simultaneous presence of different people, the ability to be afraid of each other Degrading surfactants and / or foam-suppressing soap and / or non-surfactant-like Foam inhibitors are reduced.

Among the inorganic peroxo compounds which give H202 in aqueous solution Sodium perborate tetrahydrate (NaBO2 H202. 3 H20) is of particular practical importance In its place, partially or completely, i. h dehydrated to NaBO2 o H202 Perborate are used0 They are also those in DBP 901 287 and USP 2 491 789 described borates NaB02 H202, in which the ratio Na2O o B203 is smaller is than 0.5: 1 and preferably in the range 0.4-015: 1, while the. H2O2: Na ratio falls in the range of 0.5-4: 1. All this perborate can be wholly or partially- by other inorganic peroxo compounds, in particular by peroxohydrates, e.g. Bo the peroxohydrates of ortho-, pyro- or polyphosphates, especially tripolyphosphates, and carbonates.

It is advisable to use the products to stabilize the peroxo compounds Usual water-soluble and / or water-insoluble stabilizers in amounts of 0.25 - 10% by weight of eSnsu work. As water-insoluble peroxo stabilizers, e.g.

Make up 1 - 8, preferably 2 - 7% of the weight of the entire preparation, the magnesium silicates usually obtained by precipitation from aqueous solutions are suitable MgO: SiO2 = 4: 1 to 1: 4, preferably 2: 1 to 1: 2 and in particular 1: 1. Instead, other alkaline earth metal, cadmium or tin silicates are more appropriate Composition useful0 The water-soluble stabilizer according to the invention is also used encased EDTA; in addition to this, there can also be others in the bleaching agents and detergents organic complexing agents may be present.

Serve as activators for peroxo compounds that produce H2O2 in water certain; N-acyl, O-acyl compounds that form organic peroxo acids with this H02 as well as carbonic acid or pyrocarbonic acid esters, their activation value for the peroxo compounds (= Titer) is at least 3, preferably at least 4.5. This activation value is determined in the following way: solutions containing 0.615 g / l NaBO2. H2O2. 3 H2O (4th mmol / l) and 2.5 g / l Na4P2O7. 10 H2O are contained after heating to 6o 0C with 1t mMo1 / l activator added and stirred for # minutes at the specified temperature held. 100 ml of this liquid are then added to a mixture of 250 g of ice and 15 ml of glacial acetic acid and titrated immediately after the addition of 0.5 g of potassium iodide with 0.1 n sodium thiosulfate solution and starch as an indicator; the amount used on thiosulphate solution in ml is the activation value (= titer); at a 100% Activation of the peroxide used would make it 8.0 ml.

Suitable from the types of activators still to be described below particularly compounds with a melting point of at least 70 ° C., preferably at least 100 ° C and in particular at least 150 Oc. Furthermore, the equivalent weight should of these compounds (the equivalent weight here is the quotient of the molecular weight and the number of acyl residues or carbonic acid or pyrocarbonic acid residues present in the molecule understood) at most 170, preferably at most 130 and in particular at most 110 be. The activators which can be used according to the invention include a) those from the DBP publications 1,162,967 and 1,291,317 disclosed N-diacylated and N, N'-tetraacylated Amines such as

N, J, N 'N' -Tetraacetyl-methylenediamine or -ethylenediamine, N, N-diacetylaniline and N, N-diacetyl-p-toluidine and 1,3-diacylated hydantoins, respectively, such as the compounds 1,3-diacetyl-5,5-dimethylhydantoin and 1,3-dipropionylhydantoin; Where b) the N-alkyl-N-sulfonyl-carbonamides known from British patent specification 1 003 310, for example the compounds N-methyl-N-mesyl-acetamide, N-methyl-N-mesylmbenzamidn N-.Methyl N-mesyl-p-nitrobenzamide, and N-methyl-N-mesgS-p-methoxybenzamideg c) the N-acylated cyclic compounds described in Swiss Patent 407,387 Hydrazides, acylated triazoles or urazoles such as monoacetyl maleic acid hydrazide; d) the O, N, N-trisubstituted ones described in DP application P 17 19 574.3-43 Hydroxylamines such as O-Benzyl-N, N-succinylhydroxylamine, O-acetyl-N, N-succinyl-hydroxylamine, O-p-methoxybenzoyl-N, N-succinyl-hydroxylamine, O-p-nitrobenzoyl-N, N-succinyl-hydroxylamine and O, N, N-triacetyl-hydroxylamine; e) the NN9-diacyl-sulfurylamides known from DOS 1 801 713, for example N, N'-dimethyl-N, N'-diacetyl-sulfurylamine, and N, N'-diethyl-N, N'-dipropionyl-sulfurylamide; f) the triacyl cyanurates, for example triacetyl cyanurate and tribenzoyl cyanurate the DAS 1 294 919; g) those from Swiss patent specification 347 930 or the DBP publication 893 049 or the DOS 1,444 OOl known carboxylic acid anhydrides such as e.g. Benzoic anhydride, m-chlorobenzoic anhydride, phthalic anhydride, 4-chlorophthalic anhydride g h) the sugar esters known from Swiss Patent 348 682, for example Glucose pentaacetate; i) the 1,3-diacyl-4,5-diacyloxy-imidazolidines of DOS l 801 141, for example the compounds 1,3-diformyl-4,5-diacetoxy-imidazolidine, 1,3-diacetyl-4,5-diacetoxy-imidazolidine, 1,3-diacetyl-4,5-dipropionyloxy-imidazolidine; J) those known from DOS 1,594,865 Compounds tetraacetylglycoluril and tetrapropionylglycoluril; k) those in the DP application P 20 38 106.0 described diacylated 2,5-diketopiperazines such as 1,4-diacetyl-2,5-diketopiperazine, 1,4-dipropionyl-2,5-diketopiperazine; 1,4-dipropionyl-3,6-dimethyl-2,5-diketopiperazine; 1) the acylation products of propylenediurea described in DP application P 21 12 557.5 or 2,2-dimethylpropylenediurea (2,4,6,8-tetraaza-bicyclo- (3,3,1) -nonane-3,7-dione or its 9,9-dimethyl derivative) in particular tetraacetyl or tetrapropionyl propylenediurea % between dimethyl derivatives; m) the carbonic acid esters of DOS 1 444 024, for example the sodium salts of p- (ethoxycarbonyloxy) benzoic acid and p- (propoxycarbonyloxy) benzosulfonic acid.

Those mentioned under j), r3 and 1) are of particular practical interest Activator types.

When the peroxo compounds are activated by the aforementioned N-acyl and O-acyl compounds, carboxylic acids such as. B. acetic acid, propionic acid, Benzoic acid, free, and it is recommended to use appropriate carboxylic acids for binding these Add amounts of alkali. In the case of effective activators, activation is already present recognizable when using amounts of 0.05 mol of activator per g-atom of active acid. It is preferred to work with 0.1-1 mol of activator; however, the amount can also up to 2 moles of activator per g-atom of active oxygen can be increased.

The surfactants contain at least one hydrophobic residue in the molecule of mostly S - 26, preferably 10 - 22 and in particular 12 - 18 carbon atoms and at least an anionic, nonionic or zwitterionic water-solubilizing group. The preferably saturated hydrophobic radical is usually more aliphatic, possibly also alicyclic Nature; he can work with the water-solubilizing groups directly or via intermediate links be connected, e.g. via benzene rings, carboxylic acid ester, carbonamide or sulfonic acid amide groups as well as via residues of polyhydric alcohols bound in ether or ester form 9 As anionic Active detergent substances are soaps made from natural or synthetic fatty acids. also useful from resin or naphthenic acids, especially if these acids have iodine numbers of at most 30 and preferably of less than 10.

Of the synthetic anionic surfactants, the sulmonates have and sulfates of particular practical importance.

the sulfonates include, for example, the alkylbenzenesulfonates with preferably straight-chain C9-15, in particular C10-14-alkyl radicals, the alkanesulfonates, obtainable from preferably saturated aliphatic C8-18, especially C12-18 hydrocarbons on sulfochlorination or sulfoxy dation, which comes under the name "Olefinsulfonate" known mixtures of alkene sulfonates, hydroxyalkane sulfonates and disulfonates, the acidic or alkaline hydrolysis of the terminal or central C8-18- and preferably C12-18 olefins by sulfonation with sulfur trioxide first formed sulfonation products arise. To the inventively usable Sulphonates also include salts, preferably alkali salts, of α-sulpho fatty acids as well as salts of esters of these acids with mono- or polyvalent, 1-4 and preferably 1 - 2 carbon atoms containing alcohols.

Further useful sulfonates are salts of fatty acid esters of oxethanesulfonic acid or of dioxypropanesulfonic acid, the salts of the fatty alcohol esters of lower, 1 - Aliphatic or aromatic sulfomono- or dicarboxylic acids containing 8 carbon atoms, the alkyl glyceryl ether sulfonates and the salts of the amide-like condensation products of fatty acids or sulfonic acids with aminoethanesulfonic acid.

Fatty alcohol sulfates are to be mentioned as surfactants of the sulfate type, in particular manufactured from colf fatty alcohols, tallow fatty alcohols or from oleyl alcohol, furthermore sulfated fatty acid alkylolamines or fatty acid monoglycerides and sulfated Alkoxylation products of alkylphenols (C8-15-alkyl), fatty alcohols, fatty acid amides or fatty acid alkylolamindes with 0.5-20, preferably 1-8 and especially 2 - 4 ethylene and / or propylene glycol residues in the molecule.

Suitable anionic surfactants of the carboxylate type are, for example, the Fatty acid esters or fatty alcohol ethers of hydroxycarboxylic acids and the amide-like ones Condensation products of fatty acids or sulfonic acids with aminocarboxylic acids, e.g. with glycocolla, sarcosine or with protein hydrolysates.

The anionic surfactants are mostly in the form of salts of the alkali metals, in particular sodium, ammonium, lower aliphatic amines or alkylolamines before.

To the nonionic surfactants, here for the sake of simplicity as "Nonionics" referred to, include those by attaching from 4 to 100, preferably 6 to 40 and in particular 8 - 20 moles of ethylene oxide in fatty alcohols, alkylphenols, fatty acids, fatty amines, fatty acids or sulfonic acid amides available polyethylene glycol ethers, as well as the still water-soluble Addition products of propylene or butylene oxide to them. Belong to the nonionics also those known under the trade names "Pluronics" or "Tetronics", from per se water-insoluble polypropylene glycols or from water-insoluble propoxylated lower aliphatic alcohols containing 1-8, preferably 3-6 carbon atoms or from water-insoluble propoxylated alkylenediamines by ethoxylating up to products obtained for water solubility. After all, as monoionics are too the reaction products known as "Ucon Fluid", some of which are still water-soluble to use above mentioned aliphatic alcohols with propylene oxide.

As nonionics are also from mono- or diethanolamine, from dihydroxypropylamine or other polyhydroxyalkylamines, e.g. fatty acids derived from glycamines or sulfonic acid alkylolamines are useful. The oxides can also be used as nonionics of higher tertiary amines with one hydrophobic alkyl radical and two shorter, alkyl and / or alkylol radicals containing up to 4 carbon atoms each are to be considered.

Zwitterionic surfactants contain both acidic groups, such as carboxyl, sulfonic acid, sulfuric acid half-ester; Phosphonic acid and phosphoric acid partial ester groups, as well as basic groups such as primary, secondary, tertiary and quaternary ammonium groups. Zwitterionic compounds with quaternary ammonium groups belong to the type of Betaines. Carboxy, sulphate and sulphonate betaines are well tolerated of particular practical interest with other surfactants.

The foaming power of the surfactants can be determined by a combination of suitable Increase or decrease the surfactant types, as well as the addition of non-surfactant types organic substances can be changed.

Especially suitable as foam stabilizers are sulfonate surfactants or sulfate type, capillary-active carboxy- or sulfobetaines as well as those mentioned above Alkylol amide type Nenionics; in addition, fatty alcohols or higher are used for this purpose terminal diols have been proposed.

A reduced foaming power, which is desirable when working in machines is often achieved by combining different types of surfactants, e.g. from Sulphates and / or sulphonates and Zor of nonionics on the one hand with soaps on the other hand. In the case of soaps, the foam absorption increases with the degree of saturation and the C number of the fatty acid residue on, soaps made from saturated C20-24 fatty acids have proven to be effective as shock absorbers The non-surfactant-like foam inhibitors may include

Chlorine-containing N-alkylated aminotriazines, which can be obtained by reaction of 1 mole of cyanuric acid chloride with 2-3 moles of a mono- and / or dialkylamine with. 6-209, preferably 8-18 carbon atoms in the alkyl radical, propoxylated have a similar effect and / or butoxylated aminotriazines, e.g. products obtained by adding 5 - 10 moles of propylene oxide on 1 mole of melamine and further addition of 10-50 moles of butylene oxide of this propylene oxide derivative.

Other non-surfactant foam inhibitors are water-insoluble organic compounds such as paraffins or haloparaffins with melting points below from 1000 C, aliphatic C18 to C40 ketones and aliphatic carboxylic acid esters the in the acid or alcohol radical, possibly also in each of these two radicals, at least Contain 18 carbon atoms (e.g. triglycerides or fatty acid fatty alcohol esters) a they can be used especially with combinations of surfactants of the sulfate and / or sulfonate type use with soaps to dampen the foam. As particularly low-foaming Nonionics, both alone and in combination with anionic, zwitterionic and nonionic surfactants can be used and the foaming power is better Addition products of propylene oxide are suitable to reduce foaming surfactants to the above-described capillary-active polyethylene glycol ethers as well as the same Pluronic, Tetronic and Uoon Fluid types described above0 as Builder substances are weakly acid +, neutral and alkaline reacting inorganic ones or organic salts, in particular inorganic or organic complexing agents.

According to the invention, weakly acidic, neutral or alkaline reacting salts are for example the bicarbonates, carbonates, borates or silicates the alkalis, furthermore nono-, di- or trialkali orthophosphates, di- or tetraalkali pyrophosphates, as complexing agents known metaphosphates, alkali sulfates as well. the alkali salts of organic, non-capillary-active sulfonic acids containing 1 - 8 carbon atoms, Carboxylic acids and sulfonic acids. These include, for example, water-soluble Salts of benzene, toluene or xylene sulfonic acid, water-soluble salts of sulfoacetic acid, Sulfobenzoic acid or salts of sulfodicarboxylic acids and the salts of acetic acid, Lactic acid, citric acid and tartaric acid.

Furthermore, the water-soluble salts are of higher molecular weight as structural substances Polycarboxylic acids can be used, especially polymer salts of maleic acid, itaconic acid, Mesaconic acid, fumaric acid, aconitic acid, methylenemalonic acid and citraconic acid. Even Copolymers of these acids with one another or with other polymerizable Substances, e.g. with ethylene, propylene, acrylic acid, methacrylic acid, crotonic acid, 3-butenecarboxylic acid, 3-methyl-5-butenecarboxylic acid and vinyl methyl ether, vinyl acetate, Isobutylene, acrylamide and styrene are useful.

Weak ones are also suitable as complex-forming structural substances acidic metaphosphates as well as the alkaline reacting polyphosphates, especially the polyphosphate.

They can be wholly or partially replaced by organic complexing agents earth.

The organic complexing agents include, for example, nitrilotriacetic acid, ethylenediaminetetraacetic acid, N-hydroxyethyl-ethylenediamine triacetic acid, polyalkylene-polyamine-N-polycarboxylic acids and other known organic complexing agents, and combinations of different complexing agents can also be used. The other known complexing agents also include di- and polyphosphonic acids of the following constitutions: wherein R is alkyl and R 'is alkylene radicals with 1-8, preferably with 1-4 carbon atoms, X and Y represent hydrogen atoms or alkyl radicals with 1-4 carbon atoms and Z represents the groups -OHD "N2 or -NXR. For a The following compounds are particularly suitable for practical use: methylenediphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, 1-aminoethane-1,1-diphosphonic acid, aminotri (methylenephosphonic acid), methylamino- or ethylamino-di (methylenephosphonic acid) ) as well as ethylenediamine-tetra- (methylenephosphonic acid). All these complexing agents can be present as free acids, preferably as alkali salts.

Dirt carriers can also be used in the preparations according to the invention be included that. the dirt detached from the fiber is suspended in the liquor hold and thus prevent graying. For this purpose, water-soluble colloids are usually used of an organic nature, such as, for example, the water-soluble salts of polymeric materials Carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acid sulfuric acid esters of cellulose or strength. Water-soluble polyamides containing acidic groups are also useful suitable for this purpose. Soluble starch preparations and others can also be used use as the above starch products, such as degraded starch, aldehyde starches etc. Polyvinylpyrrolidone can also be used.

The components of the laundry detergents and auxiliary agents according to the invention, in particular, the framework substances are usually selected so that the preparations react neutral to clearly alkaline, so that the pH value of a 1% solution of the preparation is usually in the range of 7-12. Thereby, mild detergents usually have neutral to slightly alkaline reaction (pH = 7 - 9.5), while soaking, Pre-wash and cooking detergents are more alkaline (pH value = 9.5 - 12, preferably 10 - 11.5) are set.

The brighteners that can be used are mostly, if not exclusively, Derivatives of aminostilbene sulfonic acid or diaminostilbene disulfonic acid, diarylpyrazolines, of carbostyril, of 1,2-di- (2-benzoxazolyl) - or 1 2 = di- (2-benzimidazolyl) -ethylene, of benzoxazolyl-thiophene and coumarin.

Examples of brighteners from the class of the diaminostilbene disulfonic acid derivatives are compounds according to formula 1: In the formula, R1 and R2 can denote alkoxyl groups, the amino group or residues of aliphatic, aromatic or heterocyclic, primary or secondary amines and residues of aminosulfonic acids, aliphatic residues present in the above groups preferably containing 1-4 and in particular 2-4 carbon atoms , while the heterocyclic ring systems are mostly 5- or 6-membered rings. The radicals of aniline, anthranic acid or anilinesulfonic acid are preferred as aromatic amines. Lighteners derived from diaminostilbene disulphonic acid are mostly used as cotton lighteners. The following9 products derived from formula 1 are commercially available, where R1 represents the radical -NHC6H5 and R2 can represent the following radicals: -NH2, -NHCH3, -NHCH2CH2OH, -NHCH2CH2OCH3, -NHCH2CH2CH2OCH3, -N (CH3) CH2CH2OCH, - N (CH2CH2OH) 2, morpholino-, -NHC6H5, -NHC6H4SO3H, -OCH3. With regard to fiber affinity, some of these brighteners are to be regarded as transition types to the polyamide brighteners, for example the brightener with R2 = -NHC6H5. The compound 4,4'-bis (4-phenyl-1,2,3-triazol-2-yl) -2,2'-stilbene disulfonic acid also belongs to the cotton whitening agents of the diaminostilbene disulfonic acid type.

The polyamide brighteners include diarylpyrazolines of the formulas II and III: In formula II, R3 and R5 denote hydrogen atoms, optionally substituted by carboxyl, carbonamide or ester groups, alkyl or aryl radicals, R4 and R6 hydrogen or short-chain alkyl radicals, Ar1 and Ar2 aryl radicals such as phenyl, diphenyl or naphthyl, which can carry further substituents such as hydroxy, alkoxy, hydroxyalkyl, amino, alkylamino, acylamino, carboxyl, carboxylic acid ester, sulfonic acid, sulfonamide and sulfone groups or halogen atoms. Commercially available brighteners of this type are derived from the formula III, where the radical R7 can represent the groups Cl, -SO2NH2, -SO2CH = CH2 and -COOCH2CH2OCH3, while the radical R8 usually means a chlorine atom.

9-cyanoanthracene is also one of the polyamide brighteners.

The polyamide brighteners also include aliphatic or aromatic ones substituted aminocoumarins, e.g. 4-methyl-7-dimethylamino- or 4-methyl-7-diethylaminocoumarin. The compounds 1- (2-benzimidazolyl) -2- (1-hydroxyethyl-2-benzimidazolyl) -ethylene are used as polyamide brighteners and 1-ethyl-3-phenyl-7-diethylamino-carbostyril can be used. As a brightener for polyester and polyamide fibers are the compounds 2,5-di- (2-benzoxazolyl) -thiophene, 2- (2-benzoxazolyl) -naphto [2,3-b] -thiophene and 1,2-di- (5-methyl-2-benzoxazolyl) -ethylene are suitable if the brighteners are put together with other components of the inventive products as an aqueous solution or paste are present and converted into a solid state by hot drying.

It is recommended to use organic complexing agents to stabilize the brightener to incorporate in amounts of at least o, preferably 0.2-1% by weight of the solid products the The enzyme preparations to be used are usually a mixture of enzymes with different ones Effect, e.g. of proteases, carbohydrases, esterases, lipases, oxidoredulctases, Catalasell, peroxidases, ureases, isomerases, lyases, transferases »desmolases or Nucleases. Of particular interest are those from bacterial strains or fungi such as Bacillus subtilis or Streptomyces griseus obtained enzymes, in particular proteases or amylases that act against alkali, peroxo compounds and anionic surfactants are relatively stable and are still effective at temperatures of up to 700 C.

Enzyme preparations are usually supplied by the manufacturers as aqueous solutions of the active ingredients or as powder, granules or as powdered products in the Trade brought. They often contain sodium sulfate, sodium chloride, Alkali ortho-, pyro- or polyphosphates, especially tripolyphosphate. Special ones Value is placed on dust-free preparations; inan receives it in a manner known per se by incorporating oily or pasty nonionics or granules With the help of molten salts containing crystalline water. On your own crystal water.

Enzymes can be incorporated for a certain type of dirt are specific, for example proteases or amylases or lipases; preferred one uses combinations of enzymes with different effects, especially combinations from proteases and amylases.

Examples The degree of coating of the preparations produced according to the invention were determined in the following way: 1.50 g of the coated substance are in a Measuring flask with occasional tilting of the flask at 20 0C of the action of 10Q ml of water exposed. After 20 minutes, 50 cm3 of the clear supernatant are pipetted Solution and mixed it with 50 cm3 of distilled water and 10 cm of a 2% Na2 CO3 solution. After adding 5 drops of a 10% alcoholic solution of 2-Hydroxy-1 - [(2-hydroxy-4-sulfo-1-naphthyl) azo -] - 3-naphtholic acid is titrated blue colored solution with a solution of 36.8 g CaCl2. 2 H20 per 1 liter volume of solution until it turns red. The amount of calcium chloride solution used is v mlf then the amount of dissolved EDTA is calculated using the following formula: 380.18. 3680. v 146.99. 15.0 In this formula, 380.18 denotes the molecular weight of the tetrasodium ethylenediamine tetraacetate and 146.99 the molecular weight of the calcium chloride dihydrate.

The amount of what is present in total is now determined in an analogous manner EDTA by adding the aqueous slurry of the product until the shell material melts heated, the solution obtained cools to room temperature, filled and them in processed as described above. From the total available and at 20 0C The amount of EDTA dissolved in water is then calculated as the percentage of the amount encased EDTA; this is equal to the degree of coverage.

Example of coating EDTA Commercially available tetrasodium ethylenediamine tetraacetate (techn.

Fluka) was distilled in the Loedige mixer by metered addition of 14.3 g Water pre-granulated to 100 g EDTA within 2-3 minutes. Subsequently were 400 g (450 g) of the granules in the fluidized bed of a Wurster device with a Sprayed a solution of 100 g (50 g) of the shell material in 600 ml of CCl4 (300 ml of CCl4). The spraying of the solution was made gradually with it after the spraying the majority of the solvent is always entrained in the air stream that is also supplied and could evaporate and the sticking together of coated particles to form larger ones Formation was avoided. After all of the fatty acid solution had been sprayed on, was leave the coated granulate 102 in the fluidized bed and then the encased EDTA exposed to a negative pressure of 5-10 torr for about 12 hours.

The following list shows the degrees of coverage achieved with different types of fat. Degree of coverage in% Shell substance at 20 ° C at 60 ° C 20 wt% lauric acid 76.0 16.0 10% by weight myristic acid 34.0 - 20 wt% myristic acid 96.0 22.5 10 wt% palmitic acid 83.5 31.5 20 wt% palmitic acid 96.0 59.5 The following examples V1-V14 describe the compositions of some washing auxiliaries or detergents in which the EDTA encased according to the invention is used. The salt-like constituents contained in the washing aids and detergents - salt-like surfactants, other organic salts and inorganic salts - are present as sodium salts, unless expressly stated otherwise. The related terms and abbreviations mean: "ABS" the salt of a condensation of straight-chain olefins with benzene and sulfonation of the resultant.

Alkylbenzene obtained alkylbenzenesulfonic acid with 10-15, preferred 11-13 carbon atoms in the alkyl chain, "alkanesulfonate" from paraffins with 12-16 carbon atoms obtained by sulfoxidation sulfonate, "Fs-ester sulfonate" a from the methyl ester of a hardened tallow fatty acid by sulfonation with SO3 obtained sulfonate, "olefin sulfonate" incorporates olefin mixtures with 12-18 carbon atoms by sulfonating with SO3 and hydrolyzing the sulfonation product with lye obtained sulfonate, which consists essentially of alkene sulfonate and oxyalkane sulfonate but also contains small amounts of disulfonates Preparation was made using two different types of olefin sulfonate; one was made from a mixture of straight-chain terminal olefins, the other made from a mixture of internal olefins has been produced, "KA sulfate" or "TA-sulfate" the salts of sulfated, by reduction of coke fatty acid or Tallow fatty acid produced, essentially saturated fatty alcohols, "KA-ÄO-sulfate" or "TA - sulfate" or "OA-ÄO-sulfate" the sulfated addition products of 2 Moles of ethylene oxide to 1 mole of coconut fatty alcohol or 3 moles of ethylene oxide to 1 mole of tallow fatty alcohol or from 2 moles of ethylene oxide to 1 mole of oleyl alcohol, "soap" is the salt of a hydrogenated one Fatty acid mixture (iodine number below c) that consists of at least 50% stearic acid and preferably consists of at least 65% palmitic and stearic acids, wherein this mixture can contain 5 - 35 ffi of behenic acid, "OA + 5 ÄO", "OA + 10 ÄO" and "KA + 20 ÄO" the addition products of ethylene oxide (ÄO) with technical oleyl alcohol (OA) or coconut alcohol (KA), where the numbers represent the molar Amount of. Identify ethylene oxide, "KA + 9 ÄO + 12 PO" a by reacting 1 Mol "KA + g ÄO" obtained with 12 mol propylene oxide nonionic, "perborate" an approx Product containing 10% active oxygen with the approximate composition NaBO2.H2O2.3 H20, "EDTA" a disodium ethylenediaminetetraacetate dihydrate coated according to Example 1 with a fatty acid content of approx. 50% and a degree of coating at 2O0C of 81 - 85%, whereby the quantities in the table are in contrast to the recipes in the description or in the patent claims consist of EDTA + fatty acids, "CMC" means the salt carboxymethyl cellulose.

A mixture of about 45% of a di (alkylamino) monochlorotriazine was used as a foam inhibitor and about 55% of an N, N'-N "-trialkylmelamine. In all of these triazine derivatives the alkyl radicals were present as a mixture of homologues with 8-18 carbon atoms. With something similar The monochlorotriazine derivative or the trialkylmelamine could also be used successfully. Unless the products described have synthetic sulfates or sulfonates together with Contained soap, the others mentioned in the description could not be surfactant-like Foam inhibitors are used, such as, for example, paraffin oil or paraffin. In the manufacture of the preparations, the foam inhibitor used was used in a suitable one organic solvent dissolved or in a molten state by means of a nozzle sprayed onto the moving powdery preparation.

The following examples v 3 V3 describe preferably washing aids Per-concentrates which can be used in commercial laundries and which describe examples V4-V14 Heavy duty detergent.

If you wash using the washing aids or detergents described in the usual way at temperatures up to 90-100 ° C, then the encased EDTA, which is only completely released at temperatures above 80 °, remains active until the end of the washing process and can during the exert its complex-forming effect throughout the washing process. The melted fatty acids are dispersed in the washing liquor and contribute to reducing the foam intensity, especially in the case of detergents containing soap. Part of the% by weight component in the preparation according to the example Preparations V1 V2 V3 V4 V5 V6 V7 ABSA - - - - 9.0 - - Olefin sulfonate - - - - - - 11.5 Soap - - - - 2.0 - 9.0 OA + 5 ÄO - - - 1.0 - - 5.0 OA + 10 AO - - 2.0 7.0 8.0 - - KA + 20 ÄO - - - - - 12.0 - KA + 9 ÄO - - - - - 7.5 - + 12 PO Foam inhibitor - - - 0.3 - - 0.8 Na2SO4 - 6.0 + - + - + Na2O. 3.3 SiO2 - 15.0 - - 4.5 4.5 6.5 Na4P2O7 - - - 9.0 - 12.0 - Na5P3O10 35.5 - - 62.0 48.0 18.0 41.0 Na2CO3 - 30.0 - - - 10.0 - Perborate 55.5 35.0 82.0 10.0 16.0 25.0 18.0 MgSiO3 - 4.0 5.0 - 1.0 1.0 1.6 EDTA (wrapped) 4.5 1.5 4.5 0.5 0.5 1.5 0.7 CMC - - - 1.6 1.5 1.5 1.3 Brightener - 0.2 0.8 0.4 0.9 0.7 0.5 In the table above and in the following table, the "+" symbols in the "Na2SO4" line mean that small amounts of sodium sulfate were introduced into the detergent as an impurity with the anionic surfactants. No numerical value is given in the last line under "Remainder"; it is calculated as the difference between 100 and the amounts of the other components. This remainder consists essentially of water; it also includes any dyes, fragrances or enzymes that may be present. If the "+" symbol is in the "Na2SO4" cell, the remainder also includes this Na2SO4. Part of the% by weight component in the preparation according to the example Preparations V8 V9 V10 V11 V12 V13 V14 ABS 8.5 - - - - - - Alkanesulfonate - - 7.5 - - - - Fs-ester sulfonate - 6.5 - - - - - Olefin sulfonate - - - 8, o - - 15.0 KA sulfate 1.6 2.8 1.7 - - 1.5 3.2 TA sulfate 0.5 - - 3.0 - 1.5 - KA-ÄO-sulfate 2.0 - - - 2.3 - 7.5 TA-ÄO-sulfate - - - - - 7.5 - OA-ÄO-sulfate - - - - 5.5 - - Soap 5.8 9.3 6.8 10.2 6.5 4,, 15 i OA + 5 ÄO - 2.5 - - 6.5 - - OA + 10 AO - - 2.7 4.2 - - - Foam inhibitor - - 0.6 - - 0.8 0.9 Na2SO4 + + + + 5.0 8.0 5.0 Na2O. 3.3 SiO2 5.0 4.0 - 4.1 3.54 3.7 - Na2P3O10 37.0 39.0 47.0 26.0 41.0 45.0 43.0 Perborate 29.0 25.0 23.6 28.0 19.0 16.0 10.0 MgSiO3 2.0 - - 3.0 - - - EDTA 2.2 2.2 1.5 1.4 1.8 1.0 2.0 CMC 1.3 1.9 1.21 1.4 1.5 1.3 1.7 Brightener 0.5 0.4 1.2 1.3 0.5 1.0 0.3 rest For the meaning of the sign "+" and the "rest" see the explanations under the table with the recipes V1 - V7,

Claims (13)

Claims for use in bleach or bleach containing active oxygen Detergents of certain complexing agents in the form of granules or agglomerates, consisting essentially of tetrasodium ethylenediamine tetraacetate (= EDTA), its Particles at least partially in a fatty acid or a mixture of fatty acids from the solidification point 35 - 80 ° C, preferably from 40 - 70 0C are enveloped. 2. Means according to claim 1, characterized in that the amount of the fatty acids used as shell material 5 - 50, preferably 10 - 30 wt .-% of entire product. 3. Means according to claim 1 and 2, characterized by such Degree of coating; that if the product is kept in water for 20 minutes for 20 minutes 0C at most 50% by weight of the EDTA go into solution. 4. A method for producing an encased EDTA according to claim 1-3, characterized in that the EDTA particles are at least partially with a film of fatty acids with a solidification point of 35 - 809, preferably 40 -70 0C and this film on those in relative motion to each other Solidified particles. 50 proceeding according to claim 4, characterized in that deC-; one the Applies fatty acids in a molten or softened state and cools them solidified. 6. The method according to claim. 4, characterized in that the Applies fatty acids dissolved in a suitable solvent and evaporates them solidified of the solvent and optionally cooling. 7. The method according to claim 4-6, characterized in that one the melted or dissolved fatty acids on the moving surface Applies trickling EDTA particles. 8. The method according to claim 4-6, characterized in that one a slurry of the EDTA particles in molten and / or dissolved fatty acids is atomized and the fatty acids are solidified by the introduction of cold gas. 9. The method according to claim 4-6, characterized in that one one made of EDTA particlesii. and at least partially melted fatty acids The paste is converted into strands and these, if necessary after cutting these strands, solidified. 10. Use of the EDTA encased according to claims 1-3 as a complexing agent containing substances delivering H202 in aqueous, II202 or in aqueous solution Bleaching and washing liquors. 11. Use of the EDTA encased according to claims 1-3 in active oxygen containing agents intended for the production of bleaching or washing liquors the following composition: 3 - 95, preferably 15 - 93% by weight in aqueous solution Peroxo compounds supplying H202 and optionally activators and / or stabilizers for these peroxo compounds, 0.05-5, preferably 0.15-3 wt .-, Ö-F: DTA in wrapped Form, whereby the quantities refer to the non-encased EDTA, - - 97, preferably 7-85% by weight of other common constituents of such agents. 12. Use of the EDTA encased according to claims 1-3 in active oxygen containing agents intended for the production of bleaching or washing liquors the following composition: 5 - 40, preferably 7 - 30% by weight of a surfactant component, containing at least one surfactant of the sulfonate, sulfate, soap and / or type Nonionics and optionally one or more of the following substances: 0-10, preferably 0.5-8 wt. Foam stabilizers, 0.-10, preferably 0.5-8 wt. Non-surfactant-like Foam inhibitors, delivering 5 to 50, preferably 10 to 35 wt.% In aqueous solution of H 2 O 2 Peroxo compounds and optionally activators and / or stabilizers for die-5e peroxo compounds, 0.05-5, preferably 0.15-3 wt .-% EDTA in the invention encased form, the quantities referring to the non-encased EDTA, 10-92, preferably 30-70% by weight, alkaline or neutrally reacting, complex-forming and / or non-complexing structural substances, the amount of the alkaline to neutrally reacting builder substances preferably 0.5 to 7 times and in particular 1 to 5 times the total surfactant component, 0-20, preferably 2 - 15% by weight of other detergent ingredients, such as fabric softeners, corrosion inhibitors, Antimicrobial substances, dirt carriers, brighteners, enzymes, perfumes, dyes and water. 13. Use of the EDTA encased according to claims 1-3 in agents according to claim 12, the surfactant component of which has the following composition: 15 - 99, preferably 35-90% by weight of sulfonates and / or sulfates with preferably 8-18 C atoms in the hydrophobic residue, 10-60, preferably 10-50, weight nonionics, as well as possibly one or more of the following substances: 5 - 70, preferably 10 - 60% by weight Soap, 0-10, preferably 0.5-8% by weight foam stabilizers, 0-10, preferably 0.5-8 wt .- / »non-surfactant-like foam inhibitors, but the foaming power the surfactant component either by the simultaneous presence of different, the Foaming capacity of mutually reducing surfactants and / or foam-suppressing substances and / or non-surfactant foam inhibitors is reduced.