DE2539071A1 - Washing or bleaching compsns. for textiles - contg. calcium binding agent and additives delaying pptn. of calcium cpds. - Google Patents

Abstract

Textiles are washed or bleached in an aq. bath contg. a substance capable of binding the agents causing hardness of water (>=50 mg CaO/g.), in partic. a finely dispersed, water-insol. opt. hydrated cpd. of formula (Cat2/nO)x. Me2O3. (SiO2)y (in which Cat is a cation that can be exchanged for Ca2+; n is the valence of this cation; x = 0.7-1.5; Me is B or Al; y = 0.8-6); and also builder(s) andopt. surfactant(s). In this addn., the mixt. contains a combination of builders contg. water-sol. salts having cations that do not hinder the formation of calcium complexes, in partic. salts of (A) a phosphonic acid which considerably delay the pptn. of calcium cpds., or a calcium complex-binding phosphate; and (B) a phosphorous-free polyanionic cpd. considerably delaying the pptn. of calcium cpds.; with the proviso that their sodium salts (0.5 g/1.), when added to a soln. of Na2SO4 (2.5 g/1.), in water having a calcium hardness of 22.4 degrees d (224 mg CaO/1.) and a bicarbonate hardness of 14 degrees d (140 mg Ca(HCO3)2/1.) with a pH adjusted to 9, prevent the formation of a visible ppte. after boiling under reflux for 30 mins. The weight ratio (A):(B) is 1:10 to 10:1, pref. 1:3 to 3:1. The use of the above calcium-binding cpd. and the above combination of builders permits the elimination or redn. of the phosphate content in the washing or bleaching bath.

Description

"Process for washing textiles and means for carrying out of the process "addition to the patent (patent application P 24 12 837.8-41 (D 4642/4787/4819)) The main patent relates to a method for washing, bleaching or cleaning solids Materials, especially textiles, by treating these materials with a A liquor that contains substances capable of binding the hardness components in the water. The method is characterized in that in the aqueous treatment liquor a calcium binding capacity of at least 50 mg CaO / g anhydrous active substance (= AS) containing, finely divided, water-insoluble, possibly bound water Compounds of the general formula 2 / n °) x. Me2O3. (SiO2) (I) in the cat Calcium exchangeable cation of valency n, x a number from 0.7 - 1.5, Me boron or aluminum and y is a number from 0.8 to 6, preferably from 1.3 to 4, suspended are. The main patent also relates to those suitable for carrying out the process Middle.

The invention on which the main patent is based makes it possible to the complex-binding calcium that is still used in the washing and cleaning process today To replace phosphates in whole or in part. The process of the main patent thus delivers a contribution to solving the so-called phosphate problem, i.e. to remedy those caused by the oversupply of phosphate in stagnant waters Eutrophication.

As described in detail in the main patent, it is useful to use the connections of the general formula I together with organic or inorganic complexing agents or to use precipitants for calcium; the use of other common components detergents and cleaning agents, in particular surfactants, can also be advantageous be.

It has now been found that it is particularly beneficial in the process of the main patent as a complexing agent a combination of very specific complexing agents to use.

The invention relates to a method for washing and bleaching, in particular of textiles, in which, according to the main patent, an aqueous liquor is used used the above-mentioned water-insoluble compounds of the general Contains formula -I in suspension and also has a content of structural substances and optionally also contains a surfactant component. The procedure is characterized by that a mixture of the following, as water-soluble salts with one, the complex bond builder substances present in calcium, which do not interfere with cations, are used: A) a considerably retarding the precipitation of poorly soluble calcium compounds Phosphonic acid, or a calcium complex binding phosphate, B) a phosphorus-free, the precipitation of poorly soluble calcium compounds considerably retarding polyanionic compounds Compound, where phosphonic acids of component A) and polyanionic compounds of component B) each in a test in which their Na salt in a concentration of 0.5 g / l is dissolved in 200 ml of an aqueous solution that dissolves 2.5 g / l Na2S04 contains and has a calcium hardness of 22.4 wa and a Bi-0 carbonate hardness of 14 d, whereupon the pH is adjusted to 9.0 and the solution is then refluxed for 30 min is boiled, and then the solution is cooled to room temperature, the emergence prevent visible precipitation, and wherein the Xomponenten A) and B) in one Weight ratio of 1:10 to 10: 1 are present.

It goes without saying that components A) and / or B) also can be used as free acids and converted into the salts in situ. The phosphonic acid of component A} can optionally bind with a calcium complex Phosphate should be replaced, e.g. by sodium triphosphate.

As already mentioned, expediency is already in the main patent a calcium complexing agent additive mentioned. Among the complexing agents for calcium There are a group of compounds that have the ability to cause precipitation poorly soluble calcium compounds from solutions containing calcium ions To delay addition in sub-stoichiometric amount considerably. These connections are able, for example, to precipitate calcium carbonate from calcium and solutions containing carbonate ions are sufficient in themselves for precipitation high pH value even with the addition of, for example, 1/10 or 1/5 of the stoichiometric to delay the amount required for the complete binding of calcium ions or even practically prevent it.

Compounds that inhibit this crystallization, i.e. also the precipitation have a retarding effect sufficient for the purposes of the invention, are characterized in that they emerge in the test given above prevent visible precipitation. If the solution is then filtered, the Wash the filter with a little saturated ammonium carbonate solution and then with hydrochloric acid treated, it can be in the hydrochloric acid by titration with EDTA - (ethylenediaminetetraacetic acid sodium salt) detect no calcium; that is, the calcium hardness (residual hardness) of the cooled Test solution is unchanged at 22.4 ° d.

It has been found that compounds which of the above Test conditions are sufficient, especially in two completely different groups of connections found. On the one hand, they are used in the water-soluble phosphonic acids found, in particular these are compounds which, in addition to a Phosphonic acid group carry at least one carboxyl function, or preferably Have 2 or more phosphonic acid groups. Examples of the as component A) The phosphonic acids to be used are 1-hydroxyethane-l, l-diphosphonic acid and N, N-dimethylaminomethane-diphosphonic acid and the 2-phosphono-1,2,4-butane tricarboxylic acid, 1-amino-1-phenylmethane-1,1-diphosphonic acid, 1-amino-p-chlorophenylmethane-1,1-diphosphonic acid, 1-hydroxy-1-phenylmethane-1,1-diphosphonic acid, 1-hydroxy-p-chlorophenylmethane-1,1-diphosphonic acid, azacycloheptane-2,2-diphosphonic acid, 1-chloro-1-phenylmethane-1-diphosphonic acid, 2-hydroxy-2, 7-dioxo-3-amino-3-phosphono-1 2 azaphosphacycloheptane and 3-amino-1-hydroxy-propane-1,1-diphosphonic acid, all of which cause a residual hardness of 22.4 ° d in the specified test. More examples of the .Phosphonic acids are.

given below.

The other large group of compounds that are anti-crystallization Effect in the sense of the test described are certain organic phosphorus-free polyanionic compounds, especially polycarboxylic acids, which are often in addition to Carboxyl groups still have substituted or unsubstituted hydroxyl groups and can optionally contain further substituents. Those suitable for the invention Connections are determined using the test described above.

The invention is based on the observation that compounds of the two different types a favorable interaction in combination with the connections of formula I show what is particularly important for washing in the complete absence of Phosphate and important for phosphate-free, but also for low-phosphate detergents is.

The following are those initially defined for binding calcium Capable compounds are referred to as aluminum silicates for the sake of simplicity. This also applies in particular to the sodium aluminum silicates to be used with preference; all information given for their production and processing apply accordingly to the entirety of the above-defined compounds of the formula I.

The preferred cation is sodium; but it can also go through Lithium, potassium, ammonium or magnesium or the cations of water-soluble organic Bases should be replaced, e.g. by those of primary, secondary or tertiary amines or alkylolamines with a maximum of 2 carbon atoms per alkyl radical or a maximum of 3 carbon atoms per alkylol radical. The above cations are the most important cations which do not interfere with the complex binding of calcium and also as a cation in salts of components A) and / or components B) are suitable.

Component A) or its constituents are hereinafter referred to as For short, referred to as phosphonic acids ".

Unless expressly stated otherwise, all percentages are given is to be understood as% by weight; unless otherwise stated, they refer to on anhydrous compounds, i.e. on active substance (= AS). This is especially true also for compounds that in practice almost always have a certain water content have or even be used in solution.

The compounds of the formula also used here according to the invention I are synthetically manufactured products that are soluble in water through the reaction Prepare silicates with water-soluble aluminates in the presence of water.

For this purpose, aqueous solutions of the starting materials can be mixed with one another mixed or one component present in the solid state with the other than aqueous solution present component are implemented. By mixing the two Solid components are obtained in the presence of water, preferably while crushing the mixture, the desired aluminum silicates.

The water-containing aluminum silicates obtained in this way are initially X-ray amorphous; they can be by heating to temperatures of 50-200 0 in the presence of Water age or transform into the crystalline state. That when creating 11 leaves amorphous or crystalline aluminum silicate obtained as an aqueous suspension be separated from the remaining aqueous solution by filtration and at temperatures from Z. B. 50 - 400 ° C dry. Depending on the drying conditions, the product contains more or less bound water. The active substance content of the aluminum silicates are determined by heating to 800 ° C for one hour.

Such high drying and dewatering temperatures are with the Aluminum silicates to be used according to the invention are not recommended. It is a particular advantage that even at much lower temperatures of z. B. 80 - 200 ° C dried products until the adhering liquid water is removed are useful for the purposes of the invention. The changing ones produced in this way Amounts of aluminum silicates containing bound water fall after division the dried filter cake as a fine powder with a maximum primary particle size 0.1 mm, but is usually much lower and down to the fineness of the dust, e.g. B. goes up to 0.1 µ. It must be taken into account that the primary particles are too bigger Forms can be agglomerated. It is easily possible to use products with primary particle sizes in the range of 30-1.

It is particularly advantageous to use aluminum silicates, which are at least 80% by weight consist of particles with a size of 10-0.01μ, preferably 8-0.1μ. These aluminum silicates preferably contain no primary or secondary particles above 30µ. As far as these are crystalline products, these will for the sake of simplicity referred to as "microcrystalline".

Precipitation conditions can already be used to form small particle sizes contribute, whereby the mixed aluminate and silicate solutions - which can also be fed into the reaction vessel at the same time - strong shear forces exposed. If the crystallized ones preferably used according to the invention are produced Aluminum silicates are used to prevent the formation of large ones, possibly even oneself penetrating crystals by slowly stirring the crystallizing liquid.

Nevertheless, at; Drying an undesired agglomeration of crystallite particles enter. In such cases it is advisable to use these secondary particles in a suitable manner Way, e.g. 13. Remove by air sifting. They also occur in a coarser condition Leave aluminum silicates that have been ground to the desired grain size use yourself. For this purpose, z. B.

Mills and / or air separators or their combinations. The latter are z. B. in Ullmann: "Encyclopedia of Industrial Chemistry" Volume 1, 1951, pages 632-634.

Particularly suitable aluminum silicates are found in compounds the composition: 0.7 - 1.1 Na2O Al2O3 1.3 - 3.3 SiO2 This molecular formula comprises two different types of crystalline aluminum silicates or their X-ray amorphous ones Preliminary products.

These two types differ in their crystal structures (to be recognized by the X-ray diffraction diagram) and by their compositions. These are: a) 0.7 - 1.1 Na2O A1203 1.3 - 2.4 S102 b) 0.7 - 1.1 Na2O. Al2O3. 2.4-3.3 SiO2.

Even products that are or are still moist immediately after precipitation even be present in suspension, can be advantageous for the purposes according to the invention be; it can, for example, a) a still flowable suspension of the aluminum silicate in the liquor in which it is at the end of the manufacturing process, b) a Aluminum silicate, from which the mother liquor was partially separated, c) one after partial or complete1 washing out of the mother liquor which is still flowable Suspension of the aluminum silicate in water, or d) an aluminum silicate, ron dem the washing water has been partially separated can be used.

What has been said about the primary particle size applies to still wet resp. Aluminum silicates present in suspension or as a slurry accordingly.

For more details on usable silicates, see referenced the main patent.

For a given gross composition of the aluminum silicates are in each case the crystalline types are preferred. Suitable compounds have in particular a calcium binding capacity in the range of 50 - 200 mg CaO / g active substance (= AS). Particularly compounds with a calcium binding ratio between 100 and 200 are preferred, mostly 100-180 mg CaO / g AS.

Compounds A) and B) are made using the above Tests determined. They are subjected to the test in the form of those sodium salts which are present in aqueous sodium hydroxide solution at a pH of 10.

Group A compounds are known for use proposed in detergents or as sequestering agents for polyvalent cations Phosphonic acids and phosphonic acid derivatives found. Many of the group's connections A are diphosphonic acids obtained by adding phosphorus trihalide or phosphorous Acid and phosphorus trihalide on compounds containing one or more carbonyl groups contain can be obtained. There are e.g. adducts of carboxylic acids, amides, Retones and aldehydes in question.

Suitable phosphonic acids can be found, for example, under the following phosphonic acids: Diphosphonic acids of the formula II in which X stands for H, OH, NH2 or Cl and Y stands for H or halogen, in particular chlorine, to be mentioned. Individual compounds are, for example, 1-amino-1-phenylmethane-1,1-diphosphonic acid; 1-amino-p-chlorophenylmethane-1,1-diphosphonic acid, 1-hydroxy-1-phenylmethane-1,1-diphosphonic acid, 1-hydroxy-p-chlorophenylmethane-1,1-diphosphonic acid. Azacycloalkan-2,2-diphosphonic acids of the formula III which are described in the unpublished German patent (patent application p 23 43 1% .1 (D 4779)). In the formula given, n stands for 3-5 and R for a hydrogen atom or an alkyl group with 1-3 carbon atoms. The compounds of this formula can be prepared, for example, by reacting lactams which correspond to the formula but in which there is a carbonyl group instead of the diphosphonomethyl group with phosphorus trihalides or phosphorous acid and phosphorus trihalides, hydrolyzing the reaction product and, if necessary,

converted into the salts. Cyclic aminophosphonic acids of the general formula IV in which R denotes an alkyl radical with 1-6 carbon atoms or a hydrogen atom and n denotes a number from 1-3 are likewise suitable; they are described in detail in the German patent (patent application P 23 43 195.fl (D 4682)).

They can be prepared by taking the carboxylic acid derivatives of the Formula X-SCE2) n-X, in which n 1 - 4 and X = CN, -COONH2 or COONHR (R = alkyl radical with 1 - 4 carbon atoms) mean, reacts with phosphorus trihalides, the reaction product hydrolyzed under acidic conditions and possibly converted into the salts. The implementation of the dicarboxylic acid derivatives with the phosphorus compounds is preferably carried out in a ratio of about 1: 4.

Pyrrolidone-5,5-di-phosphonic acids, described in the German patent (Patent application P 23 43 147.2 (D 4692)), the hydrogen atom on nitrogen can be substituted by an alkyl radical having 1-6 carbon atoms.

Compounds of this type can be obtained, for example, by reaction of succinic acid derivatives, such as succinic acid amide, optionally in each amide group carries an alkyl radical with 1 - 6 carbon atoms, with phosphorus trihalides and then alkaline hydrolysis.

Alkane polyphosphonic acids, for example methylenediphosphonic acid, xthane triphosphonic acid, propane tetraphosphonic acid, butane-7,2,3,4-tetraphosphonic acid and other aliphatic vicinal polyphosphonic acids that contain other phosphonomethylene groups contain; the amino and hydroxyalkane polyphosphonic acids, for example the 1-HydroxyAthane-1,1-diphosphonic acid, N, N-dimethylamino-methanediphosphonic acid, methanhydroxydiphosphonic acid, zthanhydroxytriphosphonic acids and 3-amino-1-hydroxypropane-1,1-diphosphonic acid; other suitable compounds are carboxyphosphonic acids, such as xthane-1,2-dicarboxy-1,2-dihydroxy-1,2-phosphonic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 2-phosphonobutane-2,3,4-tricarboxylic acid, also aminotrialkylidenephosphonic acids, such as aminotrimethylene triphosphonic acid. There are also to be mentioned the methylamino- and sthylamino-dimethylenediphosphonic acids, the ethylene-diamino-tetramethylenetetraphosph acid and copolymers of vinylphosphonic acid and acrylic acid.

Among the substances particularly suitable for component B) with As Table 1 shows, the polymeric, phosphorus-free capacities for calcium play Polycarboxylic acids play a special role. In Table 1 are some of the water-soluble, Phosphorus-free polycarboxylic acids that prevent the precipitation of poorly soluble calcium compounds delay considerably - they all prevent visible precipitation from occurring in the specified test - compared to some compounds that meet the test condition are not sufficient and are therefore not suitable for component B).

Table 1 shows the residual hardness of the solution after it has been carried out of the test indicated; these were as stated above after cooling the solution by filtering, washing and salt cleaning treatment of the filter (blue band paper filter No. 589³ from Schleicher and Schüll, Federal Republic of Germany, a very hard, narrow-pore filter) and subsequent titration of the calcium content of the hydrochloric acid determined, with the residual hardness of the cooled solution from the titration result calculated after the test.

In the case of the compounds suitable according to the invention, the residual hardness was unchanged 22.4 ° d.

Table 1 Substance residual hardness (Od) no addition 9.4 polyacrylic acid 22.4 POC 22.4 vinyl methyl ether / MSA 22.4 O-carboxymethyl-methyltartronic acid 22.4 allyl acetate / MSA 22.4 citric acid pyrolysate 22.4 (yclopentanetetracarboxylic acid 22.4 nitrilotriacetic acid 17.2 O-carboxymethyl tartronic acid 17.5 '2-oxabutane-1,1,3-tricarboxylic acid 13.6 tartronic acid 17.6 mesoxalic acid 9.4 poly (α-hydroxyacrylate) 4.6 where necessary are the abbreviations and terms used in Table 1 are explained below.

When the experiment was carried out, the complex formers to be examined were each used in the form of their sodium salts, even if, for the sake of brevity, only the Name of the acid is given.

A Ca hardness of 1 d corresponds to a calculated content of 10 mg CaO / liter.

The test solution therefore has a calculated CaO content of 224 mg / l on.

A bicarbonate hardness of 14 d means that 140 mg / l -d.h. 14th ° d - mathematically present as calcium bicarbonate.

The solution is prepared by dissolving the equivalent of 22.4 ° d the amount of CaCl2 in distilled water and subsequent addition of enough sodium bicarbonate, as is mathematically necessary to convert 140 mg CaQ / 1 into calcium bicarbonate Ca (HC03) 2 to convert.

Appropriate compounds identified in detail by applying the test are selected, are found in particular among the polymeric carboxylic acids.

These are both homo- and copolymers, being the copolymers of unsaturated carboxylic acids and polycarboxylic acids, in particular of maleic acid or maleic anhydride, with other ethylenically unsaturated Compounds such as ethylene, propylene, vinyl methyl ether, vinyl acetate, allyl acetate is of particular importance. Compounds suitable for component B are generally used found in particular among copolymers in which monomers containing carboxyl groups are copolymerized with monomers which have substituted or unsubstituted hydroxyl groups exhibit.

The substituents on the hydroxyl group of the base polymer are methyl groups and acyl groups, such as acetyl in particular, are particularly suitable. There are both Compounds in question made by copolymerization of the corresponding monomers directly are obtained, as well as compounds that are primarily through chemical conversion obtained copolymer were obtained.

Particularly suitable copolymers are those made from an esterified one unsaturated monoalcohol with maleic acid or painters anhydride, where the esterified monoalcohol has 3 - 4 carbon atoms and preferably allyl alcohol is. The carboxylic acid component of the ester is in particular acetic acid or propionic acid. A preferred product, the copolymer of allyl acetate and maleic anhydride in a ratio of 1: 1 is commercially available. The product has a molecular weight in the range between 4,000 and 10,000, and residual hardnesses of 22.4 0d were observed; however, products with higher molecular weights are also suitable.

Polyvinyl alkyl ethers / maleic anhydride copolymers are also particularly suitable, in particular the copolymer axis polyvinyl methyl ether / maleic anhydride im Ratio 1: 1.

The molecular weight is at least about 1,500 but is -im generally higher and can for example range between 100,000 and 2,500 000 lie. A very suitable commercial product is "Gantrez AN-11911 with a average molecular weight of 250,000 available from GAF Corp., New York, USA. The polyhydroxycarboxylic acids are also particularly suitable, that by polymerizing acrolein and converting the aldehyde groups into CH2OH groups on the one hand and COOH groups on the other hand can be obtained, i.e. compounds, the structure of the copolymers of acrylic acids with varying amounts of allyl alcohol are comparable.

There are more carboxyl groups than CH2OH groups, ratios from 2: 1 to 7: 1, in particular from 5: 1 to 6: 1, are particularly favorable. Such Connections are sold under the name tPOCt '- Manufacturer: DEGUSSA, Frankfurt, FRG. The molecular weights are mostly in the range between about 1,000 and 10,000, the commercial products tIpOCll have degrees of polymerization of about 20 - 60 on average.

It goes without saying that the copolymers of maleic anhydride are generally used practically completely hydrolyzed in the form of the salts. They are completely hydrolyzed under conditions of use.

Polymers of acrylic acid are particularly suitable for component B); there are low molecular weight products with molecular weights, for example in the range from 1,500 to 10,000 as well as higher molecular weight products are suitable.

There are not only synthetic ones, but also naturally occurring ones polymeric polycarboxylic acids in question, or polymeric polycarboxylic acids by chemical Conversion of natural polymers, such as water-soluble carboxymethylation products of starch or starch degradation products, suitable products by using the Tests need to be selected. The synthetic or fully synthetic ones described above However, products are preferred.

The molecular weight of the suitable polymeric polycarboxylic acids can fluctuate within wide limits. Mostly the molecular weights are the ones used Products - such products are commercially available - in the range between 1 000 and 1 000 000.

Products used with preference often have molecular weights in the low molecular weight range Range, for example in the range from 3,000 to 10,000; however, it will also be very suitable products in the higher molecular range, for example with molecular weights found from 90,000 to 500,000 and above.

Also found among the non-polymeric phosphorus-free polycarboxylic acids are those - especially among the polycarboxylic acids, the ether and / or hydroxyl functions carry - which in the test mentioned the formation of a precipitate that is visible to the naked eye impede. One of these is the "citric acid pyrolysate".

"Citric acid pyrolysate" is a commercial product from Citrex SA, Belgium, which is commercially available under the name "Citrex". It deals is a product that is produced during the pyrolysis of a citric acid alkaline earth salt is obtained when the salt is at temperatures ranging between about 250 OC to 400 OC until the titratable alkalinity rises and then the Product is hydrolyzed to form an unsaturated acid. Particularly suitable within the meaning of the invention and by the term "citric acid pyrolysate" is also included Product obtained by reacting the unsaturated acid obtained as described above with sodium bisulfite is obtained, the bisulfite attached to the unsaturated compound attaches. The product is believed to be a mixture of compounds and has approximately four or more carboxyl groups per molecule on average. The citric acid pyrolysate is for low-phosphate or essentially phosphate-free laundry detergents Invention particularly suitable.

The same applies to the cyclopentanetetracarboxylic acid (it is the product in which the carboxyl groups are all in the cis position to one another stand) and other suitable low molecular weight non-polymeric products. Another one, O-carboxymethylmethyItartronic acid is an excellent low molecular weight product for component C) .

It goes without saying that, even if this is not highlighted is, all of the connections provided for components B) and C) mostly in Form of their water-soluble salts may be used, although for the sake of brevity above mainly the free acids were listed.

The amount of use of the two components used according to the invention A) and B) are generally of a similar order of magnitude. I. E. the amounts used are often in the neighborhood of 1: 1. Fs however, ratios from 10: 1 to 1:10, in particular from about 5: 1 to 1, are also possible : 5 suitable especially about 3: 1 to 1: 3. If A) is phosphate, then in particular are Ratios of A / B = 10/1 to 2/1 are suitable.

The combination according to the invention of components A) and B) is shown in Amounts of, for example, 0.05-2 g / l are used in the process of the invention. In particular additional amounts of 0.1 - 1 g / l are used; however, it can also be essential larger amounts can be used. For further information on the method of the invention reference is made to the main patent. All information given there applies here corresponding.

This also and especially applies to the use of the invention Textile detergents: like those of the main patent, they are for washing and bleaching suitable for a wide variety of fibers of natural or synthetic origin. As Executed in the main patent, the washing effect can be made more common by using Improve components of wash liquors.

These include, for example, surfactants, surfactant-like or non-surfactant-like Foam stabilizers or inhibitors, fabric softeners, neutral or alkaline reactive structural substances, chemically acting bleaching agents and stabilizers and / or activators for these, dirt carriers, corrosion inhibitors, antimicrobial Substances, enzymes, brighteners, dyes and fragrances.

The following concentrations are expediently maintained: O - 2.5 g / l surfactants O - 0.4 g / l active oxygen or equivalent amounts of active chlorine Active oxygen or active chlorine is understood to mean compounds, the oxygen compounds or chlorine in active form and their amounts on the oxygen contained or the chlorine contained are related.

The pH of the treatment liquors can be in the range from 6-13, preferably 8.5 - 12 lie.

The wash liquors used in the process of the invention are convenient - but of course not necessarily - made from agents according to the invention. as Agents according to the main patent contain the compounds of the formula I, they contain builder substances and can also have a surfactant component. The means are characterized by the fact that they have already been discussed in detail above Contain builder combination of components A) and B).

In general, the agents according to the invention also contain one Surfactant components and others commonly used in detergents and bleaches Connections can exist.

Since in the dissolution of the agents according to the invention in the process The liquors used in the invention arise, all apply to the quantitative ratios and ingredients of the agents accordingly also for the ingredients of the fleets and vice versa.

The content of the agent in the combination of components A) and B) can, for example, be clearly recognizable in its effect in the range of 2 - 15 8. The amount of phosphorus compounds present in the agents according to the invention should not be greater than a total P content of the agent of 6%, preferably of 3% corresponds - the phosphorus content of the treatment liquor is accordingly expedient to be kept at a maximum of 0.6 g / l, preferably a maximum of 0.3 g / l. The aluminum silicate content such means can range from 2 to 95, preferably 5 to 95, in particular 15-60% by weight. Depending on the type and amount of the compound used according to the invention are relatively low aluminum silicate contents (e.g. * from 5 - 15%) or relatively high Contents (e.g. from 15 - 60%) are preferred.

The composition more typical, at temperatures in the range of 50 - 100 OC laundry detergent to be used is in the range of the following recipe: 3 - 30%, in particular 5-30% anionic and / or nonionic and / or zwitterionic Surfactants 5 - 70% aluminum silicates (based on AS) 2 - 45% of components A) and B) in a ratio of 1:10 to 10: 1, in particular 1: 3 to 3: 1 O - so% for Xcomplex formation of non-capable washing alkalis (= alkaline builder substances) 0 - 50% bleach and others, mostly in smaller quantities in laundry detergents existing additives.

The types listed in the main patent can be used as surfactants; preferably that according to patent (patent application A 4484/73 (OE 4716)) is used Surfactant combination used in which low and high ethoxylated compounds, possibly in combination with anionic surfactants. The nonionic to be used afterwards Surfactants (= nonionics) are addition products of 2 - 6 or 8 - 18 mol ethylene oxide of 1 mole of fatty alcohol, alkylphenol, fatty acid, fatty amine, fatty acid amide or alkanesulfonamide. In detail, the surfactant component consists of one part by weight of nonionic ones and 0-3 parts by weight of anionic surfactants, the nonionic surfactants being a Mixture of different highly ethoxylated, one aliphatic hydrocarbon residue represent with 10-18 carbon atoms containing compounds, in which per part by weight non-ionic compounds with 8-20 ethylene glycol ether residues in the 0.2 molecule - 2 parts by weight of compounds with 2 - 6 ethylene glycol ether residues in the molecule available. The purely aliphatic ones, e.g. from coconut or Tallow fatty alcohols, oleyl alcohol or secondary alcohols with 8, preferably 10-18 and in particular with 12-18 carbon atoms derived nonionics.

The addition products of ethylene oxide can also be used as nonionics to use terminal or internal vicinal alkanediols, preference being given to those with 2 - 4 or 8 - 14 ethylene glycol ether residues in the molecule.

Under "washing alkalis" are in particular the bicarbonates, carbonates, Understood borates or silicates of alkalis. Preferably contain according to the invention Means at least about 2% washing alkalis. Their share, which can reach 50%, exceeds 35% by weight mostly not.

Among the washing alkalis are alkali carbonate, i.e. in particular soda, and alkali liqueur, in particular sodium silicate, preferred, with combinations often being used of these two types of washing alkalis can be used. The ratio SiO2: Na2O in sodium silicate it is calculated between about 0.66: 1 and 4: 1, with mostly Ratios in the range between 2.3: 1 and 3.45: 1 are preferred. Ne after the desired alkalinity of the detergent or, depending on the desired contribution, the the silicate should contribute to the alkalinity of the detergent, can be higher or lower Circumstances be more expedient; So there can also be ratios in the range between 1: 1 and 2.3: 1 are preferred.

With regard to the rest for use in the compositions according to the invention and in the process according to the invention suitable surfactants, foam inhibitors, foam stabilizers, Bleaching agents and stabilizers and / or activators for these, dirt carriers, enzymes and brighteners, reference is made to the main patent in which the aforementioned Connection classes have been considered in detail.

Agents according to the invention are of particular practical interest from powdery to granular consistency, which are known to all in Ger technology Process can be produced. To facilitate assembly and When handling the products, it may be appropriate to use the compounds of the formula I use in the form of agglomerates. It is generally advisable to when these agglomerates are in use, for example with regression of the primary particles, disintegrate. Also with regard to further information on the production of agents according to the invention reference is made to the main patent.

S e m p i e l e First, the production of one for the Finished aluminum silicate suitable for the purposes of the invention; for which no protection is sought here. It is a microcrystalline one Product. Further examples for the production of suitable aluminum silicates are stated in the main patent. The aluminum silicates described there can be used in use according to the invention in exactly the same way as that dealt with in more detail below Aluminum silicate: In a vessel with a capacity of 15 l was the with deionized ~ water dilute aluminate solution is mixed with the silicate solution while stirring vigorously. Both Solutions were at room temperature. It was formed as a primary precipitate with an exothermic reaction an X-ray amorphous sodium aluminum silicate. The water content was by one hour Heating the product to 800 ° C determined.

After 10 minutes of vigorous stirring with a high-speed intensive stirrer (10,000 rpm; make "Ultraturrax" from Janke e Kunkel, IKA-Werk, Stauffen / Breisaau, Federal Republic of Germany) was the suspension of the amorphous precipitation product transferred to a crystallization tank, where the formation of large crystals was prevented by stirring the suspension. After vacuuming the lye from the crystal pulp and rewashing with deionized water until the draining wash water becomes one Had a pH of about 10, the filter residue was dried, then in a ball mill ground. The grain size distribution was determined with the aid of a sedimentation balance.

The degree of crystallization of an aluminum silicate can be determined from Intensity of the interference lines of an X-ray diffraction diagram of the respective Product compared to the corresponding diagrams of X-ray amorphous resp. determine fully crystallized products.

All data are percentages by weight.

The calcium binding capacity of the aluminum silicates was as follows Determined way: 1 1 of an aqueous, 0.594 g CaCl2 (= 300 mg CaO / l = 300 dH) containing and the solution adjusted to pH 10 with dilute NaOH is added with 1 g aluminum silicate added (based on AS). Then the suspension is long vigorously stirred at a temperature of 220 ° C. (+ 20 ° C.). After filtering off the aluminum silicate one determines the residual hardness x of the filtrate. The calcium binding capacity is calculated from this in rr.g CaO / g AS according to the formula: (30 - x). 10.

(AS = active ingredient) Manufacturing conditions for the aluminum silicate (Im) precipitation: 2.985 kg aluminate solution of the composition 17.7 % Na2O, 15.8% Al2O3, 66.6% H2 ° 0.15 kg caustic soda 9.420 kg water 2.445 kg a freshly made from commercially available water glass and slightly alkali-soluble silica, 25.8% sodium silicate solution with the composition 1 Na2O. 6.0 SiO2 crystallization: 6 hours at 90 OC drying: 24 hours at 100 OC Composition: 0.9 Na2O. 1 Al2O3. 2.04 SiO2. 4.3 H2O (= 21.6% H2O) Degree of crystallization: fully crystalline Calcium binding capacity: 170 mg CaO / g AS.

The particle size distribution determined by sedimentation analysis was in the following range:> 40 µ = 0% maximum of the particle size ratio <10 µ = 85 - 95% division curve: 3 - <8 »= 50 - 85% Dic in the washing or washing aids of the examples containing salt-like constituents - salt-like Surfactants, other organic salts as well as inorganic salts - lay as sodium salts unless expressly stated otherwise.

will. In particular, all of the following have been described as free acids formulated compounds are used in the form of their sodium salts.

The related terms or abbreviations mean: NABS "das Salt of a obtained by condensing straight-chain olefins in benzene and sulfonating of the resulting alkylbenzene, alkylbenzenesulfonic acid with 10-15-, preferably 11-13 carbon atoms in the alkyl chain alkanesulfonate "one from paraffins sulfonate with 12-16 carbon atoms obtained by sulfoxidation; "Fs-ester sulfonate" a from the methyl ester of a hardened tallow fatty acid by sulfonation with SO3 obtained sulfonate; Olefinsulfonat "a mixture of straight-chain internal Olefins with 12-18 carbon atoms by sulfonating with SO3 and hydrolyzing the sulfonation product sulfonate obtained with lye, consisting essentially of alkene sulfonate and oxyalkane sulfonate exists, but also contains small amounts of disulfonates; "OA + x full or "TA + x ÄO" the addition products of ethylene oxide (00) to technical Oleyl alcohol (OA) or tallow fatty alcohol (TA) (JZ = 0.5), where the numbers for x denote the molar amount of ethylene oxide added to 1 ol alcohol; "TA sulfate" the salt of a sulphated, produced by reducing sebum fatty acid, essentially saturated fatty alcohol; , "CMC" the salt of carboxymethyl cellulose; "Perborate" is a product of the approximate composition containing about 10% active oxygen NaBO2 11202 3 H2O; "Foam inhibitor" an N-alkylated aminotriazine from the reaction of cyanuric chloride with mono- or dialkylamine with 8-18 carbon atoms in the alkyl radical; according to Aluminum silicate a microcrystalline produced as described above Aluminum silicate, the percentages referring to the weight fraction of the anhydrous Refer to active ingredient; "NA-silicate" is a sodium silicate with an SiO2 / Na2O weight ratio of 3.35: 1; "Soap C12-C22 or soap C16-C18" salts of fatty acids with the specified Number of carbon atoms.

"EDTA" the salt of ethylenediaminetetraacetic acid; "POC" a polyhydroxyacrylate, that by polymerizing acrolein and then converting the aldehyde groups was obtained in acid functions on the one hand and alcohol groups on the other. Middle Molecular weight 4,200; Manufacturer: ZDEGUSSA ", BRD. The product has a relationship -COOH from about 5-6; OH citric acid pyrolysate "a pyrolysis product of citric acid with an average of four carboxyl groups, which as described above by pyrolysis a citric acid salt and reaction of the reaction product with sodium hydrogen sulfite was obtained. Manufacturer: Citrex S.A., Belgium; wAllyl acetate / MSA "a linear 1: 1 copolymer of allyl acetate and maleic anhydride, the maleic anhydride groups are hydrolyzed. Molecular weight in the range 4,000-10,000; tVinyl methyl ether / MSA " a copolymer in which vinyl methyl ether and maleic acid units in proportion 1: 1 are available. Molecular weight 250,000, hydrolyzed.

Some recipe examples of heavy duty detergents according to the invention follow. These contain sodium perborate and are used in particular for washing determined at higher temperatures (90 -95 OC, hot wash). However, you can Use with good success at lower temperatures (e.g. 50 - 60 OC) The perborate component completely absent from laundry detergents that are packaged for washing at 60 ° C, or it is combined with bleach activators such as tetraacetylglycoluril.

Table 2 Examples of detergent ingredients 1 2 3 4 5 6 7 8 ABS 6.0 - - - 7.5 - 6.0 alkanesulfonate - 6.0 - - - - - 5.5 α-olefin sulfonate - - - 7.5 - - - -Fs-ester sulfonate - 2.0 - - - - - -TA sulfate - - - - - 4.0 - -Soap C12-C22 - - - 3.5 3.5 3.5 2.5 3, 0 Soap C16-C18 2.5 - 2.5 - - - - -TA + 5 AO - 2.5 4.0 - - 2.5 2.5 -TA + 14 AO - 2.5 4.0 - - 2.5 2.5 4.0 OA + 5 AO 1.5 - - 1.2 - - - -OA + 10 AO 1.5 - - 1.2 - - - -Oxo alcohol C12-15- 7 AO - - - - 3.5 - - -CMC 1.5 1.3 1.5 1.3 1.5 1.5 1.5 i, 5 EDTA 0.2 0.2 0.2 0.2 0.2 0 , 2 0.2 0.2 MgSiO3 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 opt. Brighteners 0.3 0.2 0.25 0.3 0.3 0.2 0.3 0.3 Foam inhibitors 0.3 0.3 0.5 0.5 0.2 0.2 0.2 0.3 Perborate 24.0 30.0 25.0 24.0 26.0 30.0 24.025.0 aluminum silicate 25.0 25.0 30.0 25.0 25.0 25.0 30.0 25.0 sodium silicate 100 5.0 5.0 10.0 7.5 7.5 7.5 10.0 Vinyl methyl ether / MSA 5.0 - - - - - - -Polyacrylic acid - 3.0 - - - - - -POC - - 4 , 0 - - - - 2.0 Cyclopentanetetracarboxylic acid Citric acid pyrolysate - - - 4.5 - - - -Allyl acetate / MSA - - - - - - 3.5 - -O-Carboxymethyl-methyltartronic acid - 5.0 - - -Hydroxyethane -diphosphonic acid Examples Detergent ingredients 1 2 3 4 5 6 7 8 Azacycloheptane-2,2-diphosphonic acid - 2.0 - - - - - -3-Hydroxy-2,7-dioxo-3-amino-3-phosphono-1,2 - - - - - - - 4,5 -azaphosphacycloheptane 1-amino-1-phenylmethyne - - - 3,5 - - - -diphosphonic acid 1-hydroxy-1-phenylmethane-5,0 - - - - - - 1, 5 diphosphonic acid 1-chloro-t-phenylmethanediphosphonic acid - - - - 3.0 - - -1-hydroxy-p-chlorophenyl- - 4.5 - - - -methyn-diphosphonic acid Table 3 Detergent ingredients Example 1 e 9 10 11 12 13 AWAY S 6.0 8.0 3.0 - -alkanesulfonate - - 3.0 - -olefin sulfonate - - - - 5.0 Fs-ester sulfonate - - 7.0 -TA sulfate - - - - 3.0 Soap C12- C22 3.5 4.0 3.0 - -Soap C -C - - - 3.0 2.5 TA + 5 Ä0 1.5 - - - -TA + 14 ÄO 2.5 3.0 - - -OA + 5 Ä0 - - 1.5 - -OA + 10 ÄO - - 2.0-4.0 oxo alcohol C12-15 - 7 Ä0 - - - 3.0 -CMC 1.5 1.5 1.5 1.5 1.5 EDTA 0.2 0.2 .0.2 0.2 0.2 MgSiO3 1.5 1.5 1.5 1.5 1.5 opt. Brighteners 0.2 0.15 0.25 0.15 0.15 Foam inhibitors - - - 0.5 1.0 Na perborate 30.0 25.0 20.0 20.0 25.0 Sodium triphosphate 20.0 20, 0 15.0 10.0 25.0 aluminum silicate '15.0 20.0 25.0 25.0 10.0 sodium silicate 3.0 5.0 3.0 3.0 3.0 polyacrylic acid 5.0 - - 8.0 -POC - 3.0 - - -Vinyl methyl ether / MSA - - 4.0 - -Allyl acetate / MSA - - - - 6.0 remainder Na2S04 + H20 Table 4 Examples of detergent ingredients 13 14 ABS 6.0 Fs-ester sulfonate 7.0 Soap C12-C22 3.5 Soap C16-C18 3.0 A + 5 AO 1.5 TA + 14 AO 2.5 Oxo alcohol C12-15 + 7 AO 3.0 MC 1.5 1.5 EDTA 0.2 0.2 Mg SiO3 1.5 1.5 pt. brightener 0.2 0.15 foam inhibitors 0.5 a-perborate 30.0 20.0 atrium triphosphate 10.0 10.0 Aluminum silicate 15.0 15.0 Soda | 15.0 15.0 Na silicate 5.0 2.5 Polyacrylic acid 5.0 Vinyl methyl ether / MSA | | 4.0 Remainder Na2SO4 + H20 Examples 1-4, 6,7,9,11 and 14'lieaen present particularly advantageous surfactant combinations in which nonionic compounds with 8-20 ethylene glycol residues in the molecule are combined with nonionic compounds which have 2-6 ethylene glycol ether residues per molecule, where, in addition to the nonionic compounds, anionic surfactants are optionally present.

In example 4, 1-amino-pb chlorophenylmethanediphosphonic acid, in Example 6 also N, N-dimethylaminomethanediphosphonic acid or 3-amino-1-hydroxypropane-1,1-diphosphonic acid used in place of the phosphonic acids given in Examples 4 and 6, respectively.

Since the detergents of the invention according to any, in the art Let the known processes be produced, refer to a detailed description of the Manufacturing has been omitted.

Claims (4)

P a t e n t a n s p r ü c h e 1. Further training of the process for washing and bleaching of Textiles by treating the same with an aqueous liquor that binds the Contains substances capable of hardening the water, whereby according to patent (patent application P 24 12 837.8-41 (D 4642/4787/4819)) a calcium binding capacity in the aqueous treatment liquor of at least 50 mg CaOJg anhydrous active substance (= AS) containing, finely divided, water-insoluble, optionally bound water-containing compounds of general formula (Kt2 / nO). Me203. (SiO2) (I) in the cat an exchangeable with calcium Cation of valence n, x a number from 0.7 - 1.5, Me boron or aluminum and y mean a number from 0.8 to 6, preferably from 1.3 to 4, suspended and werner Builders are included, and where appropriate, the aqueous treatment liquor also contains a surfactant component, characterized in that a mixture of following, as water-soluble salts with one, the complex binding of calcium does not interfering cation is used: A) the precipitation poorly soluble calcium compounds considerably delaying phosphonic acid, or a Calcium complex binding phosphate, B) a phosphorus-free, the precipitation less soluble Calcium compounds significantly delaying polyanionic compound, being phosphonic acids of component A) and polyanionic compounds of component B) each in one Test in which your sodium salt is at a concentration of 0.5 g / l in 200 ml one aqueous solution is dissolved, which contains 2.5 g / l Na2SO4 dissolved and a calcium hardness of 22.4 d and a bicarbonate hardness of 14 0d, whereupon the pH value drops to 9.0 set and the solution is then boiled under reflux for 30 min, and then the Solution is cooled to room temperature, the formation of a visible precipitate prevent, and components A) and B) in a weight ratio of 1:10 up to 10: 1 are available. 2. The method according to claim 1, characterized in that the components A) and B) are present in a ratio of 1: 3 to 3: 1. 3. Means for performing the method according to claim 1, characterized by a content of the mixture specified in claim 1. 4. Means for performing the method according to claim 3, characterized characterized in that components A) and B) are present in a ratio of 1: 3 to 3: 1.