DE2113730A1 - Washing compsns - contg water-soluble salts of tetrahydrofuran tetracarboxylic acid as builder component - Google Patents

Abstract

Washing and cleaning compsns. contain, as builders, water-sol. salts of THF, tetracarboxylic acid, in combination with >=1 (in)organic substance with cleaning or bleaching action, the use of Na tripolyphosphate being avoided or reduced. The compsns. can be used to wash and/or bleach textiles, and to clean instruments, appts. pipes vessels and surfaces of all types, e.g. of ceramics, glass, metals, synthetics or wood.

Description

"Washing and cleaning agents" The washing and cleaning power of It is known that soaps and synthetic surfactants can be removed by adding certain water-soluble substances inorganic or organic salts, which generally have a complex binding capacity for alkaline earth and heavy metal ions increase considerably. Such So-called builder substances are in the commercially available detergents and cleaning agents present, sodium tripolyphosphate being preferred in commercial preparations is used as a structural substance. This polyphosphate of detergents and cleaning agents is increasingly popular with the public for the undesirably high phosphate content blamed the waters. However, the one that has been highly controversial up to now is still going strong Believed that the observed water pollution by excessive Algae growth is largely due to the phosphate content of the wastewater Detergent is due. There has therefore been a demand for low phosphate levels or phosphate-free detergents and cleaning agents that do not contain any of the phosphate-containing ones Detergents and cleaning agents have said disadvantages.

The aim of the invention is therefore to provide detergents and cleaning agents whose Up to now, structural substances consisted to a large extent of sodium polyphosphate, without the use of sodium tripolyphosphate or with a reduction in the content of Develop sodium tripolyphosphate anew.

Detergents and cleaning agents within the meaning of the invention are e.g.

Preparations for washing and / or bleaching fiber and textile materials and for legging devices, apparatus, pipelines, vessels, card surfaces of all kinds in industry, in commercial operations and in the household, such as mild detergents for hand and machine washing, high-temperature detergents, in particular For drum washing machines, prewash detergents, bleaches, cleaning agents for surfaces made of ceramic, glass, metal, plastic, wood, etc.

The invention is based on the knowledge that tetrahydrofuran-tetracrboxylic acid and their water-soluble salts, in particular the Al.lisalze, as builder substances suitable for detergents and cleaning agents.

The detergents and cleaning agents according to the invention contain water-soluble ones Salts of tetrahydrofuran-tetracarboxylic acid in combination with at least one other inorganic or organic, cleansing or bleaching substance.

The salts of tetrahydrofuran tetracarboxylic acid which can be used according to the invention have typical properties of structural substances, in particular they draw through a good complex binding capacity for alkaline earth ions as well as through a good washing power. They are therefore suitable as a phosphorus-free substitute for sodium polyphosphate in detergents and cleaning agents. The alkali salts of tetrahydrofuran-tetracarboxylic acid are particularly preferred.

The tetrahydrofuran-tetracarboxylic acid and its salts are known and available in the stores.

As a further, together with the salts of tetrahydrofuran-tetracarboxylic acid Substances that can be used are essentially surfactants, inorganic and organic Builder substances and bleaching components into consideration.

The composition of the detergents and cleaning agents is marked by the following general recipe, based on the anhydrous substances: 0 - 80, preferably 5 - 40% by weight of a surfactant component consisting of anionic and / or zwitterionic and optionally nonionic surfactants, 100 - 20, preferably 95-60% by weight of inorganic and / or organic builders, the partly, in particular to an extent of 5-90% by weight, from the water-soluble salts of tetrahydrofuran-tetracarboxylic acid exist, and 0-30, preferably 1-25% by weight of other common constituents of Detergents and cleaning agents.

To the other usual detergent and cleaning agent ingredients include e.g. foam stabilizers, non-tesidal foam inhibitors, bleaching components, Dirt carriers, fabric softeners, brighteners, antimicrobials, enzymes, dyes and fragrances.

In addition to tetrahydrofuran-tetracarboxylic acid, the builder substances in the above formulation include 10-95, preferably 10-60 percent by weight of other builder substances from such inorganic and / or organic water-soluble substances that were previously used in laundry and detergents have been used as the usual builder substances, and the others are described in detail below. The usual ones are preferred Structural substances used that do not contain phosphorus.

If the detergents and cleaning agents according to the invention in addition to the tetrahydrofuran-tetracarboxylic acid and optionally other customary phosphorus-free scaffold additives Phosphates such as sodium tripolyphosphate as well as organic, phosphorus and / or starch containing complexing agents in such an amount that they contain less than half makes up the phosphorus content of detergents and cleaning agents that have previously been soluble in almonds, then this already leads to the use in the usual washing and cleaning liquors excessively dilute wastewater in terms of phosphate concentration, so that a Impact on the phosphate content of the lakes and pluses can be largely excluded is.

The surfactant component preferably consists of the above formulation to at least 50 percent by weight of anionic surfactants, among which anionic Surfactants essentially capillary-active sulfates and / or sulfonates and / or soaps be understood.

The amount of builder substances in the agents according to the invention is preferably 0.5 to 7 times and especially 1 to 5 times the total Surfactants.

If the preparations according to the invention contain more than 40 percent by weight of the above surfactant component, then they are mostly used for commercial purposes e.g. used in laundries and in the textile industry, where they are seldom alone, more often used in combination with common additives.

The agents according to the invention can be as powders, pastes, solutions or Suspensions are present, the liquid preparations up to 50 percent by weight Solid matter and, in addition to water, also water-soluble organic solvents and hydrotropes May contain substances.

The composition of powdered preparations according to the invention that particularly used as detergents is generally in the range of the following formulation: 5 - 80, preferably 8 - 40% by weight of a surfactant component to at least 50% by weight of anionic surfactants from the group of alkylbenzenesulfonates, Alkane sulfonates, fatty acid ester sulfonates, olefin sulfonates, fatty alcohol or fatty alcohol glycol ether sulfates and soaps, and optionally nonionic and / or zwitterionic surfactants and optionally containing one or more of the following substances: 0 - 10, preferably 0.5-8% by weight foam stabilizers, 0-10, preferably 0.5 - 8% by weight of non-surfactant foam inhibitors, 20-95, preferably 60-92% by weight of builder substances, some of which, in particular 5-90% by weight water-soluble salts of tetrahydrofuran-tetracarboxylic acid, and 0 - 50, preferably 1-15% by weight of other detergent ingredients such as bleach components, Dirt carriers, fabric softeners, antimicrobial agents, enzymes, brighteners, dyes and fragrances, Water.

If the detergent should have bleaching properties, can they also have a bleaching component consisting of per compounds, stabilizers and optionally contain activators for the per compounds, which are 2-40, preferably 7-35 percent of the total detergent, with such Detergents, the amount of structural substances is reduced, but no more than reduced to 20 percent by weight, or the amount of all ingredients proportionally is.

Foam-suppressed ones suitable for use in drum washing machines Detergents according to the recipe above contain either a combination of Surfactants of the sulfonate and / or sulfate type and soap in a proportion of 70: 1 up to 1: 5, preferably 20: 1 to 1: 2, and / or a non-surfactant foam inhibitor. In such low-foam detergents contain the soaps of saturated Fatty acids with 20-24, preferably 20-22, carbon atoms, their amount at least 5 percent by weight, preferably at least 10 percent by weight of the total amount of soap.

The production of powdered detergents and cleaning agents according to the invention can be carried out by various methods known per se. So you can, for example the individual components present as a more or less fine powder or as granules bring together by mixing to powder detergents and cleaning agents. According to the technically preferred method for detergents and detergents at the moment Detergent, the aqueous batch is hot-dried in a manner known per se, what happens on hot pluches or in a stream of hot air can. If the prepalates according to the invention are placed on the base over an aqueous approach of the constituents by drying it out, certain constituents such as and foam inhibitors, bleaches, enzymes, etc. not incorporated into the aqueous mixture, but afterwards added to the powder detergent. It is where appropriate advantageous, especially for the gentle incorporation of smaller quantities of substances, which should make the product more effective or attractive, such as enzymes, antimicrobials, Detergents and fragrances, such substances by mixing with some of the structural substances first to be converted into a dry powdery preliminary product, which is then to the usual Way is added to the detergent or cleaning agent powder.

The following are those in the 'washing and cleaning agents according to the invention The constituents contained are described in more detail, sorted by substance class.

As structural substances, which may be used together with the salts of the Tetrahydrofuran-tetracarboxylic acid can be used, are weakly acidic, neutral and alkaline reacting inorganic and organic salts, in particular inorganic or organic complexing agents.

Inorganic and organic builder substances which can be used are, for example the bicarbonates, carbonates, sulfates, borates, silicates or hydroxides of alkalis as well as the alkali salts of organic, non-capillary-active, 1 - 8 carbon atoms Sulfonic acids, carboxylic acids and sulfocarboxylic acids. These include, for example water-soluble salts of benzene, toluene or xylene sulfonic acid, water-soluble salts the 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 from the group of the polymers of maleic acid, itaconic acid, mesaconic acid, Fumaric acid, aconitic acid, methylenemalonic acid and citraconic acid are suitable. Also copolymers of these acids with one another or with other polymerizable substances, e.g. with ethylene, propylene, acrylic acid, methacrylic acid, crotonic acid, 3-butene carboxylic acid, 3-methyl-3-butenecarboxylic acid and with vinyl methyl ether, vinyl acetate, isobutylene, Acrylamide and styrene are useful.

As complex-forming, phosphorus and / or nitrogen-containing structural substances, which are particularly suitable for binding traces of heavy metal ions if appropriate, in minor amounts, the alkali metal salts of the amino and polyaminopolycarboxylic acids such as nitrilotriacetic acid, ethylenediaminetetraacetic acid, N-hydroxy-ethyl-ethylenediamine triacetic acid, the di- and polyphosphonic acids such as methylenediphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, 1-aminoethane-1, 1-diphosphonic acid, amino-tri- (methylenephosphonic acid), methylamino or itthylamino-di- (methylenephosphonic acid) as well as .Nthylenediamine-tetra- (methyleneiiphosphonic acid can be used.

Additional dirt carriers can be used in the detergents according to the invention be included, which suspends the dirt detached from the fiber in the liquor hold and thus prevent graying. For this purpose, water-soluble colloids are usually used of an organic nature, such as glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acid sulfuric acid esters cellulose or starch. Also water-soluble polyamides containing acidic groups are suitable for this purpose.

Furthermore, soluble starch preparations and other than Use the above starch products such as degraded starch, aldehyde starches etc. Polyvinylpyrrolidone can also be used.

The surfactants contain at least one hydrophobic residue in the molecule of mostly 8-26, preferably 10-22 and in particular 12-18 carbon atoms and at least an anionic, nonionic or zwitterionic water-solubilizing group. The preferably saturated Llydrophobe remainder is mostly aliphatic, possibly also alicyclic in nature; he can directly or with the water-solubilizing groups be connected via intermediate links, such as - via benzene rings, carboxylic acid esters - or carbonamide groups, residues of polyhydric alcohols bonded in ether or ester fashion.

As an anionic active washing substance, soaps are made from natural or synthetic fatty acids, possibly also from resin or naphthenic acids, especially useful if these acids have iodine numbers of at most 30 and preferably less than 10 exhibit.

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

The sulfonates include, for example, the alkylbenzenesulmonates with preferably. straight-chain C9-15-, especially C10-14-alkyl radicals, the alkanesulfonates, obtainable from preferably saturated aliphatic C8-18, especially C12-18 hydrocarbons on sulfochlorination or sulfoxidation, which goes under the name "Olefinsulfonate" known mixtures of alkene sulfonates, hydroxy alkane 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. Among those that can be used according to the invention Sulphonates also include salts, preferably alkali salts, of α-sulpho fatty acids and salts of esters of these acids with mono- or polyvalent ones; 1 - 4 and preferably 1 - 2 carbon atoms containing alcohols.

Further useful sulfonates are salts of fatty acid esters of oxethanesulfonic acid or of dioxypropynesulfonic 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 made from carbon fatty alcohols, tallow fatty alcohols or from oleyl alcohol, furthermore sulfated fatty acid alkylolamides or fatty acid monoglycerides and sulfated Alkoxylation products of alkylphenols (C8-15-alkyl), fatty alcohols, fatty acid amides or fatty acid alkylolamides with 0.5-20, preferably 1-3 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" denotes, those by attaching 4 - 1QQß preferably belong 6 - 40 and in particular 8 - 20 mol of ethylene oxide in fatty alcohols, alkylphenols, fatty acids, fatty amines, fatty acid 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 prop -oxylationben lower aliphatic alcohols containing 1-8, preferably 5-6 carbon atoms or from water-insoluble propoxylated A lkylenediamines by ethoxylating to products obtained for water solubility. After all, as nonionics, the as "Ucon-Fluid" known, partly still water-soluble reaction products of the above called en allphatisohen alcohol to use with propylene oxide.

As nonionies are also from mono- or diethanolamine, from dihydroxypropylamine or other polyhydroxyalkylamines, e.g. fatty acid derived from glycamines or sulfonic acid alkylolamides, 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 & 'urehal-' ester, phosphonic acid and partial phosphoric acid ester groups, as well as basic groups, such as primary, secondary, tertiary and quaternary ammonium groupings. Zwitterionic Compounds with quaternary ammonium groups belong to the betaines type. Carboxy, sulfate and Sulphonate betaines are particularly good because of their good compatibility with other surfactants practical interest.

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.

Suitable foam stabilizers, especially in the case of sulfonate surfactants or sulfate type, capillary-active carboxy- or sulfobetaines as well as those mentioned above Alkylolamide type nonionics; 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. Sulphates and / or sulphonates andXor of Nonionios on the one hand with soaps on the other hand. In the case of soaps, the foam attenuation increases with the degree of saturation and the C number of the fatty acid residue at; Soaps made from saturated C20-24 fatty acids have proven effective as foam suppressors.

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 6-20, preferably 8-18 carbon atoms in the alkyl radical. Propoxylated ones 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 receives this propylene oxide derivative.

Other non-surfactant foam inhibitors are water-insoluble organic compounds such as paraffins or haloparaffins with melting points below 100 ° C, aliphatic C18 to C40 ketones and aliphatic carboxylic acid esters, the in the acid or alcohol residue, optionally also in each of these two residues, contain at least 18 carbon atoms (e.g. triglycerides or fatty acid fatty alcohol esters); they can be used especially with combinations of surfactants of the sulfate and / or sulfonate type use with soaps to steam the foam.

As particularly low-foaming nonionics, which may be included in Can be used in combination with anionic and zwitterionic surfactants and reduce the foaming capacity of better foaming surfactants, addition products are suitable of propylene oxide to the capillary-active polyethylene glycol ethers described above as well as the Pluronic, Tetronic and Ucon fluid types also described above.

Among the preferably inorganic per compounds used as bleaching agents Sodium perborate tetrahydrate (NaBO2. H2O2. 3 H2O) is of particular practical importance. In its place, partially or completely, i.e. up to NaB02. H202 drained Perborate can be used. There are also those in DBP 901 287 and USP 2,491,789 described Borates NaBO2. H202 usable in which the ratio Na20: B2O3 is less than 0.5: 1 and is preferably in the range of 0.4-0.15: 1, while the H202: Na ratio falls in the range of 0.5-4: 1. All this perborate can be wholly or partially by other inorganic per compounds, in particular by peroxohydrates, e.g. dio peroxoydrates of the ortho-, pyro- or Polypheephates, especially tripolyphosphates, and carbonates.

It is advisable to use the products to stabilize the per compounds Usual water-soluble and / or water-insoluble stabilizers in amounts of 0.25-10% by weight to be incorporated.

As water-insoluble perstabilizers, e.g. 1 - 8, preferably Make up 2 - 7% of the weight of the entire preparation, they are mostly suitable Precipitation of magnesium silicates obtained from aqueous solutions MgO: SiO2 = 4: 1 to 1: 4, preferably 2: 1 to 1: 2 and in particular 1: 1.

In their place are other alkaline earth metal, cadmium or tin silicates appropriate composition usable. There are also hydrous oxides of tin suitable as stabilizers.

Water-soluble stabilizers, which together with water-insoluble may be present are the organic complexing agents, the amount of which is 0.25 - 5, can preferably make up 0.5 - 2.5% of the weight of the entire preparation.

The active chlorine compounds serving as bleaching agents can. more inorganic or be organic in nature.

The inorganic active chlorine compounds include alkali hypochlorites, in particular in the form of their mixed salts or addition compounds to orthophosphates or to condensed phosphates such as pyro- and polyphosphates or can be used on alkali silicates.

If the detergents according to the invention contain monopersulphates and chlorides, active chlorine is thus formed in aqueous solution.

The organic active chlorine compounds are in particular the N-chlorine compounds in question, in which one or two chlorine atoms are bonded to a nitrogen atom, where preferably the third valence of the nitrogen atoms is attached to an electron-withdrawing one Group leads, in particular to a CO or S02 group. These connections include Dichloro and trichlorocyanuric acid or salts thereof, chlorinated alkylguanides or alkyl biguanides, chlorinated hydantoins and chlorinated melamines.

As activators for precompounds that deliver H2O2 in water certain N-acyl, C-acyl compounds that form organic peracids with this H2O2 as well as carbonic acid or pyrocarbonic acid esters, their activation value for the per 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. H2O. 3 H2O (4th mmol / l) and 2.5 g / l Na4P2O7. 10 H2O contain, after heating to 60 ° C with 4 mmol / l of activator are added and the temperature indicated is maintained for 5 minutes held. 100 ml of this liquid are then added to a mixture of 250 d of ice and 15 ml of glacial acetic acid and titrated with 0.1 immediately after adding 0.35 g of potassium iodide n Sodium thiosulphate solution and starch as indicators. Under the specified test conditions With a 100% activation of the peroxide used, 8.0 ml is consumed Thiosulphate solution, i.e. the titer is 8.0. However, this maximum value becomes practical almost never achieved; good activators have a titer of at least 4.5. Often achieved activators with a titer of at least 3.0 can already be used with activators.

Suitable from the types of activators still to be described below special compounds with a melting point of at least 70 ° C, preferably at least 100 ° C and in particular at least 150 ° C. Furthermore, the equivalent weight should of these compounds (the equivalent weight here is the quotient of the molecular weight and the number of acyl radicals present in the molecule) at most 170, preferably at most 130 and in particular at most 110.

The activators which can be used according to the invention include a) those from the German patent specifications 1,162,967 and 1,291,317 known N-diacylated and N, N'-tetracylated amines such as N, N, N ', N'-tetraacetyl-methylenediamine or ethylenediamine, N, N-diacetylaniline and N, N-diacetyl-p-toluidine or 1,3-diacylated Hydantoins, such as the compounds 1, 3-diacetyl-5,5-dimethyl-hydantoin and 1, 3-dipropionyl hydantoin; b) those known from British patent specification 1 003 310 N-alkyl-N-sulfonyl-carbonamides, for example the compounds N-methyl-N-mesyl-acetamis, N, -methyl-N-mesyl-benzamide, N-methyl-N-mesyl-p-nitrobenzamide, and N-methyl-N-mesyl-p-methoxybenzamide; c) those described in Swiss Patent 407 387 as activators N-acylated cyclic hydrazides, acylated triazoles or urazoles such as that Monoacetyl maleic hydrazide; d) in the German patent application P 17 19 574.3-43 described O, N, N-trisubstituted hydroxylamines such as e.g.

O-Benzoyl-N, N-succinyl-hydroxylamine, O-acetyl-N, N-succinylhydroxylamine, O-p-methoxybenzoyl-N, N-succinyl-hydroxylamine, O-p-nitrbenzoyl-N, N-succinyl-hydroxylamine and O, N, N-triacetylhydroxylamine; e) those from the German Offenlegungsschrift 1 801 713 known N, N'-diacyl-sulfurylamide, for example N, N-dimethyl-N, N'-diacetyl-sulfurylamide, and N, N-diethyl-N, N-dipropionylsulfurylamide; f) the triacylcyanurates, for example Triacetyl cyanurate and tribenzosyl cyanurate from German Auslegeschrift 1,294,919; g) those from Swiss patent specification 347 930 or the German patent specification 893 049 or the German Offenlegungsschriuft 1 444 001 known carboxylic acid anhydrides such as.

Benzoic anhydride, m-chlorobenzoic anhydride, phthalic anhydride, 4-chlorophthalic anhydride; h) those from the Swiss patent address 348,682 known sugar esters, for example glucose pentaacetate; i) the 1,3-diacyl-4,5-diacyloxy-imidazolidines the German Offe @ legungsschrift 1 801 141, 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 German Offenlegungsschrift 1 594 865 as activators Compounds tetraacetylglycoluril and tetrapropionylglycoluril; k) as activators diacylated 2,5-diketopiperazines suggested for per compounds 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 carbonic acid ester of the German Offenlegungsschrift 1 444 024, for example the sodium salts of p- (athoxycarbonyloxy) -benzoic acid and p- (propoxycarbonyloxy) -benzonsulfonic acid.

Often it is sufficient to only use part of the available active oxygen to activate; activator additives of at least 0.05 mol of activator are sufficient for this For each g-atom of active oxygen, activation is as extensive as possible of the active oxygen value, the activator can be added up to 2 mol, preferably Increase up to 1 Nol. It is preferred to work with 0.1-1 mol of activator per g atom Active oxygen. However, these amounts can be adjusted according to the activity of each change the activator used.

When the per compounds are activated by the aforementioned N-acyl and O-acyl compounds become part of the alkali in the washing and bleaching liquors the resulting organic pels, iures or the resulting organic Carboxylic acids such as acetic acid, propionic acid, benzoic acid consumed and advantageously replaced by adding appropriate amounts of alkalizing agent.

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 I: 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, with aliphatic residues present in the above groups preferably 1 - 4 and in particular 2 - 4 C- Atoms contain, while the heterocyclic ring systems are mostly 5- or 6-membered rings. The radicals of aniline, anthranilic acid or anilinesulfonic acid are preferred as aromatic amines. Lighteners derived from dianiinostilbene disulphonic acid are mostly used as cotton lighteners. The following products derived from formula 1 are commercially available, where R1 represents the radical -NtIC6H5 and R2 then represents the following radicals: -NH2, -NHCH3, -NHCH2CH2OH, -NHCH2CH2OCH3, -NHCH2CH2OCH3, -N (CH3) CH2CH2OH, -N (CH2CH2OH) 2, morpholino-, -NHC6H5, -NHC6H4SO3II, -OCH3. With regard to fiber affinity, some of these brighteners are to be regarded as transition types to the polyamide brighteners, e.g. 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 carry further substituents can, such as Ilydroxy, 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 denotes a chlorine atom.

The 9-cyanoanthracene is also part 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-benzilaidazolyl) -2- (1-hydroxyethyl-3-benzimidazolyl) ethylene are also 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) -naphtho [2,3-b] -thiophene and 1,2-di- (5-methyl-2-benzoxazolyl) -ethylene are suitable.

If the brighteners are used together with other components of the invention Products are present as an aqueous solution or paste and, by hot drying, become solid State, it is recommended to stabilize the brightener organic Complexing agents in amounts of at least 0.1, preferably 0.2-1% by weight of the solids Incorporate products.

The enzyme preparations to be used are usually a mixture of enzymes with different effects, e.g. of proteases, carbohydrases, esterases, lipases, Oxidoreductases, catalases, peroxidases, ureases, isomerases, lyases, transferases, Desmolases or nucleases. Those from bacterial strains are of particular interest or enzymes obtained from fungi such as Bacillus subtilis or Streptomyces griseus, in particular Proteases or amylases that oppose alkali, percompounds and anionic surfactants are relatively stable and are still effective at temperatures of up to 70 ° C.

Enzyme preparations are mostly used by the manufacturers as aqueous solutions the active ingredients or as a powder, granules or as cold atomized 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; they are obtained in a manner known per se by incorporating oily or pasty nonionics or by granulating with the help of melting salts containing water of crystallization in your own water of crystallization.

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 as proteases and amylases0 EXAMPLE The following examples describe compositions of some preparations according to the invention. The contained therein Salt-like constituents are in the form of sodium salts, unless expressly stated something else is found. The related terms and abbreviations mean: "ABS" means the salt of a product made by condensing straight chain olefins with benzene and Sulfonating the resulting alkylbenzene with the alkylbenzenesulfonic acid obtained 10-15, essentially 11-15, carbon atoms in the alkyl chain; "Alkanesulfonate" one of paraffins with 12-16 carbon atoms by means of sulfoxidation obtained sulfonate; "Fs-ester sulfonate" is a hardened one from the methyl ester Tallow fatty acid sulfonate obtained by sulfonation with SO; "Olefin sulfonate" din from olefin mixtures with 13-18 carbon atoms by sulfonation with SO3 and Hydrolyzing the sulfonation products with alkali obtained sulfonate, which is essentially consists of alkene sulfonate and oxyalkane sulfonate, but also small amounts contains of disulfonates. Each preparation containing olefin sulfonate was used made two different types of olefin sulfonate; one was a mixture straight-chain terminal olefins, the other from a mixture of internal ones Olefins have been produced; "KA-ÄO-Sulphate" the sulphated addition product of 2 moles of ethylene oxide in 1 mole of coconut fatty alcohol (C12 - C14); $ "Soap A or B ″ one of a fatty acid mixture of 9% by weight of C18, 14% by weight of C20 and 77% by weight C22 (Iodine Number 3) (A); buw.

8% by weight C16, 32% by weight C18, 12% by weight C20 and 48% by weight C22 (iodine number 4) (-B) manufactured soap; "KA + 7 ÄO" and "NP + 9 ÄO" represent the addition products of ethylene oxide on coconut alcohol (C12 - C18) or on nonylphenol; "Perborat" an approximately Product containing 10% active oxygen with the approximate composition NaBO2.H2O2.3 H2O; "NTA", "EDTA" and "ATP" are the salts of nitrilotriacetic acid, ethylenediaminetetraacetic acid or aminotrimethylene phosphonic acid; "OMO" the salt of carboxymethyl cellulose.

In the examples, e1n Mixture of about 45 ffi of an N, N'-di (alkylamino) chlorotriazine and about 55% of one N, N ', N "-Tri- (alkylamino) -triazines are used. In these triazine derivatives lie the alkyl radicals as a mixture of homologues with 8-18 carbon atoms.

The monochlorotriazine derivative was similarly successful or use the trialkylaminotriazine. If the products described are synthetic Sulphates or sulphonates along with soap contain 4 inside the other in the Description mentioned non-surfactant foam inhibitors are used as for example paraffin oil or paraffin, was used in the manufacture of the preparations dr non-surfactant foam inhibitor in a suitable organic solvent dissolved or in the molten state by means of a nozzle on the moving powdery Preparation sprayed on.

Example 1 A heavy duty detergent of the following composition was used produced by mixing the individual components: 5% by weight ABS; 4 wt% NP + 9 ÄO; 5% by weight soap A; 20% by weight perborate; 5 wt% Na2O. 3.3 SiO2; 2% by weight magnesium silicate; 0.5% by weight of brightener of the formula I on page 15, in which R1 is the anilino and R2 is the dihydroxyethylamino radical represent; 35 wt% tetrasodium tetrahydrofuran tetracarbonate; 0.5 wt% enzyme Alcalase R from Novo Industri, Copenhagen; Remainder sodium sulfate and water.

Detergent and Ca complex binding capacity of the above detergent were comparable with the corresponding properties of a comparative detergent with a similar composition, However, instead of the tetrasodium tetrahydrofuran tertacarbonate, the same amount Contained sodium tripolyphosphate.

Examples 8 - 7 In the other examples in Table I, the No. 2 - 5 heavy duty detergent, No. 6 a mildly foaming mild detergent and No. 7 represents a prewash detergent. In all examples, the quantitative data relate to on the pure substances. These substances can production-related accompanying substances such as water, sodium sulfate, sodium chloride, sodium carbonate, etc. Since such accompanying substances do not affect the effectiveness of the individual substances in any way affect, they are not mentioned in the recipes. The term "remainder" stands therefore essentially for water and the aforementioned salts as well as for color and Fragrances.

Table 1 Part of the% by weight component in the preparation Preparation example 2 3 4 5 6 7 ABS 9 7 8 Alkanesulfonate 2 Fs-ester sulfonate 7 Olefin sulfonate 6 2 KA-ÄO-sulfate 4 Soap A | 3.5 4 Soap B | 3 | | 3.0 | | 3 | NP + 9 Ao KA + 7 AO 2 1.5 4 non-surfactant Foam inhibitor 0.5 0.3 Tetrasodium tetra- hydrofuran-tetra- carbonate 20 35 15 10 10 20 Na2SO4 5 7 22 15 50 35 Na2O. 3.3 SiO2 10 3 4 5 4 Na5P3O10 10 10 20 Na2CO3 12 10 5 Perborate 25 20 25 30 MgSiO3 1.5 1.0 1.5 1.5 NTA 2 2 EDTA 3 | 2 ATP 5 CMC 1.5 1.0 1.0 Brightener 0.3 0.2 0.3 0.3 0.3 rest Example 8 A surface cleaning agent for cleaning hard surfaces such as wall tiles, tiles, sinks and wash basins, walls, smooth floor coverings, household appliances such as crockery, cutlery, etc. was obtained by hot atomization of an aqueous mixture of the ingredients in the following composition: 30.0% by weight ABS, 3.0% by weight KA-ÄO sulfate, 1.0% by weight coconut fatty acid diethanolamide, 3.0% by weight % Sodium tripolyphosphate, 3.0% by weight tetrasodium tetrahydrofuran tetracarbonate, 3.0% by weight Na2B4O7. 10 H2O, 1.0% by weight boric acid, the remainder sodium sulfate and water.

Claims (1)

P a t e n t a n s p r ü c h e 1. Washing and cleaning agents, containing water-soluble salts of tetrahydrofuran-tetracarboxylic acid in combination with at least another inorganic or organic, cleaning or bleaching effect Substance, 2. detergent and cleaning agent according to claim 1, characterized by the following general recipe, based on the anhydrous substances: 0 - 80, preferably 5 - 40% by weight of a surfactant component, consisting of anicnic and / or zwitterionic and optionally non-ionic surfactants, 100-20> preferably 95 - 60% by weight of inorganic and / or organic builders, some of which in particular from 5 to 90% by weight from the water-soluble salts of tetrahydrofuran-tetracarboxylic acid exist, and O - 30, preferably 1 - 25% by weight of other common constituents of Detergents and cleaning agents. 5. Means according to claim 1 and 2, characterized by the use the alkali salts of tetrahydrofuran-tetracarboxylic acid. 4. Means according to claim 1-3, characterized in that the structural substances from 90-5, preferably 90-40% by weight of water-soluble salts of tetrahydrofuran-tetracarboxylic acid, and 10-95, preferably 10-60% by weight of other customary builder substances. 5. Means according to claim 1-4, characterized in that it is with those present in combination with the salts of tetrahydrofuran-tetracarboxylic acid Builder substances around nitrogen uld / or phosphorus-free inorganic or organic Substances. 6. Means according to claim 1-5, characterized in that the surfactant component according to claim 3 to at least 50 wt .-% of anionic surfactants from the sulfonate and / or sulfate type and / or soap. 7. Means according to claim 1-6, characterized in that the amount of the structural substances according to claim 3 preferably 0.5 * to 7 times and in particular 1 to 5 times the total surfactants. 8. powder detergent according to claim 1 - 7, characterized in that that the composition is generally in the range of the following recipe: 5 80, preferably 8-40% by weight of a surfactant component, consisting of at least 50% by weight of anionic surfactants from the group of alkyl benzosulfonates, alkanesulfonates, Fatty acid ester sulfonates, olefin sulfonates, fatty alcohol or fatty alcohol glycol ether sulfates and the soaps, and optionally nonionic and / or the zwitterionic surfactants as well as t; possibly containing one or more of the following substances: 0 - 10, preferably 0.5-8% by weight foam stabilizers, 0-10, preferably 0.5- 8% by weight non-surfactant foam inhibitors, 20 - 95, preferably 60 - 92% by weight Builder substances, some of which, in particular 5 to 90% by weight, consist of water-soluble Salts of tetrahydrofuran-tetracarboxylic acid, in particular the alkali metal salts, and 0-30, preferably 1-15% by weight of other detergent ingredients such as e.g. Bleach components, dirt carriers, fabric softeners, antimicrobials, enzymes, brighteners, Dyes and fragrances, water. G, bleaching detergent according to claim 1 - 8, characterized in that that it contains a bleaching component, including any stabilizers present and / or activators 2-40, preferably 7-35% by weight of the total detergent matters. 10. Low-foaming detergent according to claims 1-9, characterized in that that there are tensiles of sulfonate and / or sulfattyj) and S soap in proportion ) 0: 1 to 1: 5, preferably 20: 1 to 1: 2 and optionally a non-surfactant Contains foam inhibitor. 11. Low-foaming detergent according to claim 10, characterized in that that there are soaps of saturated fatty acids with 20-24, preferably 20-22 carbon atoms, the amount of which is at least 5% by weight, preferably at least 10% by weight of the total amount of soap constitutes, contains.