DE1963897A1 - Detergent contng perborate - Google Patents

Abstract

Pulverulent to granular, perborate-contng. detergent contains 5-40, pref. 7-35% by wt. of non-ionic and opt. anionic or amphoteric tensides, 7.5-50, pref. 15-30% by wt. of a perborate, 15-80, pref. 25-70% by wt. builder compound for complex formation with Ca ions, and opt. other alkaline reacting builder compound, 0-10, pref. 1-5% by wt. detergent-inactive constituents, e.g. Na2SO4 and/or NaCl and/or bound water including the water of hydration of crystallisation.

Description

"Powdered to granular detergent containing perborate as well as Method of its manufacture "Within the last twenty years the composition of the detergents put on the market have been continuously improved to such an extent that the detergent application concentrations recommended by the detergent manufacturers could be reduced considerably. During use concentrations 20 to 15 years ago of around 10 g / l detergent were considered normal, these are application concentrations today from about 6 - 3 g / l detergent for most soiling that occurs in practice sufficient.

The invention relates to powdery to granular, perborate-containing Detergents that are characterized by a particularly low content of inactive ingredients, irisparticularly to bound water, and therefore also to those mentioned above low application concentrations add more detergent substance to the wash liquor bring than the previous commercial detergents.

Those according to the invention, present as powders, granules or agglomerates Detergents contain surfactants, builders that bind calcium complexes and perborate as well as other common detergent additives. The detergents according to the invention are characterized by the following features: They contain: 5 - 40, preferably 7-35% by weight nonionic and optionally anionic or zwitterionic Surfactants, the amount of these anionic and / or zwitterionic surfactants being less than 50% by weight and preferably less than 35% by weight of the total surfactants present make up 7.5-50, preferably 15-30% by weight of a perborate, its water of crystallization content below that of perborate tetrahydrate, preferably perborate monohydrate, 15 - 80, preferably 25-70% by weight capable of complexing with calcium ions, as well as possibly other alkaline-reacting structural substances and possibly other, Active ingredients usually only present in small quantities in detergents, O - 10, preferably 1-5% by weight of detergent-active ingredients, such as sodium sulfate and / or sodium chloride and / or bound water, including that in the above-mentioned Eomponenten existing hydrate or crystal water.

These detergents represent a mixture of at least two different ones Powder constituents of the following composition: the low-water perborate, at least one powder component which contains the above-mentioned complexing agents as well as possibly other powder ingredients that contain other detergent ingredients can be, whereby the nonionics are at least partially on the surface, possibly partly also located inside the powder particles. Containing the nonionics Powder particles can be one or more of those present in the detergent belong to different powder components.

In the simplest case, the detergents according to the invention consist of a mixture of complexing agents, the poor rectorate and nonionics in the above specified quantities. Such mixtures can be obtained, for example, by using the Nonionic at any point in the manufacturing process on one of the two powdery ingredients to be mixed or sprayed onto both. Man has the option, for example, of one of the two powder components first spray with the nonionic and then spray the product with the other powder ingredient to mix; but you can also use the nonionic while mixing the two Spray powder components onto these or onto the finished mixture.

Both inorganic hydrolyzable compounds can be used as complexing agents as well as the organic non-hydrolyzable complexing agents alone or in combination use with each other. Suitable for the production of the detergents according to the invention particularly voluminous tripolyphosphate with a bulk density of about 0.1 - 0.7, preferably 0.2-0.6 g / ml.

Such voluminous tripolyphosphates are capable of larger amounts of oily or pasty nonionics without sticky powder to deliver.

Most detergents on the market do not exist only from builder substances, perborate and surfactant; they also contain other Active ingredients that in spite of; their relatively small amounts used for the application technology Properties of the detergent are important. These include e.g. foam stabilizers, Foam inhibitors, stabilizers and activators for per compounds, dirt carriers, antimicrobial substances, brighteners, enzymes etc .. These active ingredients can of course be mixed as a powder with the ingredients present in larger quantities; it it is recommended, however, that this is usually only a minor one Quantities to be incorporated Active ingredients together with other detergent ingredients present in larger quantities via an aqueous solution or slurry by hot drying into a fine powder to convict. This fine powder is then used at any point above added ingredients mentioned. Of course, this only applies to such Substances that are not decomposed by the water and / or the hot drying or the effectiveness of which is not impaired in any other way.

For the other detergent ingredients to be incorporated in larger quantities it can be anionic surfactants and / or builders. Unless that Detergent containing anionic surfactants are preferably one component of the hot-dried powder. Nonionic surfactants can also be added, as long as they affect the properties of the powder based on their physical properties and the amount used the other components of the heat-dried product not in an undesirable manner affect.

Non-complexing structural substances can also be incorporated into the heat-dried powder and / or complexing agents are incorporated, in particular organic non-hydrolyzable Complexing agents. Hydrolyzable complexing agents, such as æ, B. Metaphosphates and in particular Tripolyphosphate should only be present in limited quantities in this powder component be.

In such a case, these detergents exhibit a mixture powder component B described below and at least one of those described below Powder ingredients A or C are: A) one obtained by hot drying an aqueous solution or slurry of such detergent ingredients, which by the hot drying not decomposed or their effect is impaired, powder component obtained, any anionic and / or zwitterionic and possibly nonionic ones present Surfactants, as well as possibly non-complexing structural substances and non-hydrolyzable Complexing agents, but not more than 20, preferably not more than 10% by weight of hydrolyzable Complexing agents such as metaphosphates and. in particular tripolyphosphate, contains, B) the low-water perborate, C) and possibly other detergent additives, especially any hydrolyzable complexing agents present, in particular tripolyphosphate.

The term t, powder ingredient1, has been used for the sake of simplicity used and intended nothing about the grain size and physical nature of the individual particles testify; it can therefore be fine or coarse powder Act granulates or agglomerates.

In addition to the nonionics, the detergents according to the invention also contain Anionics, powder component A can have the following composition: 5 - 70, preferably 7 - 60% by weight of surfactants (as above), although any surfactants may be present nonionic surfactants at most 35% by weight, preferably at most 30% by weight of this Make up powder component, 1 - 20, preferably 5 - 15 wt .-% detergent-active ingredients, 10-96, preferably 25-88% by weight of other common ingredients of heat-dried Detergents, although hydrolyzable complexing agents may be present (preferably tripolyphosphate, possibly also others, such as metaphosphates) are present in amounts of at most 20, preferably at most 10, weight percent.

In the context of the invention, non-detergent ingredients, i. E. especially for a detergent to be used at temperatures above 60 0C, water, Check Sodium Sulphate and Sodium Chloride.

Therefore, the levels of powder component A must be detergent-inactive Components or the proportion of powder component A in the total detergent so be coordinated that the above given for the entire detergent Limit values are not exceeded. The quantities of the permissible in powder component A. Inactive detergent ingredients can therefore fluctuate within a certain range, and occasionally exceed the maximum value of 20% by weight given above, provided that the amount of powder component A in the total detergent is correspondingly low is.

As other common ingredients in hot-dried detergents the following substances come into question; the quantities given relate to the Powder component A: O - 70% by weight non-hydrolyzable, preferably organic Complexing agent, 0-50, preferably 5-40% by weight for complexing with calcium ions practically incapable alkaline-reacting builder substances, O - 35, preferably 1.5 - 28% by weight organic neutral salts, water-insoluble stabilizers for per compounds, Dirt carriers, brighteners, etc.

Machine washable heavy duty detergents are of particular interest Foaming capacity above all in the temperature range 60 - 100, preferably 70 - 100 ° C, is steamed.

This foam suppression is achieved with nonionics through combinations from foaming and non-foaming nonionics, or by combining the foaming ones Nonionics with foam-suppressing soaps and / or non-surfactant-like foam inhibitors. The foam-suppressing soaps and non-surfactant-like foam inhibitors are also included suitable, the foaming capacity of possibly existing anionics, especially those from Sulfonate and / or sulfate type.

The surfactant component of such detergents is then often as follows composed, but not all components are present in powder component A. needed; this applies above all to the nonionic surfactants and the non-surfactant-like surfactants Foam inhibitors: 50 - 100, preferably 55 - 100% by weight nonionic surfactants, 0-50, preferably 0-45% by weight of anionic and / or zwitterionic surfactants, O - 8, preferably 0.5 - 5% by weight of non-surfactant foam inhibitors, the Foaming capacity of the surfactant component by selecting suitable ones in their foaming capacity inhibiting surfactants and / or due to the presence of non-surfactant foam inhibitors is muted.

The powder component A can practically completely from the anionic and optionally the nonionic surfactants. But there are some surfactants If the powder properties are inadequate, it is advisable to use the powder properties of powder component A by incorporating non-surfactant, non-hygroscopic Improve substances au.

In this sense, for example, acts in many surfactants from the sulfonate or Type of sulfate present sodium sulfate. The later ones are also suitable for this purpose still to be enumerated salts of organic, non-surfactant-like carboxylic acids or Sulphonic acids, e.g. alkali salts of toluenesulphonic acid or of sulphocarboxylic acids. Also non-hygroscopic complexing agents and / or practically not for complexing Capable alkaline builders can alter the powder properties of the ingredient A improve. Tripolyphosphate and its amount are also suitable for this purpose but for the reasons to be explained below do not exceed 20% by weight, preferably 10% by weight should.

Tripolyphosphate and non-hydrolyzable organic complexing agents can be present in powder component A at the same time. If only it matters To bind traces of heavy metals present in the aqueous mixture and thus e.g. the brighteners during the manufacturing process, especially during the hot drying process To protect decomposition, additions of 0.1-10% by weight of organic complexing agents are sufficient, based on the powder component A.

Should the non-hydrolyzable complexing agents also serve to To act as a complex-forming structural substance in the washing process, the amount thereof can up to 70 wt .-%, preferably in the range of 15-60 wt .-%, -96, Some of the nonionics present in the detergents according to the invention can be used in the powder constituent A are introduced, provided that it has its powder properties not or only insignificantly deteriorate. As many nonionics also come in anhydrous If the condition is oily to pasty, it is best to use only part of it or to incorporate no nonionic at all into powder component A and the rest or all of the nonionics on the detergent or one of its powder components spray on.

The powder component A can also contain zwitterionic surfactants; but you can also combine them with the Nonionics or separately from them on one Spray powder component or onto finished detergent, especially if they melt at temperatures up to 1500 C.

In the above framework formulation for the surfactant component are also the non-surfactant-like foam inhibitors listed because they during the washing process on the Surfactants act. These are foam inhibitors in the manufacture of detergents expediently not in the aqueous formulation of the powder component to be dried A incorporated, but on one of the powder components or on the entire detergent sprayed on; however, it is not recommended to use them with the nonionics or zwitterionic surfactants, but to be sprayed on separately from these.

Of the ones already mentioned above, mostly to be used only in smaller quantities Detergent constituents are worked into the powder constituent A, preferably the Dirt carriers, brighteners, corrosion inhibitors and possibly antimicrobial substances while detergent ingredients (e.g. alkaline Builder substances and / or non-hydrolyzable complexing agents) as desired 9m powder component A and / or in powder component C can be present.

The powder component A is carried out according to methods known per se Hot drying of an aqueous batch of its components made. This is e.g. possible on heated drums; preferably bring the finely atomized, pasty Approach in cocurrent or countercurrent with hot air in contact, so that an atomized product is obtained with the water content specified above.

The vast majority of those containing tripolyphosphate currently on the market Detergent was made by spray drying a slurry of anhydrous Tripolyphosphate produced in an aqueous solution of the surfactants. There was the Hydratability of the anhydrous tripolyphosphate gives rise to difficulties. As the tripolyphosphate gradually dissolves into the Converts hexahydrate, the viscosity of the aqueous approach increases, which thereby is getting harder and harder to process.

In addition, some of the tripolyphosphate closed during hot drying Pyro- and orthophosphate hydrolyzed, i.e. to phosphates, which are only slightly or no longer had complex-forming properties.

So there was only part of the tripolyphosphate used available as a complexing agent during the washing process.

This hydrolytic cleavage of the tripolyphosphate can of course also in the production of powder component A of the detergents according to the invention occur when the aqueous approach to be atomized contains tripolyphosphate. Here but according to claim the amount of the powder component A contained in the spray-dried powder component Tripolyphosphates limited to a maximum of 20 and preferably a maximum of 10 wt .-% is, the by-products formed by tripolyphosphate decomposition represent a so small a part of the overall recipe that they are practically negligible fall. Quite apart from that, hydrolytic tripolyphosphate decomposition can be used by incorporating alkaline substances, such as small amounts push back on alkali solutions, alkali carbonates or alkali ortho- or metasilicates.

The detergents according to the invention can also be used in this way produce that one during the hot atomization of an aqueous approach in which Anionic surfactants may be present in the spray tower dry tripolyphosphate dusted, advantageously so that the spray cone of the aqueous approach with the dusted tripolyphosphate meets. It becomes such a big part of the not yet dried or only incompletely dried particles of the aqueous mixture with the particles of the dusted tripolyphosphate agglomerated, and the other Drying takes place without significant tripolyphosphate decomposition.

In the product thus obtained, the particles are the powder components A and C at least partially agglomerated; they become the in the usual way Detergents according to the invention processed further.

The detergents according to the invention contain as a powder component B low-water perborate, preferably the so-called sodium perborate monohydrate " its composition of the formula NaB02. H202 corresponds. This formula is merely to be regarded as a molecular formula; it is not intended to make any statements about the structure of this Make connection. However, not all of the perborate is needed in this water-poor one Form to be present; it is sufficient if the water content of the perborate component is lower is as the formula NaB02. H202. 2 H20, preferably if it is lower is as the formula NaB02. H202. 1 corresponds to H20. It remains to be seen whether the last specified hydrate stages actually exist; it can also be mixtures of sodium perborate tetrahydrate and sodium perborate monohydrate. For the sake of simplicity, all of these low-water perborates are referred to below as "Perborate".

Unless the two powder components A and B are all substances that are to be incorporated into the detergent, bring the rest Substances as a separate powder component C. This is especially true for that Tripolyphosphate; However, other complex images can also be used, or practically none as Alkaline structural substances that act as complexing agents are introduced as powder component C. will. It may well happen that the same substance is used in both the spray-dried Powder component A as well as powder component C is present.

If nonionics are incorporated into the detergents according to the invention should be, especially nonionics of oily or pasty consistency, It is best to do this while moving on one of the powder ingredients to one Mixture of two powder components or the mixture of all powder components to be sprayed on, the nonionics also during the mixing of the powder components can be sprayed on.

Other detergent ingredients can also be used in the same way bring in, especially if they are only available in small quantities; For this do not include surfactant foam inhibitors or antimicrobial additives, for example at least if they melt when heated to temperatures of up to 1500C.

This is followed by a list of the substances sorted by substance class various products to be incorporated into the detergents according to the invention.

Contain the anionic, zwitterionic or nonionic surfactants in the molecule at least one hydrophobic radical of mostly 8-26, preferably 10-22 and in particular 10-18 carbon atoms and at least one anionic, nonionic or zwitterionic water-solubilizing group.

The preferably saturated hydrophobic residue is usually more aliphatic, possibly also of an alicyclic nature; he can work with the water-solubilizing groups directly or be connected via intermediate links. As intermediate links come z. B.

Benzene rings, carboxylic acid ester or carbonamide groups, ether or ester-like bonded residues of polyhydric alcohols, such as. B. that of ethylene glycol, of propylene glycol, glycerine or corresponding polyether residues.

The hydrophobic group is preferably an aliphatic hydrocarbon group with about 10-18, preferably 12-18 carbon atoms, but depending on the nature of the respective surfactant, deviations from this preferred range of numbers are possible.

To the nonionic surfactants, here for the sake of simplicity as "Nonimics" products, whose water solubility is due to the presence of polyether chains, Amine oxide, sulfoxide or phosphine oxide groups, alkylolamide groups as well as whole generally owe to an accumulation of hydroxyl groups.

Of particular practical interest are those caused by the addition of Ethylene oxide and / or glycide on fatty alcohols, alkylphenols, fatty acids, fatty amines, Fatty acid or sulfonic acid amides available products, these Nonionios 4 - 100> preferably 6 - 40 and in particular 8 - 20 atomic residues. all ethylene glycol ether residues may contain per molecule.

In addition, propylene- or butylene glycol ether residues or polyether chains may be present. 4V- Farther are among the Nonionios under the trade names fPluronics "or" Tetronics " well-known products. They are obtained from water-insoluble polypropylene glycols or from water-insoluble propoxylated lower, 1 - 8, preferably 3 - 6 carbon atoms containing aliphatic alcohols or from water-insoluble propoxylated Alkylenediamines. These water-insoluble (i.e., hydrophobic) propylene oxide derivatives are converted into the nonionios mentioned by athoxylating until they are water-soluble. Finally, nonionics are also those known as "Ucon fluids", some of which are still water-soluble Reaction products of the abovementioned aliphatic alcohols with propylene oxide can be used.

1The nonionics also include fatty acid or sulfonic acid alkylolamides, which z. B; from mono- or diethanolamine, from dihydroxypropylamine or others Polyhydroxyalkylamines, e.g. B. derive the Glycaminen. You can get through amides from higher primary or secondary alkylamines and polyhydroxycarboxylic acids.

The capillary-active amine oxides include, for. B. those of higher tertiary, a hydrophobic alkyl radical and two shorter, up to 4 carbon atoms each containing alkyl and / or products derived from amines containing alkyl radicals.

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 iodine - numbers not exceeding 30 and preferably less than 10 have.

Of the synthetic anionic surfactants, the sulfonates have and sulfates of particular practical importance.ti To the sulfonates include, for example, the alkylarylsulfonates, in particular the alkylbenzenesulfonates, which one u. from preferably straight-chain aliphatic hydrocarbons with 9-15, in particular 10-14, carbon atoms by chlorinating and alkylating benzene or from corresponding terminal or internal olefins by alkylating benzene and sulfonating the obtained alkylbenzenes. They are also aliphatic Sulfonates of interest as they + uz. B. from preferably saturated, 8-18 and hydrocarbons containing preferably 12-18 carbon atoms in the molecule by sulfochlorination with sulfur dioxide and chlorine or sulfoxidation with sulfur dioxide and oxygen and converting the products obtained thereby into the sulfonates are accessible. as aliphatic sulfonates are also alkene sulfonates, hydroxyalkane sulfonates and Mixtures containing disulfonates useful, which one z. B. from terminal or middle-class C8 18 and preferably C12-18 olefins by sulfonation with sulfur trioxide and acidic or alkali see hydrolysis of the sulfonation products. In the case of those produced in this way aliphatic sulfonates, the sulfonate group is often on a secondary Carbon atom; but you can also react terminal olefins with bisulfite Use the sulfonates obtained with a terminal sulfonate group.

The sulfonates to be used according to the invention also include Salts, preferably dialkali salts, of aL-sulfofat. acids and salts of esters of these acids with mono- or polyvalent, 1 - 4 and preferably 1 - 2 carbon atoms Alcohols.

Further useful sulfonates are salts of fatty acid esters of oxethanesulfonic acid or Dioxypropanesulfonsäure, the salts of the fatty alcohol esters of lower, 1 - Aliphatic or aromatic sulfomono- or dicarboxylic acids containing 8 carbon atoms, the alkyl glyceryl ithersulfonates and the salts of the amide-like condensation products of fatty acids or sulfonic acids with aminoethanesulfonic acid. 4th as Surfactants of the sulfate type are fatty alcohol sulfates, in particular from coconut fatty alcohols, Tallow fatty alcohols or made from oleyl alcohol. Also from final or internal C8-18 olefins are useful sulfonation products of the sulfate type available. Farther This group of surfactants includes sulfated fatty acid alkylolamides or fat -acid monoglycerides and sulfated alkoxylation products of alkylphenols (C8 l5-alkyl), fatty alcohols, fatty acid amides or fatty acid alkylolamides, which in the molecule 0.5-20, preferably 1-8 and especially 2-4 ethylene and / or propylene glycol residues may contain.

Suitable anionic surfactants of the carboxylate type are, for. B. 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. B. with glycocolla, sarcosine or with protein hydrolysates.

Zwitterionic surfactants contain both acidic and basic hydrophilic groups. The acidic groups include carboxyl, sulfonic acid, Half-ester of semi-acidic acid, phosphonic acid and partial phosphoric acid groups. As a basic Groups come primary, secondary, tertiary and quaternary ammonium groupings in question. Zwitterionic compounds with quaternary ammonium groups belong to the Type of betaine.

Carboxy, sulphate and sulphonate betaines are well tolerated of particular practical interest with other surfactants. Suitable sulfobetaines obtained for example, by reacting tertiary, at least one hydrophobic alkyl radical containing amines with sultones, for example propane or butane sultone. Appropriate Carboxybetaine receives # one by implementing the said tertiary Amines with chloroacetic acid, its salts or with chloroacetic acid esters and columns the ester bond.

The foaming power of the surfactants can be determined by combining suitable types of surfactants increase or decrease, as well as by adding non-surfactant organic substances Substances can be changed.

Foam stabilizers are particularly suitable for surfactants from the sulfonate or Sulrate-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.

Products with reduced foaming power are mainly intended for use Determined in washing machines and dishwashers, sometimes with limited foam absorption sufficient, while in other cases a stronger foam suppression is desirable can. Products which are in the medium temperature range are of particular practical importance up to about 650C, however, when changing to higher temperatures (70 - 100 ° C) develop less and less foam.

A reduced foaming capacity can be achieved by incorporating Soaps made from saturated fatty acid mixtures with 20 - 26, preferably 20 - 22 carbon atoms, the amount of which is 5 - 10% by weight of the total in the surfactant combination existing soap content can make a stronger foam dampening> above all Things in the higher temperature range, achieved.

The foaming power of the surfactants can, however, also be increased by additives known, non-surfactant foam inhibitors decrease. These include optionally chlorine-containing N-alkylated aminotriazines, which can be obtained by reacting 1 Moles of cyanuric acid chloride with 2 - 3 moles of a mono- and / or dialkylamine with 6 - 20, preferably contains 8-18 carbon atoms in the alkyl radical. aminotriazine resp. Melamine derivatives containing propylene glycol or butylene glycol ether chains, where the molecule may contain 10-100 such glycol residues. One obtains such Compounds, for example, by attaching appropriate amounts of propylene and / or Butylene oxide on aminotriazines, especially on melamine. The reaction products, for example, are preferred of 1 mole of melamine with at least 20 moles of propylene oxide or at least 10 moles of butylene oxide usable. Products that you go through have proven to be particularly effective Addition of 5-10 moles of propylene oxide to 1 mole of melamine and further addition of 10-50 moles of butylene oxide are obtained from this propylene oxide derivative.

Also other, non-surfactant, water-insoluble organic compounds, such as paraffins or haloparaffins with melting points below 1000C, aliphatic Cl8 to C40 ketones as well as aliphatic carboxylic acid esters, which in the acid or in the alcohol residue, possibly also contain at least 18 carbon atoms in each of these two radicals (e.g. triglycerides or fatty acid fatty alcohol esters), especially in the presence of soaps, use as foam inhibitors.

The non-surfactant foam inhibitors are often only at temperatures fully effective, in which they are in the liquid state, so that the foam behavior control the products in a similar manner by choosing suitable foam inhibitors lets like by the choice of soaps made from fatty acids of suitable chain lengths.

If you combine foam stabilizers with temperature-dependent foam inhibitors, so you get good at lower temperatures, as you approach the cooking temperature increasingly weaker foaming products.

As particularly low-foaming nonionics, which can be used both alone and also in combination with anionic, zwitterionic and nonionic surfactants can be used and reduce the foaming power of better foaming surfactants, Addition products of propylene oxide to the capillary-active ones described above are suitable Polyethylene glycol ether as well as the Pluronic, Tetronic- and Ucon fluid types.

Weakly acidic, neutral and alkaline substances are suitable as structural substances reacting inorganic 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 or silicates of the Alkalis, furthermore mono-, di- or trialkali orthophosphates, di- or tetraalkali pyrophosphates, as complexing agents known metaphosphates, alkali sulfates and the alkali salts of organic, non-capillary-active sulfonic acids, carboxylic acids containing 1 - 8 carbon atoms and sulfocarboxylic acids. These include, for example, water-soluble salts of the 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 useful in particular polymers 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 Storren, such as with ethylene, propylene, acrylic acid, methacrylic acid, crotonic acid, 3-butenecarboxylic acid, 3-methyl -) - butenecarboxylic acid and with vinyl methyl ether, vinyl acetate, Isobutylene, acrylamide and styrene are useful.

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

They can be completely or partially replaced by organic complexing agents. + 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, although combinations of different complexing agents can also be used. The other known complexing agents also include di- and polyphosphonic acids of the following constitutions: where R is alkyl and R '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 -OH, -NH2 or -NXR. The following compounds are particularly suitable for practical use: Methylenuiphosphonic acid, 1-hydroxyethane-1,1-disphosphonic acid, 1-aminoethane-1,1-diphosphonic acid, amino-tri- (methylenephosphonic acid), methylamino- or ethylamino-di- (methylenephosphonic acid) and xthylenediamine-tetra- (methylenephosphonic acid). All these complexing agents can be present as free acids, preferably as alkali salts. The preparations according to the invention can also contain dirt carriers that keep the dirt detached from the fibers suspended in the liquor and thus prevent graying. Water-soluble colloids of mostly organic nature are suitable for this, such as, for example, the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acid sulfuric acid esters of cellulose or starch. Water-soluble polyamides containing acidic groups are also suitable for this purpose. It is also possible to use soluble starch preparations and other starch products than those mentioned above, such as degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone can also be used.

The constituents of the 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 value æ 7 - 9.5), during soaking, Prewash and cooking detergents, more alkaline (pH value, 9.5 - 12, preferably 10 - 11.5) are set.

The detergents according to the invention can also contain enzymes; these are then present as powder component C or as part of it.

The enzymes to be used are usually a mixture of different ones of enzymatic active ingredients. Depending on their effect, they are used as proteases, carbohydrases, Esterases1 lipases, oxidoreductases, catalases, peroxidases, ureases, isomerases, Lyases, transferases, desmolases or nucleases called.

Those from bacterial strains or fungi are of particular interest enzymatic agents obtained such as Bacillus subtilis and Streptomyces griseus, especially proteases or amylases. Preparations made from Bacillus subtilis have the advantage over others that they have the advantage over alkali, per compounds and anionic washing active substances relatively stable and at temperatures up to to 70 0C are still effective.

Enzyme preparations are made by the manufacturers in the form of aqueous solutions of the active ingredients or with the addition of diluents in the form of a powder brought. Sodium sulfate, sodium chloride, alkali ortho, Pyro- or polyphosphates, especially tripolyphosphate. Often you bring them still moist enzyme preparations with calcined salts, which then if necessary under If the particles present agglomerate to form larger particles, the water of crystallization present and bind the enzymatic agent.

If the enzymatic active ingredients are in the form of a dry powder, then liquid, paste-like and possibly also solid, non-ionic, preferably capillary-active organic compounds, in particular those described above Use nonionios to add the enzymes to the powder of detergents or washing aids to tie. A mixture is preferably sprayed for this purpose from the respective product and the enzymatic active ingredient with the above non-ionic substances, or the enzyme preparation is dispersed in the said non-ionic substance and combines this dispersion with the other components of the product. If these remaining components of the product are solids, can also the dispersion of the enzymatic active ingredients in the nonionic component Spray onto the remaining solid components.

The enzymes, or combinations of enzymes with different effects, are generally used in amounts such that the finished products have protease activities from 50-5,000, preferably 100-2,500 LVU / g and / or amylase activities of 20 5,000, preferably 50-2,000 SKBE / g and / or lipase activities of 2-1 000, preferably 5-500 IU / g.

These details about the enzyme activities result from the activities of those enzyme preparations which on the day of registration for use in the detergent sector appear justifiable from an economic point of view. From the chemical-technical From the standpoint, the enzyme activities of the preparations can be increased as required, so that the activities with proteases and amylases e.g. up to 5 times, with lipases e.g. can be increased up to 10 times the maximum values given above. Therefore, preparations with high activities should also be available in the future economically suitable for use in the detergent sector appear, the enzyme activities can be increased as needed.

Regarding the determination of the enzyme activities, see the following references referenced Determination of the activity of proteases according to Löhlein-Volhard A. Künzel : "Gerbereichemisches Taschenbuch", 6th edition, Dresden and Leipzig 1955; determination the activity of amylases J. Wohlgemuth: "Biochemische Zeitschrift1 ', Volume 9, (1908), pages 1 - 9, and R.M. Sandstedt, E. Kneen and M.J. Blish "Cereal Chemistry", Volume 16 (1939), pages 712-723; Determination of the activity of the lipases R. Willstätter, E. Waldschmidt - Leitz and Fr.

Memmen: "Hoppe-Seyler's Journal for Physiological Chemistry", Volume 125 (1923), pp. 110-117; R. Boissonas: "Helvetica Chimica Acta", Volume 31 (1948), pages 1571-1576. # The brighteners that can be used are mostly, if not exclusively, derivatives of diaminostilbene sulfonic acid, the Diarylpyrazolines and the aminocoumarins.

Compounds according to formula I are examples of brighteners from the class of the diaminostilbene sulfonic acid derivatives In the formula, R1 and R2 can denote halogen atoms, alkoxyl groups, the amino group or radicals of aliphatic, aromatic or heterocyclic, primary or secondary amines and radicals of aminosulfonic acids, aliphatic radicals present in the above groups preferably 1 - 4 and in particular 2 - 4 C- Contain atoms, while the heterocyclic ring systems are usually 5- or 6-membered rings. The radicals of aniline, anthranilic acid or anilinesulfonic acid are preferred as aromatic amines. Lighteners derived from diaminostilbene sulfonic acid are mostly used as cotton lighteners. The following products derived from the formula I are commercially available, where R1 represents the radical -NH-C6H5 and R2 can represent the following radicals -NH2, -NH-CH3, -NH-CH2-CH2OH, -NH-CH2-CH2 -0-CHa, -NH-CH2-CH2-CH2-O-CH3, CH3-N'-0H2-CH20H, -N = (CH2-CH2OH) 2, Morpholino-1 -NH-C6H5, -NH-C6H4- SOaH, -OCH. 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 = -NH-C6H5.

One of the tree whiteners of the diaminostilbene sulfonic acid type also the compound 4,4'-bis - (- 4-phenyl-vicinaltriazolyl-2 -) - stilbene disulfonic acid-2,2 '.

The polyamide brighteners, some of which have a certain affinity for cotton fibers, include diarylpyrazoline of the formulas II and III s 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, Arl and Ar2 aryl radicals, such as phenyl, diphenyl or naphthyl, which carry further substituents can, 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, NH2, -SO2-CH = CH2 and -COO-CH2-CH2-O-CH3, while the radical R8 can represent all of them Means a chlorine atom. 9-cyano-anthracene is also commercially available as a polyamide brightener.

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- (benzimidazolyl-2 ') - 2- (N-hydroxyethyl-benzimidazolyl-2') - ethylene are also used as polyamide brighteners and 1-N-ethyl-3-phenyl-7-diethylamino-carbostyril can be used.

As brighteners for polyester and polyamide fibers, the compounds are 2,5-di- (benzoxazolyl-2 ") -thiophene and 1,2-di- (5'-methyl-benzoxazolyl-21) -ethylene 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 organiscne Complexing agents in amounts of at least 0.1, preferably 0.2-1% by weight of the solids Incorporate products.

Examples The following examples describe compositions of some detergent according to the invention. The salty components it contains (salty Surfactants, other organic salts as well as inorganic salts) lie as sodium salts unless expressly stated otherwise. The related names or abbreviations mean: The nonionic alkylene oxide derivatives are characterized by the Starting hydroxyl compound and the molar amount of the starting hydroxyl compound per mole accumulated alkylene oxide marked. It means: 1, FA 1618 "or" FA 1822 " Fatty alcohol mixtures with 16-18 or 18-22 0 atoms, "KA" a mixture of fatty alcohols with 12 - 18 carbon atoms, made from a corresponding fraction of coconut fatty acids, 1, NP "nonylphenol and" OA technical oleyl alcohol. Provided two different alkylene oxides (ÄO = ethylene oxide, PO = propylene oxide) indicates the order of the alkylene oxides in the abbreviation also the order in which these substances was deposited during the manufacture of the nonionics. Accordingly, means for example "FA 1822 + 20 ÄO + 30 POt 'a product that is made by adding 20 moles of ethylene oxide to 1 mol of a fatty alcohol mixture with 18-22 carbon atoms and reacting the resultant Addition product with 30 moles of propylene oxide was obtained.

Incidentally, "soap" means a soap made from a mixture of fatty acids the iodine number 4 of the following chain length distribution: C12 20% by weight, C14 9% by weight, C16 4% by weight, C18 22% by weight, C20 8% by weight, C22 37% by weight.

0M0 "the salt of carboxymethyl cellulose," NTA "or" EDTA "the salts the nitrilotriacetic acid or ethylenediaminetetraacetic acid, "phosphonate" the salt 1-hydroxyethane-1,1-diphosphonic acid; this salt can do with similar success the salts of 1-aminoethane-1,1-diphosphonic acid, amino-tri- (methylenephosphonic acid), methylamino or xthylamino-di (methylenephosphonic acid) and xthylenediamine tetra- (methylenephosphonic acid) are replaced.

"Water glass" is the compound Na2O. 3.3 SiO2.

A mixture of about 45% of a di (alkylamino) monochlorotriazine was used as a foam inhibitor and about 55% of an N-N'-N1, -trialkylmelamine. In all of these triazine derivatives the alkyl radicals were present as mixtures of homologues with 8-18 carbon atoms. With something similar The monochlorotriazine derivative or the trialkylmelamine could also be used successfully.

To prepare the detergent according to Example 1, the mixture was the nonionics sprayed onto a tripolyphosphate with a bulk density of 0.3 g / ml; then the perborate was mixed in.

To produce the detergents according to Examples 2-6, first the substances contained in powder component A in the usual way with water processed a paste-like approach, which after hot drying in the atomization tower provided a powder of the specified composition. After mixing this powder with a tripolyphosphate with a bulk weight of 0.5 g / ml, those mentioned under D. Quantities of nonionics sprayed on. If the detergents contain a foam inhibitor, this was applied in finest distribution to the perborate before it was used with the other ingredients of the detergent was mixed.

The quantities in the following tables are percentages by weight, the figures not in brackets refer to the total detergent, the numbers in brackets refer to the respective powder component.

The detergents can also be prepared in such a way that in the spray drying of the aqueous batch of powder component A the Dust tripolyphosphate into the spray cone of the aqueous mixture; you get so the powder ingredients A and C as one product, the powder particles A and C are connected to a large extent to form agglomerates.

As a brightener can be used depending on the intended use of the detergent any common substances that have an affinity for cotton, for polyamides or for polyesters. You can also use several such brighteners combine in a detergent. In addition, brighteners are also of mixed affinity known, i.e. those that attach to both cotton and synthetic fibers.

A suitable cotton whitening agent is, for example, a compound according to page 27, formula I in which R1 is aniline radicals and R2 is morpholine radicals. A compound according to this formula in which all radicals R1 and R2 represent aniline radicals is suitable as a brightener of mixed affinity. A suitable polyamide brightener is a compound according to page 28, formula III, where R7 represents the radical —SO2-NH2 and R8 represents an oil atom, while the compound 2,5-di- (benzoxazolyl-2t) -thiophene can be incorporated as a polyester brightener . Part of the example no .: Detergent 1 2 3 A CMC - - 1.7 (4.86) 1.4 (5.26) EDTA - - - - 0.4 (1.50) NTA - - - - 8.0 (30.08) Phosphonate ~ ~ 3.0 (8.57) 7.5 (28.20) Water glass - - 6.0 (17.15) 4.2 (15.79) Na2CO3 - - 15.8 (45.14) - - MgSiO3 - - 3.0 (8.57) 3.0 (11.28) Na2SO4 - - 1.3 (3.71) 0.2 (0.75) Brighter - - 0.2 (0.57) 0.2 (0.75) Water - - 4.0 (11.43) 1.7 (6.39) Total A 0.0 (0.00) 35.0 (100.00) 26.6 (100.00) B NaBO2. H2O2 35.0 (100.00) 20.0 (100.00) 18.2 (100.00) C Na5P3O10 45.0 (100.00) 35.0 (100.00) 35.2 (100.00) D KA + 9 ÄO + 12 PO - - 6.0 (33.33) 7.0 (35.00) FA 1618 + 20 ÄO - - - - 13.0 (65.00) NP + 9 X0 + 9 PO 8.0 (40.00) - - | - - NP + 20 A0 12.0 (60.00) 9.0 (66.67) - - Total D 20.0 (100.00 15.0 (100.00) 20.0 (100.00) Grand total | 100.0 | | 100.0 Part of the example no .: Detergent 4 5 6 A OA + 10 AO - - 8.0 (28.67) - - NP + 9.5 ÄO 9.0 (18.44) - - 7.0 (27.50) Soap 7.0 (14.34) 2.5 (8.96) 0.5 (197) CMC 1.3 (2.66) 1.7 (6.09) 1.0 (3.94 EDTA 0.2 (0.41) - - 1.6 (6.30) NTA 15.0 (30.75) - - 0.5 (1.97) Phosphonate 7.2 (14.75) 9.0 (32.26) 8.0 (31.50) Water glass 5.0 (10.25) 4.5 (16.13) 4.0 (15.75) MgSiO3 2.0 (4.10) - - - - Na2SO4 0.4 (0.82) 0.9 (3.23) o.8 (3.15) Brightener 0.3 (0.61) - - 0.4 (1.57) Water 1.4 (2.87) 1.3 (4.66) 1.6 (6.30) Total A 48.8 (100.00) 27.9 (100.00) 25.4 (100.00) B NaBO2. H2O2 15.6 (100.00) 20.5 (100.00) 19.8 (100.00) C Na5P3O10 35.6 (100.00) 49.4 (100.00) 51.5 (100.00 D Foam inhibitor - - 0.2 (9.09) 0.3 (9, Q9) KA + 5 ÄO + 13 PO - - 2.0 (90.91) - - FA 1822 + 20 ÄO + - - - - 3.0 - Total D - - 2.3 (100.00) 3.3 (100.00) Total 100.0 100.0 100.0

Claims (1)

Claims 1. Powdery to granular, containing perborate Detergent, characterized in that it contains: 5 - 40, preferably 7 - 35 % By weight of nonionic and optionally anionic or zwitterionic surfactants, the Amount of these anionic and / or zwitterionic surfactants less than 50% by weight and preferably make up less than 35 parts by weight of total surfactants, 7.5-50, preferably 15-30% by weight of a perborate, its water of crystallization content below that of perborate tetrahydrate, preferably perborate monohydrate, 15 - 80, preferably 25-70% by weight capable of forming complexes with calcium ions, and possibly other alkaline-reacting structural substances and possibly other, Active ingredients usually only present in small quantities in detergents, O - 10, preferably 1 - 5% by weight of detergent-active ingredients, such as sodium sulfate and / or sodium chloride and / or bound water, including that in the components mentioned above existing hydrate or crystal water, and that it is a mixture of at least represents two different powder components of the following nature: dem low-water perborate, at least one powder component of those mentioned above Contains complexing agents and possibly other powder components in which others Detergent ingredients may be included, being the Nonionics at least partially on the surface, possibly partly also inside the powder particles, located, a. Detergent according to Claim 1, characterized in that it is a mixture from the powder component B described below and at least one of those described below Powder ingredients A and C represent: A) one by hot drying an aqueous one Solution or slurry of such detergent constituents, which by the hot drying the powder component obtained is not decomposed or its effect is impaired, any anionic and / or zwitterionic and possibly nonionic ones present Surfactants, as well as possibly non-complexing structural substances and non-hydrolyzable Complexing agents, but not more than 20, preferably not more than 10% by weight of hydrolyzable Contains complexing agents, such as metaphosphates and especially tripolyphosphate, B) the low-water perborate, C) and possibly other detergent additives, especially any hydrolyzable complexing agents present, in particular tripolyphosphate, the nonionics at least partially on the surface, if appropriate but partly also in the interior of the powder particles, in particular in the interior of the particles of powder component A. 3. Detergent according to claim 1 and 2, characterized in that in the presence of anionic surfactants, powder component A has the following composition contains: 5 - 70, preferably 7 - 60% by weight of surfactants (as above), although possibly nonionic surfactants present at most 35 wt. # S, preferably at most Make up 30% by weight of this powder component, 1 - 20, preferably 5-15% by weight of detergent-active ingredients, 10-96, preferably 25-88% by weight of other ingredients Usual ingredients of hot-dried detergents, although where appropriate existing hydrolyzable complexing agents (preferably tripolyphosphate, if necessary also others, such as metaphosphates) in amounts of not more than 20, preferably at most 10% by weight are present. 4. Detergent according to claim 1-3, characterized in that the other usual ingredients of hot-dried detergents according to patent claim 3 in the following way, the quantities referring to the powder component A refer to: 0 - 70 wt. Non-hydrolyzable, preferably organic complexing agents, 0-50, preferably 5-40% by weight for complex formation with calcium ions is practical non-capable alkaline-reacting builders, 0 - 35, preferably 1.5 - 28 wt .- organic neutral salts, water-insoluble stabilizers for per compounds, Dirt carriers, brighteners, etc. 5. Detergent according to claim 1-4, characterized in that the Powder component A for binding heavy metal traces, non-hydrolyzable organic ones Contains complexing agents in amounts of 0.1-10% by weight. 6. Detergent according to claim 1-5, characterized in that the Powder component A non-hydrolyzable organic complexing agents in amounts of more than 10-70% by weight, preferably 15-60% by weight, contains.vb 7t Detergent according to Claims 1 - 6, characterized in that the crystal water content of the perborate, which is low in water as powder component B before -banks, at most of the formula NaB02 H202. 2 H20, preferably at most of the formula NaB02. H202. 1 H20. 8. Detergent according to claim 1-7, characterized in that as anhydrous perborate sodium perborate monohydrate with the approximate composition NaBO2 . H202 is present. 9. Detergent according to claim 1-8, characterized in that the Particles of the powder components A and C are agglomerated with one another. 10. Detergent according to claim 1-9, characterized in that the Surfactant component present in the detergent, regardless of which of the powder constituents is in it the surfactants are present has the following composition: 50-100, preferably 55-100% by weight nonionic surfactants, 0-50, preferably 0-45% by weight anionic and / or zwitterionic surfactants, 0-8, preferably 0.5-5% by weight, non-surfactant-like Foam inhibitors, the foaming capacity of the surfactant component by selecting suitable, Surfactants that inhibit their foaming power and / or their presence do not Surfactant-like foam inhibitors is dampened 11. Detergent according to claim 1 - 10, characterized in that the detergent present nonionic and / or Zwitterionic surfactants and optionally disinfectants and not surfactant-like Foam inhibitors as small particles on the surface of at least one of the powder components be liable.