DE1800069A1 - Halo-substd lactams as activators for bleaching - agents - Google Patents

Abstract

Lactone activators for oxidation, bleach, washing and auxiliary washing agents Are of formula (where R is F, Cl, Br or I or 1-2C alkyl in which at least one H atom but pref. 3H atoms are replaced by halogen), esp. beta-CCl3-beta-propiolactone, they are used for inorganic per-cpds., giving off active O, such as H2O2 or perborates, and are used in aqs. oxidation and bleaching solutions containing 20-500 (50-250) mg/l active O and having pH 2-12 (7-11.5, particularly 8-10.5), or in solid powdery to granular concentrates, opt. containing disinfectants. Uses include bleaching textiles, oils, fats and waxes, hair and skin cosmetics, disinfectants and sterilisers, passivating Al.

Description

Oxidizing agents, bleaching agents, detergents and washing auxiliaries Aqueous solutions of inorganic, active oxygen-releasing per compounds, in particular of Hydrogen peroxide, or perborates, have long been used as oxidizing, bleaching and Detergent used for a wide variety of materials, especially textiles. However, the active oxygen only becomes active at temperatures above 700 C and preferably in the range from 80 to 1000 C with a sufficient for practical purposes Speed effective so that sioh these oxidizing, bleaching and washing liquids do not use on temperature-sensitive materials. However, one uses such inorganic percompounds and in particular perborates containing washing liquors often also for washing temperature-sensitive textiles at high temperatures of, for example, 30 to 50 ° C, i.e. one is thus working under conditions which the active oxygen in the detergents does not have its full effect comes, but remains largely unused in the washing liquor.

The invention relates to the use of certain organic substances as activators for inorganic, active oxygen-releasing per compounds, whereby the minimum temperature necessary for a practically effective oxidation and / or bleaching lowered and / or the oxidation process is accelerated.

The invention also relates to oxidizing agents and light-emitting agents, wherein including both the aqueous treatment liquids and those in liquid, pasty or solid state concentrates are to be understood.

a particularly interesting field of application for such Oxidizing and bleaching agents or their aqueous solutions are bleach and bleaching laundry of textiles.

The invention also relates to those used as pre- or post-treatment agents for bleaching detergents used for textiles or those in the pre- or main wash cycle bleach detergent to be used.

The substances to be used according to the invention as activators for inorganic per-compounds which split off active oxygen are halogen-substituted β-lactones of the general formula in which R is a fluorine, chlorine, bromine or iodine atom or a low molecular weight alkyl radical with 1 to 2 carbon atoms in which at least one hydrogen atom, but preferably three hydrogen atoms, have been replaced by halogen atoms.

According to the invention comes as an activator for the said per compounds preferably ß-trichloromethyl-ß-propiolactone into consideration, for example according to Borrmann and Wegler, Chemischeberichte 99 (1966), 1245 or H. Ohse and coworkers, Pr.onatshefte für Chemie, 98 (1967), 2138 can be prepared. The compound has a boiling point of 103 ° / 12 mm Hg and a melting point of 32 ° C.

That plays a role among the inorganic per-compounds to be activated Hydrogen peroxide plays the most important role in practice.

It can be as such, but in the form of its mostly solid peroxohydrates or addition products to inorganic and organic compounds are used will. The latter include, for example, the addition products of hydrogen peroxide on urea or melamine; the peroxohydrants include e.g. the Perborat, Perortho- Perpyro-, perpolyphosphates, percarbonates and persilicates. The invention Activators can also be used together with real peracids, such as the Carol's acid (peroxomonosulfuric acid H2SO5) or peroxodisulfuric acid (H2S2O8) or their salts are used.

In general, each molecule of activator can have one active oxygen atom activate the respective per connection; for full activation of the The active ingredient used would therefore theoretically be activator and per-compound to be used in equimolar amounts. In many cases the practice reaches on but also Satisfactory effects even with significantly smaller amounts of activator, while on the other hand, use the activator in relatively large excesses can; in general, the amount of activator used is 0.3 to 2, preferably 0.5 to 1 mol per g atom of active oxygen.

The acceleration of the bleaching or oxidation process is evident both at low temperatures in the range of 20 ° C, as well as when they are exceeded this temperature limit, where you can go up to 95 ° C. The professional has ever according to the problem to be solved, the possibility of using the inventive Activators either lower the treatment temperature and / or the treatment duration to shorten while maintaining the same temperature. Finally, one can also use a deep and combine high temperature bleach in one operation. In such cases it can be advantageous to use the activator in a sub-layer amounts to use; at low temperatures it becomes only a part of what is present Active oxygen activated; the rest stands for the bleaching at elevated temperatures available.

The conditions to be used when working with the present invention Activators must be observed, such as concentration of the peroxide, temperature, The pH value and duration of the treatment depend essentially on the one to be oxidized or substance to be bleached, optionally also the carrier material, on or in where the substance to be bleached is located. The mostly aqueous oxidation resp. Bleaching liquids can contain 20 to 500, preferably 50 to 250 mg / l of active oxygen and have a pH in the range from 2 to 12, preferably 7 to 11.5 and in particular have 8 to 10.5 The activators to be used according to the invention can be used wherever peroxo compounds, in particular Hydrogen peroxide or perborate, as an oxidation or

Has used bleach. B. for bleaching oils, Fats and waxes - in cosmetic hair and skin treatment, in disinfection or sterilization, when passivating aluminum or other light metal surfaces and especially when bleaching all kinds of fibers Claimed agent is reacted by adding acidic, neutral or alkaline Substances, possibly adjusted by buffer mixtures, of all things also by such Additives that were previously used in corresponding, customary types of application.

These include, for example, water-soluble or water-insoluble Stabilizers for per compounds, to lower the surface tension of the aqueous oxidation resp.

Anionic, nonionic, cationic ones serving bleaching liquids or zwitterionic surface-active substances, slightly acidic to alkaline reacting Builder substances, including here inorganic or organic complexing agents for the hardness components of water and heavy metal ions are to be counted, as well as inorganic ones or organic colloids, especially water-soluble organic high polymers. This list is not to be regarded as complete; it can all with one another Purpose of use commonly used substances can also be used. One a more detailed list of these substances can be found below.

The oxidizing and bleaching agents according to the invention, which are preferred can be manufactured and sold as detergents and auxiliary washing agents are marked by a content of a combination of inorganic per compounds according to the invention Activators to be used and, if appropriate, stabilizers for the per compounds, wherein this combination makes up 10 to 100 of the total agent and the activators generally in an amount of 0.3 to 2, preferably 0.5 to 1 mol per g atom Active oxygen are present. With the remaining 0 to 90 ffi this agent can these are the components already listed above and listed in more detail later trade such products.

Finally, the invention also relates to those which are of particular practical interest bleaching detergents containing the bleaching component according to the invention, their Composition is in the general range of the following recipe: 5 - 40, preferably 12 - 30 percent by weight of surfactants or

Combinations of surfactants, consisting of 0-100, preferably 25 - 65 percent by weight of surfactants of the sulfonate or sulfate type with preferably 8 - 18 carbon atoms in the hydrophobic radical, 0-100, preferably 5-40 percent by weight nonionic surfactants, 0-100, preferably 10-50 percent by weight soap, 0 - 6, preferably 0.5 - 3 percent by weight of foam stabilizers, O - 8, preferably 0.5-5 percent by weight foam inhibitors, 10-82, preferably 35-75 percent by weight Structural substance, at least part of this structural substance having an alkaline reaction, and wherein the amount of the alkaline to neutrally reacting builder substances is preferred 0.5 to 7 times and in particular 1 to 5 times the total surfactant combination makes up 10-50, preferably 15-35 percent by weight of the combination according to the invention from per compound, in particular perborate, and activator and optionally stabilizers for the per compound, but the amount of this combination is preferably so it is great that the active acid ¢ 2 substance content of the entire detergent 1-4 is preferred thus 1.5-3.5 percent by weight is 0-15, preferably 2-12 percent by weight other detergent ingredients, such as dirt carriers, brighteners, enzymes, perfume Dyes, water.

The solid activators can be used as powder or granules with the Mix other constituents of the oxidizing agent, bleaching agent, detergent or auxiliary washing agent. As is common in the detergent industry, it is obtained by spray drying or by other methods a detergent powder which does not contain per compounds made, then you mix this with the per compound and the activator, the powder should preferably be at room temperature when the activator is added.

The liquid at room temperature, but also the solid particles of the activators to be incorporated into the oxidizing agent, bleaching agent, detergent or auxiliary washing agent can also be used with water-soluble or water-insoluble, preferably water-swellable encapsulated or

be enveloped. Suitable capsule or shell substances are e.g.

Gelatin, methyl, oxethyl or carboxymethyl cellulose, starch and Starch derivatives. Next are solid water-soluble polyglycol ethers, to which one also various types of solid nonionic detergent actives can count, such as the polyethylene glycol-polypropylene glycol mixed ethers described later for this Purpose useful.

D4e products according to the invention can be used for bleaching and Use bleaching laundry of various fibers, natural or synthetic. Except for the textiles to be treated mostly at temperatures of 70 to 100 ° C Construction rolls, regenerated celluloses or linen can also be used according to the invention Wash and / or bleach so-called "easy-care" textiles that are made from highly refined BaumwoNe or made of synthetic man-made fibers, such as polyamide, polyester, polyacrylonitrile} Polyurethane, polyvinyl chloride or polyvinylidene chloride fibers or these exist included to at least 3O ffi. To the as "easy to care for", occasionally even Textiles designated as "non-iron" also include those made from synthetic fiber-cotton blends, which can be specially equipped.

These easy-care textiles are used for bleaching or washing Temperatures of 20 to 700 ° C., preferably 30 to 600 ° C., are possible. According to the invention The high degree of whiteness that can be achieved at these temperatures is above all at the same time or subsequent treatment of the textiles with optical brighteners is advantageous.

Of the inorganic per compounds, especially those in aqueous Solution neutral to alkaline reacting compounds, especially the perborates, practical interest.

Among the various perborates, there is sodium perborate tetrahydrate (NaB02. - H202. 3 HSO) of great practical importance. In its place you can also partially or completely, i.e. up to the approximate composition NaB02. -H202 dehydrated perborate can be used. Finally, they also contain active oxygen Borates NaB02. H202 usable in which the ratio Na20: B203 is less than 0.5: 1, and preferably in the range 0.4-0.15: 1, and where the ratio is H202: Na is in the range 0.5-4: 1. These products are in German Patent specification 901 287 or in American patent specification 2,491,789.

The perborate can be wholly or partly by other inorganic per compounds, in particular by peroxyhydrates, such as, for example, the peroxyhydrates the ortho-, pyro- or polyphosphates and the carbonates.

The oxidizing agents, bleaching agents and detergents according to the invention can customary water-insoluble or water-soluble stabilizers for Per compounds in amounts of up to 10, preferably from 0.5 to 8% by weight.

The various water-insoluble perstabilizers are suitable Magnesium silicates. Mostly these are precipitation products that are unified aqueous solutions of alkali silicates with solutions of magnesium salts arise.

The ratio MgO: SiO2 can be in the range from 4: 1 to 1: 4, preferably from 2: 1 to 1: 2. Often one uses a product with a ratio MgO: Si02 = 1: 1. These magnesium silicates can be replaced by the corresponding silicates other alkaline earth metals, cadmium or tin.

Hydrous oxides of tin can also be used as stabilizers. These stabilizers are usually in amounts from 1 to 8, preferably from 2 to 7 %> based on the weight of the entire preparation present.

The water-insoluble stabilizers can be completely or partially through water soluble to be replaced. As such, those to be discussed later are suitable organic complex formers, the amount used depending on the strength of the formed Complexes in the range from 0.25 to 5, preferably from 0.5 to 2.5 ß of the weight of the total means can lie.

It is often important when using the agents according to the invention to maintain a certain pH value; therefore one often puts this weakly acidic, neutral or alkaline reacting substances. The pH of a liquid solution the average will usually be in the range from 7 to 12, with the mild detergent Generally neutral to slightly alkaline (pH 7 to 9.5) and the detergents for cooking more alkaline (pH 9.5 to 12, preferably 10 to 11.5).

The anionic, if any, present in the products according to the invention Zwitterionic or nonionic surfactants contain at least one in the molecule hydrophobic radical from 8 to 26, preferably 10 to 20 and especially 12 to 18 Carbon atoms, and an anionic, nonionic or zwitterionic water-solubilizing agent Group. The preferably saturated hydrophobic radical is mostly aliphatic or alicyclic in nature; he can directly or with the water-solubilizing groups be connected via intermediate links. There are e.g. benzene rings as intermediate links, Carboxylic acid ester or carbonamide groups, ether-like or ester-like radicals polyhydric alcohols, such as those of ethylene glycol, propylene glycol, des Glycerine or corresponding polyether residues in question.

The hydrophobic radical is preferably an aliphatic hydrocarbon radical with about 10 to 18 carbon atoms, but depending on the nature of the respective surfactant Deviations from this preferred C number range are possible.

As anionic washing active substances soaps are useful that of natural or synthetic fatty acids, possibly also resin or naphthenic acids descend. There are many fatty, resin or naphthenic acids of natural origin more or less unsaturated. They are preferably in part or in full processed in the hydrogenated state so that they have iodine numbers of at most 30 and preferably less than 10.

Of the synthetic anionic surfactants, the Sulphonates and sulphates of practical importance. The sulfonates include, for example the alkylarylsulfonates, especially the alkylbenzenesulfonates, which are et al preferably straight-chain aliphatic hydrocarbons with 9 to 15, preferably 10 to 14 carbon atoms by chlorinating and alkylating benzene or from the corresponding terminal or internal olefins by alkylating benzene and sulfonating the obtained alkylbenzenes. They are also aliphatic Sulphonates of interest, such as from preferably saturated, 8 to 18 and preferably Hydrocarbons containing 12 to 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 in the process into the sulfonates are accessible. Mixtures of alkene sulfonates and hydroxyalkene sulfonates are also used as aliphatic sulfonates and hydroxyalkanesulfonates useful, for example, from terminal or intermediate C8-C18 and preferably C12-C18 olefins by sulfonation with sulfur trioxide and acid or alkaline hydrolysis of the sulfonation products is obtained. With the so The sulfonate group is found in many of the aliphatic sulfonates produced on a secondary carbon atom; but you can also by repositioning more terminal Prepare olefins with bisulfite sulfonates with a sulfonate group at the end.

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

Further useful sulfonates are the fatty acid esters of oxethanesulfonic acid and of dioxypropanesulfonic acid, the fatty alcohol esters of lower 1 to 8 carbon atoms containing aliphatic or aromatic SulSomono- and -dicarboxylic acids, the Alkyl glyceryl ether sulfonates and the condensation products of fatty acids or Sulronic acids with aminoethanesulphonic acid.

Fatty alcohol sulfates are to be mentioned as surfactants of the sulfate type, in particular those made from coconut fatty alcohols, tallow fatty alcohols or from oleyl alcohol. Useful sulfonation products can also be obtained from terminal or internal C8 to C18 olefins Manufacture of the sulfate type. Furthermore belong to this group of Surfactants sulfated fatty acid alkylolamides, sulfated monoglycerides and sulfation products of ethoxylated and / or propoxylated fatty alcohols, alkylphenols with 8 to 15 carbon atoms in the alkyl radical, fatty acid amides, fatty acid alkylolamides, etc., where to one mole of the ethoxylated and / or propoxylated compounds mentioned 0.5 to 20, preferably 1 to 8, in particular 2 to 4 mol of ethylene and or or Propylene oxide can be attached.

The detergents according to the invention can also be synthetic capillary-active Contain carboxylates, e.g. the fatty acid esters or fatty alcohol ethers of hydroxycarboxylic acids as well as the condensation products of fatty acids or sulfonic acids with aminocarboxylic acids, e.g. with glycocolla, sarcosine or with protein hyarolysates.

To the nonionic surfactants, here for the sake of simplicity as "Nonionics" products, whose water solubility is due to the presence of polyether chains, Amine oxide, sulroxide or phosphine oxide groups, alkylolamide groups and also 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 acids and sulfonic acid amides, these nonionics 4 - 100, preferably 6 - 40 and in particular 8 - 20 atomic residues, especially ethylene glycol ether residues may contain per molecule. In addition, residues of polyglycol ethers or at the end of which propylene or butylene glycol ether residues may be present.

The nonionics also include those under the trade name 41pluronics? 1, "Tetronics" or "Ucon Fluid" known, water-soluble due to the addition of ethylene oxide made water-insoluble polypropylene glycols and addition products of propylene oxide of alkylenediamines or lower ones containing 1 to 8 and preferably 3 to 6 carbon atoms, aliphatic alcohols.

Other useful nonionics are fatty acid or sulfonic acid alkylolamides, for example, from mono- or dialkylolamine, from dioxypropylamine or other polyoxyalkylamines e.g. derive the Glycaminen. They can be replaced by amides from higher primary or replace secondary alkylamines and polyhydroxycarboxylic acids.

From the group of amine oxides are those of higher tertiary, one hydrophobic alkyl radical and two short, up to 4 carbon atoms each containing alkyl and / or Amines derived from alkylol radicals are of particular interest.

Zwitterionic surfactants contain at least one, acidic or at least a basic hydrophilic group in the molecule. The acidic groups include carboxyl Sulfonic acid, sulfuric acid half ester, phosphoric acid and phosphoric acid partial ester groups.

The basic groups are primary, secondary, tertiary and quaternary Ammonium groups in question.

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 is obtained by reacting the tertiary amines mentioned with chloroacetic acid, their salts or with chloroacetic acid esters and cleaving the ester compound.

The foaming power of the surfactants used can be determined by a combination increase or decrease suitable surfactants. But the foaming power can also be by other than surfactant-like additives. Suitable as foam stabilizers as is known, the above-mentioned nonionics of the alkylolamide type; also are for this purpose fatty alcohols or higher terminal diols can be used.

The foaming power of synthetic anionic or nonionic surfactants can be reduced by adding soaps; with certain combinations of synthetic anionic surfactants, nonionics and soap, the foaming power is reduced even more. The addition products of propylene oxide to those described above are also notable capillary-active polyethylene glycol ether is characterized by a low foaming power, whereby by varying the number of ethylene glycol and propylene glycol residues present in the molecule Have products made with a wide variety of cloud points. These nonionics act on nonionics other than at temperatures above their cloud point Foam inhibitors; but they can also be used with other surfactants or mixtures combine different surfactants.

Mixtures of anionic surfactants, especially those of the sulfonate and / or sulfate types, nonionic surfactants and soaps have great practicalities Gaining importance, with one the foam intensity of such combinations by the choice of soaps can vary. Do these soaps contain e.g. 12 to 18 carbon atoms in the fatty acid residue, the surfactant mixtures show a certain foam suppression, the however, it is often not sufficient if the detergent is used at temperatures of 60 to 1000 C are intended to be used in drum washing machines. Achieved in such cases strong foam dampening for synthetic anionic, zwitterionic and nonionic surfactants by adding soaps made from fatty acid mixtures with 20 up to 30, preferably 20 to 26, carbon atoms in the fatty acid residue.

However, the surfactants can also be combined with foam inhibitors known per se which are not surfactants.

These may include N-alkylated aminotriazines containing chlorine, which can be obtained by reacting one mole of Cy & nur acid chloride with 2 to 3 moles of a Mono- and / or dialkylamine with 6 to 20, preferably 8 to 18 carbon atoms in the alkyl radical receives. Also leave paraffins, halogen paraffins, aliphatic C8 to C20 ketones can be used as foam inhibitors, especially in combination with soaps.

By choosing suitable foam inhibitors it can be achieved that the foam-suppressing effect only sets in when a certain temperature is exceeded, so that detergents can be produced in the medium temperature range up to still foaming at 650 ° C., for example, but on transition to higher temperatures develop less and less foam. You can even use foam stabilizers and temperature dependent ones Combine foam inhibitors with one another.

The temperature-dependent foam inhibitors include those mentioned above N-alkylated aminotriazines, as well as paraffiney halogen paraffins, ketones, etc., their foam-inhibiting effect is particularly strong above their melting point. but also the higher ones, derived from fatty acids with 20 to 30 carbon atoms in the molecule Soaps have a similar effect. These soaps can come in different amounts be added; their proportion can be 5 to 100 ç of the total in the surfactant component make up the amount of soap present.

The builder substances present in the products according to the invention include weakly acidic, neutral and alkaline reacting inorganic or organic Salts, especially 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, mono-, di- or trialkali orthophosphates, di- or tetraalkali pyrophosphates, as complexing agents known metaphosphates, alkali sulfates and the alkali salts of organic, non-KapiLaractive, 1 to 8 carbon atoms containing sulfonic acids, carboxylic acids 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 the salts of sulfodicarboxylic acids as well as the salts of acetic acid, lactic acid, citric acid urd tartaric acid.

Furthermore, the water-soluble salts are of higher molecular weight as building materials Polycarboxylic acids can be used, 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 Substances such as ethylene, propylene, acrylic acid, methacrylic acid, crotonic acid 3-butenecarboxylic acid, 3-methyl-3-butenecarboxylic acid and with vinyl methyl ether, vinyl acetate, Isobutylene, acrylamide and styrene are useful.

The weakly acidic substances are suitable as complex-forming framework substances reacting metaphosphates and the alkaline reacting polyphosphates, in particular the tripolyphosphate. You can use organic complexing agents in whole or in part be replaced.

The organic complexing agents include, for example, nitrilotriacetic acid, ethylenediaminetetraacetic acid, hydroxyethylethylenediamine triacetic acid, polyalkylene-polyamine-N-polycarboxylic acids and other known organic complexing agents, and combinations of different complexing agents can also be used. The other known complexing agents also include di- and polyphosphonic acids of the following constitution: where R is alkyl and R 'is alkylene radicals having 1 to 8, preferably 1 to 4 carbon atoms, and X and Y are hydrogen atoms or alkyl radicals having 1 to 4 carbon atoms. According to the invention, carboxymethylene phosphonic acid (HOOC-CH2-PO (OH) 2) can also be used as a complexing agent. All of these complexing agents can be present as free acids, but preferably as alkali salts.

In the preparations according to the invention, lubricants can also be used be included, which suspends the dirt detached from the fiber in the liquor hold and thus prevent graying. For this purpose, water-soluble xolloids are usually used of an organic nature, such as, for example, the water-soluble salts of polymeric materials Carboxylic acids, glue, gelatine, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or of acid sulfuric acid esters of cellulose or strength.

Water-soluble polyamides containing acidic groups are also useful suitable for this purpose. Furthermore, strength and other than those mentioned above can be used Use starch products such as degraded starch, aldehyde starches, etc. Also polyvinylpyrrolidone is useful.

EXAMPLES The usefulness of the invention Activators used was demonstrated by the following experiment: Solutions that 0.615 g NaB02.H202.3 H20 (4 mmol) and 2.5 g Na4P207.

10 H20 per liter were added after adding 4 mmol of activator heated to 30, 45 and 600 C and stirred during the entire experiment on the Maintained specified temperature. 100 ml were pipetted off at certain time intervals, Immediately added to a mixture of 250 g of ice and 15 ml of glacial acetic acid and then after adding approx. 0.35 g of potassium iodide with 0.1 N sodium thiosulphate solution and starch titrated as an indicator.

Under the specified conditions, one consumes a 100 frigen Activation of the peroxo compounds used 8.0 ml of thiosulfate solution. In the Tables is both the thiosulphate consumption and the percentage of activated Peroxo compound indicated.

Activation of perborate with ß-trichloromethyl-ß-propiolactone was achieved Activation of sampling after at 30 ° C at 45 ° C at 60 ° C x minutes ml% O ml% O ml % O 0.1 n Na2S2O3 activated 0.1 n Na2 S2O3 activated 0.1 n Na2S2O3 activated X = 1 0.5 6.2 0.6 7.5 0.3 3.8 5 1.5 18.7 2.9 36.2 0.7 8.7 10 3 37.5 3.85 48.0 1 , 8 22.4 15 3.4 42.5 4.2 52.5 2.1 26.2 30 4.7 58.7 3.5 43.7 0.7 8.7 45 4.9 61.2 2.3 28, 7th 0.2 2.5 60 5.0 62.5 1.5 18.8 0.1 1.2 As can be seen from the table, shows ß-trichloromethyl-ß-propiolactone a good activation of the perborate. this applies to the entire temperature range from 30 to 600 C.

For bleaching hair, for coloring hair with the help of oxidizing dyes and for the oxidative treatment of hair after deformation under the action of reducing thio compounds (Kaltwell method) are usually used aqueous solutions containing 10 to 200 g / l H202.

If you carry out this treatment after adding 20 to 500 g / l of one of the Activators according to the invention, in particular after the addition of ß-trichloromethyl-ß-propiolactone through, a considerable increase in the oxidizing effect of the H202 can be observed, so that, if desired, you can also work with lower H 2 O 2 concentrations.

In the detergents or auxiliary washing agents according to Examples W1 to W5 ß-Trichloromethyl-ß-propiolactone was also incorporated as an activator for the perborate. The washing or. Washing auxiliaries were found to be between Temperatures from 30 to 600 C are particularly effective in bleaching.

Example W 1 A mixture of 50 ç fine-grain perborate 50% activator is suitable as a rinse aid for washed laundry. It is recommended that 5 ß des Replace perborates with MgSiO3.

Example W 2 A rinse aid for washed laundry that simultaneously Fiber incrustations, especially calcareous fiber incrustations, has the following Composition: 30% perborate 20% hydroxyethane diphosphonate 15 fi Na2S04 35 ß activator Here, too, you can incorporate 5% MgSiO) and reduce the Na2SO4-3 content accordingly.

Example W 3 A bleaching auxiliary detergent used in the commercial Laundry, possibly together with washing active substances and / or complexing agents, especially used together with tripolyphosphate in the pre- or main wash cycle can be prepared in the following way: A mixture of 30 parts by weight Perborate, 25 parts by weight tripolyphosphate and 5 parts by weight MgSiO3 is on a granulating plate while agitating with 10 parts by weight of atomized water sprayed. While the water is being sprayed on and afterwards, there is cold air for as long passed over the moving material until the ingestion of the water free heat of hydration is dissipated. Then 30 parts by weight Activator mixed in, example W 4 A mixture of 15 parts by weight of perborate, 60 parts by weight of a voluminous tripolyphosphate with a bulk density of 500 g / l, 5 parts by weight of a proteolytic enzyme and 10 parts by weight of activator with 10 parts by weight of a finely atomized liquid Addition product of 10 moles of ethylene oxide sprayed with one mole of oleyl alcohol. These Liquid nonionic washing active substance causes the particles to agglomerate underneath he binding the enzyme; however, the voluminous Ttipolyphosphat takes so much non-ionic washing act iv substance to ensure that the product is always externally dry appears.

Example W 5 By spray drying and then admixing a mechanical mixture of 66.0% sodium perborate and 34 f activator is a Cooking detergent made with the following composition: (quantities in percent by weight) 12% alkylbenzenesulfonate) as in example W 6 4% soap 3% C12-18 fatty alcohol + 10 A, 0.38% Na5P3O10 1% ethylenediamine tetracetate 1.5% CMC 18 ß perborate 9 ß Activator 0.2 ffi optical brightener, remainder sodium sulfate and water That Ethylenediamine tetraacetate present in this detergent is used to stabilize it of the perborate against catalytic decomposition due to traces of heavy metals, which in the Suds could get in.

Example W 6 A detergent taken from the atomization tower was divided into two portions after cooling. While the one serving only Received an addition of perborate and sodium sulfate, the other portion was through Addition of activator, perborate and a correspondingly reduced amount of activator Amount of Sodium Sulphate turned into an activator-based bleaching detergent. The two detergents had the following composition: alkylbenzenesulfonate 4.9 percent by weight nonylphenol + A0 2.3 percent by weight soap (total C16-22 fatty acid) 6.0 weight percent Na5P3O10 35.7 weight percent Na20. 3 SiO2 5.3 percent by weight XgSiO) 1.3 percent by weight CMC 1.2 percent by weight perborate 15 ', 4 percent by weight Activator 0 -25.3 percent by weight sodium sulfate, brightener water, the remainder as alkylbenzenesulfonate a technical straight-chain alkylbenzenesulfonate was used, its alkyl chain contained an average of 12 carbon atoms; Alkyl benzene sulfonate and soap lay as the sodium salts before.

Ss-Trichloromethyl-ß-propiolactone was used as an activator.

With the two detergents of the recipe given above was carried out a series of bleaching tests, the activator-containing detergent still divided by different amounts of the activator used and thereby so varied that the activator: perborate molar ratio ranged from 0.25 to 1.5. The perborate concentration was a constant 5 mmol / l.

Using these detergents, test swabs made of raw nettle, as well as those with tea and forest berries soiling on cotton with a detergent concentration of 5 g / l and a liquor ratio of 1:10 in water of 160 dH for 30 minutes long washed at 30, 45 and 600 C. The activator-free detergent served as a comparison product; this comparative detergent was also used for washing at 900.degree.

The lightening was measured with a reflectance photometer at 460 me and 620 mF and the values obtained on all test patches were averaged. This resulted in the following remissions: Table II (ß-trichloromethyl-ß-propiolactone) at 30.degree Activator molar ratio Achieved bleaching effect Relative whiteness concentration activator / (remission%) increase% (m mol / 1) perborate 0²) - 66.1 - 2.5 0.33 75.2 57 5.0 0.67 77.4 70.5 7.5 1 78.2 75.5 0³) - 82.1 100 1) Relative whiteness increase = R45 ° with - R45 ° without # 100% R = remission R90 ° without- R45 ° without 2) R45 ° without = remission at 45 ° without activator 3) R90 ° without = remission at 90 ° without activator Table III (ß-trichloromethyl-ß-propiolactone) at 45 ° C Activator molar ratio Achieved bleaching effect Relative whiteness concentration activator / (remission%) increase%) (m mol / l) perborate 0²) - 70.3 - 2.5 0.33 78.0 65.2 5.0 0.67 79.8 80.5 7.5 1 80.1 83.1 0³) - 82.1 100 1) Relative whiteness increase = R45 ° with - R45 ° without # 100% R = remission R90 ° without- R45 ° without 2) R45 ° without = remission at 45 ° without activator 3) R90 ° without = remission at 90 ° without activator Table IV (ß-trichloromethyl-ß-propiolactone) at 60 ° C Activator molar ratio Achieved bleaching effect Relative whiteness concentration activator / (remission%) increase%) (m mol / l) perborate 0²) - 76.8 - 2.5 0.33 78.1 24.5 5.0 0.67 78.7 36.0 7.5 1 79.3 47.0 0³) - 82.1 100 1) Relative whiteness increase = R45 ° with - R45 ° without # 100% R = remission R90 ° without- R45 ° without 2) R45 ° without = remission at 45 ° without activator 3) R90 ° without = remission at 90 ° without activator Ließ If the products according to Examples W 1, W 3, W 5 and W 6 were acted on items of laundry that were contaminated by pathogenic germs or microorganisms, these microorganisms were killed off by the addition of activator even at temperatures in the range from 30 to 600 C. .

Claims (12)

PATENT CLAIMS 1) Use of halogen-substituted β-lactones of the general formula in which R is a fluorine, chlorine, bromine or iodine atom or a low molecular weight alkyl radical with 1 to 2 carbon atoms in which at least one hydrogen atom, but preferably three hydrogen atoms are replaced by halogen atoms, as an activator for inorganic, active oxygen-releasing per compounds. 2) Use of ß-trichloromethyl-ß-propiolactone as an activator for inorganic, active oxygen-releasing per-compounds. 3)) Use of halogen-substituted ß-lact ons as activators for inorganic per compounds which split off active oxygen according to claim 1 and 2 in an amount of 0.1 to 2, preferably 0.33 to 1 mol of activator per g atom Active oxygen. 4) Use of the halogen-substituted β-lactones as activators for inorganic, active oxygen from splitting per compounds according to claim 1 and 2 in oxidizing and bleaching liquids, the 20 to 500, preferably 50 to 250 mg / l of active oxygen. 5) Use of the halogen-substituted β-lactones as activators for inorganic, active oxygen-releasing per compounds according to claim and 2 in aqueous solvents with a pH of 2 to 12, preferably before. 7 to 11.5 and especially from 8 to 10.5. 6) Use of the halogen-substituted β-lactones as activators for inorganic, active oxygen from splitting per compounds according to claim 1 and 2 in oxidizing hair treatment. 7) Use of the halogen-substituted β-lactones as activators for inorganic, active oxygen-releasing per compounds according to claim 1 and 2 in solid, powdery to granular oxidizing, bleaching, washing and washing aids. 8) Use of the halogen-substituted B-lactones as activators for inorganic, active oxygen-releasing per compounds according to claim 1 and 2 in liquid or solid, powdery, optionally containing disinfectants Oxidizing, bleaching, washing and washing auxiliaries. 9) Inorganic per compounds that split off active oxygen and activators containing oxidizing agents, bleaching agents, detergents and washing auxiliaries, characterized in that that they contain halogen-substituted β-lactones according to Claims 1 and 2 as activators. 10) Oxidizing, bleaching, washing and washing auxiliaries according to claim 9, characterized in that the combination of inorganic PerverbindurZ, Activator and possibly stabilizer for the per compound 1C makes up 100% of the agent, wherein in Oxidatlons-, bleaching, and washing auxiliaries preferably more than 50 to 90 and in particular 55-75 and in detergents preferably 10-50, in particular 15 - 35 of this combination is available. 11) Oxidizing, bleaching, washing and washing auxiliaries according to claim 9 and 10, characterized in that the activators in an amount of O, i - 2, preferably from 0.33 to 1 mol per g-atom of active oxygen are present. 12) Oxidizing, bleaching, washing and washing auxiliaries according to claim 9-11, characterized in that they are composed as follows: 5 - 40, preferably 12 - 30 percent by weight of surfactants or Combinations of surfactants consisting of O - 100, preferably 25 - 65 percent by weight of sulfonate and / or sulfate type surfactants, O - 100, preferably 5-40 percent by weight of non-ionic surfactants, 0-100, preferably 10-50 percent by weight Soap, O - 6, preferably 0.5 - 3 percent by weight foam stabilizers, O - 8, preferably 0.5-5 percent by weight foam inhibitors, -10-82, preferably 35 - 75 percent by weight of structural substances, with at least some of these structural substances reacts alkaline, and the amount of alkaline to neutrally reacting framework substances preferably 0.5 to 7 times and especially 1 to 5 times the total Active washing substance, 10-50, preferably 15-35 percent by weight the combination according to the invention as per compound, in particular perborate and activator and optionally stabilizers for the per compound, although the amount of this combination is preferably so large that the active oxygen content of the entire bleaching A mean of 1-4, preferably 1.5-3.5 percent by weight amounts to 0-15, preferably 2 - 12 percent by weight of other detergent ingredients, such as dirt carriers, Brighteners, enzymes, perfume, dyes, water.