DE3807920A1 - Activators for inorganic per compounds - Google Patents

Abstract

The activators used are acylated 3-amino-1,2,4-triazoles of the formula <IMAGE> in which R<1> is an aliphatic acyl radical comprising 2 to 8 C atoms or a substituted or unsubstituted benzoyl radical, and R<2> and R<3> are hydrogen or R<1>. R<2> and R<3> can here only simultaneously be hydrogen. The activators are suitable above all for use in oxidation liquors, disinfection liquors and bleaching liquors.

Description

Inorganic per compounds, in particular hydrogen peroxide and solid per compounds which dissolve in water to release Dissolve hydrogen peroxide, such as sodium perborate and sodium carbonate Perhydrate, have long been used as an oxidizing agent for disinfecting and bleaching purposes. The oxidation effect of these substances depends strongly on dilute solutions Temperature off; so you get for example with H₂O₂ or perborate in alkaline bleaching liquors only at temperatures above from about 80 ° C a sufficiently fast bleach dirty Textiles. At lower temperatures, the oxidation effect the inorganic per compounds by addition of so-called Activators for which numerous proposals in the literature have become known. So have that in the German Patent 16 95 219 Tetraacetylglykoluril described and more recently in German Patent 11 62 967 described tetraacetylethylenediamine input found in the practice. By adding these substances, the bleaching effect aqueous peroxide liquors are increased so much that already At 60 ° C almost the same effects as with the peroxide liquor alone at 95 ° C.

In an effort to gain energy-saving washing and bleaching processes In the last few years also application temperatures significantly  below 60 ° C, especially below 45 ° C down to the Cold water temperature in importance.

At these temperatures, the effect of known activators but already clearly after. It does not therefore have aspirations Missing, for this temperature range more effective activators without being convincing to this day Success would have been. Also the present invention has the improvement of the oxidation and bleaching action of inorganic Per compound at low temperatures below of 80 ° C, especially in the temperature range of about 15 to 45 ° C. to the goal.

It has now been found that when using certain acylated 3-amino-1,2,4-triazoles as activators in this temperature range an unusual increase in the oxidation and bleaching effect inorganic per compounds in oxidation, bleaching and Washing liquors is achieved. These are the activators to compounds of the formula

in the R¹ is an aliphatic acyl radical comprising 2 to 8 C atoms or an optionally substituted benzoyl radical and R² and R³ is hydrogen or R¹. R² and R³ should only be hydrogen at the same time. The aliphatic acyl radicals can straight-chain or branched, the benzoyl radical can be 1 or 2 Wear substituents, which are each Cl, CH₃ or CH₃O can act. Preferably, however, the benzoyl radical is  unsubstituted. In particular, 1-benzoyl-3-amino-1,2,4-triazole preferred as activator.

In the process according to the invention, these can be acylated Aminotriazoles are used as activators wherever it indicates a particular increase in the oxidation effect of inorganic Per compounds at low temperatures arrives, z. B. in the bleaching of textiles or hard surfaces, in which Oxidation of organic or inorganic intermediates and at disinfection.

The use according to the invention consists of conditions create, among which hydrogen peroxide and the activators with each other can react with the aim of being more oxidizing To obtain secondary products. Such conditions are in particular then before, when both reactants in aqueous alkaline Solution to each other.

Depending on the purpose, the conditions can vary widely become. So come in addition to purely aqueous solutions and mixtures from water and suitable organic solvents, e.g. For example the application in disinfection or in the oxidation of Intermediates, as a reaction medium in question. The pH of the Reaction medium can be within wide limits, from the weakly acidic range (pH 4) into the strongly alkaline range (pH 13), depending be selected according to application. The alkaline is preferred Range from pH 8 to pH 11, as it is responsible for the activation reaction and the stability of the formed per compound particularly is advantageous. For this reason, the inventive Activators also preferred together with a sodium perborate or with sodium carbonate perhydrate used in  their solutions already have pH values in this range. The Amounts of peroxygen compounds are generally chosen that in the solutions between 10 ppm and 10% active oxygen, preferably between 50 and 5000 ppm of active oxygen available. The amount of activator used depends on the Application from. Depending on the desired degree of activation 0.03-1 mole, preferably 0.1-0.5 mole activator per mole of inorganic Used per compound, but can be used in special If these limits are exceeded or fallen short of.

The acylaminotriazoles according to the invention can be used for activation in pure form or, if so, for example for increasing the storage stability, it is appropriate, in special forms of such as tablets, granules or finely coated form (so-called prills) are used. For the machine dosage Solutions are suitable in organic solvents or liquid dispersions containing the activator.

The use is preferably carried out in a mixture with the to be activated Per compounds and optionally further, for the desired Bleaching or oxidation process required components, such as pH regulators and stabilizers for per compounds. In addition to the activators according to the invention, it is also possible to use others Be present activators. By mixing with selected Amounts of peroxy compounds and other additives will be the Application facilitates and the user achieves the desired safer Result, but the use of the invention is not limited to this form of tender.

In the field of textile washing, the activators according to the invention can with almost all usual components of washing and  Bleaching agents are combined. You can use this way Build specifically for textile treatment at low cost Temperatures are suitable and also those, which in several temperature ranges up to the traditional range of cooking linen are suitable.

Main components of such detergents and bleaches are, in addition Per compounds and activator, builders and Surfactants. In addition, other common adjuvants, such as Grayness inhibitors, peroxide stabilizers, electrolytes, optical Brighteners, enzymes, perfume oils, foam regulators and avivierende substances are present in these agents, if so is appropriate.

Examples of common builders are polymeric phosphates, alkali silicates, Alkali carbonates, salts of aminocarboxylic acids, such as Nitrilotriacetic acid, salts of polyphosphonic acids, such as hydroxyethanediphosphonic acid, Salts of polycarboxylic acids, such as citric acid or polyacrylic acid and insoluble sodium aluminum silicates of the type zeolite NaA and NaX.

Suitable surfactants are in particular those of the nonionic type and synthetic anionic surfactants in question. examples for nonionic surfactants are those of long-chain alcohols or Alkylphenols and ethylene oxide produced polyethylene glycol monoalkyl and polyethylene glycol monophenyl ether and the long chain Alkylglycosides.

The anionic surfactants are primarily Sulfates and sulfonates of long-chain compounds, for example Alkylbenzenesulfonates, fatty acid ester sulfonates, alkanesulfonates, Olefinsulfonates, fatty alcohol sulfates and sulfates of polyethylene glycol monoethers.  Furthermore, soaps and salts can be longer chain Acylcyanamides are used.

In addition to combined detergents and bleaches come as a form of preparation the activators according to the invention for textile washing Also contemplated as additives to peroxide-containing or peroxide-free detergents are used. you contain essentially the activator or a mixture of activator and per-compound and optionally further auxiliary and Additives, in particular stabilizers, pH-regulating agents, Thickeners and surfactants.

For cleaning hard surfaces certain agents are included Per-compound and activator, in particular surfactants, builders and, in the case of polishing and abrasives, abrasive Ingredients. Because these agents are common at room temperature are applied here, the use of the inventive effect Activators particularly beneficial to the bleaching and germicidal activity.

Of particular importance have ready-made agents in the application in disinfection, since here are generally increased requirements be put to the application security. disinfectant based on the activators according to the invention besides these and inorganic per compounds in general even more auxiliaries and additives, such as pH-regulating Substances, stabilizers and surfactants. In special cases In addition, they may contain special microbicides that are added to the very broad killing effect of the activated per compound reinforce certain germs.  

However, the use according to the invention of the activators is by no means on the application in formulated form of these described or other species. For example, in the commercial sector in general, the single dosing of reagents in the foreground, as they often use the cheaper method represents.

Examples

The abbreviations used have the following meaning:

AS = acrylic acid
CMC = carboxymethylcellulose
EDTA = tetrasodium salt of ethylenediaminetetraacetic acid
EDTMP = hexasodium salt of ethylenediamine tetramethylene phosphonic acid (peroxide stabilizer)
EO = ethylene oxide
HEC = hydroxyethylcellulose
MA = maleic anhydride
TAED = tetraacetylethylenediamine

1. Testing the bleaching efficacy on various test soils on textiles in a phosphate-free detergent.

The test was carried out in Launderometer, type Atlas Standard, at following conditions:

Fleet volume 250 ml
Fabric: 6.3 g of filling fabric (white cotton); 2.1 g of test tissue
Water hardness: 17 ° d. H.
Temperature: 40 ° C
Washing time: 30 minutes including heating time (3 ° C / min)
Rinsing: 3 × 30 sec.

Detergent composition (% by weight) alkylbenzenesulfonate 7 Tallow alcohol + 5 EO 5.5 Na₂CO₃ 12 Sodium silicate (3,2) 3.3 Zeolite NaA 28 EDTA 0.3 perborate 28 CMC + HEC 1.5 Na₂SO₄ and water ad 100

Dosage: Detergent 7.16 g / l
Activators 143 mg / l

The evaluation of the experiments was by remission measurement the dried tissues. The results in The following tables summarize the remission values in%, based on BaSO₄ = 100, at a Wavelength of 460 nm were measured. Show higher values lighter tissue on.

Table 1

2. Testing the bleaching efficacy on various test soils on textiles in a phosphate-containing detergent.

Unless otherwise stated, the same tests were used in the test Conditions as in Example 1 complied with.

Detergent composition (% by weight) Soap (C₁₂-C₁₈) 1.5 dodecylbenzenesulfonate 9.0 Fatty alcohol ethoxylate (C₁₂-C₁₈ + 10 EO) 3.5 sodium triphosphate 20.0 Sodium silicate (3,2) 5.0 Zeolite NaA 15.0 EDTMP 0.3 MA-AS copolymer (60:40) 1.5 perborate 18.0 Perfume, enzyme ad 100 Carboxymethylcellulose, Na₂SO₄ and water

Dosage: Detergent: 8.0 g / l
Activators: 120 mg / l

The following activators of the formula I were investigated:

The evaluation of the tests yielded those listed in Table 2 Results:

Table 2

From the results of both examples it becomes clear that in Use of the activators of the invention an excellent Activation of perborate is achieved.  

3. Testing the disinfecting effect

This test was in the so-called qualitative suspension test according to the Guidelines for Examination and Evaluation chemical disinfection process to the German society for Hygiene and Microbiology (DGHM), as of 1981. In this test, each 10 ml of the disinfectant dilution to be tested with 0.1 ml of a germ suspension (10⁷- 10⁸ germs / ml) well mixed at 20 ° C. After exposure times of 5, 15, 30 and 60 minutes, 0.1 ml each of these mixtures and inoculated in 10 ml of a culture medium. By incubating these subcultures at 37 ° C (72 h), it is tested whether there are still germs capable of reproduction.

Test solution: Detergent according to Example 1 in water of 17 ° dH, adjusted to pH 8.
Dosage: Detergent: 10 g / l 1-Benzoyl-3-amino-1,2,4-triazole: 150, 300 or 600 mg / l
Temperature: 37 ° C
Culture medium: Casein peptone soybean meal peptone agar

The results with four test germs are in the following table given as maximum kill times in minutes:  

Table 3

Also from these data becomes the excellent activation effect the activators of the invention clearly.

Claims (5)

1. Use of acylated 3-amino-1,2,4-triazoles of the formula in which R¹ is an aliphatic acyl radical containing 2 to 8 C atoms or an optionally substituted benzoyl radical and R² and R³ are hydrogen or R¹, with the proviso that when R² is hydrogen, R³ is also hydrogen, as activators for inorganic per compounds in Oxidation, disinfection and bleaching liquors. 2. Use according to claim 1 of 1-benzoylaminotriazole. 3. Use according to one of claims 1 or 2, characterized that the activation in predominantly aqueous solution at a pH between 8 and 11 takes place. 4. Use according to one of claims 1 to 3, characterized that as inorganic per compounds sodium perborate or sodium percarbonate. 5. Use according to one of claims 1 to 4, characterized that for the activation of 1 mole of active oxygen of the inorganic per compound is 1-0.03 mol, preferably 0.5-0.1 mol activator can be used.