EP0332050A1 - Activators for inorganic per compounds - Google Patents

Abstract

Isatinic acid anhydride or certain derivatives thereof, of general formula (I), are used as activators. R denotes one of the residues H, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, propenyl, butenyl, cyclohexyl, phenyl or benzyl; X is chosen from the group methyl, methoxy, chlorine, bromine and SO3 <-> ; and n can assume the values 0,1 and 2. These compounds produce an extraordinary increase in the oxidizing action of inorganic percompounds. Preferred fields of application are oxidation, disinfection and bleaching baths.

Description

Inorganic per-compounds, especially hydrogen peroxide and solid per-compounds, which dissolve in water to release hydrogen peroxide, such as sodium perborate and sodium carbonate perhydrate, have long been used as oxidizing agents for disinfection and bleaching purposes. The oxidizing effect of these substances in dilute solutions depends strongly on the temperature; For example, with H₂O₂ or perborate in alkaline bleaching liquors, sufficiently quick bleaching of soiled textiles can only be achieved at temperatures above about 80 ° C. At lower temperatures, the oxidation effect of the inorganic per compounds can be improved by adding so-called activators, for which numerous proposals have become known in the literature. Among other things, carboxylic anhydrides have been proposed for this purpose (DE 893 049) and used in bleaching agents (DE 19 12 579). By adding these substances, the bleaching effect of aqueous peroxide liquors can be increased to such an extent that already at 60 ° C almost the same effects occur as with the peroxide liquor alone at 95 ° C.

In the effort to save energy in washing and bleaching, application temperatures well below 60 ° C, in particular below 45 ° C down to the cold water temperature, have become increasingly important in recent years.

At these temperatures, however, the effect of the known activators is already significantly reduced. There has been no shortage of efforts to develop more effective activators for this temperature range without convincing success to date. The present invention also aims to improve the oxidation and bleaching effect of inorganic per-compound at low temperatures below 80 ° C., in particular in the temperature range from approximately 15 to 45 ° C.

Isatosäureanhydrid (R = H, n = 0) hat den systematischen Namen 1H-Benz[d][1,3]oxazin-2,4-dion. Es ist als großtechnisches Pro­dukt an sich bekannt. Bei den als Aktivatoren geeigneten Deri­vaten des Isatosäureanhydrids handelt es sich um Verbindungen der Formel I, in denen R, X und n eine der folgenden Bedeutungen haben:
R = Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, Propenyl, Butenyl, Cyclohexyl, Phenyl oder Benzyl;
X = Methyl, Methoxy, Chlor, Brom oder SO₃^⊖;
n = 0,1 oder 2.It has now been found that when isatoic anhydride or some of its derivatives are used as activators in this temperature range, there is an extraordinary increase in the oxidation and bleaching action of inorganic per compounds in oxidation, bleaching and washing liquors. These activators are compounds with the formula

Isatoic anhydride (R = H, n = 0) has the systematic name 1H-Benz [d] [1,3] oxazin-2,4-dione. It is known as a large-scale product. The derivatives of isatoic anhydride which are suitable as activators are compounds of the formula I in which R, X and n have one of the following meanings:
R = methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, propenyl, butenyl, cyclohexyl, phenyl or benzyl;
X = methyl, methoxy, chlorine, bromine or SO₃ ^⊖ ;
n = 0.1 or 2.

Some of these compounds are known per se and are commercially available, or they can be synthesized analogously to the known compounds (see DE 499 822 and Beilstein's Handbook of Organic Chemistry, volume 27, system number 4298, main work and 1st to 4th supplementary work ).

Of these compounds, preference is given to the representatives (n = 0) in the benzene ring which are not substituted and in which R represents one of the radicals methyl, ethyl, n-propyl or isopropyl. The unsubstituted isatoic anhydride (R = H, n = 0) is particularly preferred.

In the process according to the invention, isatoic anhydride and its derivatives can be used as activators wherever a particular increase in the oxidation activity of inorganic per-compounds is important at low temperatures, for. B. in the bleaching of textiles, hair or hard surfaces, in the oxidation of organic or inorganic intermediates and in disinfection. Most of these activators far outperform the best carbonic anhydride activators known to date.

The use according to the invention is to create conditions under which hydrogen peroxide and isatoic anhydride or its derivatives can react with one another with the aim of obtaining secondary products which have a stronger oxidizing action. Such conditions exist in particular when the two reactants meet in an aqueous alkaline solution.

The conditions can be varied widely depending on the intended use. In addition to purely aqueous solutions, mixtures of water and suitable organic solvents, e.g. B. for the use in disinfection or in the oxidation of intermediates as a reaction medium in question. The pH of the reaction medium can be selected within wide limits, from the weakly acidic range (pH 4) to the strongly alkaline range (pH 13), depending on the application. The alkaline range from pH 8 to pH 11 is preferred since it is particularly advantageous for the activation reaction and the stability of the per compound formed. For this reason, the activator according to the invention is also preferably used together with a sodium perborate or with sodium carbonate perhydrate, which already have pH values of this range in their solutions. Examples of other suitable per compounds are phosphate perhydrates and urea peroxide. Occasionally, it can also be expedient to shift the pH of the medium again after the activation reaction has taken place by means of suitable additives, especially in the acidic range. The amounts of per compounds are generally chosen so that the solutions contain between 10 ppm and 10% active oxygen, preferably between 50 and 5000 ppm active oxygen. The amount of activator used also depends on the application. Depending on the desired degree of activation, 0.03-1 mol, preferably 0.1-0.5 mol, of activator per mol of inorganic per-compound are used, but in special cases these limits can also be exceeded or fallen short of.

The isatoic anhydride according to the invention or its derivatives can be used for activation in pure form or, if this is expedient, for example to increase the storage stability, in special forms of supply, such as tablets, granules or in finely divided coated form (so-called prills). Of particular importance are those granular shapes that are produced by agglomeration granulation. For the Machine dosing is suitable for solutions in organic solvents or liquid dispersions that contain the activator.

It is preferably used in pre-assembled agents in a mixture with the per compounds to be activated and, if appropriate, further components required for the desired bleaching or oxidation process, such as pH regulating agents and stabilizers for per compounds. In addition to isatoic anhydride and / or its derivatives, other activators can also be present. Mixing with selected amounts of per-compounds and other additives makes the application easier and the user achieves the desired result more reliably, since the optimal conditions are obtained when the agents are dissolved without further action. Such agents are therefore a further subject of the present invention.

In the field of textile washing, the activators according to the invention can be combined with almost all the usual components of detergents and bleaches. In this way it is possible to build up means which are particularly suitable for textile treatment at low temperatures and also means which are suitable in several temperature ranges up to the traditional area of cooked laundry.

The main components of such detergents and bleaches are, besides per-compounds and activators, builders and surfactants. In addition, other customary auxiliaries and accompanying substances, such as graying inhibitors, peroxide stabilizers, electrolytes, optical brighteners, enzymes, perfume oils, foam regulators and conditioning agents, can be present in these agents if this is expedient.

Examples of customary builder substances are condensed phosphates, alkali silicates, alkali carbonates, salts of amino carboxylic acids, such as nitrilotriacetic acid, salts of polyphosphonic acids, such as hydroxyethane diphosphonic acid, salts of polycarboxylic acids, such as citric acid or polyacrylic acid, and insoluble sodium aluminum silicates and NaX type NaA zeolite NaA.

Particularly suitable surfactants are those of the type of the nonionic and synthetic anionic surfactants. Examples of nonionic surfactants are the polyethylene glycol monoalkyl and polyethylene glycol monophenyl ethers prepared from long-chain alcohols or alkylphenols and ethylene oxide, 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, olefin sulfonates, fatty alcohol sulfates and sulfates of polyethylene glycol monoethers. Soaps and salts of long-chain acylcyanamides can also be used.

Typical detergents and bleaches according to the invention have approximately the following composition:
0.5 to 20% by weight, preferably 5 to 15% by weight of anionic and / or nonionic surfactants,
0.5 to 60% by weight, preferably 5 to 40% by weight, of builders from the group of condensed phosphates, alkali silicates, alkali carbonates, sodium aluminum silicates and mixtures thereof,
0 to 20% by weight, preferably 0.5 to 8% by weight, of builder substances from the group consisting of salts of aminocarboxylic acid ren, salts of polyphosphonic acids, salts of polycarboxylic acids and mixtures thereof,
2 to 35% by weight, preferably 5 to 30% by weight, of inorganic per-compounds,
0.3 to 20% by weight, preferably 1 to 10% by weight, of isatoic anhydride and / or its derivatives,
ad 100% usual auxiliary and accompanying substances and water

In addition to combined detergents and bleaches, agents which are used as additives to peroxide-containing or peroxide-free detergents are also suitable as the form of preparation of the activators according to the invention for textile washing. They essentially contain activator or a mixture of activator and per compound and, if appropriate, further auxiliaries and additives, in particular stabilizers, pH-regulating agents, thickeners and surfactants.

Typical bleach additives according to the invention have approximately the following composition:
5 to 50% by weight, preferably 15 to 35% by weight, of inorganic per-compound,
2 to 30% by weight, preferably 5 to 25% by weight, of isatoic anhydride and / or its derivatives,
0 to 5% by weight, preferably 0.1 to 3% by weight, of peroxide stabilizers,
0 to 40% by weight, preferably 5 to 30% by weight of pH-regulating agents,
ad 100% by weight of other customary auxiliaries and additives.

In addition to per compound and activator, agents intended for cleaning hard surfaces contain, in particular, surfactants and framework substance zen and, in the case of polishing and abrasive agents, abrasive components. Since these agents are often used at room temperature, the use of the activators according to the invention has a particularly advantageous effect on the bleaching and germicidal action.

Ready-made agents are of particular importance for use in disinfection, since there are generally increased demands on application safety. Disinfectants based on the activators according to the invention generally contain, in addition to this and inorganic per-compounds, further auxiliaries and additives, such as pH-regulating substances, stabilizers and surfactants. In special cases, they can additionally contain special microbicides which increase the very broad killing effect of the activated per-compound against certain germs.

Typical disinfectants according to the invention have approximately the following composition:
5 to 40% by weight, preferably 10 to 20% by weight, of inorganic per-compounds,
2 to 40% by weight, preferably 5 to 20% by weight, of isatoic anhydride and / or its derivatives,
0 to 5% by weight, preferably 0.1 to 3% by weight, of peroxide stabilizers,
0.1 to 20% by weight, preferably 0.2 to 5% by weight of surfactants,
ad 100% by weight of other auxiliaries and additives.

However, the use of the activators according to the invention is in no way limited to the use in the ready-made form of these described or other types. For example, in in the commercial field in general, the individual dosing of reagents in the foreground, since it is often the cheaper method.

Examples

The abbreviations used have the following meaning: AS = Acrylic acid CMC = Carboxymethyl cellulose EDTA = Tetrasodium salt of ethylenediaminetetraacetic acid EDTMP = Hexasodium salt of ethylenediaminetetramethylenephosphonic acid (peroxide stabilizer) EO = Ethylene oxide HEC = Hydroxyethyl cellulose MA = Maleic anhydride

1. Phosphate-containing, bleaching textile detergent in powder form.

Composition (in percent by weight): Soap (C₁₂-C₁₈) 1.5 Na 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 Sodium perborate monohydrate 18.0 Isatoic anhydride 3.0 Brightener, perfume, enzyme ad 100 Carboxymethyl cellulose, Na₂SO₄ and water

At application concentrations of 5 to 10 g / l were with this Excellent bleaching results achieved at washing temperatures of 20 to 95 ° C.

2. Testing the effectiveness of bleaching on various test soils on textiles.

The test was carried out in a launderometer, type Atlas Standard, using a phosphate-free detergent under the following conditions:
Fleet volume 250 ml
Fabric: 6.3 g fill fabric (white cotton)
2.1 g test fabric
Water hardness: 17 ° d. H.
Temperatures: 30 or 40 ° C
Washing time: 30 minutes including heating up time (3 ° C / min)
Rinse: 3 x 30 sec. Detergent composition (% by weight): Alkylbenzenesulfonate Na salt 7 Tallow alcohol + 5 EO 5.5 Na₂CO₃ 12 Sodium silicate (3.2) 3.3 Zeolite NaA 28 EDTA 0.3 Sodium perborate tetrahydrate 28 CMC + HEC 1.5 Na₂SO₄ and water ad 100 Dosage: detergent 7.16 g / l
Activator 143 mg / l or 1.26 mmol / l

The tests were evaluated by remission measurement on the dried fabrics. The results, which are summarized in the following tables, represent the reflectance values in%, based on BaSO₄ = 100, which were measured at a wavelength of 460 nm. Higher values indicate lighter tissue. Table 1 Try at 30 ° C Activator Dosage per liter Red wine on cotton Currant on cotton Tea on refined cotton Red wine on polyester / cotton without - 46.1 51.8 33.9 54.2 Isatoic anhydride 143 mg 52.6 55.4 41.0 58.6 1.26 mmol 55.1 59.2 44.5 59.1 Phthalic anhydride 143 mg 47.5 51.3 35.7 53.7 1.26 mmol 47.7 53.8 36.0 54.1 Succinic anhydride 143 mg 47.3 54.8 36.6 53.8 1.26 mmol 47.7 53.7 36.1 53.8 Try at 40 ° C Activator Dosage per liter Red wine on refined cotton Tea on refined cotton Red wine on polyester / cotton Tea on polyester / cotton without - 44.5 38.0 54.4 51.3 Isatoic anhydride 143mg 49.6 45.5 58.2 53.6 1.26 mmol 52.7 47.7 60.7 53.3 Phthalic anhydride 143 mg 45.0 39.2 55.2 50.8 1.26 mmol 45.8 41.1 54.8 51.4 Succinic anhydride 143 mg 45.0 40.0 54.8 50.4 1.26 mmol 44.6 39.2 54.8 50.3

It is clear from the reflectance values that with isatoic anhydride a much stronger activation of the perborate is achieved at both temperatures than with conventional anhydride activators.

Similar good results were obtained using N-methylisatoic anhydride.

3. Testing the effectiveness of bleaching on textiles under US washing conditions.

The test was carried out in a whirlpool type washing machine using the phosphate-containing detergent Tide under the following conditions:
Fleet volume: 65 l
Fabric: 2.3 kg fill fabric (white cotton)
+ 8 test stains (1 cloth of 2.1 g each)
Water hardness: 5.6 ° dH (99 mg CaCO₃, Ca: Mg = 3: 1)
Washing time: 14 minutes
Temperature: 24 ° C (cold wash)
Dosage: 1.35 g detergent
(per liter) + 67.5 mg perborate monohydrate
+ 54 mg activator

The evaluation was carried out by remission measurement as in Example 2. Table 3 contains the test results on various test soils in comparison to activators customary today (mean values from 4 tests): Table 3 Try at 24 ° C Activator Currant on cotton Red wine on refined cotton Tea on finished cotton Red wine on polyester / cotton Without perborate and activator 40.5 36.9 27.1 47.7 Isatoic anhydride 45.7 39.6 33.0 50.3 Tetraacetylethylenediamine 42.7 38.0 31.1 48.7 Sulfophenyl isononate Na salt 41.8 38.5 30.3 48.9

The results show that isatoic anhydride can also be used advantageously under US washing conditions.

A similar increase in the oxidation effect of inorganic per compounds is also achieved in other areas of application.

4. Checking the storage stability

The storage was carried out in a mixture with a powdered phosphate-free detergent, this mixture containing 3% by weight of activator either in pure form or in the form of agglomeration granules. The detergent had the following composition (in% by weight): Soap 1.5 Na dodecylbenzenesulfonate 8.0 Fatty alcohol ethoxylate 4.0 Na₂CO₃ 8th Sodium silicate (3.2) 3.5 Zeolite NaA 25th Hydroxyethane diphosphonate (Na salt) 0.3 MA-AS copolymer (60:40) 5 Sodium perborate tetrahydrate 26 Brightener, perfume, enzyme, carboxymethyl cellulose Na₂SO₄ and water ad 100

The activator granules had been prepared from the pure, powdery activators and carboxymethyl cellulose as binders according to DE 30 11 998 and contained 94% by weight of active substance.

The mixtures containing the activators in granular form were stored in laminated cardboard boxes in a climatic cell at 30 ° C. and 80% relative humidity. The other mixtures were stored in unlaminated boxes in the laboratory. In all cases, the peracid, which formed when the mixtures were dissolved in water, was determined iodometrically at the beginning and after 4 and 8 weeks of storage under standard conditions. Table 3 contains the results in relative numbers, based on 100% peracid formation at the start of storage. The superior stability of the isatoic anhydride is evident under both storage conditions. Table 4 Activator Peracid formation in% 0 weeks 4 weeks 8 weeks Succinic anhydrides 100 30th 0 Phthalic anhydride 100 19th 0 Isatoic anhydride 100 85 67 Succinic anhydride, granulated 100 16 0 Phthalic anhydride, granulated 100 0 - Isatoic anhydride, granulated 100 88 58

5. Disinfectant

Composition (percent by weight) Sodium perborate monohydrate 12.0 Isatoic anhydride 12.0 Na₂CO₃ 15.0 Na₄P₂O₇ 25.0 EDTMP 1.2 Nonylphenol ethoxylate (9 EO) 1.3 Na₂SO₄ and water ad 100

After being dissolved in water at room temperature, the powdery agent was used in the form of a bath for instrument disinfection. When using about 4 g per liter, the necessary disinfection times were less than 60 minutes.

6. Testing the disinfectant effect

This test was carried out in the so-called qualitative suspension test in accordance with the guidelines for the testing and evaluation of chemical disinfection processes of the German Society for Hygiene and Microbiology (DGHM), status 1981. In this test, 10 ml of the disinfectant dilution to be tested are mixed well with 0.1 ml of a germ suspension (10⁷ - 10⁸ germs / ml) at 20 ° C. After exposure times of 5, 15, 30 and 60 minutes, 0.1 ml of these mixtures are removed and inoculated in 10 ml of a culture medium. By incubating these subcultures at 37 ° C (72 h), it is checked whether germs capable of reproduction are still present.
Test solution: detergent according to Example 2 in water at 17 ° dH, adjusted to pH 10,
Dosage: Detergent: 10 g / l
Activator: 150, 300 or 600 mg / l
Temperature: 37 ° C
Culture medium: casein peptone soybean meal peptone agar

The results with four test germs are given in the table below as maximum kill times in minutes: Table 5 Activator Concentration mg / 1 Staph. aureus E. coli Pseudo aeruginosa Candida albicans 0 > 60 > 60 > 60 > 60 Isatoic anhydride 600 5 5 5 5 300 5 5 5 5 150 5 5 > 60 60 N-methylisatoic anhydride 600 5 15 30th 5 300 15 30th 60 15 150 60 > 60 > 60 > 60

The excellent activation effect of the activators according to the invention is also evident from these data.

Claims (13)

1. Use of an isatoic anhydride of the formula

in which R is one of the radicals H, methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, propenyl, butenyl, cyclohexyl, phenyl or benzyl, X from the group H, methyl, methoxy, chlorine , Bromine and SO₃ ^{⊖ is} selected and n is either 0.1 or 2, as an activator for inorganic per-compounds in oxidation, disinfection and bleaching liquors. 2. Use of an isatoic anhydride according to claim 1, wherein in the formula n is 0 and R is either H, methyl, ethyl, n-propyl or iso-propyl. 3. Use according to claim 1 of the unsubstituted isato acid anhydride. 4. Use according to one of claims 1 to 3, characterized in that the activation takes place in a predominantly aqueous solution at a pH between 8 and 11. 5. Use according to one of claims 1 to 3, characterized in that 1 = 0.03 mol, preferably 0.5-0.1 mol, of activator is used to activate 1 mol of active oxygen from the inorganic per compound. 6. Oxidizing, bleaching or disinfectant containing an inorganic per compound and an activator and optionally pH-regulating agents and stabilizers for the per compound, characterized in that it contains an isatoic anhydride as the activator, which has the formula

in which R represents one of the radicals H, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, propenyl, butenyl, cyclohexyl, phenyl or benzyl, X from the group H, methyl, methoxy , Chlorine, bromine and SO₃ ^{⊖ is} selected and n is either 0.1 or 2. 7. Composition according to claim 6, containing an isatoic anhydride, in which in the formula n has the value 0 and R is one of the radicals H, methyl, ethyl, n-propyl and iso-propyl. 8. Composition according to claim 6, containing unsubstituted isatoic anhydride. 9. Composition according to one of claims 6 to 8, characterized in that the inorganic per compound is selected from the group sodium perborates, sodium percarbonate and mixtures thereof. 10. Agent according to one of claims 6 to 8, characterized in that it contains 1 - 0.03 mol, preferably 0.5 - 0.1 mol of activator per 1 mol of the inorganic per-compound. 11. washing and bleaching agent according to claim 6, consisting of:
0.5 to 20% by weight, preferably 5 to 15% by weight of anionic and / or nonionic surfactants,
0.5 to 60% by weight, preferably 5 to 40% by weight, of builders from the group of condensed phosphates, alkali silicates, alkali carbonates, sodium aluminum silicates and mixtures thereof,
0 to 20% by weight, preferably 0.5 to 8% by weight, of builder substances from the group salts of aminocarboxylic acids, salts of polyphosphonic acids, salts of polycarboxylic acids and mixtures thereof,
2 to 35% by weight, preferably 5 to 30% by weight, of inorganic per-compounds,
0.3 to 20% by weight, preferably 1 to 10% by weight of activator,
ad 100% usual auxiliary and accompanying substances and water. 12. Bleach additive according to claim 6, consisting of:
5 to 50% by weight, preferably 15 to 35% by weight, of inorganic per-compound,
2 to 30% by weight, preferably 5 to 25% by weight of activator,
0 to 5% by weight, preferably 0.1 to 3% by weight, of peroxide stabilizers,
0 to 40% by weight, preferably 5 to 30% by weight of pH-regulating agents,
ad 100% by weight of other customary auxiliaries and additives. 13. Disinfectant according to claim 6, consisting of:
5 to 40% by weight, preferably 10 to 20% by weight, of inorganic per-compounds,
2 to 40% by weight, preferably 5 to 20% by weight of activator,
0 to 5% by weight, preferably 0.1 to 3% by weight, of peroxide stabilizers,
0.1 to 20% by weight, preferably 0.2 to 5% by weight of surfactants,
ad 100% by weight of other auxiliaries and additives.