DE1794166A1 - Bleach - Google Patents

Description

PATENT LAWYERS

DR. I. MAAS,

.DR. W. PFEIFFER '

DR. F. VOITHENLEiTNER

8. MUNICH 2 3
UNGERERSTR 25 - TEU 39 02 36

P 1794166.1-43
21 708

American Oyanamid Company, Wayne, HTew Jersey, V.St.A.

Bleach

Me invention relates to bleach containing hydrogen peroxide releasing. Contain compounds and activators for these compounds.

As a means for bleaching textiles are currently. generally liquid chlorine bleaches, e.g. sodium hypochlorite bleaches, are used. These liquid chlorine bleaches are common in aqueous: solution not stable and lose their bleaching effect with prolonged storage. The chlorine bleaches are also difficult to handle in liquid form, damages tissues during bleaching and can locally over-bleached if they come into direct contact with the fabric in the absence of water.

Because of these weak parts of liquid chlorine bleaching and before Most of the tissue damage caused by such bleaching has been the use of oxygen bleaching considered for bleaching textiles.

109842/1776

Oxygen bleaches generally contain hydrogen peroxide releasing organic peroxides or inorganic persalts, e.g. urea peroxide or alkali perborates. Using from sodium perborate, for example, the tissue damage is considerably less than when using sodium hypochlorite bleach.

Disadvantageously, however, is the bleaching action of sodium .perborat and other oxygen bleaching at relatively low Wassertemperntüren, such as occur, for example, in modern washing machines (about 50 to 7O ⁰ C) weaker than Natriumhypochloritbleichen. At water temperatures close to the boiling point - around 100 ° C - oxygen bleaching bleaches textiles just as effectively as organic bleaching. However, many tissues tolerated kedn e water temperatures above about 75 ⁰ O. The effectiveness of oxygen bleaching at high temperature use is therefore not something sensitive to these tissues or for the use of such bleaching in. Washers. ■

Since oxygen bleaching does less damage to textiles and can be used in the form of dry powders or tablets, thereby obviating the difficult handling of a liquid product, numerous attempts have been made to oxygen bleach to find that have an effective bleaching effect at relatively low water temperatures. These Bleaching agents generally contain an organic persalt which releases hydrogen peroxide and an activator which; promotes or accelerates the bleaching effect of the persalt at low water temperatures. Examples of known activators for oxygen bleaching include tris (acetyl) cyanurate and tetraacetyl methylenediamine as well as certain hydrazine derivatives set out in British Patent 1046251.

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^b oxygen bleach such activators, ⁼ however, have proved in most cases to be not fully satisfactory, because let achieve with them no bleaching effect that is comparable to 7O ⁰ C with the liquid chlorine bleach in water temperatures of about 50, and since they hydrolyze rapidly during storage.

Surprisingly, a bleaching agent has now been found which, as a hydrogen peroxide compound, hydrogen peroxide, organic peroxides or inorganic persalts and an activating one Amount of an N-acylazole of the general formula I. or II

R ₂ -Ο-

II

contains. In these formulas, R ₁ denotes hydrogen, lower-alkyl, bromine, chlorine, fluorine or nitro; R ₂ (a) alkyl of 1 to 18 carbon atoms; (b) a bromine, chlorine, fluorine, nitro or alkoxy substituted aliphatic radical having 1 to 18 carbon atoms; (c) an aliphatic, cyclic or acyclic radical; (d) an aryl radical or (e) a hydroxy, alkyl, nitro, bromine, chlorine, fluoro, lower alkoxy or imidazolylcarbonyl-substituted aryl radical; A is a mono or

10-9842 / 1776

disubstituted or unsubstituted 6-membered aromatic or N-heteroaromatic ring containing 1 to 4 nitrogen atoms contains - and as substituents nitro groups, carboxy groups, hydroxyl groups, Alkoxy groups, bromine, chlorine, fluorine, sulfo groups, May contain cyano groups or alkyl radicals. X and Y the rest

C-R ^ or a nitrogen atom, at least one of the Groups X and Y is nitrogen with the proviso that A is an N-heteroaromatic ring containing 1 to 4 nitrogen atoms is when X and Y are both nitrogen atoms.

Below is a list of exemplary compounds that contain a ring A as defined above. which compounds of the formula II by acylation in known Way can be made. The complete nomenclature and structural formulas can be found under the ones given Numbers from The Ring Index, American manual Chemical Society (1960).

Connection Revised Ring index Serial No;

Triazolotetrazine 1073

Triazolopyrimidines 1079-1081

Triazolopyrazine 1082

Triazolopyradizine 1083-1084

Triazolopyridines 1089-1092

Imidazotriazine 1159

Pyrazolotriazine. 1160

Pyrazolopyrimidines 1168, 1169, 1174

Pyrazolopyrazine 1171

Parazolopyridazine 1172,1173,1175

Imidazopyrazine 1176

Imidazopyridazine "1177

Imidazopyrimidines 1179.1180

Pyrazolopyrazine 1186,1191

Imidazopyridines. 1192.1195

Imidazoles 1209, 1210

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■ - 5 -

Rp is an organic radical and can be many substituted or mean unsubstituted aliphatic, cycloaliphatic or aromatic radicals. The aliphatic radicals can be 1 to Contain 18 carbon atoms, but preferably have 1 to 8 carbon atoms, since aliphatic radicals with more than 8 carbon atoms have only limited solubility in water to have. .

The unsubstituted aliphatic radicals for which Rp can be in the formulas given above, so include straight-chain or branched alkyl radicals such as methyl, ethyl, n-propyl, iFopropyl, tert-butyl, hexyl, octyl, nonyl, tetradecyl or octadecyl, or ethylenically or acetylenically unsaturated hydrocarbon radicals such as ethenyl, butenyl, tetradecenyl, Ithynyl or octadecynyl. The substituted aliphatic radicals include halogen-, nitro- and alkoxy-substituted ones aliphatic radicals, such as methoxymethyl, 3? rifluoromethyl, 1-chlorobutyl or 1-nitroethyl.

Rp can also be cycloaliphatic radicals, for example cycloalkanes such as cyclobutyl, cyclohexyl or I-chlorocyclohexyl, unsubstituted Aryl radicals such as phenyl or naphthyl and substituted Aryl radicals such as hydroxy, alkyl, nitro, halogen, alkoxy or carbonylimidazole-substituted aryl radicals mean. Examples of such substituted aryl radicals are toluene, p-nitrophenyl, p-methoxyphenyl or p-chlorophenyl.

The alkyl substituents on ring A can be the same as for Rg. The alkoxy radicals preferably contain lower alkyl radicals (C ₁ -C). The term halogen in the definition given above includes chlorine, bromine and fluorine.

Examples of H-acylazole compounds that act as activators which can be used in the bleaching agents according to the invention are:

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F-acetylimidazole
'N-butyrylimidazole

N-Trimethylacetylimidazole N-Benzoylimidazole
N-toluoylimidaz.ol '

N-p-chlorobenzoylimidazole N-p-nitrobenzoylimidazole N-p-Methoxybenzoylimidazole 2-ethyl-4-methyl-F-acetylimidazole 4-nitro-N-acetylimidazole <; N-acylbenzimidazole

5-Mtro-i-acetylbenzimidazole i-Benzoyl ^^ - dichlorobenzimidazole 1-acetylimidazo (Td) pyridine 1-acetylimidazo (b) pyrazine

The preferred compounds for the purposes of the invention are those which have the best ratio of activity and water solubility. The activity is related to the carbonyl group bonded to Rp and is therefore increased by the aromatic character and the presence of electron withdrawing groups in the azole part of the molecule. The solubility is improved by substituents such as those _{defined by R 1} and Rp, for example.

The preferred compounds therefore include N-acetylimidazole, N-benzoylimidazole, N-p-nitrobenzoylimi, dazole and the substituted benzimidazoles of the formula II.

The new bleach activators according to this invention (formula I and II above) can be prepared by various known processes, for example by reacting imidazole with isopropenyl acetate or acetyl chloride to form N ^ acetylimidazole under conditions that are explained in the exemplary embodiments.

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The oxygen bleaches suitable for the bleaching agents according to the invention are hydrogen peroxide, organic peroxides and inorganic persalts, which in water are hydrogen peroxide release. Examples of organic peroxides that act as bleach compounds are suitable are urea peroxide, benzoyl peroxide and methyl ethyl ketone peroxide. Examples of inorganic persalts as bleach compounds are alkali perborates, percarbonates, monopersulfates or persulfates. Palis desired, Mixtures of two or more of these bleaching compounds can also be used can be applied.

Sodium perborate is available as a bleaching compound for use in the bleaching agents according to the invention because of their ready availability and easy handling in dry form and the particularly effective binding that does not damage the tissue is achieved with it, is preferred.

The bleaching agents according to the invention preferably contain the activating N-Aeylazolverbindungen and the hydrogen · peroxide-releasing compound in a molar ratio of about 1: 1, because every mole of bleach activator with 1 mole of hydrogen peroxide-releasing compound reacts, stoichiometric ratios are preferred to the activating compound to take full advantage of it. Of course, however, the ratio of activator to bleach can vary for different applications can be changed as required.

According to an advantageous embodiment of the invention, the bleaching agent contains an equimolar mixture of sodium perborate and N-acetylimidazole in an amount that is a bleaching agent with a concentration of 50 ppm active oxygen. Such a remedy can be the porm of a dry Powders have and, when used in water, provide an effective washing machine bleach for bleaching textiles and other materials, e.g. wood or paper pulp, if

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relatively low water temperatures of about 50 "bia 7O ⁰ G.

The invention is illustrated by the following examples, which are preferred Represent embodiments explained in more detail. In these examples is the preparation of the bleach activators and the Use of the bleaching agents according to the invention for bleaching textiles described, refer to parts and percentages based on weight, unless otherwise stated.

example 1

To produce N-acetylimidazole, 78.05 g (1 mol) of acetyl chloride are dissolved in 200 ml of tetrahydrofuran. Then the acetyl chloride solution is added dropwise to a solution of 136.16 g (: 1 mol) of imidazole in 1000 ml of tetrahydrofuran. The reaction is exothermic. The reaction mixture is kept in an ice bath at a temperature below 40 ^° C. in order to separate out imidazole hydrochloride during the addition.

The reaction mixture is then refluxed for 2 hours warmed up. After cooling, the imidazole hydrochloride is filtered off and discarded.

The liquid part of the reaction mixture is taken from the solvent freed. The remaining white crystals are recrystallized from tetrahydrofuran to give 61.25 g of one white crystalline product. Analysis shows that this product consists of N-acetylimidazole. That Product has a "melting point of 102 to 103 ° ^ and has the following analysis values:

jo C 2Lu # N

Ber. for N ₂ OC ₅ H ₆ 54.55 5.48 25.44

: 54.34 5.33 25.66

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- 9 -
Example 2

To produce 4-Fitro-N-acetyl-imidazOl, 1.25 ml Sulfuric acid was added dropwise to a mixture of 5.66 g (0.05 mol) of 4-nitroimidazole and 100 ml of isopropyl acetate. The reaction mixture is refluxed for about 2 hours, cooled and then washed with anhydrous sodium carbonate ' neutralized.

The liquid portion of the reaction product is separated off and triturated with ethyl ether. Crystals form in the ethyl ether layer which, after recrystallization from tetrahydrofuran, give 3.3 g of a crystalline product which, according to analysis, consists of 4-nitro-N-acetyl-imidazole. The product has a melting point of 97.5 to 98.5 ⁰ C and has the following analytical values:

J ₀ Ή

Ber. for ΒΓ, Ο, άρ-Η, -: Found:

Example- 3

N-p_Nitroben2oylimidazole is prepared according to the procedure of Example 1 using 1 mol of p-nitrobenzoyl chloride instead of acetyl chloride. A product with a melting point of 121 to 122 ^° C., which, on the basis of the analysis, consists of ur-p-nitrobenzoylimidazole, is obtained.

39 , 02 3, 24 27 05 38 , 96 3, 36 27 14th

109842/1776

Example 4

An oxygen bleach in dry form is prepared by mixing 0.33 g of N-acetylimidazole obtained by following the procedure of Example 1 and 0.462 g of sodium perborate. The agent contains imidazole and perborate in an equimolar ratio and has a concentration of 50 ppm active oxygen. The bleaching effect of this agent is determined by the following test method. 32 Mu A most entsohlichtetem of cotton fabric with dimensions ς 13 x 13 cm (5 "x 5") are as follows soiled with tea: Five tea bags are placed in 1 1 of water and heated to boiling for 5 minutes. Then the swatches are dipped into the tea and the simmering is continued for another 5 minutes. The swatches are then wrung out, dried at high temperature, rinsed in cold water and dried again.

Two of the soiled cotton swatches are put into a Terg-0-Το-meter-container made of corrosion-resistant steel (manufactured by TJ.S. Testing Company). Then you add cut up Pieces of white terry toweling fabric, so that you get a typical household washing machine Ver-φ ratio of water to tissue of about 20: 1.

The bleaching agent is then added to each vessel a fixed amount of sodium carbonate or sulfuric acid to achieve the desired pH value. The Terg-0-Tometer is operated for 15 minutes at a temperature of 50 C with 100 cycles / minute. Be after the end of the cycle the swatches removed, rinsed with cold water and ironed dry.

Before and after the cycle, reflectance measurements are made on the samples using a Hunter reflectometer model

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D-40 made with a blue filter. Each sample becomes similar twice (warp and weft) on each side versus three soiled samples measured. Fluorescence effects are excluded from all measurements.

The measured reflection values are averaged, and the distance of dirt in $ is determined using the following formula:

Total removal of dirt in fo =

(Reflection after bleaching j - ["Reflection before bleaching ^L ; ^L (dirty)? Χ Ί00

[, Reflection before soiling] - {reflection before bleaching

(dirty) J

The bleach of this example removes an average of 60 fa of the soil from the samples, as calculated by the formula above.

Example 5

A dry bleach similar to the bleach of Example 4 is prepared by mixing 0.462 g Sodium perborate made with 0.52 g of N-benzoylimidazole. The agent contains perborate and imidazole in equimolar amounts Ratio and has a concentration of 50 ppm active Oxygen on.

Samples made of cotton fabric are soiled as in Example 4 and the bleaching effect of the agent is the same Test method as determined in Example 4.

The reflectance values of the cotton samples show that 73 $ des Dirt by treating with the bleach of this example removed.

10 9 8 4 2/1776

Example 6

A bleach in dry form that is the bleach
of Example 4, 0.462 g of sodium perborate and 0.67 g of li-p-MtrobenzQylimidi | zp, l are prepared by mixing. The remedy contains perborate and imidazo! in an equimolar ratio and has a concentration of 50 ppm active oxygen.

Cotton samples are soiled as in Example 4, and the bleaching effect of the agent is determined according to the test method of Example 4.

The ßeflexionswerte the cotton samples showed that 65 i ° of the dirt be removed by treatment with the bleaching agent of this example.

Examples 7-25

In Examples 9 to 20, bleaches are used in
dry form similar to the bleach of Example 4. The agents all have an equimolar ratio of perborate to the KT acylazole compound and a concentration of 50 ppm active oxygen.

842/1776

For comparison purposes, the examples are carried out 21 to 25, in order to explain the effect of the bleaching agents of the invention in modern automatic washing machines, which are operated at relatively low water temperatures of about 50 to 70 ⁰ O. The bleaching agents used for comparison have a concentration of 50 ppm active oxygen or active chlorine, depending on the bleach used. ·.

The test procedure of Example 4 is repeated with the bleaches listed in the table. In doing so, the dirty Samples are placed in a Terg-0-Tometer made of corrosion-resistant steel, which contains water at a temperature of 50 C.

The reflectance values of the samples are taken before and after the cycle certainly. The dirt removal in $ that is performed with the various Bleach is obtained is calculated according to the formula given above. The results are in the following Table listed.

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Tabel

at Bleach Dirt- + N-acetylimidazole + TACA * ■ - ■ · ⁱ - '' ^XJ - · 60.0 game distance, $> + N-benzoylimidazole + Solium yf.i: Si;. <Y. , 73.0 4th Sodium perborate + N-p-nitrobenzoylimida- + N-acetyibehzimidazole 5 Sodium perborate 65.0 "6 · Sodium perborate + N-propyrylimidazole 55.2 zol + N-butyrylimidazole 57.6 7th Sodium perborate + N-trimethylacetylimi- 8th Sodium perborate 41.0 9 Sodium perborate + N-octyrylimidazole 48.3 dazol + N-palmitoylimidazole 46.0 10 Sodium perborate ■ N-toluoylimidazole 61.0 11 Sodium perborate + N-p-chlorobenzoylimi- 12th lfetrium perborate 4 62.0 13th Sodium perborate + N-p-methoxybenzoyl- dazol 58.0 14th Sodium perborate + N-terephthaloylimida- imidazole 46.0 Ul Sodium perborate + 2-ethyl-4-methyl-N- zol 35.7 16 Sodium perborate + 4-nitro-N-acetylimida- acetyl imidazole 52.0 17th Sodium perborate + 4-bromo-N-acetylimida- zol 49.4 18th Sodium perborate Sodium hypochlorite (CIOROX) 74.0 zol Sodium perborate 16.0 19th Sodium persulfate 19.0 20th 19.0 21st 52.0 22nd Hydrogen peroxide 53.0 23 Sodium perborate 35.0 24 Sodium perborate 25th Sodium perborate

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* -Tris- (acetyl) eyanurate as an activator for oxygen bleaching, I ¹ MO Corp. prepared and used in the recommended amounts.

+ -Tetraacetylmethylenediamine as an activator for the oxygen bleach, manufactured by Lever Bros, and used in the recommended amounts.

■ Example 26

The dry bleach of Example 4 is aqueous Solution dissolved and placed at normal room temperature on various substrates such as bathroom »wastes, cover plates in Kitchens and hospital rooms to combat various Microbes or germs applied. The agent is "particularly effective because the active oxygen is the antimicrobial or germicide Main component, "released at lower temperatures is more common than with peroxide-type dermicides the pail is.

The agents according to the invention, which contain N-acylazole and hydrogen peroxide-providing compound in an approximately stoichiometric ratio, are in concentrations of about 5 to 200 parts / million, preferably about 10 to 50 parts / million (ppm), given as the amount of active. Oxygen provided by the means is germicidally effective. ■ ~; i

Treatment of the water and the surfaces of swimming pools with the agents according to the invention is special effective because the'normally low temperatures that are present in this environment, the application of others prevent antimicrobial agents. A similar field of application is treating water supplies to this for

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human or industrial use to make usable, e.g. the disinfection of water from open water points for consumption by the military, or the treatment of technical 'process water, so that this in the technical process or by the adjacent Community can be used again.

The agents can also be used in admixture with detergents serve as household detergents or industrial germicidal detergents.

Claims (9)

Pat entans check 1. bleach, characterized in that it is hydrogen peroxide, organic peroxides or inorganic persalts as a hydrogen peroxide-yielding compound and an activating amount of an F-acylazole of the formula H R ₂ -C- or II contains, in which: each R ^ is a hydrogen atom, a lower alkyl radical, a bromine, chlorine or fluorine atom or a nitro group; Rp (a) is an alkyl radical with 1 to 18 carbon atoms; (bJ a bromine, chlorine, fluorine, nitro or alkoxy substituted aliphatic Radical with 1 to 18 carbon atoms, (c) an aliphatic, cyclic or acyclic radical; (d) an aryl radical or (e) a hydroxy, alkyl, nitro, bromine, chlorine, fluorine, lower alkoxy or imidazolylcarbonyl substituted Aryl radical; A is a mono- or disubstituted or unsubstituted 6-membered aromatic or N-heteroaromatic ring with 1 to 4 nitrogen atoms, the nitro groups, carboxyl groups, Hydroxy groups, alkoxy groups, bromine, chlorine or fluorine atoms, sulfo groups, cyano groups or alkyl groups may contain and X and Y the radical C-R., or a nitrogen atom, where at least one of the groups X and Y f098A2 / 1776 is a nitrogen atom. fc, with the proviso that A is a N-heteroaromatic input with 1 "to 4 nitrogen atoms is when X and Y are both nitrogen atoms. 2. Composition according to claim 1, characterized in that N-acylazole is an N-acylimidazole. 3 * means according to claim 2, characterized in that the Hydrogen peroxide-producing compound is an alkali salt. 4. Composition according to claim 3, characterized in that the molar ratio of the imidazole to the persalt is about 1: 1 amounts to. 5. Composition according to claim 2, characterized in that the imidazal is N-acetylimidazole. 6. Composition according to claim 5, characterized in that the persalt is sodium perborate. 7. Composition according to claim 2, characterized in that the imidazole is N-benzoylimidazole. 8. Means according to claim 7, characterized in that the Persalt is sodium perborate. 10.984271 * 776 9. Means according to claim. 2, characterized in that the Imidazole is N-p-nitrobenzoylimidazole. .10. Process for bleaching fabrics and wood pulp, characterized in that the fabric or the wood pulp in an aqueous medium with the agent Claim 1 treated. 1098: 42/17 76