DE2061863A1 - Detergent composns - contg optical brightener and bleach activators esp tetraacetyl glycoluril - Google Patents

Abstract

Detergent compsn. of Main Patent 1 953 519 contg. a mixt. of optical brighteners of formulae (A X-Y-Z and (B) Z-Y-Z- M is alkali metal or NH4, n and m are 1-3, (A):(B) ratio is 3:1 to 1:4, esp. 2:1 to 1:2) are modified to include activator(s) for per-cpds. to prevent "greening" of textile washed, consisting of N-acyl- or O-acyl- cpds. or carbonate or pyrocarbonate esters of >3 (>4.5) titre for per-cpds. Pref. activators contain R-CO-acyl gp(s), (where R is opt. substd. 1-3 aliphatic hydrocarbyl or =8C aromatic hydrocarbyl), and pref. is an acetylated, poropionylated or benzoylated amine, amide, sulphamide, sulphurylamide, hydantoin, hydrazide, hydroxyl-amine, imidazoline, glycoluril deriv.

Description

"Detergents and detergent solutions with a content of optical Brighteners and bleach activators "Additional application to patent application P 19 53 519.4 (D 4018) From the German patent application P 19 61 775.5 are detergents and cleaning agents known, the optical brighteners of the 4,4'-bis-4,4'-bis (triazinylamino) -sti-lben-2,2-h-disulfonic acid type or their salts, per compounds and activators for per compounds. The activators are O-acyl or N-acyl compounds with the per compounds react to form peracids and thus the bleaching effect the mixtures increase or a bleaching at relatively low washing temperatures enable. According to the information in the aforementioned patent application, if the optical brighteners are contaminated in certain ways during storage of the powdered detergent and cleaning agent mixtures discoloration and odor Deteriorations occur. By removing these impurities or by However, this phenomenon can be suppressed using commercially available brightener types.

Regardless of whether impurities are present or not, has it has now been shown that with repeated use of such optical brighteners, Agents containing percompounds and bleach activators show an increasing greening of the washed textile fabric occurs. A similar appearance can already be occur in the absence of bleach activators due to whitener accumulation, however it is more noticeable in the presence of an activator and possibly to an interaction between activator, brightener and fiber surface. The task was therefore to find a means which does not have these disadvantages owns.

Subject of the patent .................. (patent application P 19 53 519.4 is a textile treatment agent, characterized by a content of a mixture of optical brighteners of the formulas A) and B): in which M is an alkali metal or an ammonium group, but preferably sodium, n and m are integers from 1 to 3 and the weight ratio of the compound mentioned under A) to the compound mentioned under B) is 3: 1 to 1: 4, preferably 2: 1 to 1: 2.

The present invention relates to agents according to the main patent 0. (Patent application P 19 53 519.4), characterized by a content of at least acting as an activator for per compounds compound from the class of N-acyl and O-acyl compounds as well as carbonic and pyrocarbonic acid esters, whose activation value for the per compounds is at least 7, preferably at least 4.5.

The activators to be used according to the invention are to those compounds that are formed with hydrogen peroxide or perhydrates of peracids react.

Its activation value (= titer) is determined in the following way.

Solutions containing Of6l5 g / l NaB02 ° H202. 3 H20 (4 mmol / l) and 2.5 g / l Na4P207. 10 H20 contain, after heating 0 to 60 c with 4 mmol / l activator added and then kept at the specified temperature for 5 minutes with stirring 100 ml of this liquid are added to a mixture of 250 g of ice and 15 ml of glacial acetic acid and titrate immediately after adding 0.35 g of potassium iodide with 0.1 N sodium thiosulphate solution and strength as an indicator. Consumption is made under the specified test conditions with 100% activation of the peroxide used, 8, o ml of thiosulfate solution, i.e. the titer is 8> o. This maximum value is almost never reached in practice. Usable activators have a titer of at least 3, preferably at least one of 4.5.

The activators also play a role in the practical usability of the activators Melting point plays a role. Activators with a melting point (F) is at least qOOC, preferably at least 1500C. Furthermore, the equivalent weight should the activators are at most 170 and preferably at most 110. Below equivalent weight here the quotient of the molecular weight and the number in the molecule becomes more present Understood radicals R-CO-.

The activators of the type of N-acyl or O-acyl compounds contain at least one acyl radical R-C0-, where R is an optionally substituted hydrocarbon radical with 1 to 8 carbon atoms. Aliphatic radicals R preferably have 1 to 3, aromatic radicals up to 8 carbon atoms.

Examples include methyl, ethyl, n-propyl, i-propyl, phenyl, Toluyl or xylyl residues. These radicals can be replaced by C1-3 alkoxyl groups, halogen atoms, Nitro or nitrile groups, may be substituted. In the case of aromatic compounds m-chlorine- or m- or p-nitro-substituted radicals R can be used in particular.

The activators which can be used according to the invention include the types of compounds listed under a - m. In the formulas, the numbered radicals R have the meaning given above for R; if there are several R radicals in a molecule> they can be identical or different. a) N-diacylated amines of the formula 1, in which X is a radical R or one of the radicals Ia, Ib or Ic. From the class of these compounds, examples include N, N, N'N'-tetraacetyl methylenediamine (F = 92-950 C) or ethylenediamine, N, N-diacetylaniline and N, N-diacetyl-p-toluidine to name. b) N-alkyl-N-sulfonyl-carbonamides of the formula II, in which R23 is preferably a C1-3-alkyl radical. Activators of this type are, for example, N-methyl-N-mesyl-acetylamide (F = 73-790 "), N-methyl-N-mesyl-bensoylamide (F = 116-118.5 ° C), N-methyl -N-mesyl-p-nitrobenzoylamide (F = 159-1600 C) and the N-methyl-N-mesyl-p-methoxybenzoyl = amide (F - 117-117.5 ° C). c) N-acylhydantoins of the formula III, in which at least one of the radicals X31 and X32 represents a radical R-C0-, while the other can also represent a radical R or an optionally esterified carboxymethyl radical; Y31 and Yg2 are hydrogen or alkyl radicals having 1 or 2 carbon atoms. Suitable compounds are, for example, 1,3-diacetyl-5,5-dimethylhydantoin, 1,3-dipropionylhydantoin (F = 104.5-1060 ° C.) and ethyl 3-benzoylhydantoin-1-acetic acid. d) Cyclic N-acyl hydrazides of the formula IV, in which the two nitrogen atoms are part of a 5- or 6-membered hetero ring from the group of maleic hydrazide, phthalic acid are hydrazids, triazoles or urazoles. One example is monoacetyl maleic acid hydrazide. e) Carbonic acid esters of the formula V in which X51 is an electron-withdrawing radical, preferably from the group consisting of p-carboxyphenyl, p-sulfophenyl or alkoxycarbonyl.

For example, p-ethoxycarbonyloxy-benzoic acid (F. = 1570 C). f) Pyrocarbonic acid esters of C1-C4 alcohols, such as the pyrocarbonic acid ethyl ester. g) triacyl cyanurates of the formula VI; e.g. triacetyl or tribenzoyl cyanurates. H) Possibly substituted anhydrides of benzoic acid or phthalic acid, especially @ that Benzoic anhydride itself or m-chloro-benzoic anhydride (F = 950 C). i) O, N, N-trisubstituted hydroxylamines of the formula VII, in which R @ 3 is a radical R, preferably a methyl or ethyl radical, an optionally substituted aryl radical or the group VIIa means, while X71 or X72 is one of the radicals R-C0-, R-SO2- or represent one of the aromatic radicals R described above, or each with the corresponding radical R71 or R72 connected to form a succinyl or phthalyl radical can be. n means an integer from 0 to 2.

Activators of this type include, for example, O-benzoyl-N, N-succinyl-hydroxylamine (F = 137-139 ° C), O-acetyl N, N-succinyl-hydroxylamine (F-152-1340 C), Op-methoxybenzoyl -N, N-succinyl-hydroxylamine (F = 142-145 ° C, Op-nitrobenzoyl-N, N-succinyl-hydroxylamine (F = 212 ° 2150 C) and O, N, N-triacetyl-hydroxylamine. J) N , N'-diacylsulfurylamides of the formula VTII, in which R81 and R83 are preferably C1-4-alkyl radicals or aryl radicals, while R82 and R84 are preferably C1-5-alkyl radicals, in particular C1-3-alkyl radicals. Examples are N, N'-dimethyl-N, N'-diacetyl-sulfurylamide (F = 58-60 ° C) and N, N'-diethyl-N, N'-dipropionyl-sulfurylamide (F = 95-97 ° C) ) called. k) 1,3-Diacyl-4,5-diacyloxy-imidazolidines of the formula IX, in which X90 is hydrogen or R. These include: 1,3-Diformyl-4,5-diacetoxy-imidazolidine (F = 160 - 165.5 ° C), 1,3-Diacetyl-4,5-diacetoxy-imidazolidine (F = 139 - 140.5 ° C), 1,3-diacetyl-4,5-dipropionyloxy-imidazolidine (F = 85-87 ° C).

1) Acylated glycolurils of the general formula X, in which X101 represents one of the radicals R or R-CO. m) Diacylated 2,5-diketopiperazines of the formula XI in which R111 and # R112 denote one of the radicals R and R113 or R114 hydrogen or optionally substituted hydrocarbon radicals having 1 to 8 carbon atoms. These include: Diacetyl-> Dipropionyl- or Dibenzoyl-2,5-diketopiperazine.

Tetraacylated glycolurils are preferably used, and in particular the tetraacetyl glycoluril (F = 233-2400 C); in addition to this, the following are acylated Glycolurils suitable: Di- (chloroacetyl) -diacetyl-glycoluril (F = 267 - 2690 C), tetrapropionyl-glycoluril (F = 144-1460 c), 1-methyl-3,4,6-triacetylglycoluril (F = 179-1800 C), diacetyl-dipropionyl-glycoluril (F = 144 - 1460 C) and diacetyl-dibenzoyl-glycoluril (F = 244 - 249 ° C). The. acylated Glycolurils are special because of their excellent properties as activators practical importance. Their high melting point makes them more storable for production, powdery products are particularly suitable.

The mixtures consisting of optical brighteners and activators can be used together with per compounds and other common detergent ingredients present in a mixture or immediately before use to form ready-to-use mixtures or solutions are combined.

In addition to hydrogen peroxide and alkali metal peroxides, per compounds are used primarily perhydrates, for example water-free or water-crystalline Sodium perborate, as well as alkali percarbonates, perpyrophosphates and persilicates Urea perhydrate.

Sodium perborate tetrahydrate is preferably used.

The detergents according to the invention can have customary surfaces active Washing active substances, such as anionic, nonionic and zwitterionic detergents, also non-surface-active cultivation salts, e.g. condensed phosphates, Sequestrants and washing alkalis and possibly others in detergent formulations Contain the usual auxiliaries and additives.

Suitable washing raw materials are those of the sulfonate or sulfate type, for example alkylbenzenesulfonates, in particular n-dodecylberzenesulfonate, furthermore Olefin sulfonates, such as those obtained, for example, by sulfonation of primary or secondary aliphatic monoolefins with gaseous sulfur trioxide and then alkaline or acid hydrolysis, as well as alkyl sulfonates, such as those obtained from n-alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization or by bisulfite addition to olefins. Also suitable are -Sulfofettsä.ureester, primary and secondary alkyl sulfates and the sulfates of ethoxylated or propoxylated higher molecular weight alcohols.

Other compounds of this class that may be used in detergents are the higher molecular weight sulfated partial ethers and partial esters of polyhydric alcohols, such as the alkali metal salts of the monoalkyl ethers or the monofatty acid esters of glycerol monosulfuric acid ester or l, 2-dioxypropanesulfonic acid.

There are also sulfates of ethoxylated or propoxylated fatty acid amides and alkylphenols as well as fatty acid taurides and fatty acid isethionates.

Other suitable anionic detergent raw materials are alkali soaps from Fatty acids of natural or synthetic origin, e.g. the sodium soaps from Coconut, palm kernel or tallow fatty acids. Come as zwitterionic washing raw materials Alkylbetaines and in particular alkylsulfobetaines in question, e.g. the) - (N, N-dimethyl-N-alkylammonium) -propane-1-sulfonate and 3- (N, N-dimethyl-N-alkylammonium) -2-hydroxypropane-1-sulfonate The anionic Detergent raw materials can be in the form of the sodium, potassium and ammonium salts as well as the Salts of organic bases, such as mono-, di- or triethanolamine, are present. Unless the said anionic and zwitterionic compounds are an aliphatic hydrocarbon radical have, this should preferably be straight-chain and have 8 to 22 carbon atoms. The compounds with an araliphatic hydrocarbon radical contain the preferably unbranched alkyl chains with an average of 6 to 16 carbon atoms.

As nonionic surface-active washing-active substances come in primarily polyglycol ether derivatives of alcohols, fatty acids and alkylphenols in question, the 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the hydrocarbon radical contain. 3Xpecially suitable are polyglycol ether derivatives in which the number of Ethylene glycol ether groups is 5 to 15 and their hydrocarbon radicals of straight-chain, primary alcohols with 12 to 18 carbon atoms or of alkylphenols derive with a straight-chain alkyl chain having 6 to 14 carbon atoms. By adding 3 to 15 moles of propylene oxide to the polyethylene glycol ethers mentioned above or by converting them into the acetals, detergents are obtained which are able to carry through are characterized by a particularly low foaming power.

Other suitable non-ionic washing raw materials are the water-soluble, Containing 20 to 250 ethylene glycol ether groups and 10 to lC0 propylene glycol ether groups Polyethylene oxide adducts on polypropylene glycol> ethylene diamino polypropylene glycol and alkyl polypropylene glycol having 1 to 10 carbon atoms in the alkyl chain. the compounds mentioned usually contain 1 to per propylene glycol unit 5 ethylene glycol units.

Also non-ionic compounds of the amine oxide and sulfoxide type, which can optionally also be thoxylated can be used.

The building salts include the tripolyphosphates, especially that Pentasodium triphosphate. The triphosphates can also be condensed in a mixture with higher Phosphates, such as tetraphosphates, or their hydrolysis products, such as acidic or neutral pyrophosphates.

The condensed phosphates can also be wholly or partially through organic, complexing aminopolyearboxylic acids be replaced. Which includes especially alkali salts of nitrilotriacetic acid and ethylenediaminotetraacetic acid. The salts of diethylenetriaminopentaacetic acid and the higher salts are also suitable Homologues of the aminopolycarboxylic acids mentioned. These homologues can, for example by polymerization of an ester, amide or nitrile of N-acetic acid aziridine and subsequent saponification to give carboxylic acid salts or by converting polyamines with a molecular weight of 500 to 10,000 with chloroacetic acid or bromoacetic acid Salts are produced in an alkaline medium. Further suitable aminopolycarboxylic acids are Poly (N-succinic acid) ethylene imines and poly (N-tricarballylic acid) ethylene imines with an average molecular weight of 500 to 500,000, which are analogous to the N-acetic acid derivatives are available.

Other suitable building salts are the complexing water-soluble salts Potassium and especially sodium salts of higher molecular weight polycarboxylic acids, for example of polymers of ethylenically unsaturated mono-, di- and vricarboxylic acids, such as acrylic acid, Maleic acid, fumaric acid, itaconic acid, citric acid, aconitic acid, mesaconic acid and methylenemalonic acid. Copolymers of these carboxylic acids with one another or with other copolymerizable substances, such as ethylenically unsaturated hydrocarbons, such as ethylene, propylene, isobutylene and styrene, with ethylenically unsaturated monocarboxylic acids, such as acrylic acid, methacrylic acid, crotonic acid and 3-butene carboxylic acid or with others Ethylenically unsaturated alcohols, ethers, esters, amides and nitriles, such as vinyl alcohol, Allyl alcohol, vinyl methyl ether, acrolein, vinyl acetate, acrylamide and acrylonitrile, are useful. Copolymers of ethylenically unsaturated mono-, Di- and tricarboxylic acids and several ethylenically unsaturated compounds of different types Structure suitable. The polymers and copolymers have a middle Degree of polymerization from 3 to 6000 and should, based on 3 monomer units, Contain 1 to 9, preferably 2 to 9, carboxyl groups capable of salt formation.

The homopolymeric and copolymeric polycarboxylic acids capable of salt formation according to the above definition can be represented by the following formula: R1 = H or -CH3, R2 = H or -CH3, R3 = H, = CH3, -phenyl, -OH, -CH2OH, -OCH3, -CHO, -COOH, -CONH2, -CN, X = H or -COOH, Y = H, -COOH or -CH2COOH, where X and Y should not represent -COOH at the same time, Z = H or (if X = COOH and Y = H) also -CH ,, m = a any numerical value from 0 to 2, n - an integer between 3 and 6000.

The value of m is not restricted to integer values, but rather can be any numerical value, including fractional values of whole numbers from 0 to 2 accept.

Furthermore, complexing polyphosphonic acid salts can be present be, e.g. the alkali salts of aminopolyphosphonic acids, especially aminotri- (methylenephosphonic acid), 1-hydroxyethane-1,1-diphosphonic acid, methylene phosphonic acid, ethylene diphosphonic acid and salts of the higher homologues of the polyphosphonic acids mentioned. Mixtures too the aforementioned complexing agents can be used.

So-called washing alkalis come into question as further building salts, such as alkali silicates, especially sodium silicate, in which the ratio of Na20 : SiO2 is 1: 3.5 to 1: 1, furthermore carbonates, bicarbonates, borates and citrates of sodium or potassium. The amount of alkaline substances including the washing alkalis and phosphates should be measured so that at least half the carboxylic acids released from the bleach activator are bound as alkali salts and the pH of a usable lye for coarse washing 9 to 12 and for delicates is 6 to 9.

Other additives include stabilizers for per compounds, in particular magnesium silicate, which is based in amounts of 3 to 20 percent by weight on the per connection, can be present.

There are also additional ones suitable for lightening synthetic fibers optical brighteners in question, for example 1,3-diphenylpyrazoline, in which the Phenyl radicals can carry further substituents? such as hydroxy, alkoxy, hydroxyalkyl, Amino, alkylamino, acylamino, carboxyl, carboxylalkyl, sulfonic acid and sulfamido groups or halogen atoms. Examples are 1- (p-sulfamidophenyl) -3- (p-chlorophenyl) pyrazoline or 1- (p-carboxymethylphenyl) -3- (p-chlorophenyl) pyrazoline.

Other suitable whiteners are those of the naphthotriazole stilbene sulfonate type, Ethylene-bis-benzimidazole, ethylene-bis-benzoxazole, thiophene-bis-benzoxazole, dialkylaminocoumarins and cyanoanthracene. Mixtures of the aforementioned optical brighteners are also possible usable.

The agents can also include enzymes from the class of the proteases, lipases and amylases or mixtures thereof.

The enzymes can be of animal or vegetable origin, e.g. be obtained from digestive enzymes or yeast, such as pepsin, pancreatin, trypsin, Papain, catalase and diastase. Preferably from bacterial strains or fungi, such as Bacillus subtilis and Streptomyces griseus obtained enzymatic agents used against alkali, per-compounds and anionic washing active substances are relatively stable and not yet even at temperatures between 50 ° and 70 ° are significantly inactivated.

Further components contained in the agents according to the invention are neutral salts, especially sodium sulphate, bacteriostatic substances, such as halogenated phenolic ethers and thioethers, halogenated carbanilides and salicylanilides as well as halogenated diphenylmethanes, as well as dyes and fragrances.

Known graying inhibitors, in particular sodium cel lu lo segly colate (carboxymethyl cellulose) was added will.

If appropriate, the detergents can also be known foam suppressants contain, such as saturated fatty acids or their alkali metal soaps with 20 to 24 Carbon atoms, higher molecular weight fatty acid esters or triglycerides, trialkylmelamines or dialkyl or tetraalkyl ureas.

The agents according to the invention include both solid constituents to understand existing mixtures as well as aqueous solutions of the constituents. the Solid mixtures can, for example, as powders, granules, flakes, needles, tablets or pieces are present as they are produced by spray drying, granulation, extrusion, Milling and pressing are available. The various components can thereby together, processed as individual components or as partial mixtures or solidified or deformed in the specified manner and mixed with one another will. The agents are preferably in the form of granular powder mixtures, with the per compound, especially the sodium perborate, the remaining powdery ll detergent ingredients is subsequently added in powder form. With the liquid, i.e. water-containing mixtures are used immediately before or washing and bleaching solutions prepared during use, whereby the bleaching agent, preferably hydrogen peroxide, stored separately from the other components will.

The qualitative and quantitative composition of the funds depends largely depends on their area of application. The content of optical brighteners is 0.001 to 2, preferably 0> 05 to 1 percent by weight of the per compounds generally 0.5 to 40 percent by weight of sodium perborate tetrahydrate and 5 to 25 percent by weight of hydrogen peroxide 0.5 to 5 percent by weight, based in each case on anhydrous Mixture. The proportion of the bleach activator should be such that ate per mole of peroxygen 0.1 to 4 mol, preferably 0.2 to 2 mol of N-acyl capable of peracid formation or O-acyl compound is omitted. In the case of the tetraacetylglycoluril to be used with preference this corresponds to a proportion of 3 to 25 percent by weight, based on anhydrous Substance.

The following are possible further components, whereby the The weight percentages given relate to anhydrous substance: 1 up to 20 percent by weight of at least one compound from the class of anionic, nonionic and zwitterionic washing active substances, 10 to 50 percent by weight at least one compound from the class of the complexing building salts and washing alkalis, 1 to 25 percent by weight of other auxiliaries and additives.

The washing active substances can contain up to 100, preferably 5 to 70 % from compounds of the sulronate and / or sulfate type, up to 100 i preferably 5 to 40% of nonionic compounds of the polyglycol ether type and up to 100 , preferably 10 to 50 ffi of soap. The building salts can contain up to 100 %, preferably 25 to 95 ffi, from alkali metal triphosphates and mixtures thereof with alkali metal pyrophosphates, up to 100%, preferably 5 to 50% of one Alkali metal salt of a complexing agent from the class of polyphosphonic acids, Nitrilotriacetic acid, ethylenediaminotetraacetic acid and up to 100%, preferably 5 to 75% of at least one compound from the class of alkali metal silicates> Be composed of alkali metal carbonates and alkali metal borates.

The other auxiliaries and additives include graying inhibitors, Foam inhibitors, stabilizers for per compounds, enzymes and avalanche agents Compounds, each of these ingredients in amounts up to 5% by weight, preferably from 0.2 to 3% by weight can be present in the agents, furthermore biocides, their proportions 0.1 to 2 percent by weight, as well as neutral salts, especially sodium sulfate, which can be present in amounts of 1 to 20 percent by weight.

Examples 1 to 6 Unlightened cotton fabric was washed 20 times each 10 minutes at a temperature of 6 ° C, a weight ratio of textile material washed to wash liquor of 1:20 and a detergent concentration of 5 g / l.

The detergent had the following composition (data in Weight percent anhydrous substance): 6.5 X n-dodecylbenzenesulfonate (Na salt) 3.0 % Oleyl alcohol with 10 ethylene glycol groups, 4.5% Na soap from saturated C12-C22 fatty acids 34.0% pentasodium triphosphate 8.0% soda 4.5 ß sodium silicate (Na20: Si02 = 1: 3.3) 2.5 ß magnesium silicate 0.2% sodium ethylenediamine tetraacetate 1.5% sodium cellulose glycolate 4.9% sodium sulfate 15.0% sodium perborate tetrahydrate 15.0 ß tetraacetylglycoluril 0.4% brightener mixture The optical brighteners were used as sodium salts.

The connection referred to below as A1 is uu .in.n brightener of the formula A, in which the group -CmH2n-O-Cn-H2n + 1 of the formula -C2H4-O-CH3. This group corresponds to the brightener marked A2 of the formula -CH6-0-CH3. Brightener B consists of the sodium salt of 4,4'-bis- (2-anilino-4-morpholino-1,3,5-triazinyl 6-amino) -stilbene-2,2'-disulfonic acid according to formula B. The proportion of brighteners is can be found in the table.

The brightness and the discoloration that occurred were determined photometrically using the "Elrepho" device (manufacturer Carl Zeiss, Oberkochen, Federal Republic of Germany) using a xenon lamp and the three color filters FMX / L, FMY / L and FMZ / L. The standardized color values X = 0.785 RX + 0.167 RZ Y = RY Z = 1.008 RZ were calculated from the measured reflection values RXJ Ry and Rz using the conversion factors specified by the device manufacturer. From this, the coordinates x and y, also called color value components, can be calculated in the CIE standard color table (CIE = Commission International de l'Eclairage) as follows: X and d gH X + Y + ZX + Y + Z One clearly visible to the eye perceptible shift to green is associated with a greater increase in y and a simultaneous small decrease in x. The following table shows the color coordinates as a function of the amount of brightener, the lightness Y of the textile samples and the color shift that is visually perceptible when the amount of brightener is increased. While when using the pure brightener types a color shift to green occurs with the number of washing attempts, which is expressed in an increase in the y-coordinate, no color shift can be seen in the examples according to the invention. With regard to lightness, the individual fabric samples do not differ significantly from one another. Examples 7 to 12 A wash liquor was prepared using the following ingredients (the percentages relate to anhydrous substance): 3.0 β n-dodecylbenzenesulfonate (Na salt) 2.0 ß oleyl alcohol with 10 ethylene glycol ether groups 1.0% oleyl alcohol with 5 ethylene glycol ether groups 8.0 f Na soap made from saturated C12-C20 fatty acids 19.0% pentasodium triphosphate 15.0% soda 25.0 ß sodium silicate (Na2O: SiO2 = 1: 3 , 3) 2.5, magnesium silicate 1.5% sodium cellulose glycolate 4.6% sodium sulfate 15.0 ß tetraacetylglycoluril 0.4% brightener mixture (as in Example 1) 3.0 / 3 hydrogen peroxide The hydrogen peroxide was added to the wash liquor immediately before use added to a 10% aqueous solution. The wash liquor contained 5 g / l of the specified mixture. The washing tests and the evaluation of the measurement results were carried out in the manner indicated in Example 1. In this case, too, as can be seen from the table values and confirmed by visual comparison, when the brightener mixture is used instead of the pure brightener types, there is no perceptible greening of the fabric. Brightener Brightness Color Coordinates Visual Examples% A1% A2% BY xy assessment Comparison 0.400 - - 92.5 0.3005 0.3098 weak green - prickly Comparison - 0.400 - 92.6 0.3004 0.3098 weak green - prickly Comparison - - 0.400 93.0 0.3005 0.3107 green-tinged 1 0.267 - 0.133 92.8 0.3010 0.3086 white 2 0.200 - 0.200 92.9 0.3007 0.3085 white 3 0.133 - 0.267 92.9 0.3006 0.3086 white 4 - 0.267 0.133 92.8 0.3011 0.3085 white 5 - 0.200 0.200 92.9 0.3008 0.3086 white 6 - 0.133 0.267 93.0 0.3007 0.3084 white 7 0.267 - 0.133 92.8 0.3009 0.3084 white 8 0.200 - 0.200 92.8 0.3007 0.3083 white 9 0.133 - 0.267 93.0 0.3006 0.3081 white 10 - 0.267 0.133 92.8 0.3010 0.3086 white 11 - 0.200 0.200 92.9 0.3009 0.3082 white 12 - 0.133 0.267 92.9 0.3008 0.3083 white If the tetra-acetylglycoluril contained in the agents of the examples is replaced by corresponding amounts of tetrapropionyl-glycoluril, methyl-triacetyl-glycoluril, diacetyl-dibenzoyl-glycoluril, diacetyl-diketopiperazine, dibenzoyl-diketopiperazine, dibenzoyl-diketopiperazine, diacetyl-acetyl aniline, Tetraacetyl-methylenediamine or tetraacetyl-ethylenediamine, one arrives at similar results. The activation of the per compounds is better when using the acylated glycolurils and acylated diketopiperazines than when using the other mentioned activators.

Claims (10)

Claims 1. Detergent containing a mixture of optical brighteners of the formulas (A) and (B) in which M is an alkali metal or an ammonium group, but preferably sodium, n and m are integers from 1 to 3 and the weight ratio of the compound mentioned under A) to the compound mentioned under B) is 3: 1 to 1: 4, preferably 2: 1 to 1: 2, according to patent .............. (patent application P 19 53 519.4) characterized by a content of at least one compound from the class of N-acyl and N-acyl compounds which acts as an activator for per compounds O-acyl compounds and the carbonic acid and pyrocarbonic acid esters whose activation value for the per compounds is at least 3, preferably at least 4.5. 2. Means according to claim 1, characterized in that the activator contains at least one acyl radical R-CO-, where R is an optionally substituted aliphatic Hydrocarbon radical with 1 to 7 carbon atoms or an optionally substituted one aromatic hydrocarbon radical with up to 8 carbon atoms. 3. Means according to claim 1 and 2, characterized in that the activator from acetylated, propionylated or benzoylated amines, amides, sulfamides, Sulfurylamides, hydantoins, hydrazides, hydroxylamines, imidazolines or glycolurils consists. 4. Means according to claim 1 to 3, characterized in that the activator consists of tetraacetylglycoluril. 5. Means according to claim 1 to 4, characterized by a content on at least one per connection. 6. Means according to claim 1 to 5, characterized in that it is in solid, preferably powdery to granular form, the per compound consists of sodium perborate tetrahydrate. 7. Composition according to claim 1 to 5, characterized in that it is in aqueous solution is present, the per compound consisting of hydrogen peroxide. 8. Composition according to claim 1 to 7, characterized in that the on anhydrous mixtures related content of optical discs 0.01 to 2 percent by weight, 5 to 25 percent by weight of sodium perborate tetrahydrate and of octraacetylglycoluril 3 to 25 percent by weight. 9. Means according to claim 1 to 8, characterized by an additional, content of at least 1 to 20 percent by weight based on anhydrous substance a compound from the class of the anionic, nonionic and zwitterionic Washing active substances, 10 to 50 percent by weight of at least one compound the class of complexing building salts and washing alkalis, 1 to 25 percent by weight of other auxiliaries and additives. 10. Composition according to claim 1 to 9, wherein the washing active substances to 100%, preferably 5 to 70 ffi, from compounds of the sulfonate and / or or Sulphate type, up to 100%, preferably 5 to 40% of non-ionic compounds of the polyglycol ether type and up to 100%> preferably 10 to 50 ß from soap, the synthesis salts up to 100%, preferably 25 to 95% from alkali metal triphosphates and their mixtures with alkali metal pyrophosphates, up to 100%> preferably 5 to 50% of an alkali metal salt of a complexing agent from the class of polyphosphonic acids, nitrilotriacetic acid, ethylenediaminotetraacetic acid and up to 100%, preferably 5 to 75%, of at least one compound from the class the alkali metal silicates, alkali metal carbonates and alkali metal borates.