DE1955431A1 - Stilbene sulphonic acid derivative brighten- - ing agents - Google Patents

Abstract

Stilbene sulphonic acid derivative brightening agents. Title cpds. have the formula:- where M is H, alkali metal or - NH4; R1 is -NH2, -NHC6H4SO3M; -NHC6H4COOM, -NHC2H4OH, -NCH3C2H4OH, -N(C2H4OH)2 or a morpholino group; R2 is alkyl- or alkylene-phenol with C1-C3 in the alky l group; and R3 is a defined s-triazole group. The compounds are used in washing agents.

Description

"Optical brightening agent" The invention relates to optical brightening agents consisting of a 4,4'-bis-triazinylamino-stilbene-2,2'-disulfonic acid derivative of the formula in which M stands for hydrogen, an alkali metal or an ammonium group, R1 for -NH2, -NHC6H5, -NH-C6H4-SO3M, -NH-C6H4-COOM, -NHC2H4OH, -NCH3C2H4OH, -N (C2H4OH) 2 or a morpholino group, R2H4OH) 2 represents hydrogen, an alkyl or alkylenephenyl group with 1 to 3 carbon atoms in the alkyl or alkylene group and R5 represents an s-triazole group, the triazole group optionally being replaced by one or two alkyl groups with 1 to 5 carbon atoms, one or two phenyl groups or one Carboxyl group can be substituted.

The group R, -N-R contained in the above formula.

can therefore correspond to one of the following isomeric structures: in which the groups R4 and R5 are either hydrogen, an alkyl group having 1 to 3 carbon atoms or a phenyl group, or one of the groups R4 and R5 is a carboxyl group.

Examples of the group R2-NR) are: s-triazol-3-ylaminos-triazol-4-ylamino-5-phenyl-s-triazol-3-ylamino-5-phenyl-s-triazoi-4-ylamino-5- Methyl-s -triazol-4-ylamino-5-carboxy-s-triazol-3-ylamino-5-carboxy-s-triazole -4 -ylamino-1-phenyl-5-carboxy-s-triazol-3-ylamino-1-methyl -5-carboxy-s-triazol-3-ylamino-N-methyl-s-triazol -) - ylamino-N-benzyl-s-triazol-3-ylamino-N-benzyl-5-carboxy-s-triazol-3 -ylamino- the The lightening agents are produced in a manner known per se, for example by reacting cyanuric chloride with 4,4'-diaminostilbene-2,2'-disulfonic acid in a molar ratio 2: 1 implements. The reaction product obtained is, preferably in alkaline Environment with one of the two amino compounds provided, for example the optionally substituted 5-amino-s-triazole or 4-amino-s-triazole in a molar ratio of 1 : 2 condensed. Then the product obtained with the second amino compound, in the present case an amine of the formula R1H, in a molar ratio of 1: 2 to 1: 5 implemented. The aminotriazole or the amine of the formula R H can also be added done in reverse order.

The amino compound added in the second position is expediently added used in excess in order to achieve an accelerated, quantitative conversion. Examples of amines of the formula R.1H are aniline, p-sulfanilic acid, p-aminobenzoic acid, Morpholine, ethanolamine, diethanolamine and N-methylethanolamine. From the solutions the salts of the optical brighteners according to the invention can be achieved by adding neutral salts be salted out. In the case of the sodium salts to be used with preference, this is done appropriately used sodium chloride.

The optical brighteners can be used in the usual way. They are suitable for lightening textile materials made of cellulose fibers, wool and synthetic polyamides, papers, plastic films, soaps and cosmetic Preparations.

They can be used with advantage in detergents, rinsing agents and stiffeners are used and point to the textiles treated with it. a pure white Fluorescence. Their good solubility in water and detergent solutions should be emphasized and concentrated detergent solutions, which ensures rapid and homogeneous distribution and easy processing or even drawing on to the treated material Textile material is important. A particular advantage is their good tolerance with higher molecular weight quaternary ammonium salts, such as those in textile softeners commonly used. Unlike most known Brighteners containing anionic groups occur with those of the invention Agents in connection with higher molecular quaternary salts do not have any significant fluorescence quenching on. They are therefore particularly suitable for use in household detergents, according to their use usually with a softening agent containing quaternary ammonium salts is rinsed and as an additive to such plasticizers.

The amounts of whitening agent required for the particular application can easily be determined by preliminary tests. In the case of Jasch or textile softeners their proportion is appropriately 0.005 to 2 percent by weight, based on the solids contained in these agents.

The agents according to the invention can also be used with other known optical brighteners are combined, for example those of the 4,4'-bis-triazinyl-stilbene disulfonate type, Naphtotriazole stilbene sulfonates, ethylene-bis-benzimidazole, ethylene-bis-benzoxazole, Bis-benzoxazolyl-thiophenes, N-dialkylcoumarins and especially the substituted ones 1,5-diphenylpyrazolines. Such mixtures show an increase in effectiveness in many cases compared to the individual components.

The brighteners according to the invention can be part of any composition Be textile treatment agent.

Under textile treatment agents, everyone warts to the treatment, i.e. to the Cleaning, bleaching, finishing and finishing of textile fibers, yarns and fabrics suitable agents, but preferably detergents, rinsing agents with a finishing effect as well as stiffening agents for textiles made of cellulose fibers. The textile detergents have a content of surface-active detergent raw materials as well as inorganic and / or organic non-surface-active building salts and contain those according to the invention Brighteners in a preferred amount of 0.01 to 1% by weight, based on the solids content. The fabric softening agents essentially contain a water-dispersible, higher molecular weight ammonium compound, in particular a quaternary ammonium salt. the Stiffening and finishing agents essentially contain one which is soluble in water or dispersible polymer of natural or synthetic origin. The on Solids content of the softening, stiffening and finishing agents on the brighteners according to the invention is preferably 0.01 to 1 wt.

The detergents and cleaning agents can be customary anionic washing raw materials of the sulfonate or sulfate type.

First and foremost are alkylbenzenesulfonates, for example n-dodecylbenzenesulfonate, into consideration, also olefin sulfonates, such as those primary by sulfonation or secondary aliphatic monoolefins with gaseous sulfur trioxide and then alkaline or acidic hydrolysis can be obtained, as well as alkyl sulfonates such as those from n-alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization or by bisulfite addition to olefins.

Primary and secondary ç sulfo fatty acid esters are also suitable Alkyl sulfates and the sulfates of ethoxy-hard or propoxylated higher molecular weight Alcohols.-Other compounds of this class which may be present in the 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

of 1,2-dioxypropanesulfonic acid. Furthermore, sulfates come from ethoxylated or propoxylated fatty acid amides and alkylphenols and fatty acid taurides and Fatty acid isethionates in question. Other suitable anionic detergent raw materials are alkali soaps of fatty acids of natural or synthetic origin, e.g. sodium soaps of coconut, palm kernel or tallow fatty acids. Come as zwitterionic washing raw materials Alkyl betaines and in particular alkyl sulfo tables are suitable, e.g. 3- (N, N-dimethyl-N-alkylammonium) propane-1-sulfonate and 3- (N, N-dimethyl-N-alkylammonium) -2-hydroxypropane-1-sulfonate.

The anionic ash raw materials can be in the form of sodium, potassium and ammonium salts and as salts of organic bases, such as mono-, di- or triethanolamine, are present.

If the mentioned anionic and zwitterionic compounds have an aliphatic hydrocarbon radical, this should preferably be straight-chain and have 8 to 22 carbon atoms. In compounds with an araliphatic The preferably unbranched alkyl chains contain hydrocarbon radicals on average 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. 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 latter polyethylene glycol ethers or by transferring them into the acetals, detergents are obtained which are 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 100 propylene glycol ether groups Polyethylene oxide adducts with polypropylene glycol, ethylene diamino polypropylene glycol and A Ilcylpolypropy lenglyko 1 with 1 to 10 carbon atoms in the alkyl chain. The straight connections usually contain per propylene glycol sol unit 1 to 5 Pthy lnglycol units Also non-ionic compounds of the amine oxide type and sulfoxides, which can optionally also be ethoxylated, can be used.

Suitable detergent ingredients are also inorganic cleaning salts, in particular condensed phosphates, such as pyrophosphates, triphosphates, tetraphosphates, Trimetaphosphates, tetrametaphosphates and more highly condensed phosphates in the form of neutral or acidic sodium, potassium or ammonium salts. Preferably be Alkali triphosphates and their mixtures with pyrophosphates are used. Keep coming Silicates in question, especially sodium silicate, in which the ratio of Na2O: SiO2 is 1: 3.5 to 1: 1.

The condensed phosphates can also be wholly or partially through organic, cleansing, nitrogen- or phosphorus-containing complexing agents be replaced. These include the alkali or ammonium salts of nitrilotriacetic acid, Ethylenediaminotetraacetic acid, diethylenetriaminopentaacetic acid and the higher Homologues of the aminopolycarboxylic acid mentioned. Suitable homologs can, for example by polymerizing an ester, amide or nitrile of N-acetic acid aziridine and subsequent saponification to carboxylic acid salts or by reaction of polyamines with a molecular weight of 500 to OC 000 with chloroacetic acid or bromoacetic acid Salts are produced in an alkaline medium. Other suitable minopolycarboxylic acids are poly (N-ß-propionic acid) -äthylenimine with an average molecular weight of 500 to 200,000, which are available analogously to the N-acetic acid derivatives. Bra'chable phosphorus Complexing agents are the alkali and ammonium salts of aminopolyphosphonic acids, in particular aminotri (methylenephosphonic acid), ethylenediaminotetra (methylenephosphonic acid), 1-hydroxyethane-1,1-diphosphonic acid, methylenediphosphonic acid, ethylenediphosphonic acid as well as the higher liomologists of the polyphosphonic acids mentioned. Also mixtures of The aforementioned complexing agents can be used.

Neutral salts such as sodium sulfate are also used as components of the mixture and sodium chloride, as well as substances for regulating the pH value, such as bicarbonates, Carbonates, borates and hydroxides of sodium or potassium and acids such as lactic acid and citric acid. Those of the alkaline-reacting substances including the alkali silicates and phosphates should be dimensioned so that the pE value of a usable lye for coarse laundry is 9 to 12 and for delicates 6 to 9.

Through a suitable combination of different surface-active detergent raw materials or building salts with one another can in many cases increase the effectiveness, for example improved detergency or reduced foam bonding can be achieved. Such improvements are possible, for example, by combining anionic ones with non-ionic and / or zwitterionic compounds with one another, through combination different nonionic compounds with one another or also through mixtures of washing raw materials of the same type, which differ in terms of the number of carbon atoms or the number and position of double bonds or chain branches in the hydrocarbon differentiate. Mixtures of inorganic and organic compounds with a synergistic effect can also be used Build-up salts can be used or combined with the mixtures mentioned above.

Depending on their intended use, the agents can be oxygen-releasing agents Contain bleach, such as hydrogen peroxide, alkali perborates, alkali percarbonates, Alkali perphosphates, urea perhydrate and alkali persulfates or those containing active chlorine Compounds such as alkali hypochlorites, chlorinated trisodium phosphate and chlorinated Cyanuric acid or its alkali salts. The per compounds can be mixed with blood activators and stabilizers such as magnesium silicate are present.

Other suitable detergent ingredients are graying inhibitors, e.g. sodium cellulose glycolate, as well as the water-soluble alkali salts of synthetic Polymers that contain free carboxyl groups. The polyester resp. Polyamides made from tri- and tetracarboxylic acids and dihydric alcohols or diainines, also polymeric acrylic, methacrylic, maleic, fumaric, itaconic, citraconic and aconitic acid and the copolymers of the unsaturated carboxylic acids mentioned or their Copolymers with olefins.

Agents intended for use in drum washing machines, suitably contain known foam suppressants, such as saturated Fatty acids or their alkali soaps with 20 to 24 carbon atoms or triazine derivatives, the reaction of 1 mole of cyanuric chloride with 2 to 5 moles of an aliphatic, straight-chain, branched or cyclic primary monoamine or by propoxylation respectively.

Butoxylation of melamine are available.

To further improve the dirt-releasing properties of the invention These can also be enzymes from the class of proteases, lipases and amylases contain.

The enzymes can be of animal and vegetable origin, e.g. from Digestive enzymes or yeasts such as pepsin, pancreatin, trypsin, papain, Catalase and diastase.

Preferably, bacteria or fungi, such as Bacillus subtilis and Streptomyces griseus, extracted enzymatic active ingredients used, those relative to alkali, per-compounds and anionic washing active substances are stable and are not worth mentioning even at temperatures between 45 and 700C be inactivated.

Furthermore, bactericidal substances, in particular halogenated diphenyl ethers, halogenated diphenylurea derivatives and halogenated salicylic acid anilides present be. Non-quaternary higher molecular ammonium compounds can be used to improve the grip can be added, e.g. the tallow fatty acid amide of aminoethylethanolamine. As a skin protection agent come mono- and diethanolamides or isopropanolamides of higher molecular weight fatty acids into consideration.

The detergents can be liquid, pasty or solid, for example powdery, especially spray-dried, granulated or lumpy form are present. Liquid preparations can be mixed with water for the purpose of better solubility Solvents, in particular ethanol and i-propanol, and solubilizers, such as contain the alkali salts of benzene, toluene, xylene or ethylbenzenesulfonic acid.

The composition of the various detergent ingredients, their The total proportion is 99 to 99.99 percent by weight, based on the solids content, can correspond to the following scheme for the heavy-duty detergents of particular interest (Data in percent by weight): 1 to 40% of at least one compound from the class of anionic, nonionic and zwitterionic washing active substances, 10 to 80 ß at least one non-surface-active, cleaning-enhancing or complex-acting assembly kit, 10 to 50, a per connection, in particular Sodium perborate containing water of crystallization or anhydrous, and mixtures thereof with Stabilizers and activators, 0.1 to 20% other auxiliaries and additives.

The washing active substances can contain up to 100, preferably 5 to 70 % from compounds of the sulfone .t and / or sulfate type, up to 100, preferably 5 to 40% of nonionic compounds of the polyglycol ether type and up to 100 , 4, preferably 10 to 50% of soap. The building salts can contain up to 100 %, preferably 25 to 95% of alkali metal triphosphates and their mixtures with Alkali metal pyrophosphates, up to 100%, preferably 5 to 50% of an alkali metal salt a complexing agent from the class of polyphosphonic acids, nitrilotriacetic acid, Ethylenediamino tetraacetic acid and up to 100%, preferably 5 to 75% of at least a compound from the class of the alkali metal silicates, alkali metal carbonates and alkali metal borates.

The other auxiliaries and additives include the optical ones Brighteners in particular the foam inhibitors that are in the agents according to the invention in an amount up to 5%, preferably in an amount from 0.2 to 3, present can be, furthermore, the enzymes in an amount up to 5, preferably 0.2 to 5 ß can be present and the graying inhibitors, their proportion up to 5%, preferably 0.2 to 5 / j.

The higher molecular weight ammonium compounds preferably contained in the softeners can have the following formulas: in which R1 and R2 are identical or dissimilar, saturated or unsaturated aliphatic hydrocarbon radicals with 11 to 25, preferably 15 to 21 carbon atoms, R5 is an alkyl or llydroxyl group with 1 to 7 carbon atoms, R4 = R3 or a benzyl group, R5 = R) or a Hydrogen atom, R6 is an alkylene group with 1 to 5 carbon atoms and A is an anion, for example a halide, acetate or alkyl sulfate ion or an equivalent of a sulfate or phosphate ion or the anion of a polybasic carboxylic acid, e.g. oxalic or citric acid.

Also mixtures of different surface-active ammonium compounds can be used. The agents according to the invention preferably contain quaternary Ammonium salts according to formula 1, in which the radicals R1 and R2 are straight-chain, saturated Hydrocarbon radicals with 16 to 18 carbon atoms and the radicals R3 and R4 methyl or represent ethyl groups.

The quaternary ammonium compounds can also be wholly or partially are replaced by condensation products that are produced by the reaction of hardened tallow fatty acid triglyceride obtained with Aminoäthyläthanolamid in a molar ratio of 1: 1 and with inorganic or organic acids, in particular glycolic acid, have been neutralized.

The mixtures of higher molecular weight ammonium compounds and optical Brighteners can be in anhydrous form or in the presence of or with water Water-miscible solution should be mixed with a medium. In the former case one obtains Mixtures of firm to lardy consistency, which may be

solidified by the addition of inert fillers or into granular, pourable Powder can be transferred. However, the mixtures are preferably in the form water-based, pourable dispersions or pastes. Contain such dispersions generally 3 to 15, preferably 5 to 10% by weight of surface-active ammonium compound.

The storage stability of the aqueous dispersions can, if necessary,

can be improved by adding small amounts of stabilizers. Suitable stabilizers are, for example, fatty acid alkylolamides, in particular Fatty acid mono- or diethanolamide, fatty acid mono- or dipropanolamide and fatty acid mono- or diisopropanolamide, and also polyethylene glycols with a molecular weight of 200 to 10,000 and polyethylene glycol ether derivatives of higher molecular weight alcohols, amines, fatty acids and alkylphenols or polyvalent alkyl partial ethers or fatty acid partial esters Alcohols. In the aforementioned polyglycol ether derivatives, the hydrophobic hydrocarbon radical 10 to 24 carbon atoms and the polyglycol ether residue 2 to 50 ethylene glycol ether groups exhibit.

The dispersions can contain the stabilizers in amounts from 0.05 to 5, preferably 0.1 to 1%> contain.

The customary additives can also be added to the aqueous dispersions and solvents are added. Neutral salts such as sodium chloride are suitable, Sodium sulfate, sodium borate, sodium acetate, sodium citrate, as well as the corresponding Potassium and ammonium salts in amounts up to 2%, preferably 0.05 to 1%. Farther come organic solvents such as low molecular weight alcohols, especially ethanol and isopropanol, fither alcohols, glycols, di- and triglycols, glycerin, polyglycerin and glycerol ethers, ketones and alkylolureas in amounts up to 10, preferably 0.5 to 5 ffi in question. In addition, suitable preservatives, Dyes and fragrances are added.

As far as the detergents and softeners mentioned also for simultaneous use Treatment of textiles made from synthetic fibers or

Blended fabrics made from cellulose and synthetic fibers are to be used, Optical brighteners can also be added which are based on synthetic fibers, but not draw on cellulose fibers.

These include brighteners of the l, 3-Diarylpyrazolineß coumarine type, Carbostyryls, benzoxazoles and benzimidazoles.

Another area of application is the use of optical brighteners in textile stiffening and finishing agents. Such agents usually contain polymers of natural or synthetic origin that are soluble or dispersible in water, such as starch, for example corn or rice starch, alkoxylated starch, carboxymethyl cellulose, Methyl or ethyl cellulose, oxyethyl cellulose, polyethylene oxides, especially those from molecular weight 2000 to 20,000, polyvinyl alcohol, polyvinyl acetate, partially saponified Polyvinyl acetate, polyvinyl pyrrolidone, polyacrylonitrile, polyacrylic acid and copolymers from the vinyl polymers mentioned. Mixtures of different polymers are also used. Neutral salts such as sodium chloride, Borax or sodium acetate, solvents and plasticizers such as methanol, ethanol or isopropanol, ether alcohols, glycols, glycol ethers, glycerine and other polyalcohols, also anionic uld / or nonionic wetting agents, preservatives> fragrances and ironing aids such as paraffin and hard waxes can be added. The means can be in the form of a powder, paste or aqueous dispersions. Your salary the brightener combination according to the invention is 0.01 to 1 percent by weight, based on on solid substance.

Examples Example 1 To a solution of 18.5 g (0.1 mol) of cyanuric chloride in 80 ml of acetone, 100 ml of H2O and 100 g of ice were added at 0 to 50C a solution of 18.5 g (0.05 mol) of 4,4'-diamino-stilbene-2,2'-disulfonic acid with stirring and 19 g of borax in 200 ml of water were added and the mixture was stirred at this temperature for 50 minutes. A concentrated aqueous solution of 5 g (0.05 mol) of soda was then added allowed a solution of 12 g of boric acid and 8.4 at 200C within 10 minutes g (0.1 mol) of 5-amino-s-triazole in an aqueous glycerol run in and stirred after admixing with 5.3 g (0.05 mol) of soda further for 1 hour. To the reaction mixture were 47,) g (0.15 mol) diethanolamine as a 40% aqueous solution and 5.3 g (0.05 mol) Soda was added, whereupon the mixture was heated to 70 ° C. for 10 hours.

The precipitated after cooling with the addition of 120 g of table salt Precipitate was washed out with hot isopropanol.

After drying at 600 ° C., the disodium salt was 4,4t-bis-F4-diethanolamino-6- (s-triazoi-5-ylamino) -s-triazin-2-ylamino] stilbene-2,2'-disulfonate obtained as a light yellow powder in a yield of 34.5 g.

For the compound synthesized, is shown in the above formula R1 for a diethanolamino group, R2 for a hydrogen atom and R3 for an in 3-position added triazolyl group.

) Example 2 As described in Example 1, the reaction product was from 0.1 mol of cyanuric chloride and 0.05 mol of di-sodium-4> 41-diaminostilbene-2,2'-disulfonic acid (hereinafter referred to as precondensate) with 8.4 g (0.1 mol) of 3-amino-s-triazole and then reacted with 14 g (0.15 mol) of aniline. The reaction product was with 120 g of sodium chloride salted out. In the formula picture, M stands for sodium, R1 for one Anilino group, R2 for hydrogen and R5 for a triazolyl group attached in the 3-position.

The yield was 31.5 g.

Example 3 As described in Examples -1 and 2, 0.05 mol of precondensate with 8.4 g (0.1 mol) 5-amino-s-triazole and 13.7 g (0> 15 mol) p-aminobenzoic acid, which had been neutralized with NaOH, reacted and the reaction product worked up.

It was worked without the addition of borax and boric acid. In the above Formula scheme M stands for sodium, R1 for the sodium salt of the p-carboxy-anilino group, R2 for hydrogen and R3 for a triazolyl group attached in the 3-position. the The yield was 57.9 g.

Example 4 As described in Examples 1 and 2, 0.05 mol of precondensate with 17.3 g (0.1 mol) of p-sulfanilic acid together with 4 g of NaOH and 22 g (0.14 mol) of 5-amino-5-phenyl-s-triazole implemented and the reaction product worked up. Are in the formula scheme above M for sodium, Rl for the sodium salt of the p-sulfo-anilino group> R2 for hydrogen and R5 for a 5-phenyl-s-triazolyl group attached in the 3-position. The yield was 16.6 g.

Example 5 As described in Examples 1 and 2, 0.05 mol of precondensate were used reacted with 8.4 g (0.1 mol) of 4-amino-s-triazole and 15.75 g (0.15 mol) of diethanolamine and the reaction product worked up. In the formula scheme above, M stands for Sodium, R1 for a diethanolamino group, R2 for hydrogen and R3 for an in 4-position added triazolyl group.

The yield was 40> 4 g.

Example 6 As described above, 0.05 mol of precondensate with 17.5 g (0.1 mol) of solfanilic acid together with 4 g of NaOH and 12.6 g (0.15 mol) of 4-amino-s-triazole implemented and the reaction product worked up. In the above format scheme is M for sodium, R1 for the sodium salt of the p-sulfo-anilino group, R2 for hydrogen and R5 for a triazolyl group attached in the 4-position. The yield was 6), 7 G.

Example 7 As described above, 0.05 mol of precondensate reacted with 8.4 g (0.1 mol) of 3-amino-s-triazole and 15.06 g (0.15 mol) of morpholine and the reaction product worked up. In the formula scheme above, M stands for Sodium, R1 for a morpholino group, R2 for hydrogen and R5 for one in the 3-position attached s-triazolyl group. The yield was 30.4 g.

Example 8 As described above, 0.05 moles of precondensate with 12.8 g (0.1 mol) of 3-amino-s-triazole-5-carboxylic acid, which is neutralized with NaOH had been, and 15.06 g (0.15 mol) of morpholine reacted and the reaction product worked up.

In the formula scheme above, M stands for sodium, R1 for a morpholino group, R2 for hydrogen and R) for the sodium salt of a 5-carboxy-s-triazolyl group attached in the 3-position. The yield was 56.2 g.

Example 9 As described above, 0.05 moles of precondensate with 12.8 g (0.1 mol) of 3-amino-s-triazole-5-carboxylic acid, which is neutralized with NaOH had been, and 15.75 g (0.15 mol) of diethanolamine reacted and the reaction product worked up. In the formula scheme above, M stands for sodium, R1 for a diethanolamino group, R2 for hydrogen and R3 for the sodium salt of a 5-carboxy-striazolyl group attached in the 3-position. The yield was 6.6 g.

Example 10 As described above, 0.05 moles of precondensate with 17.42 g (0.1 mole) 3-N-benzylamino-s-triazole and 15.75 g (0.15 mole) diethanolamine implemented and the reaction product worked up. Are in the formula scheme above M for sodium, R1 for a diethanolamino group, R2 for a benzyl group and R5 for an s-triazolyl group attached in the 3-position. The yield was 38.5 g.

Example 11 As described above, 0.05 moles of precondensate with 8.4 g (0.1 mol) of 5-amino-s-triazole and 10.2 ml (0.15 mol) of 25% aqueous ammonia implemented and the reaction product worked up. Are in the formula scheme above M for sodium, R1 for an amino group, R2 for hydrogen and R3 for an in) position attached s-triazolyl group. The yield was 55 g.

The brighteners were tested as follows.

A. Non-lightened cotton fabric was tested 10 times in a row. 90 to 1000C 15 minutes with a weight ratio of textile material to wash liquor of 1:10 and a detergent concentration of 5 g / 1 and then washed rinsed and dried. The detergent had the following composition (data in percent by weight): 10 «n-Dodexylbenzenesulfonat (Na salt) 3% oleyl alcohol with 10 ethylene glycol ether groups 5% Na soap from saturated C12-C22 fatty acids 45 ß Pentasodium triphosphate 22, sodium perborate 3.5% sodium silicate (Na2O: SiO2 = 1: 3.3) 2.5 magnesium silicate 0.5% Na-ethylenediaminetetraacetate 0.5 ffi sodium cellulose glycolate 2.4 ffi sodium sulfate 7.5% water 0.1% of the optical brightener according to the invention B. nichtaufg, bright cotton fabric was rinsed at 25 0C in a solution, the 5 g / l of an aqueous softener had been added. The softener contained 8 percent by weight of dimethyl distearyl ammonium chloride, 0.1 percent by weight of 2-hydroxy-2 ', 4,4'-trichlorodiphenyl ether, 0.2 percent by weight of a polyethylene glycol ether and 0.2 percent by weight of the invention Brightener.

The whiteness W of the washed or finished textile samples was determined by photometric means, using three standardized color filters and the results are calculated using the formula W = Ry + -) (Rz-Rx) given by BERGER became. In the formula, Rx denotes the reflection value for the red, Ry denotes the green and R den for the blue standard color filter. The results of the whiteness measurements are compiled in the following table.

C. With a detergent of the composition given above, which contained 0.1 ffi of a lightening agent according to Example 2, were textile samples Washed from polyamide fabric, the washing temperature 600C and the ratio from textile to wash liquor was 1:40 and the rest of the test conditions were the same were complied with.

The increase in the degree of whiteness compared to the initial value was after of washing treatment 24 units.

White value for cotton after the washing treatment according to the example Avivage initial value 78.2 74.5 1 130.0 103.2 2 132.0 105.0 3 153.1 109.1 4 148.2 108.5 5 136.8 112.1 6 148.8 110.8 7 140.5 110.5 8 147.1 -9 138.8 10 139.2 11 128.6 In the following table are examples of washing, bleaching and softening agents according to the invention compiled.

Ingredients a to e and g to 1 were present as sodium salts, the Pyrophosphate (ingredient m) came as the potassium salt in Example 14, in all others Examples as sodium salt for use. An from served as the enzyme (component s) Maxatase R from the Koninklijke Nederlandsche Gist, obtained from Bacillus subtilis en Spiritusfabriek N.V. Delft, with an activity of 100,000 LVU / g.

The plasticizer (ingredient w) consisted of Examples 15 and 15 16 from a reaction product of hardened tallow fatty acid triglyceride with aminoethylethanolamine in a molar ratio of 1: 1, which had been neutralized with glycolic acid, in example 20 from a mixture of this reaction product with a di-tallow alkyl dimethyl ammonium chloride in a weight ratio of 3: 5. The foam suppressant (component y) is it is a reaction product of 1 mole of cyanuric chloride with 2> 7 moles of a primary n-alkylamine of chain length C8-C18.

Examples (data in% by weight) constituent 12 13 14 15 16 17 18 19 20 a) Optical brightener 0.5 0.3 0.2 0.1 0.2 0.5 0.4 0.2 0.1 b) n-Dodecylbenzenesulfonate 6 - 5 15 - - - 10 -c) C12-C18 olefin sulfonate 3 - - - 8.5 - 7.5 - -d) C14-C17 alkanesulfonate - 10 5 - - 0.5 - - -e) Coconut fatty alcohol glycol ether sulfate (2 ÄO) - - 5 10 - - - - -f) Oleyl alcohol polyglycol ether (10 ÄO) 3 4 - 5 1.5 - 2.5 - 0.7 g) C12-C15 soap 3 - - - 2 - 4 - -h) C20-C22 soap - 2.2 - - 2 - 0.5 - -i) nitrilotriacetate 25 - - - 10 - - - -k) ethylenediaminetetraacetate - 0.5 1 0.4 - 0.5 0.5 - -l) tripolyphosphate 10 20 - - 25 - 45 - -m) pyrophosphate - - 20 - - - 3 2 -n) soda - 20 - - - 25 - 35 -o) Sodium silicate 5 4.5 - - 5 20 3.5 25 -p) Sodium sulfate 4.4 - - 45 12 - 0.4 - 0.5 q) sodium perborate 25 30 - - 20 50 25 10 -r) magnesium silicate 3 - - - 2 - 3.0 4 -s) Enzyme 1.5 - - - 0.5 - 0.5 - -t) Na cellulose glycolate 1.5 0.5 - - - - 0.5 - -u) Na toluenesulfonate - - 7 - - - - - -v) Coconut fatty acid diethanolamide - - - 5 - - - - 2.5 w) plasticizers - - - 5 3 - - - 6.5 x) dyes and fragrances 0.1 0.1 0.2 - - - 0.1 0.1 0.1 y) Foam suppressant 0.5 - - - - - 0.2 - -z) Water 8.5 7.9 56.6 14.5 8.3 3.5 3.4 13.7 89.6

Claims (1)

Patent claims 1. Optical brightening agents consisting of a 4,4'-bistriazinylamino-stilbene-2,2'-disulfonic acid derivative of the formula in which M stands for hydrogen or an alkali metal or an ammonium group, R1 for -NH2, -NHC6H4-SO3M, -NH-C6H4-COOM, -NHC2H4OH, -NHCH3C2H4OH, -N (C2H4OH or or a morpholino group, R2 for hydrogen, a Alkyl or alkylenephenyl group with 1 to 5 carbon atoms in the alkyl or alkylene group and R) represents an s-triazole group, one of the hydrogen atoms of the triazole group optionally being replaced by an alkyl group containing 1 to 3 carbon atoms or a phenyl group, the other hydrogen atom being the Triazole group can optionally be substituted by a carboxyl group. 2. Agent according to claim 1, in which the group R2-NR) corresponds to one of the following isomeric structures: in which the groups R4 and R5 are either hydrogen, an alkyl group having 1 to 3 carbon atoms or a phenyl group, or one of the groups R4 and R5 is a carboxyl group. 5. Composition according to claim 1 and 2, in which M stands for sodium. 4. A method for producing optical brighteners according to claim 1, characterized in that a reaction product of 1 mole of 4,4'-diaminostilbene-2,2'-disulfonic acid and 2 moles of cyanuric chloride in an alkaline medium, one after the other, each with an amino compound converts, one of which consists of ammonia or one of the formula H2N C6H5, H2N-C -SO, M, H2N-C6H4-COOM, H2N-C6H4-COOM, H2NC2H40H, HN (CH) C2H40H, HN (C2H40H) 2 or morpholine, the second amino compound from an optionally substituted 5-amino-s-triazole or 4-Amino-striazole consists and the amount to be applied in the first place Amino compound 2 moles, the amount of the second amino compound to be used Is 2 to 5 moles. 5. The method according to claim 4, characterized in that the Implementation with an aminotriazole compound according to claim 2, in which the free valence is saturated by a hydrogen atom. 6. Laundry detergent containing optical brighteners according to claim l to 3, characterized in that the solids-based content of optical Brightening is 0.005 to 2, preferably 0.01 to 1 wt .-%. 7. Composition according to claim 6, wherein the non-optical brighteners existing detergent ingredients to 1 to 40 wt .-% of at least one compound from the class of anionic, nonionic and zwitterionic surface-active Washing active substances, 10 to 80% by weight of at least one non-surface-active, Cleansing-enhancing or complexing building salt, 10 to 50 wt.% ' from per compounds and their mixtures with stabilizers and activators and 0.1 to 20% by weight of additives from the class of foam inhibitors, graying inhibitors, There are enzymes, biocides, substances with a finishing effect and neutral salts. 8. Composition according to claim 7> wherein the detergent substances up to 100,%, preferably 25 to 70% of those of the sulfonate and / or sulfate type, up to 100%, preferably 5 to 40%, of nonionic compounds of the glycol ether type and up to 100, preferably 10 to 50% of soap. 9. Composition according to claim 7, wherein the building salt 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, ethylenediaminetetraacetic acid and up to 100%, preferably 5 to 75% of at least one compound from the Class of alkali metal silicates, alkali metal carbonates and alkali metal borates. 10. Composition according to claim 7, wherein the per compound of anhydrous and / or sodium perborate containing water of crystallization. 11. Means according to claim 7, characterized in that it is up to 5%, preferably 0.2 to 3% of at least one foam inhibitor from the class the saturated fatty acids containing 20 to 22 carbon atoms and their alkali metal soaps, as well as the substituted triazines by implementing 1 mole of cyanuric chloride with 2 to 7 moles of a primary monoamine or by propoxylation and / or butoxylation of melamine. 12. Means according to claim 7, characterized in that it is up to 5, preferably 0.2 to 5 ß of enzymes. 13. Means according to claim 7, characterized in that it is up to 5, preferably 0.2 to 3%, of graying inhibitors, 14. agents, thereby characterized in that they are based on solids, 0.01 to 1 wt .-% of optical brighteners according to claims 1 to 3 and 99 to 99.99 percent by weight of enhancing agents, higher molecular weight ammonium compounds as well as their mixtures with emulsifiers, stabilizers, Contains neutral salts and other additives.