EP0032483A2 - Stable aqueous formulations of stilbene brighteners - Google Patents

Abstract

Stilbene brightener formulations which are stable to metal ions and which contain a stilbene brightener substituted by sulfo groups and an acidic phosphoric acid ester of a fatty aminoxalkylation product of the formula <IMAGE>, in which R is an aliphatic hydrocarbon radical having 8-22 C atoms Y1 and Y2, preferably hydrogen, X the acid radical of phosphoric acid and n and m are integers, where n + m is between 2 and 30, especially between 4 and 20. The formulations can also contain various formulation auxiliaries such as nonionic or anionic surfactants and / or organic solvents or polar compounds. The formulations are used for the optical brightening of natural and synthetic fiber materials e.g. made of polyamide, cellulose and blended fabrics as well as paper.

Description

The present invention relates to aqueous, storage-stable formulations of stilbene brighteners containing sulfo groups, which are stable against metal ions and thus also against metal catalysts, their use for optically brightening natural and synthetic fiber materials or of paper, and a brightening bath containing said formulations.

Solutions or formulations of stilbene brighteners containing sulfonic acid groups are unstable in the presence of metal ions and / or metal catalysts. Interfering metal ions are in particular alkaline earth and heavy metal ions. On the one hand, such ions (calcium, magnesium) come into contact with the brightener through non-softened water when preparing or diluting solutions, which is why it has not hitherto been possible to prepare stable formulations of such stilbene brighteners or brightener baths containing them with ion-containing water. On the other hand, heavy metal ions, but also magnesium ions, are introduced into baths containing stilbene brighteners by means of crosslinking catalysts for textile finishing, such as MgCl ₂ , ZnCl ₂ etc., in which the brightener often fails from the latter.

British Patent 1,453,261 discloses a process for optically brightening nitrogen-containing fiber materials and cellulose fiber materials with the aid of stilbene whiteners using certain fatty amine oxalkylation products, the disadvantages described above being able to be partially avoided.

It has now surprisingly been found that said disadvantages can be virtually completely eliminated by _adding an acidic phosphoric acid ester of a certain fatty amine _oxalkylation product to the brightener formulations or the brightener baths as a stabilizing aid. In addition, acid-stable brightener formulations or baths are obtained in this way, which is of great advantage in a number of application processes.

The brightener formulations according to the invention have excellent storage stability, even if ion-containing water (tap water) was used to prepare them. In addition, they can absorb a high concentration of brightener, which makes them particularly important as commercial formulations. The stability of these formulations can be increased by additional formulation aids.

oder dessen Alkalimetall-,Ammonium- oder Aminsalz, worin R einen aliphatischen Kohlenwasserstoffrest mit 8-22 C-Atomen, Y₁ und Y₂ beide Wasserstoff oder eines dieser beiden Symbole Wasserstoff und das andere Methyl, X den Säurerest der Posphorsäure, wobei die sauren Wasserstoffatome dieses Restes durch Alkalimetall-, Ammonium- oder Aminsalzionen ersetzt sein können,und n und m ganze Zahlen bedeuten, wobei die Summe von n + m zwischen 2 und 30 liegt, enthält.The aqueous, metal-stable, storage-stable formulation of stilbene brighteners according to the invention is characterized in that it contains a stilbene brightener containing sulfo groups and an acidic phosphoric acid ester of a fatty amine oxyalkylation product of the formula

or its alkali metal, ammonium or amine salt, wherein R is an aliphatic hydrocarbon radical having 8-22 carbon atoms, Y ₁ and Y _{2 are} both hydrogen or one of these two symbols is hydrogen and the other methyl, X is the acid radical of phosphoric acid, the acidic Hydrogen atoms of this residue by alkali metal, ammonium or Amine salt ions can be replaced, and n and m are integers, the sum of n + m being between 2 and 30.

In formula (1) the aliphatic radical R preferably denotes an alkyl or alkenyl radical (branched or unbranched) having 10 to 18 carbon atoms and the sum of n + m is preferably 4 to 20, in particular 6 to 8. Y and Y ₂ preferably represent hydrogen.

Very particularly preferred aid of formula (1) than the rest of R _L aurylrest (C ₁₂ H _25), and the sum n + m is the number. 8

In general, the radical R does not have to have a certain number of carbon atoms, but can also be a mixture of hydrocarbon chains of different lengths, as is the case with many fatty amines derived from natural fats. Another preferred residue of this type is the hydrocarbon residue of tallow fatty amine.

The acid component of the ester of formula (I) is phosphoric acid. X is therefore the rest of the phosphoric acid, and the terminal OH groups of the ethylene oxide or propylene oxide chains can be completely or only partially esterified. The number of acidic hydrogen atoms in the phosphoric acid residue X depends on the degree of esterification, which need not be an integer. These acidic hydrogen atoms can also be replaced by alkali metal, ammonium or amine salt ions, so that the radical X is in salt form. However, the radical X is preferably in its acidic form.

Als Stilbenaufheller in erfindungsgemässen Formulierungen kommen insbesondere solche vom Typ der Bis-triazinylaminostilbendisulfonsäuren, der Bis-styrylbiphenyle oder der Bis-triazolylstilben-disulfonsäuren in Betracht. Als Beispiele solcher Aufheller seien Verbindungen der Formel

worin M Wasserstoff, ein Alkalimetall-, Ammonium- oder Aminsalzion,

Depending on the degree of esterification, possible boundary structures of the compounds of the formula (1) would be, for example, the following (for Y ₁ = Y ₂ = H):

Suitable stilbene brighteners in formulations according to the invention are, in particular, those of the bis-triazinylaminostilbenedisulfonic acid, bis-styrylbiphenyl or bis-triazolylstilbene disulfonic acid type. Examples of such brighteners are compounds of the formula

where M is hydrogen, an alkali metal, ammonium or amine salt ion,

worin

• R Wasserstoff, Alkyl mit 1 bis 4 Kohlenstoffatomen, Alkoxy mit 1 bis 4 Kohlenstoffatomen, Halogen oder S0₃M,
• R₄ Wasserstoff oder Alkyl mit 1 bis 4 Kohlenstoffatomen und
• M Wasserstoff, ein Alkalimetall-, Ammonium- oder Aminsalzion bedeuten, und der Formel

worin

• M Wasserstoff, ein Alkalimetall-, Ammonium- oder Aminsalzion und
• R₅ und R₆ unabhängig voneinander Wasserstoff, CH₃,

oder R₅ und R₆ zusammen die Ergänzung zu einem Benzolring bedeuten, genannt. Die Formulierungen können auch Mischungen der vorgenannten Aufheller enthalten, z.B. Mischungen von verschiedenen Bis-Styrylbiphenylaufhellern der Formel (3). Beispielsweise kann eine derartige Mischung aus den beiden Aufhellern 4,4'-Bis-(2-sulfostyryl)-biphenyl und 4,4'-Bis-(3-sulfo-4-chlorstyryl)-biphenyl bzw. deren Salzen bestehen.mean the formula

wherein

• R is hydrogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, halogen or S0 ₃ M,
• R _{4 is} hydrogen or alkyl of 1 to 4 carbon atoms and
• M is hydrogen, an alkali metal, ammonium or amine salt ion, and the formula

wherein

• M is hydrogen, an alkali metal, ammonium or amine salt ion and
• R ₅ and R ₆ independently of one another are hydrogen, CH ₃ ,

or R ₅ and R ₆ together mean the addition to a benzene ring. The formulations can also contain mixtures of the aforementioned brighteners, for example mixtures of various bis-styrylbiphenyl brighteners of the formula (3). For example, such a mixture can consist of the two brighteners 4,4'-bis (2-sulfostyryl) biphenyl and 4,4'-bis (3-sulfo-4-chlorostyryl) biphenyl or their salts.

worin R₇ Wasserstoff oder -SO₃M' und M' Wasserstoff, ein Natrium-, Kalium-, Ammonium-oder Aminsalzion bedeuten, bzw. der Formel

worin M' Wasserstoff, ein Natrium-, Kalium-, Ammonium- oder Aminsalzion bedeutet.Preferred formulations contain those of the formula as stilbene whiteners

wherein R _{7 is} hydrogen or -SO ₃ M 'and M' is hydrogen, a sodium, potassium, ammonium or amine salt ion, or the formula

wherein M 'is hydrogen, a sodium, potassium, ammonium or amine salt ion.

The sulfo group -SO ₃ M in the compounds of the formulas (2) - (4) can be in free form (M = H) or in salt form. M then denotes an alkali metal ion, in particular a sodium or potassium ion, an ammonium ion or an amine salt ion, for example a primary or secondary alkylamine, it being possible for the alkyl group (s) to be substituted by halogen, hydroxy (for example ethanolamine, diethanolamine, triethanolamine) or alkoxy or a cyclic amine, for example a piperidine, pyrrolidine, piperazine or morpholine.

The acidic hydrogen atoms in the phosphoric acid residue X of the compounds of formula (1) can optionally be replaced by the same ions as defined for M above. The rest X is then in salt form.

To further increase the stability of the formulations according to the invention, it is often expedient to add one or more customary formulation agents. Such formulation aid agents can be nonionic or anionic surfactants, organic solubilizers and other organic polar compounds.

• Niedere einwertige Alkohole, mehrwertige Alkohole, Aetheralkohole, nicht zu hochmolekulare Polyglykole oder Carbonsäureamide. Beispiele solcher Lösungsmittel sind Propanol, Isopropanol, Aethylenglykol, Propylenglykol, Butylenglykol, Glycerin, Aethylenglykolmonomethyl-, -monoäthyl-, -monopropyl- oder -monobutyläther, Dipropylenglykol, Formamid, Dimethylformamid, Dimethylacetamid und N-Methylpyrrolidon. Bevorzugt sind hierbei Aethylenglykol und Polyäthylenglykole. Weiters kommen Amine wie Triäthanolamin und andere wasserlösliche polare Verbindungen wie Dimethylsulfoxid, Dimethylmethanphosphonat, Dimethylsulfon, Sulfolan (=Tetrahydrothiophen-1,1-dioxid), Aethylen- oder Propylencarbonat sowie Harnstoff oder substituierte Harnstoffe, beispielsweise Tetramethylhamstoff, in Betracht. Auch anorganische oder organische Säuren, z.B. Salzsäure, Essigsäure oder Ameisensäure können als zusätzliche Formulierungshilfsmittel zugegeben werden.

The following can be used as organic solubilizers and polar organic compounds:

• Lower monohydric alcohols, polyhydric alcohols, ether alcohols, not too high molecular weight polyglycols or carboxamides. Examples of such solvents are propanol, isopropanol, ethylene glycol, propylene glycol, butylene glycol, glycerin, ethylene glycol monomethyl, monoethyl, monopropyl or monobutyl ether, dipropylene glycol, formamide, dimethylformamide, dimethylacetamide and N-methylpyrrolidone. Ethylene glycol and polyethylene glycols are preferred. Amines such as triethanolamine and other water-soluble polar compounds such as dimethyl sulfoxide, dimethyl methane phosphonate, dimethyl sulfone, sulfolane (= tetrahydrothiophene-1,1-dioxide), ethylene or propylene carbonate and urea or substituted ureas, for example tetramethyl urea, are also suitable. Inorganic or organic acids, for example hydrochloric acid, acetic acid or formic acid, can also be added as additional formulation auxiliaries.

• Anlagerungsprodukte von Alkylenoxiden, insbesondere von Aethylenoxid, an höhere Fettsäuren, Fettsäureamide, aliphatische Alkohole, Mercaptane oder Amine, an Alkylphenole oder Alkylthiophenole, deren Alkylreste mindestens 7 Kohlenstoffatome aufweisen oder an Phenylphenole wie z.B. Polyglykol- (monoalkyl-phenyl)-äther, deren Alkylgruppe 8 bis 12 Kohlenstoffatome aufweist, mit mindestens 8 gegebenenfalls substituierten Glykoleinheiten, wie Decaäthylenglykol-mono-octyl-phenyläther oder das Umsetzungsprodukt von Monononylphenol mit 5 bis 35 Molen Aethylenoxid; Blockpolymere aus _Aethylenoxid und höheren Alkylenoxiden, wie z.B. Propylenoxid oder Butylenoxid; nichtionogene Ester der Anlagerungsprodukte von Alkylenoxiden, wie z.B. der tertiäre Phosphorsäureester des Anlagerungsproduktes von 40 Molen Aethylenoxid an Monononylphenol; Ester von Polyalkoholen, insbesondere Monoglyceride von Fettsäuren mit 12 bis 18 Kohlenstoffatomen, z.B. die Monoglyceride der Laurin-, Stearin- oder Oelsäure; N-acylierte Alkanolamine des gleichen Typs wie bei den Sulfaten dieser Verbindungen erwähnt (siehe unten), so z.B. die N,N-Bis-(W-hydroxyalkyl)-amide der unter dem Sammelbegriff "Cocosölfettsäuren" zusammengefassten Säuregemische, vor allem N,_N-Bis-(ß-hydroxyäthyl)- oder N,N-Bis-(y-hydroxypropyl)-amide, ferner die Anlagerungsprodukte von Aethylenoxid an diese N-acylierten Alkanolamine; Reaktionsprodukte von höheren Fettsäuren mit einem Alkanolamin, wobei das Molverhältnis Alkanolamin zu Fettsäure grösser als 1, z.B. 2, ist. Als Fettsäuren kommen vor allem solche mit 8 bis 18 Kohlenstoffatomen sowie die als Cocosölfettsäuren bezeichneten Gemische, als Alkanolamine insbesondere Diäthanolamin, in Betracht.

Examples of nonionic surfactants that can be used are:

• Addition products of alkylene oxides, in particular of ethylene oxide, with higher fatty acids, fatty acid amides, aliphatic alcohols, mercaptans or amines, with alkylphenols or alkylthiophenols whose alkyl radicals have at least 7 carbon atoms or with phenylphenols such as polyglycol (monoalkylphenyl) ether, the alkyl group 8 has up to 12 carbon atoms, with at least 8 optionally substituted glycol units, such as decaethylene glycol mono-octyl phenyl ether or the reaction product of mono nonylphenol with 5 to 35 moles of ethylene oxide; Block polymers of ethylene oxide and higher alkylene oxides _A, such as propylene oxide or butylene oxide; nonionic esters of the adducts of alkylene oxides, such as, for example, the tertiary phosphoric acid esters of the adducts of 40 moles of ethylene oxide with monononylphenol; Esters of polyalcohols, especially monoglycerides of fatty acids with 12 to 18 carbon atoms, for example the monoglycerides of lauric, stearic or oleic acid; N-acylated alkanolamines of the same type as mentioned for the sulfates of these compounds (see below), for example the N, N-bis (W-hydroxyalkyl) amides of the acid mixtures summarized under the collective term "coconut oil fatty acids", especially N, _N -Bis- (ß-hydroxyethyl) - or N, N-bis- (y-hydroxypropyl) amides, furthermore the addition products of ethylene oxide with these N-acylated alkanolamines; Reaction products of higher fatty acids with an alkanolamine, the molar ratio of alkanolamine to fatty acid being greater than 1, for example 2. Suitable fatty acids are, in particular, those having 8 to 18 carbon atoms and the mixtures referred to as coconut oil fatty acids, and in particular diethanolamine as alkanolamines.

• Sulfatierte Alkylenoxidaddukte, insbesondere sulfatierte Aethylenoxidaddukte, wie sulfatierte Anlagerungsprodukte von 1 bis 40 Mol Aethylenoxid an Fettsäureamide, Mercaptane oder Amine, besonders aber an Fettsäuren, aliphatische Alkohole oder Alkylphenole mit 8 bis 20 Kohlenstoffatomen in der Alkylkette, z.B..an Stearinsäure, Oelsäure, Laurylalkohol, Myristylalkohol, Stearylalkohol, Oleylalkohol, Octylphenol oder Nonylphenol. Anstelle der Sulfate können auch die Ester anderer mehrwertiger Säuren eingesetzt werden. Hierher gehören z.B. die primären und sekundären Ester der Phosphorsäure sowie die Halbester der Sulfobernsteinsäure; Sulfate N-acylierter Alkaholamine, z.B. die sulfatierten Amide von Capryl-, Pelargon-, Caprin-, Laurin-, Myristin- oder Stearinsäure oder von durch Alkylphenoxygruppen substituierten niederen Fettsäuren, wie Octyl- oder Nonylphenoxyessigsäure, mit Mono- oder Bis-hydroxyalkylaminen, wie ß-Hydroxyäthylamin, y-Hydroxypropylamin, ß,y-Dihydroxy- propylamin, Bis-(ß-hydroxyäthyl)-amin oder mit N-Alkyl-N-hydroxyalkylaminen, wie N-Methyl- bzw. N-Aethyl-N-(ß-hydroxyäthyl)-amin; Sulfatierte veresterte Polyoxyverbindungen, z.B. sulfatierte partiell veresterte mehrwertige Alkohole, wie das Natriumsalz des sulfatierten Monoglycerids der Palmitinsäure.

The following can be used as anionic surfactants:

• Sulphated alkylene oxide adducts, especially sulphated ethylene oxide adducts, such as sulphated addition products of 1 to 40 mol ethylene oxide with fatty acid amides, mercaptans or amines, but especially with fatty acids, aliphatic alcohols or alkylphenols with 8 to 20 carbon atoms in the alkyl chain, e.g. with stearic acid, oleic acid, lauryl alcohol, Myristyl alcohol, stearyl alcohol, oleyl alcohol, octylphenol or nonylphenol. Instead of the sulfates, the esters of other polyvalent acids can also be used. This subheading includes, for example, the primary and secondary esters of phosphoric acid and the half esters of sulfosuccinic acid; Sulfates of N-acylated alkaholamines, for example the sulfated amides of caprylic, Pelargonic, capric, lauric, myristic or stearic acid or of lower fatty acids substituted by alkylphenoxy groups, such as octyl or nonylphenoxyacetic acid, with mono- or bis-hydroxyalkylamines, such as ß-hydroxyethylamine, ß-hydroxypropylamine, ß, y-dihydroxy- propylamine, bis (ß-hydroxyethyl) amine or with N-alkyl-N-hydroxyalkylamines, such as N-methyl or N-ethyl-N- (ß-hydroxyethyl) amine; Sulfated esterified polyoxy compounds, for example sulfated partially esterified polyhydric alcohols, such as the sodium salt of the sulfated monoglyceride of palmitic acid.

worin die allgemeinen Symbole wie in Formel (1) definiert sind, mit Phosphorsäure, Phosphorpentoxid oder einem Halogenid der Phosphorsäure erhalten werden. Bevorzugt ist die Umsetzung mit Phosphorpentoxid. Die Veresterung erfolgt zweckmässig durch einfaches Vermischen der Reaktionspartner unter Erwärmen, z.B. auf 50 - 100°C. Die sauren Ester können, falls erwünscht, in die entsprechenden Salze (Alkalimetall-, Ammonium- oder Aminsalze) übergeführt werden, z.B. in üblicher Weise durch Zugabe der entsprechenden Basen, z.B.The acidic phosphoric acid esters of fatty amine oxalkylation products of the formula (1) contained in the formulations according to the invention are known and can be obtained simply by esterification of a fatty amine oxalkylation product of the formula

wherein the general symbols as defined in formula (1) can be obtained with phosphoric acid, phosphorus pentoxide or a halide of phosphoric acid. The reaction with phosphorus pentoxide is preferred. The esterification is conveniently carried out by simply mixing the reactants with heating, for example to 50-100 ° C. If desired, the acidic esters can be converted into the corresponding salts (alkali metal, ammonium or amine salts), for example in a conventional manner by adding the appropriate bases, for example

Ammonia, monoethanolamine, triethanolamine, alkali metal hydroxides.

worin n"+ m"die Zahl 8 ist und X einen sauren Phosphorsäurerest bedeutet, kann wie folgt vorgegangen werden:For the preparation of the compound of the formula

where n "+ m" is the number 8 and X is an acidic phosphoric acid residue, can be carried out as follows:

worin n"+ m" = 8 werden bei Raumtemperatur in einem Kolben vorgelegt und unter Rühren mit einem Wasser/Eisbad auf 18°C gekühlt. Dann werden 8₀,94 g Phosphorpentoxid schnell zugegeben. Nach Entfernung des Kühlbades steigt die Temperatur der gelblichen Suspension auf Raumtemperatur an. Nun wird mit einem Oelbad innerhalb 2 Stunden auf 40°C und anschliessend innerhalb weiterer 2 Stunden auf 60°C erwärmt. Es wird noch eine Stunde bei 60°C gerührt. Das erhaltene Produkt der Formel (8) ist bei Raumtemperatur ein gelbes, gut giessbares Gel. Die analogen Verbindungen der Formeln (19) - (22) (siehe Beispiele) können nach derselben Vorschrift hergestellt werden.914.6 g of the compound of the formula

where n "+ m" = 8 are placed in a flask at room temperature and cooled to 18 ° C. with stirring with a water / ice bath. Then 8 ₀ , 94 g of phosphorus pentoxide are added quickly. After removing the cooling bath, the temperature of the yellowish suspension rises to room temperature. Now it is heated with an oil bath to 40 ° C within 2 hours and then to 60 ° C within a further 2 hours. The mixture is stirred at 60 ° C for one hour. The product of formula (8) obtained is a yellow, easily pourable gel at room temperature. The analogous compounds of the formulas (19) - (22) (see examples) can be prepared according to the same procedure.

The addition products of the formula (7) are known and can be prepared in a known manner by adding 2 to 30 mol of ethylene oxide or propylene oxide to an aliphatic amine having a hydrocarbon radical of 8 to 22 carbon atoms.

The formulations according to the invention are generally obtained by dissolving the corresponding stilbene brightener in water or in a mixture of water and an additional formulation aid with the addition of a compound of the formula (1), if appropriate with heating and stirring.

Depending on the type of brightener dissolved, the formulations according to the invention can be used for the optical brightening of a wide variety of high-molecular organic materials. This use and methods for brightening these materials with the aid of the formulations according to the invention are also the subject of the invention. Suitable substrates to be lightened are, for example, synthetic, semisynthetic or natural textile fibers, paper or detergent.

Paper can be lightened directly by adding the formulations according to the invention to the paper pulp, if appropriate after adding auxiliaries customary in paper manufacture.

Since the formulations according to the invention can be diluted very well and quickly with water, they are also excellently suitable for lightening textile substrates by the customary brightener application processes (e.g. exhaust process, pad thermal process).

For this purpose, the concentrated formulations are diluted with water so that the resulting application solutions, to which conventional auxiliaries can still be added, contain the desired brightener concentrations.

For whitening textile fibers are made from synthetic materials such as polyamide, regenerated from semi-synthetic materials such as cellulose, and natural materials such as wool or cotton, as well as otton of mixed fibers, for example polyester / _B, into consideration, the natural fibers, also as in the Textile industry can usually be equipped.

The textile materials to be optically brightened can belong to various processing states (raw materials, semi-finished or finished products). Fiber materials can be used, for example, as Staple fibers, flakes, hanks, textile threads, yarns, threads, _F aservliese, felts, cotton, Beflockungs-entity are present textile composites or knitted fabrics, but preferably a textile fabric.

Treatment of the latter is carried out with the dilute solutions according to the invention, optionally after addition of _D ispergier-, stabilizers, wetting agents and further auxiliaries.

Depending on the brightener dissolved, it may prove advantageous to work preferably in a neutral, alkaline or acid bath. The treatment is usually carried out at temperatures of approximately 20 to 140 ° C., for example at the boiling point of the bath or in the vicinity thereof (approximately 90 ° C.).

The following auxiliaries can also be added to the bath: dyes (shading), pigments (color or in particular, for example, white pigments), so-called "carriers", wetting agents, plasticizers, swelling agents, antioxidants, light stabilizers, heat stabilizers, chemical bleaching agents (chlorite bleach, bleaching baths Additives), crosslinking agents, finishing agents (for example starch or synthetic finishes) and agents which are used in a wide variety of textile finishing processes, in particular agents for synthetic resin finishes (for example crease-resistant finishes such as "wash-and-wear", "permanentpress", "no-iron "), also flame-resistant, soft-grip, dirt (" anti-soiling ") or antistatic equipment or antimicrobial equipment.

In certain cases, after-treatment with the brightener solution is carried out. This can be, for example, a chemical (eg acid treatment), a thermal or a combined chemical-thermal treatment. For example, the optical brightening of a number of fiber substrates is expediently carried out in such a way that these fibers are mixed with the described aqueous solutions at temperatures below 75 ° C, for example at room temperature, impregnated and subjected to a dry heat treatment at temperatures above 100 ° C, it being generally recommended that the fiber material be previously at a moderately elevated temperature, for example at least 60 ° C to about 130 ° C to dry. The heat treatment in the dry state is then advantageously carried out at temperatures between 120 and 225 ° C., for example by heating in a drying chamber, by ironing in the specified temperature interval or by treatment with dry, superheated steam. Drying and dry heat treatment can also be carried out immediately one after the other or combined in a single operation.

The dilution of the concentrated brightener formulations according to the invention to the corresponding application baths is carried out in such a way that when the corresponding substrate is impregnated onto the brightener in an amount of at least 0.0001 percent by weight, but at most 2 percent by weight, preferably between 0.0005 and 0.5 Weight percent lifts. Depending on the liquor ratio to be used, the type of substrate and the dissolved brightener, the required concentration results in a simple manner from these values.

The aqueous application baths which are used for the treatment of textile fibers and, as described above, represent a dilution of the formulations according to the invention and which may also contain auxiliaries which are customary in dyeing practice, as listed above, for example, are also an object of the present invention.

The liquor used (the bath) can be prepared by adding the liquor according to the invention lighter formulation as such or the components of this brightener formulation are added individually.

The formulations according to the invention can also be added to washing baths or detergents. A quantity of the solution which contains the desired amount of brightener is simply metered into washing baths. For detergents, the solutions according to the invention can be used in any phase of the manufacturing process, e.g. be added to the so-called "slurry" before atomizing the washing powder or when preparing liquid detergent combinations.

The known mixtures of detergent substances such as soap in the form of chips and powder, synthetics, soluble salts of sulfonic acid semi-esters of higher fatty alcohols, higher and / or multiple alkyl-substituted arylsulfonic acids, sulfocarboxylic acid esters of medium to higher alcohols, fatty acid acylaminoalkyl or aminoaminoate fatty alcohol phosphonic acid sulfonate etc. in question. Eg Alkalipoly- as builders, so-called "Builders" come and polymetaphosphates, alkali metal pyrophosphates, alkali metal salts of carboxymethylcellulose and other "soil redeposition inhibitors", and also _A lkalisilikate, alkali metal carbonates, alkali metal borates, alkali metal perborates, nitrilotriacetic acid, ethylenediaminetetraacetic acid, foam stabilizers such as alkanolamides of higher fatty acids, are also suitable. The detergents may also contain, for example: antistatic agents, lipid-replenishing skin protection agents such as lanolin, enzymes, antimicrobials, perfumes and dyes.

The amount of formulation according to the invention that is added to the detergent is measured so that the latter then contains about 0.001 to 0.5 percent by weight of brightener, based on the solids content of the detergent.

The formulations according to the invention preferably contain 10 to 60 parts of an acid ester of the formula (1), 5 to 30 parts of the corresponding stilbene whitener and 10 to 85 parts of water, part of the water being able to be replaced by one or more optional formulation auxiliaries, but at most 1 / 3 of the water.

As already mentioned, for the preparation of the formulations according to the invention and also for the dilution of these formulations to the application baths, ion-containing water, e.g. Tap water) can be used. Tap water can also be used for paper applications, which is a particular advantage there. Furthermore, when brightening and finishing processes are combined on textile fibers, in which polymerization catalysts based on metal salts are used, no impairment of the brightener and thus the brightener performance can be observed. All of these advantages are brought about by the addition of an acidic ester of the formula (1) to the formulations according to the invention or to the application liquors.

In the following examples, in which, as in the rest of the description and in the patent claims, parts and percentages are always parts by weight and percentages by weight, unless stated otherwise, some formulations according to the invention and their use are described. However, with other stilbene brighteners containing sulfo groups not mentioned in the examples, analogous formulations can be produced with equally good success.

werden mit 20 g des sauren Esters der Formel (8) unter Zusatz von 10 g eines Anlagerungsproduktes von 9 Mol Aethylenoxid an Nonylphenol, 15 g Aethylenglykol und 18 g Polyäthylenglykol 300 in 26,5 g vollentsalztem Wasser bei 70-80°C gelöst. Diese Aufhellerformulierung kann z.B. zum Aufhellen von Baumwolle/Polyester, Baumwolle und Polyamid verwendet werden, wobei diese Applikationen sowohl mit Hartwasser wie auch in Gegenwart von Metallsalzkatalysatoren durchführbar sind.Example 1: 10 g of the brightener of the formula

are dissolved with 20 g of the acidic ester of formula (8) with the addition of 10 g of an adduct of 9 moles of ethylene oxide with nonylphenol, 15 g of ethylene glycol and 18 g of polyethylene glycol 300 in 26.5 g of deionized water at 70-80 ° C. This brightener formulation can be used, for example, to lighten cotton / polyester, cotton and polyamide, these applications being able to be carried out both with hard water and in the presence of metal salt catalysts.

Example 2: 10 g of the brightener of the formula (10) are mixed with 20 g of the acid ester of the formula (8) with the addition of 10 g of an adduct of 8 mol of ethylene oxide with o-phenylphenol, 15 g of ethylene glycol and 18 g of polyethylene glycol 300 in 26 , 5 g of fully demineralized water at 70-80 ° C. This brightener formulation can e.g. can be used to lighten cotton / polyester, cotton and polyamide, these applications being possible both with hard water and in the presence of metal salt catalysts.

werden mit 20 g des sauren Esters der Formel (8) unter Zusatz von 10 g eines Anlagerungsproduktes von 9 Mol Aethylenoxid an Nonylphenol, 15 g Aethylenglykol und 18 g Polyäthylenglykol 300 in 26,5 g vollentsalztem Wasser bei 70-80°C gelöst. Diese Aufhellerformulierung kann z.B. zum Aufhellen von Baumwolle/Polyester, Baumwolle und Polyamid verwendet werden, wobei diese Applikationen sowohl mit Hartwasser wie auch in Gegenwart von Metallsalzkatalysatoren durchführbar sind.Example 3: 10 g of the brightener of the formula

are dissolved with 20 g of the acidic ester of formula (8) with the addition of 10 g of an adduct of 9 moles of ethylene oxide with nonylphenol, 15 g of ethylene glycol and 18 g of polyethylene glycol 300 in 26.5 g of deionized water at 70-80 ° C. This brightener formulation can be used, for example, to lighten cotton / polyester, cotton and polyamide, these applications being able to be carried out both with hard water and in the presence of metal salt catalysts.

werden mit 20 g des sauren Esters der Formel (8) unter Zusatz von 10 g eines Anlagerungsproduktes von 9 Mol Aethylenoxid an Nonylphenol, 15 g Aethylenglykol und 18 g Polyäthylenglykol 300 in 26,5 g vollentsalztem Wasser bei 70-80°C gelöst. Diese Aufhellerformulierung kann z.B. zum Aufhellen von Baumwolle/Polyester, Baumwolle und Polyamid verwendet werden, wobei diese Applikationen sowohl mit Hartwasser wie auch in Gegenwart von Metallsalzkatalysatoren durchführbar sind.Example 4: 10 g of the brightener of the formula

are dissolved with 20 g of the acidic ester of formula (8) with the addition of 10 g of an adduct of 9 mol of ethylene oxide with nonylphenol, 15 g of ethylene glycol and 18 g of polyethylene glycol 300 in 26.5 g of deionized water at 70-80 ° C. This brightener formulation can be used, for example, to lighten cotton / polyester, cotton and polyamide, these applications being able to be carried out both with hard water and in the presence of metal salt catalysts.

werden mit 20 g des sauren Esters der Formel (8) unter Zusatz von 10 g eines Anlagerungsproduktes von 9 Mol Aethylenoxid an Nonylphenol, 15 g Aethylenglykol und 18 g Polyäthylenglykol 300 in 26,5 g vollentsalztem Wasser bei 70 - 80°C gelöst. Diese Aufhellerformulierung kann z.B. zum Aufhellen von Baumwolle/Polyester, Baumwolle und Polyamid verwendet werden, wobei diese Applikationen sowohl mit Hartwasser wie auch in Gegenwart von Metallsalzkatalysatoren durchführbar sind.Example 5: 10 g of the brightener of the formula

are dissolved with 20 g of the acidic ester of formula (8) with the addition of 10 g of an adduct of 9 moles of ethylene oxide with nonylphenol, 15 g of ethylene glycol and 18 g of polyethylene glycol 300 in 26.5 g of deionized water at 70-80 ° C. This brightener formulation can be used, for example, to lighten cotton / polyester, cotton and polyamide, these applications being able to be carried out both with hard water and in the presence of metal salt catalysts.

Example 6: 10 g of the brightener of the formula (13) are mixed with ₂₀ g of the acid ester of the formula (8) with addition of 10 g of an adduct of 9 mol of ethylene oxide with nonylphenol in 60 g of deionized water at 70-80 ° C. solved. This brightener formulation can be used, for example, to lighten cotton / polyester, cotton and polyamide, these applications being able to be carried out both with hard water and in the presence of metal salt catalysts.

werden mit 20 g des sauren Esters der Formel (8) unter Zusatz von ₁₀ g eines Anlagerungsproduktes von 9 Mol Aethylenoxid an Nonylphenol, 15 g Aethylenglykol und 18 g Polyäthylenglykol 300 in 26,5 ^g vollentsalztem Wasser bei 70 - 80°C gelöst. Diese Aufhellerformulierung kann z.B. zum _Aufhellen von Baumwolle/Polyester, Baumwolle und Polyamid verwendet werden, wobei diese Applikationen sowohl mit Hartwasser wie auch in Gegenwart von Metallsalzkatalysatoren durchführbar sind.Example 7: 10 g of the brightener of the formula

are dissolved with 20 g of the acidic ester of formula (8) with the addition of ₁₀ g of an adduct of 9 moles of ethylene oxide with nonylphenol, 15 g of ethylene glycol and 18 g of polyethylene glycol 300 in 26.5 ^{g of} deionized water at 70-80 ° C. This whitener formulation may, for example to _A ufhellen of cotton / polyester, cotton and polyamide are used, these applications are feasible both with hard water as well as in the presence of metal salt catalysts.

Example 8: 10 g of the brightener of the formula (14) are _mixed with 20 g of the acid ester of the formula (8) with the addition of 10 g of an _adduct of _{9 mol of ethylene oxide} with nonylphenol in 60 g of deionized water at _70-80 ° C. solved. This whitener formulation may, for example to _A ufhellen of cotton / polyester, cotton and polyamide are used, these applications are feasible both with hard water as well as in the presence of metal salt catalysts.

werden mit 20 g des sauren Esters der Formel (8) unter Zusatz von 10 g eines Anlagerungsproduktes von 9 Mol Aethylenoxid an Nonylphenol, 15 g _Aethylenglykol und 18 g Polyäthylenglykol 300 in 26,5 g vollentsalztem Wasser bei 70-80°C gelöst. Diese Aufhellerformulierung kann z.B. zum Aufhellen von Baumwolle/Polyester, Baumwolle und Polyamid verwendet werden, wobei diese Applikationen sowohl mit Hartwasser wie auch in Gegenwart von Metallsalzkatalysatoren durchführbar sind.Example 9: 10 g of the brightener of the formula

are mixed with 20 g of the acid ester of formula (8) with addition of 10 g of an adduct of 9 moles of ethylene oxide with nonylphenol, 15 g _A ethylene glycol and 18 g of polyethylene glycol 300 in 26.5 g of deionized water at 70-80 ° C dissolved. This brightener formulation can be used, for example, to lighten cotton / polyester, cotton and polyamide, these applications being able to be carried out both with hard water and in the presence of metal salt catalysts.

werden mit 20 g des sauren Esters der Formel (8)unter Zusatz von 10 g eines Anlagerungsproduktes von 9 Mol Aethylenoxid an Nonylphenol, 15 g Aethylenglykol und 18 g Polyäthylenglykol 300 in 26,5 g vollentsalztem Wasser bei 70-80°C gelöst.Example 10: 10 g of the brightener of the formula

are dissolved with 20 g of the acidic ester of formula (8) with the addition of 10 g of an adduct of 9 moles of ethylene oxide with nonylphenol, 15 g of ethylene glycol and 18 g of polyethylene glycol 300 in 26.5 g of deionized water at 70-80 ° C.

This brightener formulation can be used in particular for lightening paper.

(Aktivsubstanzgehalt: 77,3 %) und 17 g des sauren Esters der Formel (8) werden in 61 g vollentsalztem Wasser bei 70 bis 80°C gelöst. Man erhält so eine gegen Metallionen und Metallkatalysatoren stabile wässrige Formulierung.Example 11: 22 g of the brightener of the formula

(Active substance content: 77.3%) and 17 g of the acid ester of the formula (8) are dissolved in 61 g of fully demineralized water at 70 to 80 ° C. An aqueous formulation which is stable against metal ions and metal catalysts is thus obtained.

(Aktivsubstanzgehalt: 85,5 %) werden bei 70 bis 80°C in eine Lösung von 20 g des sauren Esters der Formel (8) in 68,4 g Wasser eingerührt. Es entstehen zwei Phasen. Die untere, den Aufheller und die Verbindung der Formel (8) enthaltende Phase wird abgetrennt. Es resultieren 51 g einer klaren, bernsteinfarbigen Lösung, welche ca. 20 % Aufheller enthält und welche gegen Metallionen und Metallkatalysatoren stabil ist.Example 12: 11.6 g of the brightener of the formula

(Active substance content: 85.5%) are stirred at 70 to 80 ° C in a solution of 20 g of the acidic ester of formula (8) in 68.4 g of water. There are two phases. The lower phase containing the brightener and the compound of the formula (8) is separated off. The result is 51 g of a clear, amber-colored solution which contains about 20% brightener and which is stable against metal ions and metal catalysts.

worin n"' + m"' die Zahl 4 ist und X einen sauren Phosphorsäurerest bedeutet,unter Zusatz von 10 g eines Anlagerungsproduktes von 9 Mol Aethylenoxid an Nonylphenol, 15 g Aethylenglykol und 18 g Polyäthylenglykol 300 in 27 gvollentsalztem Wasser bei 70 bis 80°C gelöst. Man erhält so eine gegen Metallionen und Metallkatalysatoren stabile wässrige Formulierung.Example 13: 10 g of the brightener of the formula (10) are mixed with 20 g of the acid ester of the formula

where n "'+ m"' is the number 4 and X is an acidic phosphoric acid residue, with the addition of 10 g of an adduct of 9 moles of ethylene oxide with nonylphenol, 15 g of ethylene glycol and 18 g of polyethylene glycol 300 in 27 g of deionized water at 70 to 80 ° C solved. An aqueous formulation which is stable against metal ions and metal catalysts is thus obtained.

Example 14: If Example 13 is repeated, but using 20 g of the compound of the formula (19) in which n "'+ m"' is the number 6, a brightener formulation which is stable against metal ions and metal catalysts is likewise obtained.

Example 15: 10 g of the brightener of the formula (10) are mixed with 20 g of the acid ester of the formula (8) with the addition of 10 g of an adduct of 9 mol of ethylene oxide with nonylphenol, 16 g of tetramethylurea and 18 g of polyethylene glycol 300 in 26 g of fully desalinated Dissolved water at 70 to 80 ° C. An aqueous brightener formulation which is stable against metal ions and metal catalysts is thus obtained.

Example 16: If Example 15 is repeated, but 16 g of sulfolane are used instead of 16 g of tetramethylurea, a brightener formulation which is stable against metal ions and metal catalysts is likewise obtained.

Example 17: If Example 15 is repeated, but 16 g of ethylene carbonate is used instead of 16 g of tetramethylurea, a brightener formulation which is stable against metal ions and metal catalysts is likewise obtained.

Example 18: 15 g of the brightener of the formula (10) are dissolved in 30 g of the acidic ester of the formula (8) with the addition of 20 g of ethylene carbonate in 35 g of deionized water at 70 to 80 ° C. You get such an aqueous brightener formulation that is stable against metal ions and metal catalysts.

Example 19: 15 g of the brightener of the formula (10) are dissolved in 70 g of deionized water at 70 to 80 ° C. with 30 g of the acid ester of the formula (8) with the addition of 5 g of sulfolane. An aqueous brightener formulation which is stable against metal ions and metal catalysts is thus obtained.

Example 20: 15 g of the brightener of the formula (10) are dissolved in 30 g of the acidic ester of the formula (8) with the addition of 5 g of tetramethylurea in 50 g of deionized water at 70 to 80 ° C. An aqueous brightener formulation which is stable against metal ions and metal catalysts is thus obtained.

worin n^IV + _m ^IV die Zahl 12 ist und X einen sauren Phosphorsäurerest bedeutet, unter Zusatz von 10 g eines Anlagerungsproduktes von 9 Mol Aethylenoxid an Nonylphenol, 15 g Aethylenglykol und 18 g Polyäthylenglykol 300 in 27 g vollentsalztem Wasser bei 70 bis 80°C gelöst. Man erhält so eine gegen Metallionen und Metallkatalysatoren stabile wässrige Aufhellerformulierung.Example 21: 10 g of the brightener of the formula (10) are mixed with 20 g of the acid ester of the formula

where n ^IV + _m ^{IV is} the number 12 and X is an acidic phosphoric acid residue, with the addition of 10 g of an adduct of 9 moles of ethylene oxide with nonylphenol, 15 g of ethylene glycol and 18 g of polyethylene glycol 300 in 27 g of deionized water at 70 to 80 ° C. solved. An aqueous brightener formulation which is stable against metal ions and metal catalysts is thus obtained.

worin n^V + m^V die Zahl 20 ist und X einen sauren Phosphorsäurerest bedeutet; unter Zusatz von 10 g eines Anlagerungsprodukts von 9 Mol Aethylenoxid an Nonylphenol, 15 g Aethylenglykol und 18 g Polyäthylenglykol 300 in 17 g vollentsalztem Wasser bei 70 bis 80°C gelöst. Man erhält so eine gegen Metallionen und Metallkatalysatoren stabile wässrige Aufhellerformulierung.Example 22: 10 g of the brightener of the formula (10) are mixed with 30 g of the acid ester of the formula

wherein n ^V + m ^{V is} 20 and X represents an acidic phosphoric acid residue; with the addition of 10 g of an adduct of 9 mol of ethylene oxide with nonylphenol, 15 g of ethylene glycol and 18 g of polyethylene glycol 300 dissolved in 17 g of deionized water at 70 to 80 ° C. An aqueous brightener formulation which is stable against metal ions and metal catalysts is thus obtained.

worin n" + m" die Zahl 8 ist und R₁ den Kohlenwasserstoffrest des Talgfettamins bedeutet, unter Zusatz von 10 g eines Anlagerungsprodukts von 9 Mol Aethylenoxid an Nonylphenol, 15 g Aethylenglykol und 18 g Polyäthylenglykol 300 in 17 g vollentsalztem Wasser bei 70 bis 80°C gelöst. Man erhält so eine gegen Metallionen und Metallkatalysatoren stabile wässrige Aufhellerformulierung.Example 23: 10 g of the brightener of the formula (10) are mixed with 30 g of the acid ester of the formula

where n "+ m" is the number 8 and R _{1 is} the hydrocarbon residue of tallow fatty amine, with the addition of 10 g of an adduct of 9 moles of ethylene oxide with nonylphenol, 15 g of ethylene glycol and 18 g of polyethylene glycol 300 in 17 g of deionized water at 70 to 80 ° C solved. An aqueous brightener formulation which is stable against metal ions and metal catalysts is thus obtained.

(Aktivsubstanzgehalt: 87 %) werden mit 20 g des sauren Esters der Formel (8) unter Zusatz von 6 g Dimethylmethanphosphonat in 62,6 g vollentsalztem Wasser bei 70 bis 80°C gelöst. Man erhält so eine gegen Metallionen und Metallkatalysatoren stabile wässrige Aufhellerformulierung.Example 24: 11.4 g of the brightener of the formula

(Active substance content: 87%) are dissolved with 20 g of the acid ester of the formula (8) with the addition of 6 g of dimethyl methanephosphonate in 62.6 g of deionized water at 70 to 80 ° C. An aqueous brightener formulation which is stable against metal ions and metal catalysts is thus obtained.

Example 25: 11.4 g of the brightener of the formula (23) (active substance content 87%) are dissolved in 20.6 of the acidic ester of the formula (8) with the addition of 30 g of sulfolane in 38.6 g of water at 70 to 80 ° C. . An aqueous brightener formulation which is stable against metal ions and metal catalysts is thus obtained.

Example 26: 11.4 g of the brightener of the formula (23) (active substance content 87%) are dissolved in 20.6 of the acidic ester of the formula (8) with the addition of 30 g of ethylene carbonate in 38.6 g of water at 70 to 80 ° C. . An aqueous brightener formulation which is stable against metal ions and metal catalysts is thus obtained.

(Aktivsubstanzgehalt: 81,9 %) werden mit 20 g des sauren Esters der Formel (8) unter Zusatz von 10 g eines Anlagerungsproduktes von 9 Mol Aethylenoxid an Nonylphenol, 15 g Aethylenglykol und 18 g Polyäthylenglykol 300 in 24,8 g vollentsalztem Wasser bei 70 bis 80°C gelöst. Man erhält so eine gegen Metallionen und Metallkatalysatoren stabile wässrige Aufhellerformulierung.Example 27: 12.2 g of the brightener of the formula

(Active substance content: 81.9%) with 20 g of the acid ester of the formula (8) with the addition of 10 g of an adduct of 9 moles of ethylene oxide with nonylphenol, 15 g of ethylene glycol and 18 g of polyethylene glycol 300 in 24.8 g of deionized water 70 to 80 ° C solved. An aqueous brightener formulation which is stable against metal ions and metal catalysts is thus obtained.

The stable brightener formulations obtained according to Examples 11 to 27 can e.g. can be used to lighten cotton / polyester, cotton and polyamide as well as paper, whereby these applications can be carried out both with hard water and in the presence of metal salt catalysts.

Example 27a: A. 22 g of the brightener of the formula (17) and 10.2 g of the acid ester of the formula (22) are dissolved in 67.8 g of fully demineralized water at 70 to 80 ° C.

B. 22 g of the brightener of the formula (17) and 10.2 g of the acid ester of the formula (20) are dissolved in 67.8 g of deionized water at 70 to 80 ° C.

C. 22 g of the brightener of the formula (17) and 10.2 g of the acid ester of the formula (21) are dissolved in 67.8 g of deionized water at 70 to 80 ° C.

In all three cases, an aqueous brightener formulation which is stable against metal ions and metal catalysts is obtained and which can advantageously be used for lightening paper pulps.

Example 28: A bath is produced which contains 1 g of the brightener formulation according to Example 1 and 5 g of sodium sulfate per liter of hard water. A cotton fabric in a liquor ratio of 1:25 is introduced at 20 ° C. Over the course of 15 minutes, the mixture is warmed to 50 ° C. and kept at this temperature for a further 15 minutes. The treated tissue is rinsed in running cold water for 30 seconds and then dried with an iron at 150 ° C.

The fabric treated in this way has a strong lightening effect. Similar effects are also achieved if metal salt catalysts are present in the liquor.

If, instead of the brightener formulation according to Example 1, an equivalent amount of a brightener formulation according to Examples 2 to 9 and 12 to 26 is used in the above regulation, similarly well-lightened cotton fabric is obtained.

If a blend of polyester and cotton is used instead of cotton, the amount of brightener is adjusted to the proportion of cotton.

Example 29: A bath is produced which contains 1 g of the brightener formulation according to Example 1 and 3 g of a mixture of sodium hydrosulfite and sodium pyrophosphate per liter of hard water.

At 40 ° C, a polyamide 6.6 woven jersey is introduced in a 1:20 liquor ratio. The mixture is heated to 97 ° C. in the course of 30 minutes, kept at this temperature for 30 minutes and then cooled to 40 ° C. within 15 minutes. The treated tissue is rinsed in running cold water for 30 seconds and then dried with an iron at 180 ° C.

The fabric treated in this way has a strong lightening effect. Similar effects are also achieved if metal salt catalysts are present in the liquor.

If, instead of the brightener formulation according to Example 1, an equivalent amount of a brightener formulation according to Examples 2 to 9 and 12 to 26 is used in the above regulation, similarly brightened polyamide 6.6 fabric is obtained.

Example 30: A cotton fabric is padded at 20 ° C. with a hard water liquor, which contains 10 g of the brightener formulation according to Example 1 per liter, to a liquor absorption of 75%. The treated fabric is then dried at 130 ° C for 30 seconds.

The fabric treated in this way has a strong lightening effect.

If, instead of the brightener formulation according to Example 1, an equivalent amount of a brightener formulation according to Examples 2 to 9 and 12 to 26 is used in the above regulation, similarly well-lightened cotton fabric is obtained.

Example 31: A polyamide 6.6 woven jersey (not fixed) is foamed at 20 ° C. with a hard water liquor to a liquor absorption of 110%, which contains 10 g of the brightener formulation according to Example 1, 2 g of sodium hexametaphosphate and 15 g of a polyethylene glycol per liter contains a molecular weight of approx. 600 and 5 ml of 80% acetic acid. The treated tissue is then heat set at 190 ° C for 40 seconds.

The fabric treated in this way has a strong lightening effect. If, in the above regulation, instead of the brightener formulation according to Example 1, an equivalent amount of a brightener formulation according to Examples 2 to 9 and 12 to 26 is used, similarly brightened polyamide 6.6 fabric is obtained.

Example 32: 50 g of bleached cellulose (10% suspension) are mixed in a metal beaker with 99 ml of water and 1 ml of aluminum sulfate solution 10%. After 2 minutes 7.5 ml of a 10% filler slurry (kaolin), after 10 minutes 0.036 g of a formulation obtained according to Examples 10, 11, 27 or 27a are added. At intervals of a further 2 minutes, 2 ml of 5% resin glue solution and 1.5 ml of 10% aluminum sulfate solution are added. Then make up to 500 ml with water, place the suspension in a blender jar, make up to 1000 ml with water and mix for 2 seconds. The processing of the mass into sheets of paper incl active pressing and drying takes place in a known manner.

The paper obtained in this way has a strong brightening effect of good lightfastness in all four cases.

Example 33: 50 g of bleached cellulose (10% suspension) are mixed in a metal beaker with 99 ml of water and 1 ml of 10% aluminum sulfate solution. After 2 minutes, 7.5 ml of a 10% filler slurry (kaolin), after 10 minutes 0.1 g of the formulation obtained according to Example 1 are added. At intervals of a further 2 minutes, 2 ml of 5% resin glue solution and 1.5 ml of 10% aluminum sulfate solution are added. It is then made up to 500 ml with water, the suspension is placed in a mixing beaker, made up to 1000 ml with water and mixed for 2 seconds. The mass is processed into sheets of paper, including pressing and drying, in a known manner.

The paper thus obtained has a strong lightening effect with good light fastness.

If corresponding amounts of the brightener formulations according to Examples 10, 11, 27 or 27a are used in the above regulation, similarly brightened paper is obtained.

Claims (11)

1. Aqueous, stable to metal ions, storage-stable formulation of stilbene brighteners, characterized in that they contain a stilbene brightener containing sulfo groups and an acidic phosphoric acid ester of a fatty amine oxyalkylation product of the formula

or its alkali metal, ammonium or amine salt, in which R is an aliphatic hydrocarbon radical having 8-22 carbon atoms, Y ₁ and Y _{2 are} both hydrogen or one of these two symbols is hydrogen and the other methyl, X is the acid radical of phosphoric acid, the acidic Hydrogen atoms of this radical can be replaced by alkali metal, ammonium or amine salt ions, and n and m are integers, the sum of n + m being between 2 and 30. 2. Formulation according to claim 1, characterized in that it is an acidic phosphoric acid ester of a fatty amine oxalkylation product of the formula

contains in which R 'is an alkyl or alkenyl radical having 10 to 18 carbon atoms, preferably the lauryl radical or the hydrocarbon radical of tallow fatty amine, X' the acid radical of phosphoric acid, the acidic hydrogen atoms of this radical can also be replaced by alkali metal or ammonium ions and n 'and m' mean integers, the sum n '+ m' is between 4 and 20, preferably between 6 and 8. 3. Formulation according to claim 1 or 2, characterized in that it contains as the stilbene brightener one of the type of bis-triazinylaminostilbene-disulfonic acids, the bis-styrylbiphenyls or the bistriazolylstilbene-disulfonic acids, in particular one of the formula

wherein M is hydrogen, an alkali metal, ammonium or amine salt ion,

means wherein M is hydrogen, an alkali metal, ammonium or _A minsalzion means of the formula

wherein R _{3 is} hydrogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, halogen or SO ₃ M, R _{4 is} hydrogen or alkyl of 1 to 4 carbon atoms and M is hydrogen, an alkali metal, ammonium or amine salt ion, or the formula

wherein _{M is} hydrogen, an alkali metal, ammonium or amine salt ion and R ₅ and R ₆ independently of one another are hydrogen, CH ₃ ,

or R and R ₆ together mean the addition to a benzene ring. 4. Formulation according to claim ^3, characterized in that as a stilbene brightener one of the formula

wherein R _{7 is} hydrogen or -SO ₃ M 'and M' is hydrogen, a sodium, potassium, ammonium or amine salt ion, and in particular one of the formula

contains, wherein M 'is hydrogen, a sodium, potassium, ammonium or amine salt ion. 5. Formulation according to one of claims 1-4, characterized in that it additionally contains one or more formulation auxiliaries, for example one or more substances from the following classes of substances: nonionic or anionic surfactants, organic solubilizers and / or polar organic compounds. 6. Formulation according to claim 5, characterized in that hydrophilic organic solvents such as lower monohydric alcohols, polyhydric alcohols, ether alcohols, glycols, polyglycols, glycol and polyglycol ethers, amides, amines or polar organic compounds such as dimethyl sulfoxide, dimethyl methane phosphonate, dimethyl sulfone are used as formulation auxiliaries , Sulfolan, ethylene or propylene carbonate and urea or substituted ureas. 7. Formulation according to claim 5, characterized in that non-ionic surfactants such as addition products of alkylene oxides to higher fatty acids, fatty acid amides, aliphatic alcohols, mercaptans or amines, to alkylphenols, alkylthiophenols or phenylphenols, block polymers of ethylene oxides and higher alkylene oxides, as non-ionic surfactants Esters of the adducts of alkylene oxides, esters of polyalcohols, N-acylated alkanolamines and their adducts with ethylene oxide and reaction products from higher fatty acids with an alkanolamine or anionic surfactants such as alkylene oxide adducts with sulfate or other acid residues, sulfates of N-acylated alkanolamines and sulfated esterified polyoxy compounds . 8. A process for the optical brightening of natural and synthetic fiber materials, in particular of polyamide, cellulose and mixtures of polyesters and cellulose or wool, characterized in that the fiber material is treated with a liquor which contains a brightener formulation according to claims 1 to 7 , for example in the pull-out process. 9. A process for the optical brightening of paper pulps, characterized in that a brightening formulation according to claims 1 to 7 is incorporated into the paper pulp. 10. Use of a brightener solution defined in one of claims 1 to 7 for optically brightening natural and synthetic fiber materials, in particular those made of polyamide, cellulose and mixtures of polyesters and cellulose or wool. or paper pulp. 11. Aqueous bath for optically brightening natural and synthetic fiber materials, containing a portion of a formulation according to one of claims 1 to 7 necessary for the brightening and, if appropriate, auxiliaries customary in dyeing practice.