EP0030917A2 - Optical brighteners from bistyryl benzene, process for their preparation and their use - Google Patents

Abstract

An optical brightener is proposed which consists of 51-99% of an asymmetrically substituted compound of the formula <IMAGE> in which R and R1 are the same or different, in which in the event that R and R1 are the same, R1 is a different position in the phenyl ring, to which it is bound must occupy as R in its phenyl ring and in which R and R1 independently denote CN or a carboxylic acid ester group, and 49-1% of a symmetrically substituted compound of the formula <IMAGE> in which R has the above meaning and both R in their phenyl rings are attached to the same position, as well as agents which contain this brightener and the use of these brighteners for optically brightening textile materials, preferably made of polyester. The optical brighteners mentioned are prepared by reacting terephthalaldehyde, preferably with an appropriately substituted benzylphosphonate, and further reacting the mixture obtained from an appropriately substituted 4-stilbenaldehyde and a symmetrical p-bis-styrylbenzene with a benzylphosphonate different from the first.

Description

The present invention relates to optical brighteners consisting of two bis-styrylbenzene compounds, a process for their preparation and new intermediates which occur, agents containing such optical brighteners and the use of these optical brighteners or the agents containing them for optically brightening organic high-molecular materials .

A large number of bis-styrylbenzene compounds and their use as optical brighteners for various substrates are known from the literature. See also Swiss patents 366.512, 382.709, 388.294, 388.929, 389.585, 411.329, 416.078 and 465.548. Some individual components which are contained in the composite optical brighteners according to the invention are disclosed in the publications mentioned, such as 1,4-bis (2-, 3- or 4-cyanostyryl) benzene or 1,4-bis (4-methoxycarbonylstyryl) benzene. Some of these compounds are also commercially available. Mixtures of 1,4-bis-styrylbenzene compounds are known which consist of three components, namely about 50% of an asymmetrically substituted and about 25% of two different symmetrically substituted bis-styrylbenzene compounds. Such mixtures arise purely statistically when reacting one mole of terephthalaldehyde with a mixture of one mole each of two optionally substituted benzylphosphonates.

Mixtures of two or more symmetrically substituted bis-styrylbenzenes are also known, which can be obtained by simply mixing pure symmetrical compounds.

The use of the mixtures just described as optical brighteners for various organic substrates, especially polyester, is also known. See also Swiss patents 366.512, 382.709, 416.078 and 465.548.

Further mixtures of three bis-styrylbenzene compounds are known from Swiss patents 366,512 and 382,709. Such mixtures are obtained by simultaneous reaction of terephthalaldehyde with a mixture of 50-98, especially 80-87%, a substituted benzylphosphonate and 50-2, especially 20-3% of such a differently substituted benzylphosphonate.

However, due to the production process, these known three-component mixtures mentioned can contain at most about 50% of the respective asymmetrically substituted bis-styrylbenzene compound.

It has now surprisingly been found that an optical brightener consisting of 51-99%, preferably 80-99%, in particular 90-99%, of an asymmetrically substituted 1,4-bis-styrylbenzene compound and 49-1%, preferably 20-1 %, in particular 10-1% of a symmetrically substituted 1,4-bis-styrylbenzene compound is able to achieve significantly higher brightening effects than the known corresponding individual compounds and the mixtures mentioned above.

In addition, this composite brightener can be produced very well by the new method according to the invention.

worin R und R₁ gleich oder verschieden sind, worin für den Fall, dass _R und _R1 gleich sind, R₁ eine andere Position im Phenylring, an den es gebunden ist, besetzen muss als R in seinem Phenylring und worin R und R₁ unabhängig voneinander CN oder eine Carbonsäureestergruppe bedeuten:, und 49-1 % einer symmetrisch substituierten Verbindung der Formel

worin R die obige Bedeutung hat und beide R in ihren Phenylringen an die gleiche Position gebunden sind.The optical brightener according to the invention consists of 51-99% of an asymmetrically substituted compound of the formula

wherein R and R _{1 are the} same or different, wherein in the event that _R and _{R1 are the} same, R ₁ must occupy a different position in the phenyl ring to which it is attached than R in its phenyl ring and wherein R and R _{1 are} independent from each other CN or a carboxylic acid ester group mean:, and 49-1% of a symmetrically substituted compound of the formula

where R has the above meaning and both R are attached to the same position in their phenyl rings.

The bis-styrylbenzene compound (1) must therefore be unsymmetrically substituted in any case. The substituents R and R ₁ , regardless of whether they are the same or different, are preferably attached to different positions of the respective phenyl ring. The compound (2) is symmetrical both with regard to the substituent R and with regard to its position.

H X-O)_n-Alkyl bedeutet, wobei in der letztgennanten Gruppe X für Wasserstoff oder Methyl und n für eine Zahl zwischen 1 und 4 stehen und die Alkylgruppe 1 bis 6 Kohlenstoffatome aufweist. Unter Halogen ist Chlor, Brom und Fluor, insbesondere Chlor oder Brom zu verstehen. Die Substituenten Halogenalkyl und Hydroxyalkyl können ein oder mehrere Halogenatome bzw. eine oder mehrere Hydroxylgruppen enthalten.Preferred carboxylic ester groups are those of the formula -COOY, in which Y is alkyl having 1 to 6 carbon atoms, alkenyl having 3 to 6 carbon atoms, cycloalkyl having 5 or 6 carbon atoms, haloalkyl, aralkyl, especially phenylalkyl, especially benzyl, carbalkoxyalkyl, cyanoalkyl, hydroxyalkyl , Aminoalkyl, alkylaminoalkyl, dialkylaminoalkyl, it being possible for all of the composite alkyl groups mentioned above to have 1 to 6 carbon atoms in each alkyl part; Propargyl, tetrahydrofurfuryl or a group of the formula (CH ₂ -

H XO) _n -alkyl, where in the latter group X is hydrogen or methyl and n is a number between 1 and 4 and the alkyl group has 1 to 6 carbon atoms. Halogen is chlorine, bromine and fluorine, especially to understand chlorine or bromine. The substituents haloalkyl and hydroxyalkyl can contain one or more halogen atoms or one or more hydroxyl groups.

Y particularly preferably represents alkyl having 1 to 6, in particular 1 to 4, carbon atoms, alkenyl with 3 to 6 carbon atoms and benzyl, especially alkyl with 1 to 4 carbon atoms. All alkyl groups belonging to compound groups (which form the substituent Y) preferably have 1 to 4 carbon atoms.

Optical brighteners according to the invention, in which the individual components R and R _{1 are} identical and each denote CN, have particularly good properties.

und 49-1 % der Verbindung der Formel

sowie aus 51-99 7 der Verbindung der Formel

und 49-1 % der Verbindung der Formel

Of particular practical interest are the two optical brighteners consisting of 51-99% of the compound of the formula

and 49-1% of the compound of the formula

and from 51-99 7 of the compound of the formula

and 49-1% of the compound of the formula

The optical brighteners according to the invention have particularly valuable properties if they consist of 70-99, in particular 80-99, but above all 90-99% of the asymmetrically substituted compound, for example of the formula (1) or (3), and 30-1, in particular 20-1, but especially 10-1 7 of the symmetrically substituted compound, for example the formula ( 2), (4) or (6).

Particularly noteworthy is the optical brightener consisting of 90-99% of the compound of formula (3) and 10-1 Z of the compound of formula (4) and that consisting of 90-99 Z of the compound of formula (3) and 10 -1% of the compound of formula (6).

Unless stated otherwise, all percentages in this application are based on weight.

The optical brighteners according to the invention are produced by a new process which is also the subject of the invention.

In the discussion of the known bis-styrylbenzenes and the known mixtures thereof, the processes which lead to such mixtures (statistical mixtures of 3 components) have already been discussed. Furthermore, it is known from German Offenlegungsschrift 26 47 179 how 2'-cyanostilben-4-aldehyde, which occurs as an intermediate in the process according to the invention, can be obtained in pure form using a multistage synthesis. In this publication, see page 25, last paragraph to page 27, first paragraph: Preparation of the starting compound (3).

It has surprisingly been found that the optical brighteners according to the invention can be produced from two individual components by a very simple synthesis process.

zu einem Gemisch der Verbindungen der Formeln

und

umsetzt und dieses Gemisch dann weiter mit einer Verbindung der Formel

zu dem Aufheller bestehend aus den Verbindungen (1) und (2) umsetzt, wobei R und R₁ die in Formeln (1) und (2) angegebenen Bedeutungen haben und die dort angegebenen Bedingungen bezüglich ihrer Stellungen in den Phenylringen erfüllen müssen und wobei X und Y gleich oder verschieden sind und unabhängig voneinander Wasserstoff oder einen Rest der Formel -COOZ, worin Z für Alkyl steht,

bedeuten.The process according to the invention is characterized in that terephthalaldehyde with a compound of the formula

to a mixture of the compounds of the formulas

and

and this mixture is then reacted further with a compound of the formula

to the brightener consisting of the compounds (1) and (2), where R and R _{1 have} the meanings given in formulas (1) and (2) and must meet the conditions specified there with regard to their positions in the phenyl rings and where X and Y are identical or different and independently of one another are hydrogen or a radical of the formula -COOZ, in which Z is alkyl,

mean.

The quantitative ratio between terephthalaldehyde and the compound of formula (7) depends on which quantitative ratio is desired in the final mixture of asymmetrically and symmetrically substituted bis-styrylbenzenes. Accordingly, the quantitative ratio between the monoaldehyde (8) and the compound of formula (9) reacting therewith can be adjusted. In this way, each quantitative ratio defined in claim 1 can be easily adjusted by the selection of the quantitative ratios in the starting products. The content of monoaldehyde (8) in the reaction mixture can easily be determined analytically.

The reaction is preferably carried out with compounds of the formulas (7) and (9) in which X and Y each represent a group of the formulas (10) to (13), in particular one of the formula (12). In the formulas (10) to (13), alkyl preferably denotes an unsubstituted alkyl group having 1 to 6 carbon atoms or the benzyl group and aryl, preferably phenyl, optionally substituted with chlorine, methyl or methoxy.

zu einem Gemisch der Verbindungen der Formel

und der Formel (4) bzw. zu einem Gemisch der Verbindungen der Formel

(17) und der Formel (6) umsetzt und das jeweils erhaltene Gemisch anschliessend mit einer Verbindung der Formel

zu den erfindungsgemässen optischen Aufhellern bestehend aus den Verbindungen der Formeln(3) und (4) bzw. (3) und (6) umsetzt,A preferred implementation in the process according to the invention is characterized in that terephthalaldehyde with a compound of the formula

to a mixture of the compounds of the formula

and of the formula (4) or to a mixture of the compounds of the formula

(17) and formula (6) reacted and the mixture obtained in each case subsequently with a compound of the formula

to the optical brighteners according to the invention consisting of the compounds of the formulas (3) and (4) or (3) and (6),

The reaction of terephthalaldehyde with a compound of the formula (7), in which X denotes one of the groups (10) - (13) or with a compound of the formula (14) or (15) (first stage) is preferably carried out in the presence of an alkaline Condensing agent that serves as a proton acceptor performed. Such condensation agents are inorganic or organic bases, e.g. Hydroxides, hydrides, alkoxides and amides of the alkali or alkaline earth metals, monomeric or polymeric strongly basic amines and resin exchangers of the OH series in question. Sodium and potassium hydroxide and sodium methylate are of particular practical importance. A mixture of different bases can also be used. The amount of condensing agent to be used is within wide limits. The equivalent amount is advantageously used, but an excess can also be used. The second stage (reaction of the mixture of monoaldehyde and symmetrical bis-styrylbenzene compound) is preferably carried out in the presence of the same condensing agent as described for the first stage.

The process according to the invention is expediently carried out in a solvent which is inert under the reaction conditions. Such solvents are apolar and dipolar aprotic and protic solvents such as hexane, octane, cyclohexane, toluene, xylene, chlorobenzene, etc; Formamide, dimethylformamide, N-methylpyrrolidone, acetonitrile, dimethyl sulfoxide, etc .; methanol, ethanol, isopropanol, hexanol etc. into consideration. The process of the invention can also be carried out in water or in water-containing mixtures in the presence or absence of phase transfer catalysts.

The first stage is preferably carried out in a solvent in which the resulting monoaldehydes of the formulas (8) or (16) and (17) are sparingly soluble, e.g. in methanol, ethanol, hexane or toluene. The aldehydes formed precipitate during the reaction together with the symmetrical compounds of the formulas (2) or (4) and (6) and can be isolated by filtration or, preferably, can be reacted further without isolation. If the mixtures obtained are isolated, they are preferably used further without purification.

The reaction of the monoaldehydes of the formulas (8) or (16) and (17), as mixtures together with the symmetrical compounds of the formulas (2) or (4) and (6), with a compound of the formula (9) or (15) or (14) (second stage) is preferably carried out in a solvent in which the monoaldehydes are partially or completely soluble. Aprotic dipolar solvents such as e.g. Dimethyl- and diethylformamide and dimethyl sulfoxide in question.

The reaction temperature varies within wide limits depending on the solvent selected and can easily be determined by preliminary tests. The first stage is expediently carried out at temperatures between 0 ° C. and 50 ° C., preferably between 20 ° C. and 30 ° C. Temperatures between 20 ° C. and 100 ° C., preferably between 30 ° C. and 50 ° C., are particularly suitable for the second stage.

The compounds of the formulas (7) and (9) used as starting products are known or can be used in analogy to known processes (see, for example, German Offenlegungsschrift 1 921 466, British Patents 920,988 and 929,436) or according to Example 14 below (preparation of the starting product).

worin R₂ eine Carbonsäureestergruppe, insbesondere eine solche der Formel -COOY bedeutet, worin Y Alkyl, Halogenalkyl, Aralkyl, Carbalkoxyalkyl, Cyanoalkyl, Hydroxyalkyl, Aminoalkyl, Alkylaminoalkyl, Dialkylaminoalkyl, wobei alle vorgenannten Alkylgruppen und Alkylteile in zusammengesetzten Gruppen jeweils 1 bis 6 Kohlenstoffatome aufweisen; Alkenyl mit 3 bis 6 Kohlenstoffatomen, Cycloalkyl mit 5 bis 6 Kohlenstoffatomen, Propargyl, Tetrahydrofurfuryl oder eine Gruppe der Formel (CH₂-

H X-O)_n-Alkyl darstellt, worin X für Wasserstoff oder Methyl und n für eine ganze Zahl zwischen 1 und 4 stehen und die Alkylgruppe 1 bis 6 Kohlenstoffatome aufweist, sowie ein Verfahren zu deren Herstellung. Dieses Verfahren ist dadurch gekennzeichnet, dass man Terephthalaldehyd mit einer Verbindung der Formel

umsetzt, worin X' einen Rest der Formel

bedeutet, und aus dem erhaltenen Gemisch den entsprechenden Aldehyd durch gegebenenfalls mehrmalige Umkristallisation oder durch Chromatographie abtrennt.The invention further relates to the new compounds of the formulas (17) and (302) which occur as intermediates, namely 4'-cyanostilben-4-aldehyde and 3'-cyanostilben-4-aldehyde, and the ester aldehydes of the formula

in which R _{2 is} a carboxylic acid ester group, in particular one of the formula -COOY, in which Y is alkyl, haloalkyl, aralkyl, carbalkoxyalkyl, cyanoalkyl, hydroxyalkyl, aminoalkyl, alkylaminoalkyl, dialkylaminoalkyl, all of the abovementioned alkyl groups and alkyl parts in compound groups each having 1 to 6 carbon atoms ; Alkenyl with 3 to 6 carbon atoms, cycloalkyl with 5 to 6 carbon atoms, propargyl, tetrahydrofurfuryl or a group of the formula (CH ₂ -

H represents XO) _n -alkyl, where X is hydrogen or methyl and n is an integer between 1 and 4 and the alkyl group has 1 to 6 carbon atoms, and a process for their preparation. This process is characterized in that terephthalaldehyde with a compound of the formula

where X 'is a radical of the formula

means, and the corresponding aldehyde is separated from the mixture obtained by repeated recrystallization, if necessary, or by chromatography.

worin X' wie oben definiert ist, mit einem Aldehyd der Formel

umgesetzt werden.Alternatively, a compound of the formula

wherein X 'is as defined above with an aldehyde of the formula

be implemented.

The process conditions for the reaction of terephthalaldehyde with the compounds of the formulas (18), (19) and (24) correspond to those specified for the first stage of the process according to the invention for the preparation of the brightener mixtures. The final purification of the aldehydes is conveniently carried out by chromatography, e.g. Column chromatography or preferably by recrystallization, if necessary by multiple recrystallization, optionally with the addition of activated carbon or bleaching earth. Dioxane is preferred as the solvent for the recrystallization.

Of the new ester aldehydes of the formula (23), those are preferred in which R _{2 is} a group of the formula -COOY ₁ , in which Y _{1 is} alkyl having 1 to 4 carbon atoms.

The optical brighteners according to the invention are used for optically brightening a wide variety of synthetic, semi-synthetic or natural organic materials.

• I. Synthetische organische hochmolekulare Materialien:
  • a) Polymerisationsprodukte auf Basis mindestens eine polymerisierbare Kohlenstoff-Kohlenstoff-Doppelbindung enthaltender organischer Verbindungen, d.h. deren Homo- oder Copolymerisate sowie deren Nachbehandlungsprodukte wie beispielsweise Vernetzungs-, Pfropfungs- oder Abbauprodukte, Polymerisat-Verschnitte oder durch Modifizierung reaktionsfähiger Gruppen erhaltene Produkte, beispielsweise Polymerisate auf Basis von a,ß-ungesättigten Carbonsäuren oder Derivaten solcher Carbonsäuren, insbesondere von Acrylverbindungen (wie z.B. Acrylestern, Acrylsäure, Acrylnitril, Acrylamiden und deren Derivaten oder deren Methacryl-Analoga), von Olefin-Kohlenwasserstoffen (wie z.B. Aethylen, Propylen, Styrole oder Diene, ferner sogenannte ABS-Polymerisate), Polymerisate auf Basis von Vinyl- und Vinyliden-Verbindungen (wie z.B. Vinylchlorid, Vinylalkohol, Vinylidenchlorid),
  • b) Po1ymerisationsprodukte,die durch Ringöffnung erhältlich sind, z.B. Polyamide vom Polycaprolactam-Typ, ferner Polymere, die sowohl über Polyaddition als auch Polykondensation erhältlich sind, wie Polyäther oder Polyacetale,
  • c) Polykondensationsprodukte oder Vorkondensate auf Basis bi- oder polyfunktioneller Verbindungen mit kondensationsfähigen Gruppen, deren Homo- und Mischkondensationsprodukte sowie Produkte der Nachbehandlung, wie beispielsweise Polyester, insbesondere gesättigte (z.B. Aethylenglykolterephthalsäure-Polyester) oder ungesättigte (z.B. Maleinsäure-Dialkohol-Polykondensate sowie deren Vernetzungsprodukte mit anpolymerisierbaren Vinylmonomeren), unverzweigte sowie verzweigte (auch auf Basis höherwertiger Alkohole, wie z.B. Alkydharze) Polyester, Polyamide (z.B. Rexamethylendiamin-adipat), Maleinatharze, Melaminharze, deren Vorkondensate und Analoga, Polycarbonate, Silikone,
  • d) Polyadditionsprodukte wie Polyurethane (vernetzt und unvernetzt), Epoxidharze.
• II. Halbsynthetische organische Materialien, z.B. Celluloseester verschiedener Veresterungsgrade (sogenanntes 2 1/2-Acetat, Triacetat) oder Celluloseäther, regenerierte Cellulose (Viskose, Kupferammoniak-Cellulose) oder deren Nachbehandlungsprodukte, Casein-Kunststoffe.
• III. Natürliche organische Materialien animalischen oder vegetabilischen Ursprungs, beispielsweise auf Basis von Cellulose oder Proteinen wie Baumwolle, Wolle, Leinen, Seide, natürliche Lackharze, Stärke, Casein.

For this purpose, the following groups of organic materials, to the extent that they can be optically brightened, may be mentioned, for example, without the following overview being intended to express any restriction to this:

• I. Synthetic organic high molecular materials:
  • a) Polymerization products based on organic compounds containing at least one polymerizable carbon-carbon double bond, ie their homopolymers or copolymers and their aftertreatment products such as crosslinking, grafting or degradation products, polymer blends or products obtained by modifying reactive groups, for example polymers Basis of a, ß-unsaturated carboxylic acids or derivatives of such carboxylic acids, in particular of acrylic compounds (such as acrylic esters, acrylic acid, acrylonitrile, acrylamides and their derivatives or their methacrylic analogs), of olefin hydrocarbons (such as ethylene, propylene, styrenes or dienes , also so-called ABS polymers), polymers based on vinyl and vinylidene compounds (such as vinyl chloride, vinyl alcohol, vinylidene chloride),
  • b) polymerization products which can be obtained by ring opening, for example polyamides of the polycaprolactam type, furthermore polymers which are obtainable both by polyaddition and polycondensation, such as polyethers or polyacetals,
  • c) polycondensation products or precondensates based on bifunctional or polyfunctional compounds with condensable groups, their homo- and mixed condensation products as well as post-treatment products such as polyesters, in particular saturated (e.g. ethylene glycol terephthalic acid polyesters) or unsaturated (e.g. maleic acid dialcohol polycondensates and their crosslinking products with polymerizable vinyl monomers), unbranched and branched (also on Basis of higher quality alcohols, such as alkyd resins) polyesters, polyamides (e.g. rexamethylene diamine adipate), maleate resins, melamine resins, their precondensates and analogues, polycarbonates, silicones,
  • d) polyaddition products such as polyurethanes (crosslinked and uncrosslinked), epoxy resins.
• II. Semi-synthetic organic materials, for example cellulose esters of various degrees of esterification (so-called 2 1/2 acetate, triacetate) or cellulose ether, regenerated cellulose (viscose, copper ammonia cellulose) or their aftertreatment products, casein plastics.
• III. Natural organic materials of animal or vegetable origin, for example based on cellulose or proteins such as cotton, wool, linen, silk, natural lacquer resins, starch, casein.

The organic materials to be optically brightened can belong to the most varied of processing states (raw materials, semi-finished or finished products). On the other hand, they can be in the form of a wide variety of shaped structures, i.e. For example, as predominantly three-dimensionally extended bodies such as plates, profiles, injection moldings, various workpieces, chips, granules or foams, furthermore as predominantly two-dimensionally designed bodies such as films, foils, lacquers, coatings, impregnations and coatings or as predominantly one-dimensionally designed bodies such as threads, fibers , Flakes, wires. On the other hand, said materials can also be in unshaped states in a wide variety of homogeneous or inhomogeneous forms of distribution, such as e.g. as powders, solutions, emulsions, dispersions, latices, pastes or waxes.

Fiber materials can be, for example, as endless threads (drawn or undrawn), staple fibers, flakes, strand goods, Textile threads, yarns, threads, non-woven fabrics, felts, wadding, flocking structures or as textile fabrics or textile composites, knitted fabrics and as papers, cardboards or paper pulps.

The brighteners to be used according to the invention are of particular importance for the treatment of textile organic materials, in particular textile fabrics. If fibers which can be in the form of staple fibers or continuous threads, in the form of strands, fabrics, knitted fabrics, nonwovens, flocked substrates or composites, are to be optically brightened according to the invention, this is advantageously done in an aqueous medium, in which the compounds in question are in finely divided form (suspensions, so-called microdispersions, optionally solutions) are present. If necessary, dispersants, stabilizers, wetting agents and other auxiliaries can be added during the treatment.

When applying, you can work in 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.). For the finishing of textile substrates according to the invention, solutions or emulsions in organic solvents are also suitable, as is practiced in dyeing practice in so-called solvent dyeing (foulard heat-fixing application, pull-out dyeing process in dyeing machines).

The optical brighteners according to the present invention can also be added or incorporated into the materials before or during their deformation. For example, they can be added to the molding compound or injection molding compound during the production of films, foils (e.g. rolling in polyvinyl chloride in the heat) or moldings.

• - Zugabe zu den Ausgangssubstanzen (z.B. Monomeren) oder Zwischenprodukten (z.B. Vorkondensaten, Praepolymeren), d.h. vor oder während der Polymerisation, Polykondensation oder Polyaddition,
• - Aufpudern auf Polymerisatschnitzel oder Granulate für Spinnmassen,
• - Badfärbung von Polymerisatschnitzeln oder Granulaten für Spinnmassen,
• - Dosierte Zugabe zu Spinnschmelzen oder Spinnlösungen,
• - Applikation auf Spinnkabel vor dem Verstrecken.

If fully or semi-synthetic organic materials are shaped by spinning processes or spinning masses, the optical brighteners can be applied by the following processes:

• Addition to the starting substances (for example monomers) or intermediates (for example precondensates, prepolymers), ie before or during the polymerization, polycondensation or polyaddition,
• - powdering onto polymer chips or granules for spinning masses,
• - bath coloring of polymer chips or granules for spinning masses,
• - metered addition to spinning melts or spinning solutions,
• - Application on spinning cable before stretching.

• a) Mischungen mit Farbstoffen (Nuancierung) oder Pigmenten (Farb-oder insbesondere z.B. Weisspigmenten) oder als Zusatz zu Färbebädern, Druck-, Aetz- oder Reservepasten, ferner auch zur Nachbehandlung von Färbungen, Drucken oder Aetzdrucken,
• b) in Mischungen mit sogenannten "Carriern", Netzmitteln, Weichmachern, Quellmitteln, Antioxydantien, Lichtschutzmitteln, Hitzestabilisatoren, chemischen Bleichmitteln (Chlorit-Bleiche, Bleichbäder-Zusätze),
• c) in Mischung mit Vernetzern, Appreturmitteln (z.B. Stärke oder synthetischen Appreturen) sowie in Kombination mit den verschiedensten Textilveredlungsverfahren, insbesondere Kunstharzausrüstungen (z.B. Knitterfest-Ausrüstungen wie "wash-and-wear", "permanent-press", "noniron"), ferner Flammfest-, Weichgriff-, Schmutzablöse ("anti-soiling")-oder Antistatisch-Ausrüstungen oder antimikrobiellen Ausrüstungen,
• d) Einarbeiten der optischen Aufhellmittel in polymere Trägermaterialien (Polymerisations-, Polykondensations- oder Polyadditionsprodukte) in gelöster oder dispergierter Form für Anwendung z.B. in Beschichtungs-, Imprägnier- oder Bindemitteln (Lösungen, Dispersionen, Emulsionen) für Textilien, Vliese, Papier, Leder,
• e) als Zusätze zu den verschiedenstan industriellen Produkten, um dieselben marktfähiger zu machen (z.B. Aspektverbesserung von Seifen, Waschmitteln, Pigmenten),
• f) in Spinnbadpräparationen, d.h. als Zusätze zu Spinnbädern, wie sie zur Gleitfähigkeitsverbesserung für die Weiterverarbeitung von Synthese-Fasern verwendet werden, oder aus einem speziellen Bad vor der Verstreckung der Faser,
• g). in Mitteln zum optischen Aufhellen von hochmolekularen organischen Materialien der vorstehend angegebenen Zusammensetzungen, welche Mittel gegebenenfalls übliche Formulierungszusätze und/oder gegebenenfalls weitere optische Aufheller aus anderen Aufhellerklassen enthalten,
• h) als Scintillatoren, für verschiedene Zwecke photographischer Art, wie z.B. für elektrophotographische Reproduktion und Supersensibilisierung,
• j) je nach Substitution als Laser-Farbstoffe.

The optical brighteners according to the invention can also be used, for example, in the following application forms:

• a) mixtures with dyes (shading) or pigments (color or, in particular, for example, white pigments) or as an additive to dye baths, printing pastes, etching pastes or reserve pastes, and also for the aftertreatment of dyeings, prints or etching prints,
• b) in mixtures with so-called "carriers", wetting agents, plasticizers, swelling agents, antioxidants, light stabilizers, heat stabilizers, chemical bleaches (chlorite bleach, bleach bath additives),
• c) in a mixture with crosslinking agents, finishing agents (eg starch or synthetic finishes) and in combination with a wide variety of textile finishing processes, in particular synthetic resin finishes (eg crease-resistant finishes such as "wash-and-wear", "permanent-press", "noniron"), furthermore flame-resistant, soft-grip, dirt ("anti-soiling") or antistatic equipment or antimicrobial equipment,
• d) incorporation of the optical brighteners into polymeric carrier materials (polymerization, polycondensation or polyaddition products) in dissolved or dispersed form for use, for example, in coating, impregnating or binding agents (solutions, dispersions, emulsions) for textiles, nonwovens, paper, leather,
• e) as additives to the various industrial products in order to make them more marketable (eg improving aspects of soaps, detergents, pigments),
• f) in spin bath preparations, ie as additives to spin baths, such as those used to improve the slidability for the further processing of synthetic fibers, or from a special bath before drawing the fiber,
• G). in agents for the optical brightening of high-molecular organic materials of the above-mentioned compositions, which agents optionally contain customary formulation additives and / or optionally further optical brighteners from other brightener classes,
• h) as scintillators, for various purposes of a photographic nature, such as for electrophotographic reproduction and super-sensitization,
• j) depending on the substitution as laser dyes.

Such agents, which contain the optical brighteners according to the invention, are also the subject of the invention.

The usual formulation additives are e.g. various auxiliaries and coupling agents, e.g. anhydrous sodium sulfate, sodium sulfate decahydrate, sodium chloride, sodium carbonate, alkali metal phosphates such as sodium or potassium orthophosphate, sodium or potassium pyrophosphate and sodium or potassium tripolyphosphates or alkali metal silicates. However, aqueous formulations also fall under the agents according to the invention, e.g. also the application solutions with which textile fibers are brightened optically and which contain the usual additives.

Particularly preferred in the context of the agents according to the invention are those which, in addition to a greenish one on the substrate to be treated optical brighteners according to the invention which produce a bluish shade (for example mixtures of the compounds (1) and (2), (3) and (4) or (3) and (6)) additionally contain an optical brightener which is based on the material to be treated Produces a reddish shade.

Such combinations have the advantage that a particularly beautiful neutral white tone of high brilliance can be achieved on textile fibers, especially on polyester fibers.

Means which have an optical brightener consisting of the compounds (3) and (4) or (3) and (6) or other mixtures of a symmetrical and asymmetrical component from which the brighteners according to the invention consist and additionally an optical brightener are therefore very advantageous from the class of naphthalimides, bis-benzoxazolyl-ethylenes, bis-benzoxazolyl-thiophenes, stilbenylbenzoxazoles, naphthotriazol-2-yl-stilbenes (known from German Offenlegungsschriften 25 39 537 and 25 39 461) or coumarins, for example the 3-phenyl-7-pyrazolylcoumarins, the 3-pyrazolyl-7-v-triazolylcoumarins or the 3-v-triazolylcoumarins (known from the Swiss patents 566,359 and 592,189), in particular those which contain 5-90 as a brightening active substance %, in particular 30-70% of an optical brightener according to the invention which produces a greenish to bluish shade on the treated substrate (for example mixtures of the compounds (1) and (2), (3) and (4) or (3) and ( 6)) and 95-10%, in particular 70-30%, of an optical brightener which produces a reddish shade on the treated substrate, the latter brightener preferably being one of the above-mentioned classes.

Particularly suitable in agents according to the invention as brighteners which produce a reddish shade are those from the class of the naphthotriazolyl-stilbene and the triazolylcoumarins.

• 2,5-Bis-(benzoxazol-2-yl)-thiophen, 4-(5-Methylbenzoxazol-2-yl)-4'-carbomethoxystilben,
• l-Methyl-5-methoxynaphthalimid,
• 3-Phenyl-7-(4-phenyl-5-methyl-v-triazol-2-yl)cumarin,
• 3-(4-Chlorpyrazol-1-yl)-7-(4-phenyl-5-methyl-v-triazol-2-yl)cumarin sowie insbesondere
• 3-(2-Phenyl-v-triazol-4-yl)-7-methoxycumarin und
• 4-(Naphtho[1,2-d]triazol-2-yl)-4'-carbäthoxystilben.

Examples of brighteners which produce a reddish shade and which can be used in agents according to the invention are among other:

• 2,5-bis (benzoxazol-2-yl) thiophene, 4- (5-methylbenzoxazol-2-yl) -4'-carbomethoxystilbene,
• l-methyl-5-methoxynaphthalimide,
• 3-phenyl-7- (4-phenyl-5-methyl-v-triazol-2-yl) coumarin,
• 3- (4-chloropyrazol-1-yl) -7- (4-phenyl-5-methyl-v-triazol-2-yl) coumarin and in particular
• 3- (2-phenyl-v-triazol-4-yl) -7-methoxycoumarin and
• 4- (Naphtho [1,2-d] triazol-2-yl) -4'-carbäthoxystilben.

Substrates made of polyester are particularly preferably brightened with the optical brighteners according to the invention, in particular textile materials made of polyester.

If the lightening process is combined with textile treatment or finishing methods, in many cases the combined treatment can advantageously be carried out with the aid of corresponding stable preparations which contain the optically brightening compounds in such a concentration that the desired lightening effect is achieved.

In some cases, the brighteners are brought to full effect by post-treatment. 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, for example polyester fibers, with the brighteners according to the invention is expediently carried out in such a way that these fibers are mixed with the aqueous dispersions (if appropriate also solutions) of the brighteners at temperatures below 75 ° C., for example at Room temperature, impregnated and subjected to a dry heat treatment at temperatures above 100 ° C, where it is generally recommended that the fiber material before moderately elevated temperature, eg to dry at least 60 ° C to about 130 ° C. 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. The drying and dry heat treatment can also be carried out immediately one after the other or combined in a single operation.

The amount of the optical brightener to be used according to the invention, based on the material to be optically brightened, can vary within wide limits. Even with very small quantities, in certain cases e.g. of 0.001 percent by weight, a clear and durable effect can be achieved. However, amounts of up to about 0.8 percent by weight and optionally up to about 2 percent by weight can also be used. For most practical purposes, amounts between 0.01 and 0.5 percent by weight are preferred.

Unless otherwise stated, parts in the following examples are always parts by weight and percentages are always percentages by weight.

versetzt wird, wobei das Reaktionsprodukt sofort kristallin ausfällt.Example 1: 53.6 g of terephthalaldehyde are suspended in 300 ml of absolute ethanol and 144 g of a 30% methanolic sodium methylate solution are added at 20 to 25.degree. C. with stirring and nitrogen within 15 minutes. An almost clear solution is formed which, at 20 to 25 ° C. with stirring and nitrogen, with 102 g of the phosphonate of the formula within 20 minutes

is added, the reaction product immediately precipitating crystalline.

und 11,3 % der Verbindung der Formel

identifizieren lässt.The resulting thick crystalline slurry is then stirred for six hours at 20 to 25 ° C under nitrogen, then suction filtered, washed with about 50 ml of absolute ethanol and dried under vacuum at 50 ° C to constant weight. 60.06 g (about 64.4% of theory) of a light yellow crystalline powder of melting point 144 to 149 ° C. are obtained, which by gas chromatographic analysis is a mixture consisting of 87.8% of the compound of the formula

and 11.3% of the compound of the formula

can be identified.

The phosphonate of the formula (14) used as starting material is prepared in analogy to Example 1 of German Offenlegungsschrift ₁ 921 466 and purified by distillation (K _{p 0.35} : 136-138 ° C).

werden in 200 ml Dimethylformamid suspendiert und bei 30°C unter Rühren und Stickstoff innerhalb 30 Minuten mit 19,0 g einer 30 Zigen methanolischen Natriummethylat-Lösung versetzt, wobei die Reaktionstemperatur bis 40°C steigt. Es entsteht zuerst eine fast klare Lösung, aus welcher das Reaktionsprodukt gegen Ende der Zugabe der Natriummethylat-Lösung als dicker kristalliner Brei ausfällt. Das Reaktionsgemisch wird nun bei 30°C unter Stickstoff vier Stunden weitergerührt, dann bei 20°C mit 200 ml Wasser verdünnt und mit etwa 1 ml Eisessig neutralisiert. Das Reaktionsprodukt wird abgenutscht, mit etwa 100 ml Dimethylformamid/ Wasser (1:1) und dann mit etwa 100 ml Methanol gewaschen und unter Vakuum bei 100°C bis zum konstanten Gewicht getrocknet. Man erhält 28,9 g (etwa 86,9 % der Theorie) eines hellgelben kristallinen Pulvers vom Schmelzpunkt 188 bis 233°C, das sich nach gaschromatographischer Analyse als ein Gemisch bestehend aus 91,2 % der Verbindung der Formel

und 7,7 der Verbindung der Formel (4) erweist.23.3 g of a mixture of the compounds (16) and (4) obtained as described above and 25.3 g of the phosphonate of the formula

are suspended in 200 ml of dimethylformamide and 19.0 g of a 30% methanolic sodium methylate solution are added at 30 ° C. with stirring and nitrogen within 30 minutes, the reaction temperature rising to 40 ° C. First an almost clear solution is formed, from which the reaction product precipitates as a thick crystalline slurry towards the end of the addition of the sodium methylate solution. The reaction mixture is then stirred for a further four hours at 30 ° C. under nitrogen, then at 20 ° C. diluted with 200 ml of water and neutralized with about 1 ml of glacial acetic acid. The reaction product is filtered off with suction, washed with about 100 ml of dimethylformamide / water (1: 1) and then with about 100 ml of methanol and dried under vacuum at 100 ° C. to constant weight. 28.9 g (about 86.9% of theory) of a light yellow crystalline powder of melting point 188 to 233 ° C. are obtained, which, according to gas chromatographic analysis, is a mixture consisting of 91.2% of the compound of the formula

and 7.7 of the compound of formula (4).

The phosphonate of the formula (15) used as starting material is prepared in accordance with Example 1 of German Offenlegungsschrift 1 921 466.

und 7,1 % der Verbindung der Formel

erweist.Example 2: 67 g of terephthalaldehyde are suspended in 300 ml of absolute methanol and 180 g of a 30% strength methanolic sodium methylate solution are added at 20 to 25 ° C. with stirring and nitrogen within 15 minutes. An almost clear solution is formed, to which a solution of 126.6 g of the phosphonate of the formula (15) in 100 ml of absolute methanol is added at 20 to 25 ° C. with stirring and nitrogen within 20 minutes, the reaction product immediately precipitating out in crystalline form . The resulting crystalline reaction mixture is further treated as described in Example 1. 106.1 g (about 91.0% of theory) of a light yellow crystalline powder of melting point 198 to 205 ° C. are obtained, which can be analyzed analytically as a mixture consisting of 92.3% of the compound of the formula

and 7.1% of the compound of the formula

turns out.

After three recrystallizations from dioxane and with the aid of activated carbon, 40.6 g of the aldehyde of the formula (17) are obtained in the form of long pale yellow needles with a melting point of 207 to 210 ° C.

23.3 g of a mixture of the compounds (17) and (6) obtained as described above and 25.3 g of the phosphonate of the formula (14) are suspended in 200 ml of dimethylformamide and at 30 ° C. with stirring and nitrogen within 20 minutes 19 g of a 30% methanolic sodium methylate solution are added, the reaction temperature rising to 40 ° C. The result is an almost clear solution from which the reaction product precipitates as a thick crystalline slurry towards the end of the addition of the sodium methylate solution. The reaction mixture is further treated as described in Example 1. 30.56 g (about 91.9% of theory) of a light yellow crystalline powder with a melting point of 200 to 230 ° C. are obtained, which can be analyzed as a mixture consisting of 95.7% of the compound of the formula (3) and 3.2 % of the compound of formula (6) proves.

in 60 ml absolutem Methanol versetzt wird, wobei das Reaktionsprodukt langsam kristallin ausfällt. Die enstandene kristalline Reaktionsmischung wird nun 24 Stunden bei 20 bis 25°C unter Stickstoff weitergerührt, auf 0°C abgekühlt, dann abgenutscht, mit etwa 50 ml absolutem Aethanol gewaschen und unter Vakuum bei 50°C bis zum konstanten Gewicht getrocknet. Man erhält 32,0 g(etwa 68,7 7 der Theorie) eines hellgelben kristallinen Pulvers vom Schmelzpunkt 117 bis 192°C, das sich analytisch als ein Gemisch bestehend aus 81,5 % der Verbindung der Formel

und 17,2% der Verbindung der Formel

erweist.Example 3: 26.8 g of terephthalaldehyde are suspended in 100 ml of absolute methanol and 72 g of a 30% methanolic sodium methylate solution are added at 20 to 25 ° C. with stirring and nitrogen within 15 minutes. An almost clear solution is formed which, at 20 to 25 ° C. with stirring and nitrogen, within 20 minutes with a solution of 50.6 g of the phosphonate of the formula

in 60 ml of absolute methanol, the reaction product slowly precipitating out in crystalline form. The resulting crystalline reaction mixture is then stirred for 24 hours at 20 to 25 ° C under nitrogen, cooled to 0 ° C, then suction filtered, with about 50 ml of absolute Washed ethanol and dried under vacuum at 50 ° C to constant weight. This gives 32.0 g (about 68.7 7 of theory) of a light yellow crystalline powder with a melting point of 117 to 192 ° C., which can be analyzed analytically as a mixture consisting of 81.5% of the compound of the formula

and 17.2% of the compound of the formula

turns out.

After recrystallization from alcohol twice and removal of the alcohol-insoluble compound of the formula (303), 14.5 g of the aldehyde of the formula (302) are obtained in the form of pale yellow needles with a melting point of 117 to 119 ° C.

The phosphonate of the formula (301) used as starting material is prepared according to Example 2 of GB-PS 920,988.

und 10,9 % der Verbindung der Formel 1303) erweist.23.3 g of a mixture of the compounds (302) and (303) obtained as described above and 25.3 g of the phosphonate of the formula (15) are suspended in 200 ml of dimethylformamide and at 30 ° C. with stirring and nitrogen within 15 minutes 19 g of a 30% methanolic sodium methylate solution were added. First, an almost clear solution is formed, from which the reaction product precipitates as a thick crystalline slurry towards the end of the addition of the sodium methylate solution, the reaction temperature rising to 40 ° C. The reaction mixture is then stirred for a further four hours at 30 ° C. under nitrogen, then diluted with 200 ml of water at 0 ° C. and neutralized with about 1 ml of glacial acetic acid. The reaction product is filtered off with about 100 ml Dimethylformamide / water (1: 1) and then washed with about 80 ml of ethanol and dried under vacuum at 100 ° C to constant weight. 28.55 g (about 85.9% of theory) of a light yellow crystalline powder with a melting point of 199 to 217 ° C. are obtained, which can be analyzed as a mixture consisting of 88.3% of the compound of the formula

and 10.9% of the compound of formula 1303).

Example 4: 23.3 g of the mixture of compounds (17) and (6) obtained according to Example 2 and 25.3 g of the phosphonate of the formula (301) are reacted as described in Example 3. 29.4 g (about 88.5% of theory) of a light yellow crystalline powder with a melting point of 204 to 220 ° C. are obtained, which can be analyzed as a mixture consisting of 95.7% of the compound of the formula (304) and 3 , 8% of the compound of formula (6) proves.

und 13,8 % der Verbindung der Formel (303) erweist.Example 5: 23.3 g of the mixture of compounds (302) and (303) obtained according to Example 3 and 25.3 g of the phosphonate of the formula (14) are reacted in 100 ml of dimethylformamide as described in Example 3. 23.5 g (about 70% of theory) of a pale yellow crystalline powder with a melting point of 174 to 183 ° C. are obtained, which can be analyzed analytically as a mixture consisting of 85.1% of the compound of the formula

and 13.8% of the compound of formula (303).

Example 6: 23.3 g of the mixture obtained according to Example 1. Compounds (16) and (4) and 25.3 g of the phosphonate of the formula (301) are reacted in 100 ml of dimethylformamide as described in Example 3. 24.5 g (about 73.5% of theory) of one are obtained pale yellow crystalline powder with a melting point of 176 to 188 ° C, which analytically turns out to be a mixture consisting of 91.6% of the compound of formula (501) and 7.1% of the compound of formula (4).

werden in 80 ml Dimethylformamid wie im Beispiel 3 beschrieben umgesetzt. Man erhält 9,5 g (etwa 87 % der Theorie) eines gelben kristallinen Produktes mit einem Schmelzpunkt von 187 bis 205°C, das sich analytisch als ein Gemisch bestehend aus 93,3 7 der Verbindung der Formel

und 5,6 % der Verbindung der Formel (4) erweist.Example 7: 7 g of the mixture of compounds (16) and (4) obtained according to Example 1 and 7.8 g of the phosphonate of the formula

are reacted in 80 ml of dimethylformamide as described in Example 3. 9.5 g (about 87% of theory) of a yellow crystalline product having a melting point of 187 to 205 ° C. are obtained, which can be analyzed analytically as a mixture consisting of 93.3 7 of the compound of the formula

and 5.6% of the compound of formula (4).

The phosphonate of the formula (701) used as starting material is prepared according to Example 2 of GB-PS 929,436.

werden in 120 ml Dimethylformamid suspendiert und bei 30°C unter Rühren und Stickstoff innerhalb 15 Minuten mit 22 ml einer äthanolischen 2M Natriumäthylat-Lösung versetzt. Das Reaktionsgemisch wird wie in Beispiel 3 beschrieben aufgearbeitet. Man erhält 13 g (etwa 86 der Theorie) eines gelben kristallinen Produktes mit einem Schmelzpunkt von 178 bis 181°C., das sich analytisch als ein Gemisch bestehend aus 95,3 % der Verbindung der Formel

und 3,9 % der Verbindung der Formel (4) erweist.Example 8: 9.3 g of the mixture of compounds (16) and (4) obtained according to Example 1 and 12 g of the phosphonate of the formula

are suspended in 120 ml of dimethylformamide and 22 ml of an ethanolic 2M sodium ethylate solution are added at 30 ° C. with stirring and nitrogen within 15 minutes. The reaction mixture is worked up as described in Example 3. 13 g (about 86 of theory) of a yellow crystalline product with a Melting point of 178 to 181 ° C., which can be analyzed analytically as a mixture consisting of 95.3% of the compound of the formula

and 3.9% of the compound of formula (4).

The phosphonate of the formula (801) used as starting material is prepared analogously to Example 2 of GB-PS 929,436 and purified by distillation (K _p0.25 : 181-185 ° C).

und 9,1 % der Verbindung der Formel

identifizieren lässt.Example 9: 40 g of terephthalaldehyde are suspended in 100 ml of absolute ethanol and 300 ml of an ethanolic 2M sodium ethylate solution are added at 20 to 25 ° C. with stirring and nitrogen within 15 minutes. An almost clear solution is formed, to which 90 g of the phosphonate of the formula (801) are added at 20 to 25 ° C. with stirring and nitrogen within 20 minutes, the reaction product immediately precipitating in crystalline form. The resulting thick crystalline slurry is then stirred for 16 hours at room temperature under nitrogen, then suction filtered, washed with about 50 ml of absolute ethanol and dried under vacuum at 50 ° C to constant weight. 64 g (about 76% of theory) of a light yellow crystalline powder with a melting point of 102 to 169 ° C. are obtained, which can be analyzed analytically as a mixture consisting of 89.5% of the compound of the formula

and 9.1% of the compound of the formula

can be identified.

After recrystallizing twice from ethanol and removing the ethanol-insoluble compound of the formula (902) 32 g of the aldehyde of the formula (901) in the form of long pale yellow needles with a melting point of 103 to 105 ° C.

und 5,5 % der Verbindung der Formel (303) erweist.Example 10: 8 g of the mixture of compounds (302) and (303) obtained according to Example 3 and 9 g of the phosphonate of the formula (701) are reacted in 80 ml of dimethylformamide as described in Example 3. 10 g (about 78% of theory) of a pale yellow crystalline powder with a melting point of 228 to 236 ° C. are obtained, which can be analyzed analytically as a mixture consisting of 93.4% of the compound of the formula

and 5.5% of the compound of formula (303).

und 6,5 % der Verbindung der Formel (303) erweist.Example 11: 9.3 g of the mixture of the compounds (302) and (303) obtained according to Example 3 and 12 g of the phosphonate of the formula (801) are suspended in 120 ml of dimethylformamide and at 30 ° C. with stirring and nitrogen within 15 minutes treated with 22 ml of an ethanolic 2 M sodium ethylate solution. The reaction mixture is worked up as described in Example 3. This gives 12.5 g (about 82% of theory) of a yellow crystalline product with a melting point of 194 to 197 ° C., which can be analyzed analytically as a mixture consisting of 92.6% of the compound of the formula

and 6.5% of the compound of formula (303).

und 2,6 % der Verbindung der Formel (6) erweist.Example 12: 11.7 g of the mixture of compounds (17) and (6) obtained according to Example 2 and 13 g of the phosphonate of the formula (701) are reacted in 100 ml of dimethylformamide as described in Example 3. 16 g (about 87% of theory) of a yellow crystalline powder with a melting point of 219 to 225 ° C. are obtained analytically as a mixture consisting of 97.2% of the compound of the formula

and 2.6% of the compound of formula (6).

und 3,4 % der Verbindung der Formel (6) erweist.Example 13: 9.3 g of the mixture of compounds (17) and (6) and 12 g of the phosphonate of the formula (801) obtained according to Example 2 are suspended in 120 ml of dimethylformamide and at 30 ° C. with stirring and nitrogen within 15 minutes treated with 22 ml of an ethanolic 2 M sodium ethylate solution. The reaction mixture is worked up as described in Example 3. 13.5 g (about 89% of theory) of a yellow crystalline powder having a melting point of 219 to 221 ° C. are obtained, which can be analyzed as a mixture consisting of 95.5% of the compound of the formula

and 3.4% of the compound of formula (6).

werden in 60 ml Dimethylformamid suspendiert und bei 30°C unter Rühren und Stickstoff innerhalb 15 Minuten mit 35 ml einer äthanolischen 2,5 M Natriumäthylat-Lösung versetzt.. Das Reaktonsgemisch wird wie im Beispiel 3 beschrieben aufgearbeitet. Man erhält 11,5 g (etwa 38 % der Theorie) eines gelben kristallinen Pulvers vom Schmelzpunkt 143 bis 169°C, das sich analytisch als ein Gemisch bestehend aus 90,6 % der Verbindung der Formel

und 8,3 % der Verbindung der Formel (6) erweist.Example 14: 18.6 g of the mixture of compounds (17) and (6) obtained according to Example 2 and 24 g of the phosphonate of the formula

are suspended in 60 ml of dimethylformamide and 35 ml of an ethanolic 2.5 M sodium ethylate solution are added at 30 ° C. with stirring and nitrogen within 15 minutes. The reaction mixture is worked up as described in Example 3. 11.5 g (about 38% of theory) of a yellow crystalline powder of melting point 143 to 169 ° C. are obtained, which can be analyzed analytically as a mixture consisting of 90.6% of the compound of the formula

and 8.3% of the compound of formula (6).

The phosphonate of formula (1401) used as the starting material is prepared as follows:

innerhalb einer Stunde zugetropft, wobei Natriumbromid ausfällt. Die erhaltene Suspension wird 20 Stunden bei 60°C unter Vibro-Mischung gehalten, dann auf Raumtemperatur abgekühlt, in Methylenchlorid aufgenommen, mit einer 2N-Natriumcarbonat-Lösung und dann mit Wasser neutral gewaschen, mit Natriumsulfat getrocknet und unter Vakuum am Rotationsverdampfer zur Trockne eingeengt. Man erhält 696 g eines gelb-braunen Oels, das nach Destillation 503 g (70 % der Theorie) des Phosphonates der Formel (1401) als gelbes Oel (K_p0,08 : 158-160°C) liefert.55.2 g of sodium are placed in 360 ml of toluene and the toluene is heated to the reflux temperature. The molten sodium is finely powdered with the help of a vibrator while cooling rapidly. 5 ml of anhydrous ethanol and then 331 g of diethyl phosphite are then added dropwise to the toluene sodium suspension obtained at 60.degree. C. with a strong vibro mixture, the sodium rapidly dissolving. After a further hour at 60 ° C, the sodium has completely dissolved, giving a clear solution. ' 600 g of the compound of the formula are now added to this solution of the sodium salt of the phosphorous acid diethyl ester at 60 ° C. with a vibro mixture

added dropwise within one hour, whereby sodium bromide fails. The suspension obtained is kept for 20 hours at 60 ° C. with a vibro mixture, then cooled to room temperature, taken up in methylene chloride, washed neutral with a 2N sodium carbonate solution and then with water, dried with sodium sulfate and concentrated to dryness in vacuo on a rotary evaporator . This gives 696 g of a yellow-brown oil which, after distillation, gives 503 g (70% of theory) of the phosphonate of the formula (1401) as a yellow oil (K _p0.08 : 158-160 ° C.).

The 2-bromomethyl-benzoic acid ethyl ester of formula (1403) is according to J. Chem. Soc. 121, 2202-2215 (1922).

Example 15: 19.6 g of the mixture of compounds (901) and (902) obtained according to Example 9 and 21 g of the phosphonate of the formula (1401) are suspended in 60 ml of dimethylformamide and at 30 ° C. with stirring and nitrogen within 15 minutes mixed with 31 ml of an ethanolic 2.5M sodium ethylate solution. The reaction mixture is worked up as described in Example 3.

und 12,1 % der Verbindung der Formel (902) erweist.11 g (about 37% of theory) of a pale yellow crystalline powder of melting point 125 to 250 ° C. are obtained, which can be analyzed analytically as a mixture consisting of 87.5% of the compound of the formula

and 12.1% of the compound of formula (902).

werden in 50 ml Dimethylformamid suspendiert und bei 30°C unter Rühren und Stickstoff innerhalb 15 Minuten mit 31 ml einer äthanolischen 2,5 M Natriumäthylat-Lösung versetzt. Das Reaktionsgemisch wird wie im Beispiel 3 beschrieben aufgearbeitet. Man erhält 23 g (etwa 74 % der Theorie) eines blassgelben kristallinen Pulvers vom Schmelzpunkt 183 bis 250°C, das sich analytisch als ein Gemisch bestehend aus 94,7 % der Verbindung der Formel

und 5,4 % der Verbindung der Formel (902) erweist.Example 16: 19.6 g of the mixture of compounds (901) and (902) obtained according to Example 9 and 21 g of the phosphonate of the formula

are suspended in 50 ml of dimethylformamide and mixed with 31 ml of an ethanolic 2.5 M sodium ethylate solution at 30 ° C. with stirring and nitrogen within 15 minutes. The reaction mixture is worked up as described in Example 3. 23 g (about 74% of theory) of a pale yellow crystalline powder of melting point 183 to 250 ° C. are obtained, which can be analyzed analytically as a mixture consisting of 94.7% of the compound of the formula

and 5.4% of the compound of formula (902).

The phosphonate of the formula (1601) used as starting material is prepared in analogy to Example 2 of GB-PS 929,436 and purified by distillation (K _p0.3 : 183-185 ° C).

Example 17: From brighteners consisting of 91, ^2% of the compound of formula (3) and 7.7% of the compound of formula (4) 1 g in 1000 ml of water dispersed. 7.5 ml of this dispersion are added to 100 ml of water containing 0.1 g of a fatty alcohol polyglycol ether. A 15 g polyester fabric is added to this brightener dispersion heated to 60 ° C. The temperature is raised to 120 ° C. in the course of 15 to 20 minutes and left at this temperature for 30 minutes. Then it is cooled to 60 ° C. within 10 to 15 minutes. The tissue is then rinsed in running cold water for 2 minutes and then dried at 60 ° C. for 20 minutes.

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

If, instead of the brightener mentioned, one uses from 95.7% of the compound of the formula (3) and 3.2% of the compound of the formula (6) or one from 88.3% of the compound of the formula (304) and 10.9% of the compound of formula (303), similarly good lightening effects are obtained.

Example 18: Polyester fabric is padded at room temperature with an aqueous dispersion which contains 0.5 g of a brightener in a liter consisting of 91.2% of the compound of the formula (3) and 7.7% of the compound of the formula (4) and 1 g contains an adduct of about 8 moles of ethylene oxide with 1 mole of p-tert-octylphenol. The fluid intake is 60 to 70%. The fabric is dried at 100 ° C and then heated to 180 ° C for 15 seconds.

The fabric treated in this way has a strong fogging effect with good lightfastness.

If, instead of the brightener mentioned, one uses from 95.7% of the compound of the formula (3) and 3.2% of the compound of the formula (6) or one from 88.3% of the compound of the formula (304) and 10.9% of the compound of formula (303), similarly good lightening effects are obtained.

Similar brightening effects are achieved by the two methods of Examples 17 and 18, if the brightener used is a two-component brightener consisting of 95.7% of the compound of the formula (304) and 3.8% of the compound of the formula (6); 85.1% of the compound of formula (501) and 13.8% of the compound of formula (303); 91.6% of the compound of formula (501) and 7.1% of the compound of formula (4); 93.3% of the compound of formula (702) and 5.6% of the compound of formula (4); 95.3% of the compound of formula (802) and 3.9% of the compound of formula (4); 93.4 2 of the compound of formula (1001) and 5.5% of the compound of formula (303); 92.6% of the compound of formula (1101) and 6.5% of the compound of formula (303); 97.2 Z of the compound of formula (1201) and 2.6% of the compound of formula (6); 95.5% of the compound of formula (1301) and 3.4% of the compound of formula (6); 90.6% of the compound of formula (1402) and 8.3% of the compound of formula (6); 87.5% of the compound of formula (1501) and 12.1% of the compound of formula (902); or 94.7% of the compound of formula (1602) and 5.4% of the compound of formula (902).

Example 19: From the brightener consisting of 91.2% of the compound of formula (3) and 7.7% of the compound of formula (4), 1 g is dispersed in 1000 ml of water. 3 ml of this dispersion are added to 100 ml of water containing 0.06 g of an alkyl polyglycol ether. A 3 g heavy polyamide fabric (polyamide 6 or 66) is added to this brightener dispersion heated to 60 ° C. The temperature is raised to 95 to 97 ° C. within 10 to 15 minutes and left at this temperature for 30 minutes. The tissue is then rinsed in running cold water for 2 minutes and then dried at 60 ° C. for 20 minutes.

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

If, instead of the brightener mentioned, one uses from 95.7% of the compound of the formula (3) and 3.2% of the compound of the formula (6) or one from 88.3% of the compound of the formula (304) and 10.9% of the compound of formula (303), similarly good lightening effects are obtained.

in einem Mischungsverhältnis von 1:2 bzw. 2:1, sowie 1 g eines Fettalkoholpolyglykoläthers enthält.Example 20: A bath is produced which contains 0.0125, 0.025 or 0.05% by weight, based on the polyester material to be lightened, of a brightener mixture consisting of a brightener composed of 95.7% of the compound of the formula per liter of soft water (3) and 3.2% of the compound of formula (6) and a brightener of the formula

in a mixing ratio of 1: 2 or 2: 1, and 1 g of a fatty alcohol polyglycol ether.

At 40 ° C. a polyester fabric ("Terylene type 540") in a liquor ratio of 1:20 is introduced into the bath, which is located in a conventional HT dyeing machine. The mixture is heated to 110, 120 and 130 ° C. over a period of 30 minutes and the bath is kept at the respective temperature for 30 minutes. The mixture is then cooled to 40 ° C. within 15 minutes. The treated tissue is rinsed in flowing, softened water for 30 seconds and then dried.

The treated fabric pieces show strong, brilliant lightening effects with a pleasing nuance. The greenish-bluish one obtained from the compounds (3) and (6) when lightened with the brightener Nuance is clearly shifted into the reddish area.

Example 21: Polyester fabric ("Terylene type 540") is padded at room temperature with an aqueous dispersion which contains 0.125, 0.25, 0.5 or 1 g of a brightener mixture per liter, consisting of a brightener made from 95.7% of the compound of the formula (3) and 3.2% of the compound of the formula (6) and a brightener of the formula (2001) in a mixing ratio of 1: 2 or 2: 1, and 1 ml of an alkylphenol polyglycol ether. The fleet intake is 80%. The fabric is dried at 80 ° C for 10 minutes and then heat-set at 180 °, 200 or 220 ° C for 30 seconds.

The treated fabric pieces show strong, brilliant lightening effects with a pleasing nuance. The greenish-bluish shade obtained from the compounds (3) and (6) when lightening with the brightener is clearly shifted into the reddish area.

oder

ein, so erhält man auf den behandelten Gewebestücken ähnlich gute Effekte, wie sie in den Beispielen 20 und 21 beschrieben sind.Example 22: If Example 20 or 21 is repeated, but instead of the brightener of the formula (2001), the same amount of one of the brighteners of the formulas is used

or

a, similarly good effects are obtained on the treated tissue pieces as described in Examples 20 and 21.

The brightener from the compounds (3) and (6) can also be replaced by any other two-component brightener obtainable according to Examples 1, 3-8 and 10-16.

Claims (19)

1. Optical brightener, consisting of 51-99% of an asymmetrically substituted compound of the formula

wherein R and R _{1 are the} same or different, wherein in the event that R and R _{1 are the} same, R ₁ must occupy a different position in the phenyl ring to which it is attached than R in its phenyl ring and in which R and R ₁ independently represent CN or a carboxylic acid ester group, and 49-1% of a symmetrically substituted compound of the formula

where R has the above meaning and both R are attached to the same position in their phenyl rings. 2. Optical brightener according to claim 1, consisting of 51-99% of an asymmetrically substituted compound of the formula

wherein R and R _{1 are the} same or different, R ₁ must occupy a different position in the phenyl ring to which it is attached than R in its phenyl ring, and R and R ₁ independently of one another denote CN or a carboxylic acid ester group, and 49-1% a symmetrically substituted compound of the formula

where R has the above meaning and both R are attached to the same position in their phenyl rings. 3. Optical brightener according to claim 1 or 2, characterized in that in the two individual components R and R independently of one another denote CN or a group of the formula -COOY, where Y is alkyl, haloalkyl, aralkyl, carbalkoxyalkyl, cyanoalkyl, hydroxyalkyl, aminoalkyl, alkylaminoalkyl , Dialkylaminoalkyl, where all the aforementioned alkyl groups and alkyl parts in composite groups each have 1 to 6 carbon atoms; Alkenyl with 3 to 6 carbon atoms, cycloalkyl with 5 to 6 carbon atoms, propargyl, tetrahydrofurfuryl or a group of the formula (CH ₂ -

H represents XO) _n -alkyl, where X is hydrogen or methyl and n is an integer between 1 and 4 and the alkyl group has 1 to 6 carbon atoms. 4. Optical brightener according to claim 3, characterized in that R and R _{1 are} each independently of one another -CN or -COOY 'where Y' is alkyl having 1 to 4 carbon atoms, but preferably R and R _{1 are} each -CN. 5. Optical brightener according to claim 4, consisting of 51-99% of the compound of formula

and 49-1% of the compound of the formula

or the formula

6. Optical brightener according to one of claims 1-5, consisting of 70-99%, preferably 80-99%, in particular 90-99% of the asymmetrically substituted compound, in particular of the formula (1) or (3) and 30 to 1% , preferably 20-1%, in particular 10-1% of the symmetrically substituted compound, in particular of the formula (2), (4) or (6). 7. A method for producing an optical brightener as defined in claim 1 or 2, characterized in that terephthalaldehyde with a compound of the formula

to a mixture of the compounds of the formulas

and

and this mixture is then reacted further with a compound of the formula

to the brightener defined in claim 1 or 2, where R and R have the meanings given in claim 1 or 2 and must meet the conditions specified there with regard to their positions in the phenyl rings and where X and Y are identical or different and are independently hydrogen or a radical of the formula -COOZ, in which Z represents alkyl,

preferably of the formula

especially the formula

mean. 8. The method according to claim 7, characterized in that the reaction of terephthalaldehyde with a compound of the formula

in a solvent or solvent mixture in which the resulting monoaldehyde is sparingly soluble and crystallizes out. 9. The method according to claim 7 or 8, characterized in that the reaction of terephthalaldehyde with a compound of the formula

in the presence of an alkaline condensing agent, preferably an alkali metal alcoholate, at temperatures between 0 and 50 ° C., preferably between 20 and 30 ° C. _10th A method according to claim 7, characterized in that the reaction of the mixture obtained in the first stage with a compound of the formula

in the presence of an alkaline condensing agent, preferably an alkali metal alcoholate, at temperatures between 20 and 100 ° C., preferably between 30 and 50 ° C. 11. A composition for the optical brightening of high molecular weight organic materials, characterized in that it contains a defined in claims ₁ -6 optical brightener and optionally conventional formulation additives. 12. Composition according to claim ₁₁ , characterized in that it additionally contains an optical brightener which produces a greenish to bluish nuance on the treated substrate and which is defined in claims 1-6 and which produces a reddish shade on the treated substrate , in particular one from the class of naphthalimides, bis-benzoxazolyl-ethylenes, bis-benzoxazolyl-thiophenes, stilbenyl-benzoxazoles, naphthotriazolyl-stilbenes or triazolylcoumarins. 13. Composition according to claim 12, characterized in that it as a brightener active substance 5-90%, in particular 30-70 X, of a on the treated substrate producing a greenish to bluish shade, defined in claims 1-6 brighteners and 95- 10%, in particular 70-30 Z, of an optical brightener, which produces a reddish shade on the treated substrate. 14. Composition according to claim 13, characterized in that it contains an optical brightener consisting of the compounds (3) and (4) or (3) and (6) and additionally an optical brightener from the class of the naphthotriazolyl-stilbene or the triazolylcoumarins . 15. A method for optically brightening natural, semi-synthetic or synthetic high molecular weight organic substrates, e.g. made of polyester, especially textile fibers, e.g. Polyester fibers, characterized in that an optical brightener as defined in claims 1-6 or an agent according to one of claims 11-14 is incorporated into the substrates or applied to the substrates, preferably textile fibers. 16. Use of brighteners defined in claims 1 to 6 for the optical brightening of natural, semi-synthetic or synthetic high molecular weight organic materials, in particular of polyester, especially of polyester fibers. 17. 4 '.- Cyanostilben-4-aldehyde and 3'-cyanostilben-4-aldehyde. 18. Stilbenaldehydes of the formula

in which R _{2 is} a carboxylic acid ester group, in particular one of the formula -COOY, in which Y is alkyl, haloalkyl, aralkyl, carbalkoxyalkyl, cyanoalkyl, hydroxyalkyl, aminoalkyl, alkylaminoalkyl, dialkylaminoalkyl, all of the aforementioned alkyl groups and alkyl parts in combined groups each having 1 to 6 carbon atoms ; Alkenyl with 3 to 6 carbon atoms, cycloalkyl with 5 to 6 carbon atoms, propargyl, tetrahydrofurfuryl or a group of the formula

represents, in which X is hydrogen or methyl and n is an integer between 1 and 4 and the alkyl group has 1 to 6 carbon atoms, Y being preferably alkyl with 1 to 4 carbon atoms. _19th Process for the preparation of stilbene aldehydes of the formula

wherein R _'2 is cyano or a Carbonsäureestergruppe, in particular an _{s che} ol of the formula -COOY, wherein Y is alkyl, haloalkyl, aralkyl, Carbal- _kox y _al kyl, cyanoalkyl, hydroxyalkyl, aminoalkyl, alkylaminoalkyl, dialkyl _k y _lam i _noalk y _l , where all the aforementioned alkyl groups and alkyl parts in composite groups each have 1 to 6 carbon atoms; Alkenyl with 3 to 6 carbon atoms, cycloalkyl with 5 to 6 carbon atoms, propargyl, tetrahydrofurfuryl or a group of the formula (CH ₂ -

H XO) _n -alkyl, where X is hydrogen or methyl and _{n is} an integer between 1 and 4 and the alkyl group has 1 to 6 carbon atoms, characterized in that terephthalaldehyde with a compound of the formula

where X 'is a radical of the formula

means, and the desired stilbenaldehyde is separated from the mixture obtained by repeated recrystallization, if necessary, or by chromatography.