EP0023028B1 - Mixtures of optical brighteners and their use - Google Patents
Mixtures of optical brighteners and their use Download PDFInfo
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- EP0023028B1 EP0023028B1 EP80104163A EP80104163A EP0023028B1 EP 0023028 B1 EP0023028 B1 EP 0023028B1 EP 80104163 A EP80104163 A EP 80104163A EP 80104163 A EP80104163 A EP 80104163A EP 0023028 B1 EP0023028 B1 EP 0023028B1
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- 0 N#CC1C=CC=C[C@]1C=C*1C=CC(C=Cc(cccc2)c2C#N)=CC1 Chemical compound N#CC1C=CC=C[C@]1C=C*1C=CC(C=Cc(cccc2)c2C#N)=CC1 0.000 description 9
- JGDLUGKNDDIMSQ-UHFFFAOYSA-N Bc1ccc(C)cc1 Chemical compound Bc1ccc(C)cc1 JGDLUGKNDDIMSQ-UHFFFAOYSA-N 0.000 description 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Cc1ccccc1 Chemical compound Cc1ccccc1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
- FQAWBFKSPCQARO-BUHFOSPRSA-N N#Cc1ccccc1/C=C/c1ccc(C=[ClH]=[I]c(cccc2)c2C#N)cc1 Chemical compound N#Cc1ccccc1/C=C/c1ccc(C=[ClH]=[I]c(cccc2)c2C#N)cc1 FQAWBFKSPCQARO-BUHFOSPRSA-N 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
- D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
- D06L4/60—Optical bleaching or brightening
- D06L4/65—Optical bleaching or brightening with mixtures of optical brighteners
Definitions
- optical brighteners Venkataraman, The Chemistry of Synthetic Dyes, Vol. V, Chapter VIII.
- French Patent No. 1,415,977 it is also known from French Patent No. 1,415,977 to use mixtures of optical brighteners consisting of 1,4-bis (cyano-2-styryl) benzene, 1,4-bis (cyano-4-styryl) benzene and 4- (cyano-2-styryl) -1- (cyano-4-styryl) benzene.
- a mixture which consists of one of these isomeric bis (cyanostyryl) benzenes, namely 1,4-bis (cyano-2-styryl) benzene and a brightener from the series of naphthalimide derivatives (Chemical Abstracts Vol. 83 , No. 61504 c). It has now been found that the effect of these known mixtures can be exceeded if the mixture known from the French patent mentioned is mixed with other brighteners of the formulas 4 to 8 listed below.
- alkyl and alkoxy groups and other groups derived therefrom contain 1 to 4 carbon atoms.
- the term “non-chromophoric substituents” is to be understood as meaning alkyl, alkoxy, aryl, aralkyl, trifluoromethyl, cycloalkyl, halogen, alkylsulfonyl, carboxy, sulfonic acid, cyano, carbonamide, sulfonamide, carboxylic acid alkyl ester, sulfonic acid alkyl ester.
- component B consisting of one or more compounds of the formulas 2b-6b where R 1 in the 5-position is a hydrogen or chlorine atom, a methyl or phenyl group and R 2 is a hydrogen atom or R 1 and R 2 are both a methyl group in the 5,6- or 5,7-position, n 0 or 1 and B.
- R 14 is (C 1 -C 6 ) alkyl, (C 1 -C 6 ) chloroalkyl, (C 1 -C 4 ) alkoxy- (C 1 -C 4 ) alkyl, hydroxy (C 1 -C 4 ) alkyl or a group of the formula - (CH 2 CH 2 O) n ⁇ R, n 2 or 3 and R hydrogen or (C 1 -C 4 ) alkyl, R, 5 phenyl, halophenyl, (C 1 -C 4 ) -alkylphenyl or (C 1 -C 4 ) -alkoxiphenyl, R 22 is (C 1 -C 4 ) -alkyl and R 23 is cyano or carbo- (C 1 -C 4 ) -alkoxy, where R 3 is hydrogen or (C 1 -C 6 ) alkyl, (C 1 -C 6 ) chloroalkyl, (C 1 -C 4 ) alk
- component B consisting of one or more compounds of the following formulas: wherein R 1 and R 2 in the 5,6-position methyl and B carbomethoxy, R hydrogen, R 1 hydrogen or methyl in the 5-position and B carbomethoxy, cyano or a group of the formulas wherein R 14 and R 22 are (C 1 -C 3 ) alkyl and R 15 is phenyl, 4-methylphenyl or 4-methoxyphenyl, or R 1 is hydrogen, methyl or t-butyl in the 5-position, R 2 is hydrogen or methyl in 7-position and B is phenyl, where R 3 is hydrogen or methoxy, or or where R 2 is hydrogen or methyl.
- component A Mixtures of the following composition are particularly preferred as component A: the proportion of compounds 1 and 3 should be approximately the same.
- the proportion of the individual compounds 1 to 3 in component A can fluctuate within the limits specified, preference being given to mixtures which contain the compounds 1 and 3 in approximately equal parts. From the limits given above for the weight ratios of compounds 1 to 3, it follows that the proportion of compounds 1 and 3 can be 0% and the proportion of compound 2 can be 100%. In this case there is pure connection 2. It is understood that the composition of component A is chosen within the various limits given above so that the sum of all individual compounds is 100%.
- the ratio of compounds 10 and 11 determines the composition of the mixture. If the proportion of 10 is higher, the proportion of compound 1 increases at the expense of compound 3, if the proportion of compound 11 is higher, the proportion of compound 3 in mixtures will be higher than 1.
- one of the symbols X or Q represents an aldehyde group and the other symbol a group of the formulas where R represents an optionally substituted alkyl radical having preferably 1-6 C atoms, an aryl radical preferably phenyl, a cycloalkyl radical or an aralkyl radical, preferably benzyl.
- the process is preferably carried out in solvents in the presence of a proton acceptor.
- solvents which may be mentioned are hydrocarbons such as toluene, xylene, alcohols such as methanol, ethanol, isopropanol, butanol, glycols, hexanols, cyclohexanols, and furthermore ethers such as diisopropyl ether, tetrahydrofuran, dioxane and dimethyl sulfoxide.
- Polar organic solvents such as formamide, dimethylformamide and N-methylpyrrolidone are particularly suitable, with dimethylformamide being particularly emphasized.
- Suitable proton acceptors are primarily basic compounds, such as alkali or alkaline earth metal hydroxides, alcoholates or amides, strongly basic amines and anion exchange resins in the hydroxyl form.
- alkali hydrodes in particular potassium hydroxide, is preferred.
- the reaction temperature depends on the type of components to be reacted, in particular on the type of organic compound containing carbonyl groups and the proton acceptor; it is between - 10 ° C and + 100 ° C, advantageously between 0 ° -50 ° C.
- a preferred embodiment is to bring the reactants together at lower temperatures and to complete the reaction at a higher temperature.
- the claimed process can be carried out, for example, by introducing the proton acceptor in the solvent and adding a solution of the reaction components 9-11 in the solvent, but it is also possible to introduce the compounds 9-11 and adding them to the proteone acceptors.
- a further embodiment consists in presenting the compounds 9-11, in which X or Q represents a group of the formula 12a-d, then first adding the proton acceptor and then the aldehyde component. The reaction generally takes place with intense heat so that cooling may be necessary.
- the reactor mixture is worked up in a known manner, e.g. by adding methanol or ethanol and separating the precipitated products.
- the product mixtures obtained in this way can be analyzed and characterized by HPLC (high pressure liquid chromatography).
- the starting compounds of the formulas 9-11 are known or can be prepared by known processes.
- R, " and R 2" are hydrogen or alkyl and B "is a group of the formulas ⁇ CN or ⁇ COOalkyl and R, 4 .
- Alkyl or methoxyethyl means.
- the following compounds under formula 4 are of particular importance: and
- the mixing ratio for the individual components is between 0.05 and 0.95 parts by weight for component A and correspondingly 0.95 to 0.05 parts by weight for the other compounds of the formulas 4 to 8.
- These compounds of the formulas 4 to 8 can be used individually or in any mixture with one another, the mixing ratio of these compounds with one another being completely uncritical and being able to be varied as desired.
- a mixing ratio of 5 to 50% by weight for component A and 95 to 50% by weight of one or more brighteners of the formulas 4 to 8 (component B) is preferred.
- the optimal mixing ratio of all compounds depends in individual cases on the structure of the respective compounds and can be easily determined by simple preliminary tests.
- the individual components are dispersed in a liquid medium e.g. Water brought into the commercial form.
- the individual components can be dispersed individually and the dispersions can then be added together.
- the individual components can also be mixed together in bulk and then dispersed together. This dispersion process takes place in the usual way in ball mills, colloid mills, bead mills or dispersion kneaders.
- the mixtures according to the invention are particularly suitable for lightening textile material made from linear polyesters, polyamides and acetyl cellulose. However, these mixtures can also be used with good results in mixed fabrics which consist of linear polyesters and other synthetic or natural fiber materials, in particular fibers containing hydroxyl groups, in particular cotton.
- optical brighteners are applied under the conditions customary for the use of optical brighteners, for example using the exhaust process at 90 ° C. to 130 ° C. with or without the addition of accelerators (carriers) or using the thermosol process.
- the water-insoluble brighteners and the mixtures according to the invention can also be used in organic solvents, e.g. Perchlorethylene, fluorinated hydrocarbons can be used in solution.
- the textile material can be treated in the exhaust process with the solvent liquor which contains the optical brightener, or one can impregnate, splash, spray the textile material with the brightener-containing solvent liquor and then dry at temperatures of 120-220 ° C, the optical brightener being used is completely fixed in the fiber.
- the material is squeezed between rollers with a padder so that a moisture absorption of approx. 80% results. This corresponds to an absorption of optical brighteners on the goods of 0.064%.
- the material which had been blocked in this way was then thermosolated on a stenter for 30 seconds at 170 ° (Table I) or 210 ° (Table 11).
- the specified degrees of whiteness according to Ganz were obtained. The degrees of whiteness were measured using a DMC-25 reflectance spectrophotometer. (Carl Zeiss company, Oberkochen).
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Abstract
Description
Es ist bereits eine sehr große Anzahl von Einzelverbindungen bekannt, die als optische Aufheller verwendet werden können (Venkataraman, The Chemistry of Synthetic Dyes, Bd. V, Kapitel VIII). Darüberhinaus ist es auch aus der französischen Patentschrift 1 415977 bekannt, Mischungen von optischen Aufhellern einzusetzen, bestehend aus 1,4-Bis(cyano-2-styryl)-benzol, 1,4-Bis-(cyano-4-styryl)-benzol und 4-(Cyano-2-styryl)-1-(cyano-4-styryl)-benzol. Auch ist eine Mischung bekannt, die aus einem dieser isomeren Bis(Cyanostyryl)-benzole, nämlich 1,4-Bis(cyano-2-styryl)-benzol und einem Aufheller aus der Reihe der Naphthalimid-Derivate besteht (Chemical Abstracts Bd. 83, Nr. 61504 c). Es wurde nun gefunden, daß man die Wirkung dieser bekannten Mischungen noch übertreffen kann, wenn man die aus der genannten französischen Patentschrift bekannte Mischung mit weiteren Aufhellern der weiter unten aufgeführten Formeln 4 bis 8 abmischt.A very large number of individual compounds are already known which can be used as optical brighteners (Venkataraman, The Chemistry of Synthetic Dyes, Vol. V, Chapter VIII). In addition, it is also known from French Patent No. 1,415,977 to use mixtures of optical brighteners consisting of 1,4-bis (cyano-2-styryl) benzene, 1,4-bis (cyano-4-styryl) benzene and 4- (cyano-2-styryl) -1- (cyano-4-styryl) benzene. A mixture is also known which consists of one of these isomeric bis (cyanostyryl) benzenes, namely 1,4-bis (cyano-2-styryl) benzene and a brightener from the series of naphthalimide derivatives (Chemical Abstracts Vol. 83 , No. 61504 c). It has now been found that the effect of these known mixtures can be exceeded if the mixture known from the French patent mentioned is mixed with other brighteners of the formulas 4 to 8 listed below.
Gegenstand der vorliegenden Erfindung sind Mischungen von optischen Aufhellern bestehend aus
- A) 0,05 bis 0,95 Gew.-Teilen eines Gemisches bestehend aus 0 bis 80 Gew.-% der Verbindung der Formel 1
- B) 0,95 bis 0,05 Gew.-Teilen einer oder mehrerer Verbindungen der Formeln 4, 5, 6, 7 oder 8
- n 0 oder 1,
- X ein Sauerstoff- oder Schwefelatom,
- R1 und R2 gleiche oder verschiedene Reste aus der Gruppe Wasserstoff-, Fluor- oder Chloratome, Phenyl, Trifluormethyl, C1-C9 Alkyl, Alkoxy, Dialkylamino, Acylamino, Cyano, Carboxy, Carboalkoxy, Carbonsäureamid, Sulfonsäure, Sulfonsäureamid oder Sulfonsäurealkylester, bedeutet, wobei zwei benachbarte Reste R1 und R2 zusammen auch für einen Benzoring, eine niedere Alkylen- oder eine 1,3-Dioxapropylengruppe stehen können, Cyano, eine Gruppe der Formel ―COOR11 oder CONR11R11 wobei R11 Wasserstoff, C1-C18 Alkyl, Cycloalkyl, Aryl, Alkylaryl, Halogenaryl, Aralkyl, Alkoxyalkyl, Halogenalkyl, Hydroxyalkyl, Alkylaminoalkyl, Carboxyalkyl oder Carboalkoxyalkyl bedeutet oder zwei Alkyl- bzw. Alkylenreste unter der Bedeutung von R11 zusammen mit dem Stickstoffatom auch einen Morpholin-, Piperidin- oder Piperazinring bilden können, bedeutet, oder B eine Gruppe der Formel
- R22 ein Wasserstoffatom, eine Triphenylmethylgruppe oder einen niederen Alkylrest bedeutet, der gegebenenfalls durch eine niedere Carbalkoxy-, Carbonamido-, Mono- oder Dialkylcarbonamido-, Carboxy- oder Benzoylgruppe substituiert ist und R23 eine Cyangruppe oder eine Gruppe der Formeln
bedeutet, - R3 und R4 gleich oder verschieden sein können und Wasserstoff, Alkyl, Cycloalkyl, Alkoxy, Hydroxyalkoxyethyl, Halogenalkyl, Aralkyl, Aryl oder N,N-di-alkylamin bedeuten oder R3 und R4 bilden zusammen einen fünfgliedrigen Heterocyclus mit 1 bis 3 Heteroatomen, vorzugsweise N-Atomen,
- R5 geradkettige oder verzweigtes Alkyl, Alkoxyalkyl, Dialkylaminoalkyl oder einen Rest der Formel
- R7 Wasserstoff, Alkyl, Alkoxy, Aryl, oder einen über ein Stickstoffatom gebundenen fünfgliedrigen Heterocyclus mit 1-3 N oder O Heteroatomen bedeutet, der durch Alkyl, Aryl, Hydroxy, Oxalkyl, Oxalkenyl, Oxaryl, Oxarylalkyl, Oxalkoxycarbonyl, Oxcarbamoyl, Oxepoxyalkyl, Styryl oder Halogenstyryl, einen anellierten Phenyl-, Naphthyl- oder Phenanthrylring, oder eine anellierte Gruppe der Formeln
- R8 ein polycyclischer, aromatischer Rest mit mindestens drei kondensierten Ringen, die.gegebenenfalls nichtchromophore Substituenten tragen,
- Rg eine Aminogruppe, die durch ein oder zwei Alkyl-, Hydroxyalkyl-, Acyl- oder Phenylgruppen substituiert ist, wobei die Phenylgruppe eine oder mehrere nichtchromophore Reste enthalten kann und zwei Alkylgruppen zusammen mit dem Stickstoffatom der Aminogruppe einen Pyrrolidin- oder Piperidinring oder unter Einschluß eines weiteren Stickstoff- oder Sauerstoffatoms einen Piperazin- oder Morpholinring bilden können ; eine Alkoxy-, Hydroxyalkoxy-, Acyloxy-, Alkylthio- oder Carbalkylmercaptogruppe darstellt,
- R10 unabhängig von R8 die gleiche Bedeutung wie Rg hat und zusätzlich ein Chloratom bedeuten kann,
und - V eine Gruppe der Formeln
- A) 0.05 to 0.95 parts by weight of a mixture consisting of 0 to 80% by weight of the compound of formula 1
- B) 0.95 to 0.05 part by weight of one or more compounds of the formulas 4, 5, 6, 7 or 8
- n 0 or 1,
- X is an oxygen or sulfur atom,
- R 1 and R 2 are identical or different radicals from the group consisting of hydrogen, fluorine or chlorine atoms, phenyl, trifluoromethyl, C 1 -C 9 alkyl, alkoxy, dialkylamino, acylamino, cyano, carboxy, carboalkoxy, carboxylic acid amide, sulfonic acid, sulfonic acid amide or sulfonic acid alkyl ester , means, where two adjacent radicals R 1 and R 2 together can also represent a benzo ring, a lower alkylene or a 1,3-dioxapropylene group, cyano, a group of the formula ―COOR 11 or CONR 11 R 11 where R 11 is hydrogen C 1 -C 18 alkyl, cycloalkyl, aryl, alkylaryl, haloaryl, aralkyl, alkoxyalkyl, haloalkyl, hydroxyalkyl, alkylaminoalkyl, carboxyalkyl or carboalkoxyalkyl or two alkyl or alkylene radicals under the meaning of R 11 together with the nitrogen atom also mean a morpholine -, Piperidine or piperazine ring means, or B is a group of the formula
- R 22 represents a hydrogen atom, a triphenylmethyl group or a lower alkyl radical which is optionally substituted by a lower carbalkoxy, carbonamido, mono- or dialkylcarbonamido, carboxy or benzoyl group and R 23 represents a cyano group or a group of the formulas
means - R 3 and R 4 can be the same or different and represent hydrogen, alkyl, cycloalkyl, alkoxy, hydroxyalkoxyethyl, haloalkyl, aralkyl, aryl or N, N-di-alkylamine or R 3 and R 4 together form a five-membered heterocycle with 1 to 3 Heteroatoms, preferably N atoms,
- R 5 straight-chain or branched alkyl, alkoxyalkyl, dialkylaminoalkyl or a radical of the formula
- R 7 denotes hydrogen, alkyl, alkoxy, aryl, or a five-membered heterocycle with 1-3 N or O heteroatoms which is bonded via a nitrogen atom and which is characterized by alkyl, aryl, hydroxy, oxalkyl, oxalkenyl, oxaryl, oxarylalkyl, oxalkoxycarbonyl, oxcarbamoyl, oxepoxyalkyl, Styryl or halostyryl, a fused phenyl, naphthyl or phenanthryl ring, or a fused group of the formulas
- R 8 is a polycyclic, aromatic radical with at least three condensed rings which may carry non-chromophoric substituents,
- Rg is an amino group which is substituted by one or two alkyl, hydroxyalkyl, acyl or phenyl groups, where the phenyl group can contain one or more non-chromophoric radicals and two alkyl groups together with the nitrogen atom of the amino group form a pyrrolidine or piperidine ring or including one further nitrogen or oxygen atom can form a piperazine or morpholine ring; represents an alkoxy, hydroxyalkoxy, acyloxy, alkylthio or carbalkyl mercapto group,
- R 10 has the same meaning as Rg independently of R 8 and can additionally represent a chlorine atom,
and - V is a group of formulas
Soweit nicht anders definiert, enthalten Alkyl- und Alkoxygruppen sowie andere, davon abgeleitete Gruppen 1 bis 4 C-Atome. Unter dem Begriff « nichtchromophore Substituenten" sind zu verstehen Alkyl, Alkoxy, Aryl, Aralkyl, Trifluormethyl, Cycloalkyl, Halogen, Alkylsulfonyl, Carboxy, Sulfonsäure, Cyan, Carbonamid, Sulfonamid, Carbonsäurealkylester, Sulfonsäurealkylester.Unless otherwise defined, alkyl and alkoxy groups and other groups derived therefrom contain 1 to 4 carbon atoms. The term “non-chromophoric substituents” is to be understood as meaning alkyl, alkoxy, aryl, aralkyl, trifluoromethyl, cycloalkyl, halogen, alkylsulfonyl, carboxy, sulfonic acid, cyano, carbonamide, sulfonamide, carboxylic acid alkyl ester, sulfonic acid alkyl ester.
Diese Aufheller der Formeln 4 bis 8 sind dem Fachmann hinreichend bekannt, etwa aus « The Chemistry of Synthetic Dyes », Bd. V, Kapitel VIII von Venkataraman.These brighteners of the formulas 4 to 8 are sufficiently known to the person skilled in the art, for example from “The Chemistry of Synthetic Dyes”, vol. V, chapter VIII of Venkataraman.
Bevorzugt sind erfindungsgemäße Mischungen von optischen Aufhellern, wobei die Komponente B besteht aus einer oder mehreren Verbindungen der Formeln 2b-6b
Bevorzugt sind weiterhin erfindungsgemäße Mischungen von optischen Aufhellern, wobei die Komponente B aus einer oder mehreren Verbindungen der folgenden Formeln besteht :
Als Komponente A der Verbindungen der Formeln 1-3 sind Mischungen der folgenden Zusammensetzung bevorzugt :
Besonders bevorzugt sind als Komponente A Mischungen der folgenden Zusammensetzung :
Der Anteil der einzelnen Verbindungen 1 bis 3 in der Komponente A kann innerhalb der angebenen Grenzen schwanken, wobei solche Mischungen bevorzugt sind, die die Verbindungen 1 und 3 in etwa gleichen Teilen enthalten. Aus den oben angegebenen Grenzen für die Gewichtsverhältnisse der Verbindungen 1 bis 3 ergibt sich, daß der Anteil der Verbindungen 1 und 3 0 % und der Anteil der Verbindung 2 100 % betragen kann. In diesem Fall liegt die reine Verbindung 2 vor. Es versteht sich, daß die Zusammensetzung der Komponente A innerhalb der verschiedenen, oben angegebenen Grenzen so gewählt wird, daß die Summe aller Einzelverbindungen 100 % ausmacht.The proportion of the individual compounds 1 to 3 in component A can fluctuate within the limits specified, preference being given to mixtures which contain the compounds 1 and 3 in approximately equal parts. From the limits given above for the weight ratios of compounds 1 to 3, it follows that the proportion of compounds 1 and 3 can be 0% and the proportion of compound 2 can be 100%. In this case there is pure connection 2. It is understood that the composition of component A is chosen within the various limits given above so that the sum of all individual compounds is 100%.
Das als Komponente A bezeichnete Gemisch wird hergestellt, indem man 1 Mol-Äquivalent einer Verbindung der Formel
Das Verhältnis der Verbindungen 10 und 11 bestimmt die Zusammensetzung des Gemisches. Liegt der Anteil an 10 höher, wächst der Anteil der Verbindung 1 auf Kosten der Verbindung 3, liegt der Anteil an Verbindung 11 höher wird der Anteil der Verbindung 3 in Gemische höher als 1 sein.The ratio of compounds 10 and 11 determines the composition of the mixture. If the proportion of 10 is higher, the proportion of compound 1 increases at the expense of compound 3, if the proportion of compound 11 is higher, the proportion of compound 3 in mixtures will be higher than 1.
Vorteilhaft ist es, die Umsetzung von 9 mit je einem Mol-Äquivalent der Verbindungen 10 und 11, durchzuführen, wobei ein Überschuß von 10 und 11 bis zu 10 % möglich, aber nicht von Vorteil ist. In den Formeln 9-10 bedeutet eines der Symbole X oder Q eine Aldehydgruppe und das andere Symbol eine Gruppe der Formeln
Eine bevorzugte Verfahrensvariante besteht darin, daß man eine Verbindung der Formel 9, wobei X für eine Aldehydgruppe steht, mit Verbindungen der Formel 10 und 11, wobei Q für eine Gruppe der Formel 12a mit R = C1-4 Alkyl steht, umsetzt.A preferred process variant consists in reacting a compound of formula 9, where X is an aldehyde group, with compounds of formulas 10 and 11, where Q is a group of formula 12a with R = C1-4 alkyl.
Man führt das Verfahren vorzugsweise in Lösungsmitteln durch in Gegenwart eines Protonenacceptors. Als Lösungsmittel seien bespielsweise genannt Kohlenwasserstoffe wie Toluol, Xylol, Alkohole wie Methanol, Äthanol, Isopropanol, Butanol, Glykole, Hexanole, Cyclohexanole, ferner Äther wie Diisopropyläther, Tetrahydrofuran, Dioxan und Dimethyisulfoxyd genannt. Besonders geeignet sind polare organische Lösungsmittel wie Formamid, Dimethylformamid und N-Methylpyrrolidon, wobei Dimethylformamid besonders hervorzuheben ist.The process is preferably carried out in solvents in the presence of a proton acceptor. Examples of solvents which may be mentioned are hydrocarbons such as toluene, xylene, alcohols such as methanol, ethanol, isopropanol, butanol, glycols, hexanols, cyclohexanols, and furthermore ethers such as diisopropyl ether, tetrahydrofuran, dioxane and dimethyl sulfoxide. Polar organic solvents such as formamide, dimethylformamide and N-methylpyrrolidone are particularly suitable, with dimethylformamide being particularly emphasized.
Als Protonenacceptoren eignen sich vornehmlich basische Verbindungen, wie Alkali- oder Erdalkalihydroxyde, -alkoholate oder -amide, stark basische Amine und Anionenaustauscherharze in der Hydroxylform. Bevorzugt ist der Einsatz von Alkalihydröxyden, im besonderen Kaliumhydroxyd.Suitable proton acceptors are primarily basic compounds, such as alkali or alkaline earth metal hydroxides, alcoholates or amides, strongly basic amines and anion exchange resins in the hydroxyl form. The use of alkali hydrodes, in particular potassium hydroxide, is preferred.
Die Umsetzungstemperatur hängt von der Art der umzusetzenden Komponenten, insbesondere von der Art der Carbonylgruppen enthaltenden organischen Verbindung und dem Protonenacceptor ab ; sie liegt zwischen - 10 °C und + 100 °C, vorteilhaft zwischen 0°-50°C. Eine bevorzugte Ausführungsform besteht darin, die Reaktionspartner bei tieferen Temperaturen zusammenzugeben und die Reaktion bei höherer Temperatur zu Ende zu führen.The reaction temperature depends on the type of components to be reacted, in particular on the type of organic compound containing carbonyl groups and the proton acceptor; it is between - 10 ° C and + 100 ° C, advantageously between 0 ° -50 ° C. A preferred embodiment is to bring the reactants together at lower temperatures and to complete the reaction at a higher temperature.
Das beanspruchte Verfahren läßt sich beispielsweise so durchführen, daß man den Protonenacceptor im Lösungsmittel vorlegt und eine Lösung der Reaktionskomponenten 9-11 im Lösungsmittel zutropft, es ist aber ebenfalls möglich, die Verbindungen 9-11 vorzulegen und den Proteonacceptoren zuzugeben. Eine weitere Ausführungsform besteht darin, die Verbindungen 9-11, worin X oder Q für eine Gruppe der Formel 12a-d steht, vorzulegen, anschließend zuerst den Protonenacceptor und dann die Aldehydkomponente zuzugeben. Die Umsetzung läuft im allgemeinen unter starker Wärmeentwicklung ab, so daß man gegebenenfalls kühlen muß. Die Aufarbeitung des Reaktorgemisches erfolgt in bekannter Weise z.B. durch Zusatz von Methanol oder Äthanol und Abtrennen der ausgefallenen Produkte. Die so erhaltenen Produktgemische lassen sich durch HPLC (High pressure liquid chromatography) analysieren und charakterisieren.The claimed process can be carried out, for example, by introducing the proton acceptor in the solvent and adding a solution of the reaction components 9-11 in the solvent, but it is also possible to introduce the compounds 9-11 and adding them to the proteone acceptors. A further embodiment consists in presenting the compounds 9-11, in which X or Q represents a group of the formula 12a-d, then first adding the proton acceptor and then the aldehyde component. The reaction generally takes place with intense heat so that cooling may be necessary. The reactor mixture is worked up in a known manner, e.g. by adding methanol or ethanol and separating the precipitated products. The product mixtures obtained in this way can be analyzed and characterized by HPLC (high pressure liquid chromatography).
Die Ausgangsverbindungen der Formeln 9-11 sind bekannt bzw. können nach bekannten Verfahren hergestellt werden.The starting compounds of the formulas 9-11 are known or can be prepared by known processes.
Von den Verbindungen unter den Formeln 4 bis 8 sind in den erfindungsgemäßen Gemischen die Verbindungen der folgenden Formeln bevorzugt :
- Formel 4 :
- Formel 5 :
- Formel 6 :
- Formel 7 :
- Formel 8 :
- Formula 4:
- Formula 5:
- Formula 6:
- Formula 7:
- Formula 8:
Ganz besonders bevorzugt sind von den Verbindungen unter der Formel 4 die Verbindungen der Formel
und R,4. Alkyl oder Methoxyäthyl bedeutet. Von besonderer Wichtigkeit sind die folgenden Verbindungen unter der Formel 4 :
and R, 4 . Alkyl or methoxyethyl means. The following compounds under formula 4 are of particular importance:
Das Mischungsverhältnis für die einzelnen Komponenten liegt zwischen 0,05 und 0,95 Gew.-Teilen für die Komponente A und entsprechend 0,95 bis 0,05 Gew.-Teilen für die übrigen Verbindungen der Formeln 4 bis 8. Diese Verbindungen der Formeln 4 bis 8 können einzeln aber auch in beliebiger Mischung untereinander eingesetzt werden, wobei das Mischungsverhältnis dieser Verbindungen untereinander gänzlich unkritisch ist und beliebig variiert werden kann.The mixing ratio for the individual components is between 0.05 and 0.95 parts by weight for component A and correspondingly 0.95 to 0.05 parts by weight for the other compounds of the formulas 4 to 8. These compounds of the formulas 4 to 8 can be used individually or in any mixture with one another, the mixing ratio of these compounds with one another being completely uncritical and being able to be varied as desired.
Bevorzugt ist ein Mischungsverhältnis von 5 bis 50 Gew.-% für die Komponente A und 95 bis 50 Gew.-% eines oder mehrerer Aufhellern der Formeln 4 bis 8 (Komponente B).A mixing ratio of 5 to 50% by weight for component A and 95 to 50% by weight of one or more brighteners of the formulas 4 to 8 (component B) is preferred.
Das optimale Mischungsverhältnis aller Verbindungen hängt im Einzelfall von der Struktur der jeweiligen Verbindungen ab und läßt sich durch einfache Vorversuche unschwer ermitteln.The optimal mixing ratio of all compounds depends in individual cases on the structure of the respective compounds and can be easily determined by simple preliminary tests.
Wie bei optischen Aufhellern üblich, werden die einzelnen Komponenten durch Dispergierung in einem flüssigen Medium z.B. Wasser in die Handelsform gebracht. Man kann dabei die einzelnen Komponenten jede für sich dispergieren und dann die Dispersionen zusammen geben. Man kann aber auch die Einzelkomponenten in Substanz miteinander mischen und dann gemeinsam dispergieren. Dieser Dispergiervorgang geschieht in üblicher Weise in Kugelmühlen, Kolloidmühlen, Perlmühlen oder Dispersionsknetern. Die erfindungsgemäßen Mischungen eignen sich besonders zum Aufhellen von Textilmaterial aus linearen Polyestern, Polyamiden und Acetylcellulose. Man kann diese Mischungen aber auch mit gutem Ergebnis bei Mischgeweben verwenden, die aus linearen Polyestern und anderen synthetischen oder natürlichen Faserstoffen namentlich hydroxylgruppenhaltigen Fasern, insbesondere Baumwolle bestehen. Die Applikation dieser Mischungen geschieht dabei unter den für die Anwendung von optischen Aufhellern üblichen Bedingungen so beispielsweise nach dem Ausziehverfahren bei 90 °C bis 130 °C mit oder ohne Zusatz von Beschleunigern (Carriern) oder nach dem Thermosolverfahren. Die in Wasser unlöslichen Aufheller und die erfindungsgemäßen Mischungen können auch in organischen Lösemitteln z.B. Perchloräthylen, fluorierten Kohlenwasserstoffen gelöst zum Einsatz kommen. Dabei kann das Textilmaterial im Ausziehverfahren mit der Lösemittelflotte, welche den optischen Aufheller gelöst enthält, behandelt werden, oder man imprägniert, pflatscht, sprüht das Textilgut mit der aufhellerhaltigen Lösemittelflotte und trocknet anschließend bei Temperaturen von 120-220 °C, wobei der optische Aufheller dabei restlos in der Faser fixiert wird. Man erhält dabei eine hervorragend aufgehellte Ware mit ausgezeichneter Lichtbeständigkeit, sowie Beständigkeit gegenüber Oxidations-und Reduktionsmitteln. Diese erfindungsgemäßen Mischungen weisen im Vergleich zu den Mischungen des japanischen Patents Sho 50 (1975)-25 877 höhere Weißgrade auf ; sie ergeben ferner auch bereits bei niedrigen Thermosoliertemperaturen von z.B. 150 °C hervorragende Weißgrade.As usual with optical brighteners, the individual components are dispersed in a liquid medium e.g. Water brought into the commercial form. The individual components can be dispersed individually and the dispersions can then be added together. However, the individual components can also be mixed together in bulk and then dispersed together. This dispersion process takes place in the usual way in ball mills, colloid mills, bead mills or dispersion kneaders. The mixtures according to the invention are particularly suitable for lightening textile material made from linear polyesters, polyamides and acetyl cellulose. However, these mixtures can also be used with good results in mixed fabrics which consist of linear polyesters and other synthetic or natural fiber materials, in particular fibers containing hydroxyl groups, in particular cotton. These mixtures are applied under the conditions customary for the use of optical brighteners, for example using the exhaust process at 90 ° C. to 130 ° C. with or without the addition of accelerators (carriers) or using the thermosol process. The water-insoluble brighteners and the mixtures according to the invention can also be used in organic solvents, e.g. Perchlorethylene, fluorinated hydrocarbons can be used in solution. The textile material can be treated in the exhaust process with the solvent liquor which contains the optical brightener, or one can impregnate, splash, spray the textile material with the brightener-containing solvent liquor and then dry at temperatures of 120-220 ° C, the optical brightener being used is completely fixed in the fiber. This gives an excellently lightened product with excellent lightfastness and resistance to oxidizing and reducing agents. These mixtures according to the invention have higher degrees of whiteness than the mixtures of the Japanese patent Sho 50 (1975) -25,877; they also result in low thermal insulation temperatures of e.g. 150 ° C excellent whiteness.
Die folgenden Tabellen-Beispiele illustrieren die Erfindung. Das angewandte Applikationsverfahren soll hier beispielgebend geschildert werden :
- Gewebeabschnitte aus Polyester-Stapelfasern werden gewaschen, getrocknet und auf einen Foulard mit wäßrigen Dispersionen imprägniert, die entweder den reinen optischen Aufheller der Formeln 4 bis 8 (Komponente B) mit einer Einsatzmenge von 0,08 Gew.-% oder ein Gemisch aus 0,064 Gew.-%, 0,04 Gew.-% bzw. 0,016 Gew.% der Komponente A mit 0,016, 0,04 bzw. 0,064 Gew.-% der Aufheller der Komponente B enthalten. Als Komponente A wurde in allen Beispielen ein Gemisch aus 1,5 Gew.-Teilen 1,4-Bis-(4'-cyano-styryl)-benzol, 1,5 Gew.-Teilen 1,4-Bis-(2'-cyano-styryl)-benzol und 7-Gew.-Teilen 1-(2-Cyano-sturyl)-4-(4'-cyano-styryl)-benzol eingesetzt.
- Fabric sections made of polyester staple fibers are washed, dried and impregnated onto a foulard with aqueous dispersions which either contain the pure optical brightener of the formulas 4 to 8 (component B) with an amount of 0.08% by weight or a mixture of 0.064% by weight %, 0.04% by weight or 0.016% by weight of component A with 0.016, 0.04 or 0.064% by weight of the brightener of component B. In all examples, component A was a mixture of 1.5 parts by weight of 1,4-bis (4'-cyano-styryl) benzene, 1.5 parts by weight of 1,4-bis- (2 ' -cyano-styryl) -benzene and 7 parts by weight of 1- (2-cyano-sturyl) -4- (4'-cyano-styryl) -benzene.
Das Material wird mit einem Foulard zwischen Rollen so abgequetscht, daß sich eine Feuchtigkeitsaufnahme von ca. 80 % ergibt. Das entspricht einer Aufnahme an optischen Aufhellern auf die Ware von 0,064 %. Das so geklotzte Material wurde anschließend auf einem Spannrahmen 30 Sek. bei 170° (Tabelle I) bzw. 210° (Tabelle 11) thermosoliert. Dabei wurden die jeweils angegebenen Weißgrade nach Ganz erhalten. Die Weißgrade wurden mit einem Remissionsspektralphotometer Typ DMC-25 gemessen. (Firma Carl Zeiss, Oberkochen).The material is squeezed between rollers with a padder so that a moisture absorption of approx. 80% results. This corresponds to an absorption of optical brighteners on the goods of 0.064%. The material which had been blocked in this way was then thermosolated on a stenter for 30 seconds at 170 ° (Table I) or 210 ° (Table 11). The specified degrees of whiteness according to Ganz were obtained. The degrees of whiteness were measured using a DMC-25 reflectance spectrophotometer. (Carl Zeiss company, Oberkochen).
Claims (8)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT80104163T ATE2017T1 (en) | 1979-07-21 | 1980-07-16 | MIXTURES OF OPTICAL BRIGHTENERS AND THEIR USE. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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DE19792929687 DE2929687A1 (en) | 1979-07-21 | 1979-07-21 | MIXTURES OF OPTICAL BRIGHTENERS |
DE2929687 | 1979-07-21 |
Publications (2)
Publication Number | Publication Date |
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EP0023028A1 EP0023028A1 (en) | 1981-01-28 |
EP0023028B1 true EP0023028B1 (en) | 1982-12-15 |
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ID=6076455
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EP80104163A Expired EP0023028B1 (en) | 1979-07-21 | 1980-07-16 | Mixtures of optical brighteners and their use |
Country Status (10)
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US (1) | US4330427A (en) |
EP (1) | EP0023028B1 (en) |
JP (1) | JPS5618655A (en) |
AT (1) | ATE2017T1 (en) |
AU (1) | AU533417B2 (en) |
BR (1) | BR8004478A (en) |
CA (1) | CA1151806A (en) |
DE (2) | DE2929687A1 (en) |
ES (1) | ES8105055A1 (en) |
ZA (1) | ZA804365B (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3313332A1 (en) * | 1983-04-13 | 1984-10-18 | Hoechst Ag, 6230 Frankfurt | Mixtures of optical brighteners for brightening polyvinyl chloride |
Families Citing this family (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CH650792A5 (en) * | 1979-12-13 | 1985-08-15 | Ciba Geigy Ag | Optical brighteners from bisstyrylbenzene compounds and preparation thereof |
DE3070041D1 (en) * | 1979-12-13 | 1985-03-07 | Ciba Geigy Ag | Optical brighteners from bistyryl benzene, process for their preparation and their use |
DE3001065A1 (en) * | 1980-01-12 | 1981-07-16 | Basf Ag, 6700 Ludwigshafen | METHOD FOR PRODUCING OPTICAL BRIGHTENERS |
DE3027479A1 (en) * | 1980-07-19 | 1982-03-04 | Hoechst Ag, 6000 Frankfurt | MIXTURES OF OPTICAL BRIGHTENERS AND THEIR USE |
DE3104992A1 (en) * | 1981-02-12 | 1982-08-26 | Hoechst Ag, 6000 Frankfurt | "MIXTURES OF OPTICAL BRIGHTENERS" |
DE3339383A1 (en) * | 1983-10-29 | 1985-05-09 | Bayer Ag, 5090 Leverkusen | DISTYRYLIC COMPOUNDS |
JPS60217999A (en) * | 1984-03-31 | 1985-10-31 | 株式会社新潟鐵工所 | Fluid cargo gear |
US4778622A (en) * | 1986-03-21 | 1988-10-18 | Ciba-Geigy Corporation | Mixtures of fluorescent whitening agents |
EP0252009B1 (en) * | 1986-07-01 | 1990-08-01 | Ciba-Geigy Ag | 1,4-distyryl benzene compounds and their mixtures with other 1,4-distyryl benzene compounds |
CH671956A5 (en) * | 1987-01-29 | 1989-10-13 | Ciba Geigy Ag | |
US4830763A (en) * | 1987-02-26 | 1989-05-16 | Ciba-Geigy Corporation | Process for increasing the degree of whiteness of polyester-containing textile material |
DE3878550D1 (en) * | 1987-11-27 | 1993-03-25 | Ciba Geigy Ag | LIGHTER DISPERSION. |
ES2053806T3 (en) * | 1987-11-27 | 1994-08-01 | Ciba Geigy Ag | STABLE WHITENING DISPERSION AND PROCEDURE FOR ITS PREPARATION. |
US6492032B1 (en) | 2000-10-12 | 2002-12-10 | Eastman Chemical Company | Multi-component optically brightened polyolefin blend |
DE10219993A1 (en) * | 2002-05-03 | 2003-11-20 | Basf Ag | Process for lightening textile materials |
ES2316862T3 (en) * | 2002-12-10 | 2009-04-16 | Ciba Holding Inc. | FLUORESCENT WHITENING AGENTS MIXTURES. |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1469821B2 (en) * | 1959-06-24 | 1972-03-23 | Badische Anilin & Soda Fabrik AG, 6700 Ludwigshafen | Optical brighteners for macromolecular organic substances |
CH533670A (en) * | 1968-12-05 | 1973-02-15 | Ciba Geigy Ag | Inorganic white pigments containing optical brighteners |
DE2037854C2 (en) * | 1970-07-30 | 1983-07-07 | Bayer Ag, 5090 Leverkusen | 3- (4-Chloro-1-pyrazolyl) -7-v-triazol-2-yl-coumarin compounds and their use for optical brightening |
JPS51100522A (en) * | 1975-03-01 | 1976-09-04 | Kubota Ltd | SAGYOKI RATSUKABOSHISOCHI |
JPS544973A (en) * | 1977-06-13 | 1979-01-16 | Daiken Trade & Industry | Waterproof treatment for board |
-
1979
- 1979-07-21 DE DE19792929687 patent/DE2929687A1/en not_active Withdrawn
-
1980
- 1980-07-15 ES ES493376A patent/ES8105055A1/en not_active Expired
- 1980-07-16 US US06/169,296 patent/US4330427A/en not_active Expired - Lifetime
- 1980-07-16 AT AT80104163T patent/ATE2017T1/en not_active IP Right Cessation
- 1980-07-16 DE DE8080104163T patent/DE3061345D1/en not_active Expired
- 1980-07-16 EP EP80104163A patent/EP0023028B1/en not_active Expired
- 1980-07-18 ZA ZA00804365A patent/ZA804365B/en unknown
- 1980-07-18 AU AU60636/80A patent/AU533417B2/en not_active Ceased
- 1980-07-18 JP JP9769380A patent/JPS5618655A/en active Granted
- 1980-07-18 CA CA000356458A patent/CA1151806A/en not_active Expired
- 1980-07-18 BR BR8004478A patent/BR8004478A/en not_active IP Right Cessation
Non-Patent Citations (1)
Title |
---|
"The Chemistry of Synthetic Dyes", Band V, Kapital VIII, Venkataraman * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3313332A1 (en) * | 1983-04-13 | 1984-10-18 | Hoechst Ag, 6230 Frankfurt | Mixtures of optical brighteners for brightening polyvinyl chloride |
Also Published As
Publication number | Publication date |
---|---|
ATE2017T1 (en) | 1982-12-15 |
ES493376A0 (en) | 1981-05-16 |
CA1151806A (en) | 1983-08-16 |
US4330427A (en) | 1982-05-18 |
EP0023028A1 (en) | 1981-01-28 |
ES8105055A1 (en) | 1981-05-16 |
AU533417B2 (en) | 1983-11-24 |
AU6063680A (en) | 1981-01-22 |
DE2929687A1 (en) | 1981-02-12 |
JPH0116867B2 (en) | 1989-03-28 |
DE3061345D1 (en) | 1983-01-20 |
ZA804365B (en) | 1981-07-29 |
BR8004478A (en) | 1981-01-27 |
JPS5618655A (en) | 1981-02-21 |
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