EP0056157A1 - Use of 7-hydroxy-coumarin compounds for impregnating paper - Google Patents

Use of 7-hydroxy-coumarin compounds for impregnating paper Download PDF

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EP0056157A1
EP0056157A1 EP81110811A EP81110811A EP0056157A1 EP 0056157 A1 EP0056157 A1 EP 0056157A1 EP 81110811 A EP81110811 A EP 81110811A EP 81110811 A EP81110811 A EP 81110811A EP 0056157 A1 EP0056157 A1 EP 0056157A1
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Prior art keywords
phenyl
alkyl
hydroxy
coumarin compounds
chlorine
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German (de)
French (fr)
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EP0056157B1 (en
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Horst Dr. Harnisch
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Bayer AG
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Bayer AG
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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/30—Luminescent or fluorescent substances, e.g. for optical bleaching
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/28—Colorants ; Pigments or opacifying agents
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/40—Agents facilitating proof of genuineness or preventing fraudulent alteration, e.g. for security paper
    • D21H21/44—Latent security elements, i.e. detectable or becoming apparent only by use of special verification or tampering devices or methods
    • D21H21/46—Elements suited for chemical verification or impeding chemical tampering, e.g. by use of eradicators
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/914—Transfer or decalcomania
    • Y10S428/915—Fraud or tamper detecting
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/916—Fraud or tamper detecting

Definitions

  • German Offenlegungsschrift 27 47 349 emphasizes the superiority of pyranine for impregnating counterfeit-proof papers over previously used indicators.
  • compounds of the formula I can advantageously be used to impregnate such papers, despite the absence of sulfonic acid groups which make water soluble. They show a superior yellow effect when exposed to alkaline ink extinguishers . or red coloring, which is characterized by high color strength and durability.
  • Heterocyclic radicals A can, for example, the oxazole, benzoxazole, thiazole, benzthiazole, imidazole, benzimidazole, furan, benzo [b] furan, thiophene, benzo [b] thiophene, pyridine, quinoline, Pyrimidine, quinazolone, quinoxaline, 1,2,4-benzthiadiazine-1,1-dioxide, 1,3,4-oxadiazole, 1,3,4-thiadiazole, 1,2,3-triazole 1-, 1,2,3-triazole-2-, 1,2,4-triazole-1 or benzo-s-triazole series belong to the benzanellated heterocycles listed, a further benzo ring may also be fused.
  • Preferred heterocyclic radicals A are those of the benzothiazole, benzoxazole, benzimidazole, quinazol-4-one, benz [b] furan, benz [b] thiophene, 5-phenyl-1,3,4-oxadiazole, 5-phenyl-1,3,4-thiadiazole or pyridine series.
  • Suitable functionally modified carboxyl groups are in particular C 1 - to C 4 -alkyl esters, carbonamides, carbopiperidide, carbopyrrolidide, carbomorpholide, carbothiomorpholide, carbopiperazide and the nitrile group, optionally substituted by 1 - 2 C 1 - to C 4 -alkyl radicals.
  • an aqueous mineral acid such as hydrochloric acid or sulfur acid
  • the 7-hydroxy-coumarin compounds of the formula I are advantageously in the form of an aqueous suspension or dispersion with an active ingredient content of 0.01 to 0.5, preferably 0.05 to 0.2 percent by weight in the pH range below 6, in particular from 5 to 1.
  • a very fine distribution can advantageously be achieved by adding 1-10 percent by weight of an acid-resistant, preferably nonionic, dispersant, such as, for example, a polyether made from oleyl alcohol and 20-50 mol ethylene oxide.
  • a paper glue is advantageously produced from the dispersion obtained by adding a conventional sizing agent, such as oxidized starch (5-15% by weight), and a paper is impregnated with it in such a way that the concentration is about 0.05 to 0.2 g of reagent per m is 2 .
  • a white paper is obtained which, when treated with an ink eraser or other alkaline reagent, gives a strong, very stable yellow or red color.
  • 0.1 g compound of the formula prepared by condensation of benzoxazol-2-yl-ethyl acetate and resorcylaldehyde in boiling ethanol with piperidine acetate as catalyst, are finely dispersed in 100 ml of water with the addition of 0.005 g of a dispersant (polyether from oleyl alcohol and 50 mol of ethylene oxide), and 10 g of oxidized starch are added and adjusted to pH 2 with hydrochloric acid.
  • a paper is impregnated with the dispersion obtained in such a way that the concentration is about 0.1 g reagent / m 2 .
  • a white paper is obtained which, when treated with an ink eraser, gives a strong, yellow-green, very stable color.

Abstract

7-Hydroxy-cumarin-Verbindungen der allgemeinen Formel <IMAGE> worin A für einen heterocyclischen Rest, der in der Farbstoffchemie übliche nichtionogene Substituenten enthalten kann, R für Wasserstoff oder Cyan und Z für Sauerstoff oder NH stehen und der Ring B nichtionisch Weiter substituiert sein kann, finden Verwendung zum Imprägnieren von Papier, insbesondere von fälschungssicher zu machendem Papier.7-hydroxy-coumarin compounds of the general formula <IMAGE> in which A is a heterocyclic radical which may contain nonionic substituents customary in dye chemistry, R is hydrogen or cyano and Z is oxygen or NH and ring B is further nonionically substituted can be used to impregnate paper, in particular paper that can be made secure against forgery.

Description

Gegenstand der Erfindung ist die Verwendung von 7-Hydroxy-cumarin-Verbindungen der allgemeinen Formel

Figure imgb0001
worin

  • A für einen heterocyclischen Rest, der in der Farbstoffchemie übliche nichtionogene Substituenten enthalten kann,
  • R für Wasserstoff oder Cyan und
  • Z für Sauerstoff oder NH stehen und
  • der Ring B nichtionisch weiter substituiert sein kann, insbesondere durch eine C1- bis C3-Alkylgruppe oder ein Chloratom,
The invention relates to the use of 7-hydroxy-coumarin compounds of the general formula
Figure imgb0001
 wherein
  • A for a heterocyclic radical which can contain nonionic substituents customary in dye chemistry,
  • R is hydrogen or cyan and
  • Z stands for oxygen or NH and
  • the ring B can be further substituted nonionically, in particular by a C 1 to C 3 alkyl group or a chlorine atom,

zum Imprägnieren von Papier, insbesondere zum Imprägnieren von fälschungssicher zu machenden Papieren.for impregnating paper, in particular for impregnating tamper-proof paper.

In der Deutschen Offenlegungsschrift 27 47 349 wird die Überlegenheit des Pyranins zum Imprägnieren von fälschungssicher zu machenden Papieren gegenüber bisher verwendeten Indikatoren hervorgehoben. Überraschenderweise lassen sich Verbindungen der Formel I trotz des Fehlens wasserlöslich machender Sulfonsäuregruppen vorteilhaft zum Imprägnieren derartiger Papiere verwenden. Sie zeigen bei der Einwirkung alkalisch reagierender Tintenlöscher eine überlegene Gelb-.bzw. Rotfärbung, die sich durch hohe Farbstärke und Beständigkeit auszeichnet.German Offenlegungsschrift 27 47 349 emphasizes the superiority of pyranine for impregnating counterfeit-proof papers over previously used indicators. Surprisingly, compounds of the formula I can advantageously be used to impregnate such papers, despite the absence of sulfonic acid groups which make water soluble. They show a superior yellow effect when exposed to alkaline ink extinguishers . or red coloring, which is characterized by high color strength and durability.

Heterocyclische Reste A können beispielsweise der Oxazol-, Benzoxazol-, Thiazol-, Benzthiazol-, Imidazol-, Benzimidazol-, Furan-,Benzo[b]furan-, Thiophen-, Benzo[b]thiophen-, Pyridin-, Chinolin-, Pyrimidin-, Chinazolon-, Chinoxalin-, 1,2,4-Benzthiadiazin-1,1-dioxid-, 1,3,4-Oxadiazol-, 1,3,4-Thiadiazol-, 1,2,3-Triazol-1-, 1,2,3-Triazol-2-, 1,2,4-Triazol-1-oder Benzo-s-triazol-Reihe angehören, wobei den aufgeführten benzanellierten Heterocyclen auch noch ein weiterer Benzoring ankondensiert sein kann.Heterocyclic radicals A can, for example, the oxazole, benzoxazole, thiazole, benzthiazole, imidazole, benzimidazole, furan, benzo [b] furan, thiophene, benzo [b] thiophene, pyridine, quinoline, Pyrimidine, quinazolone, quinoxaline, 1,2,4-benzthiadiazine-1,1-dioxide, 1,3,4-oxadiazole, 1,3,4-thiadiazole, 1,2,3-triazole 1-, 1,2,3-triazole-2-, 1,2,4-triazole-1 or benzo-s-triazole series belong to the benzanellated heterocycles listed, a further benzo ring may also be fused.

Bevorzugte heterocyclische Reste A sind solche der Benzthiazol-, Benzoxazol-, Benzimidazol-, Chinazol-4-on-, Benz[b]furan-, Benz[b]thiophen-, 5-Phenyl-1,3,4-oxadiazol-, 5-Phenyl-1,3,4-thiadiazol- oder Pyridin-Reihe.Preferred heterocyclic radicals A are those of the benzothiazole, benzoxazole, benzimidazole, quinazol-4-one, benz [b] furan, benz [b] thiophene, 5-phenyl-1,3,4-oxadiazole, 5-phenyl-1,3,4-thiadiazole or pyridine series.

Geeignete,in der Farbstoffchemie übliche Substituenten sind beispielsweise C1- bis C4-Alkyl, C1- bis C4-Alkoxy, Phenyl-C1- bis C3-alkyl, Cyclohexyl, gegebenenfalls durch 1 - 2 C1 = bis C4-Alkyl, C1- bis C2-Alkoxy und/oder Chlor substituiertes Phenyl, Trifluormethyl, Chlor, C1- bis C4-Alkoxycarbonyl, Carboxyl, gegebenenfalls durch 1 - 2 C1- bis C4-Alkylreste substituierte Carbamoyl- oder Sulfamoylgruppen, C1- bis C4-Alkylsulfonyl, Phenyl-C1- bis C3-alkylsulfonyl, Phenylsulfonyl, C1- bis C4-Alkylmercapto und Phenylmercapto.To C 4 alkyl, C 1 - - to C 4- alkoxy, phenyl-C 1 - appropriate, in dyestuff chemistry customary substituents C 1 are, for example, to C 3 alkyl, cyclohexyl, optionally substituted by 1 - 2 is C 1 = up to C 4- alkyl, C 1 - to C2-alkoxy and / or chlorine substituted phenyl, trifluoromethyl, chlorine, C 1 - to C 4 -alkoxycarbonyl, carboxyl, optionally substituted by 1 - 2 C 1 - to C 4 -alkyl radicals or carbamoyl or Sulfamoyl groups, C 1 to C 4 alkylsulfonyl, phenyl C 1 to C 3 alkylsulfonyl, phenylsulfonyl, C 1 to C 4 alkylmercapto and phenylmercapto.

Im Rahmen der Erfindung sind bevorzugte Verbindungen solche der Formel

Figure imgb0002
worin

  • Z für Sauerstoff oder NH,
  • R für Wasserstoff oder Cyan,
  • X für -0-, -S- oder -N(R1)-,
  • R1 für Wasserstoff, C1- bis C4-Alkyl, Benzyl oder Phenyl und
  • D für die restlichen Glieder eines Benzoxazol-2-yl-, Benzthiazol-2-yl-, Benzimidazol-2-yl, Chinazol-4-on-2-yl-, 5-Phenyl-1,3,4-oxadiazol-2-yl- oder 5-Phenyl-1,3,4-thiadiazol-2-yl-Restes stehen, wobei
  • D gegebenenfalls durch 1 - 2 C1- bis C4-Alkyl, 1 - 2 Chlor, C1- bis C2-Alkoxy, Phenyl, Cyclohexyl, C1- bis C4-Alkylsulfonyl, Carboxy oder C1- bis C2-Alkoxycarbonyl substituiert sein kann.
In the context of the invention, preferred compounds are those of the formula
Figure imgb0002
 wherein
  • Z for oxygen or NH,
  • R represents hydrogen or cyan,
  • X for -0-, -S- or -N (R 1 ) -,
  • R 1 is hydrogen, C 1 to C 4 alkyl, benzyl or phenyl and
  • D for the remaining members of a benzoxazol-2-yl, benzthiazol-2-yl, benzimidazol-2-yl, quinazol-4-one-2-yl, 5-phenyl-1,3,4-oxadiazol-2 -yl- or 5-phenyl-1,3,4-thiadiazol-2-yl radical, where
  • D optionally by 1 to 2 C 1 to C 4 alkyl, 1 to 2 chlorine, C 1 to C 2 alkoxy, phenyl, cyclohexyl, C 1 to C 4 alkylsulfonyl, carboxy or C 1 to C 2 -Alkoxycarbonyl can be substituted.

Von besonderer technischer Bedeutung sind diejenigen Verbindungen der Formel II, in welchen

  • Z für Sauerstoff und
  • R für Wasserstoff stehen und
  • XundD zusammen ein gegebenenfalls in der angegebenen Weise substituiertes Benzoxazol-Ringsystem bilden.
Of particular technical importance are those compounds of formula II in which
  • Z for oxygen and
  • R stand for hydrogen and
  • X and D together form an optionally substituted benzoxazole ring system in the manner indicated.

Die Verbindungen der Formel I sind großenteils bekannt (DE-OS 27 02 337) oder können nach bekannten Verfahren hergestellt werden, insbesondere dadurch, daß man einen Resorcylaldehyd

Figure imgb0003
worin

  • B die oben genannte Bedeutung besitzt,
  • mit einer Verbindung der Formel
    Figure imgb0004
    worin
  • Q für eine gegebenenfalls funktionell abgewandelte Carboxylgruppe steht und
  • A die oben angegebene Bedeutung besitzt,

unter Cumarinringschluß kondensiert und gegebenenfalls anschließend mit Alkalicyanid/Brom in an sich bekannter Weise cyanidiert.The compounds of the formula I are largely known (DE-OS 27 02 337) or can be prepared by known processes, in particular by adding a resorcyl aldehyde
Figure imgb0003
 wherein
  • B has the meaning given above,
  • with a compound of the formula
    Figure imgb0004
     wherein
  • Q represents an optionally functionally modified carboxyl group and
  • A has the meaning given above,

condensed with coumarin ring closure and optionally subsequently cyanidated with alkali metal cyanide / bromine in a manner known per se.

Als funktionell abgewandelte Carboxylgruppe kommen insbesondere C1- bis C4-Alkylester, gegebenenfalls durch 1 - 2 C1- bis C4-Alkylreste substituierte Carbonamide, Carbopiperidid, Carbopyrrolidid, Carbomorpholid, Carbothiomorpholid, Carbopiperazid und die Nitrilgruppe in Betracht.Suitable functionally modified carboxyl groups are in particular C 1 - to C 4 -alkyl esters, carbonamides, carbopiperidide, carbopyrrolidide, carbomorpholide, carbothiomorpholide, carbopiperazide and the nitrile group, optionally substituted by 1 - 2 C 1 - to C 4 -alkyl radicals.

Im Falle Q = CN kann das primär bei der Kondensation entstehende Cumarin-2-imid (Formel I mit Z = NH) anschließend gewünschtenfalls noch durch Behandlung mit einer wäßrigen Mineralsäure, wie Salzsäure oder Schwefelsäure, zur Cumarinverbindung I (mit Z = 0) verseift werden.In the case of Q = CN, the coumarin-2-imide (formula I with Z = NH) primarily formed during the condensation can then, if desired, also by treatment with an aqueous mineral acid, such as hydrochloric acid or sulfur acid, to saponify the coumarin compound I (with Z = 0).

Die an sich bekannte Methode der Einführung einer 4-Cyangruppe in das Cumarinringsystem mit Alkalicyanid und Brom, die hier zur Herstellung von Verbindungen der Formel I, in welchen R = CN bedeutet, dient, ist in Dyes and Pigments 1 (1980) 3-15 sowie in der DE-OS 28 44 299 beschrieben. Als Lösungsmittel kommt Dimethylformamid in Betracht. Man setzt beispielsweise bei 10 - 50°C zunächst mit einer Alkalicyanidlösung um und oxidiert dann bei 0 - 10°C mit Brom.The known method of introducing a 4-cyano group into the coumarin ring system with alkali metal cyanide and bromine, which is used here for the preparation of compounds of the formula I in which R = CN, is described in Dyes and Pigments 1 (1980) 3-15 and described in DE-OS 28 44 299. Dimethylformamide can be used as a solvent. For example, it is first reacted at 10-50 ° C. with an alkali metal cyanide solution and then oxidized at 0-10 ° C. with bromine.

Die 7-Hydroxy-cumarin-Verbindungen der Formel I werden zweckmäßig in Form einer wäßrigen Suspension oder Dispersion mit einem Wirkstoffgehalt von 0,01 bis 0,5, vorzugsweise 0,05 bis 0,2 Gewichtsprozent im pH-Bereich von unter 6, insbesondere von 5 bis 1, eingesetzt. Vorteilhaft kann durch Zusatz von 1 - 10 Gewichtsprozent eines säurebeständigen, vorzugsweise nichtionischen Dispergiermittels, wie beispielsweise eines Polyethers aus Oleylalkohol und 20 - 50 mol Ethylenoxid, eine sehr feine Verteilung erzielt werden. Aus der erhaltenen Dispersion wird vorteilhaft durch Zusatz eines üblichen Leimungsmittels, wie oxidierte Stärke (5 - 15 Gewichtsprozent)', ein Papierleim hergestellt und mit diesem in der Weise ein Papier imprägniert, daß die Konzentration etwa 0,05 bis 0,2 g Reagenz pro m2 beträgt. Man erhält ein weißes Papier, das bei der Behandlung mit einem Tintenlöschstift oder einem anderen alkalischen Reagenz eine kräftige, sehr beständige gelbe oder rote Färbung ergibt.The 7-hydroxy-coumarin compounds of the formula I are advantageously in the form of an aqueous suspension or dispersion with an active ingredient content of 0.01 to 0.5, preferably 0.05 to 0.2 percent by weight in the pH range below 6, in particular from 5 to 1. A very fine distribution can advantageously be achieved by adding 1-10 percent by weight of an acid-resistant, preferably nonionic, dispersant, such as, for example, a polyether made from oleyl alcohol and 20-50 mol ethylene oxide. A paper glue is advantageously produced from the dispersion obtained by adding a conventional sizing agent, such as oxidized starch (5-15% by weight), and a paper is impregnated with it in such a way that the concentration is about 0.05 to 0.2 g of reagent per m is 2 . A white paper is obtained which, when treated with an ink eraser or other alkaline reagent, gives a strong, very stable yellow or red color.

Beispiel 1example 1

0,1 g Verbindung der Formel

Figure imgb0005
hergestellt durch Kondensation vonBenzoxazol -2-yl-essigsäureethylester und Resorcylaldehyd in siedendem Ethanol mit Piperidinacetat als Katalysator, werden in 100 ml Wasser unter Zusatz von 0,005g eines Dispergiermittels (Polyether aus Oleylalkohol und 50 mol Ethylenoxid) fein dispergiert, mit 10 g oxidierter Stärke versetzt und mit Salzsäure auf pH 2 gestellt. Mit der erhaltenen Dispersion wird ein Papier in der Weise imprägniert, daß die Konzentration etwa 0,1 g Reagenz/m2 beträgt. Man erhält ein weißes Papier, das bei der Behandlung mit einem Tintenlöschstift eine kräftige,gelbgrüne, sehr beständige Färbung ergibt.0.1 g compound of the formula
Figure imgb0005
 prepared by condensation of benzoxazol-2-yl-ethyl acetate and resorcylaldehyde in boiling ethanol with piperidine acetate as catalyst, are finely dispersed in 100 ml of water with the addition of 0.005 g of a dispersant (polyether from oleyl alcohol and 50 mol of ethylene oxide), and 10 g of oxidized starch are added and adjusted to pH 2 with hydrochloric acid. A paper is impregnated with the dispersion obtained in such a way that the concentration is about 0.1 g reagent / m 2 . A white paper is obtained which, when treated with an ink eraser, gives a strong, yellow-green, very stable color.

Ähnlich gute Effekte werden erhalten, wenn man anstelle der Verbindung 1 eine äquivalente Menge einer der folgenden Substanzen einsetzt:

Figure imgb0006
Figure imgb0007
Figure imgb0008
Figure imgb0009
 Similar good effects are obtained if an equivalent amount of one of the following substances is used instead of compound 1:
Figure imgb0006
Figure imgb0007
Figure imgb0008
Figure imgb0009

Claims (4)

1. Verwendung von 7-Hydroxy-cumarin-Verbindungen der allgemeinen Formel
Figure imgb0010
worin A für einen heterocyclischen Rest, der in der Farbstoffchemie übliche nichtionogene Substituenten enthalten kann, R für Wasserstoff oder Cyan und Z für Sauerstoff oder NH stehen und der Ring B nichtionisch weiter substituiert sein kann,
zum Imprägnieren von Papier.1. Use of 7-hydroxy-coumarin compounds of the general formula
Figure imgb0010
 wherein A for a heterocyclic radical which can contain nonionic substituents customary in dye chemistry, R is hydrogen or cyan and Z stands for oxygen or NH and ring B can be further nonionically substituted,
for impregnating paper. 2. Verwendung von 7-Hydroxy-cumarin-Verbindungen gemäß Anspruch 1, dadurch gekennzeichnet, daß der heterocyclische Rest A der Benzthiazol-, Benzoxazol-, Benzimidazol-, Chinazol-4-on-, Benzo[b]thiophen-, Benzo[b]furan-, 5-Phenyl-1,3,4-oxadiazol-, 5-Phenyl-1,3,4-thiadiazol- oder Pyridin-Reihe angehört und die Substituenten in A · ausgewählt sind aus der Reihe C1- bis C4-Alkyl, C1- bis C4-Alkoxy, Phenyl-C1- bis C3-alkyl, Cyclohexyl, gegebenenfalls durch 1-2 C1- bis C4-Alkyl, C1- bis C2-Alkoxy und/oder Chlor substituiertes Phenyl, Trifluormethyl, Chlor C1- bis C4-Alkoxycarbonyl, Carboxyl, gegebenenfalls durch 1-2 C1- bis C4-Alkylreste substituierte Carbamoyl- oder Sulfamoylgruppen, C1- bis C4-Alkylsulfonyl, Phenyl-C1- bis C3- alkylsulfonyl, Phenylsulfonyl, C1- bis C4-Alkylmercapto und Phenylmercapto und der Ring B gegebenenfalls noch eine C1- bis C3-Alkylgruppe oder Chlor enthält. 2. Use of 7-hydroxy-coumarin compounds according to claim 1, characterized in that the heterocyclic radical A the benzothiazole, benzoxazole, benzimidazole, quinazol-4-one, benzo [b] thiophene, benzo [b] furan, 5-phenyl-1,3,4-oxadiazole, 5- Phenyl-1,3,4-thiadiazole or pyridine series and the substituents in A · are selected from the series C 1 - to C 4 -alkyl, C 1 - to C 4 -alkoxy, phenyl-C 1 - to C 3 -alkyl, cyclohexyl, optionally by 1-2 C 1 - bis C 4 alkyl, C 1 to C 2 alkoxy and / or chlorine-substituted phenyl, trifluoromethyl, chlorine C 1 - to C 4 -alkoxycarbonyl, carboxyl, carbamoyl or sulfamoyl groups optionally substituted by 1-2 C 1 to C 4 -alkyl radicals, C 1 - to C 4 -alkylsulfonyl, phenyl C 1 to C 3 alkylsulfonyl, phenylsulfonyl, C 1 to C 4 alkylmercapto and phenylmercapto and the ring B optionally also contains a C 1 -C 3 -alkyl group or chlorine. 3. Verwendung von 7-Hydroxy-cumarin-Verbindungen der Formel
Figure imgb0011
worin Z für Sauerstoff oder NH, R für Wasserstoff oder Cyan, X für -0-, -S- oder -N(R1)-, R für Wasserstoff, C1- bis C4-Alkyl, Benzyl oder Phenyl und D für die restlichen Glieder eines Benzoxazol-2-yl-; Benzthiazol-2-yl-, Benzimidazol-2-yl-, Chinazol-4-on-2-yl-, 5-Phenyl-1,3,4-oxadiazol-2-yl- oder 5-Phenyl-1,3,4-thiadiazol-2-yl-Restes stehen, wobei D gegebenenfalls durch 1 - 2 C1- bis C4-Alkyl, 1 - 2 Chlor, C1- bis C2-Alkoxy, Phenyl, Cyclohexyl, C1- bis C4-Alkylsulfonyl, Carboxy oder C1- bis C2-Alkylcarbonyl substituiert sein kann,
zum Imprägnieren von Papier.3. Use of 7-hydroxy-coumarin compounds of the formula
Figure imgb0011
 wherein Z for oxygen or NH, R represents hydrogen or cyan, X for -0-, -S- or -N (R 1 ) -, R represents hydrogen, C 1 - to C 4 -alkyl, benzyl or phenyl and D for the remaining members of a benzoxazol-2-yl-; Benzothiazol-2-yl-, benzimidazol-2-yl-, quinazol-4-one-2-yl-, 5-phenyl-1,3,4-oxadiazol-2-yl- or 5-phenyl-1,3, 4-thiadiazol-2-yl radical, where D optionally by 1 to 2 C 1 to C 4 alkyl, 1 to 2 chlorine, C 1 to C 2 alkoxy, phenyl, cyclohexyl, C 1 to C 4 alkylsulfonyl, carboxy or C 1 to C 2 Alkylcarbonyl may be substituted,
for impregnating paper. 4. Verwendung von 7-Hydroxy-cumarin-Verbindungen gemäß Anspruch 3, dadurch gekennzeichnet, daß Z für Sauerstoff und R für Wasserstoff stehen und X und D zusammen ein gegebenenfalls in der in Anspruch 3 angegebenen Weise substituiertes Benzoxazol-Ringsystem bilden. 4. Use of 7-hydroxy-coumarin compounds according to claim 3, characterized in that Z for oxygen and R stand for hydrogen and X and D together form an optionally substituted benzoxazole ring system as specified in claim 3.
EP81110811A 1981-01-08 1981-12-29 Use of 7-hydroxy-coumarin compounds for impregnating paper Expired EP0056157B1 (en)

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DE3100295 1981-01-08
DE19813100295 DE3100295A1 (en) 1981-01-08 1981-01-08 USE OF 7-HYDROXY-CUMARINE COMPOUNDS FOR IMPREGNATING PAPER

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Cited By (1)

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FR2647820A1 (en) * 1989-06-01 1990-12-07 Aussedat Rey INFALSIFIABLE SAFETY PAPER AND USEFUL AQUEOUS OR ORGANIC COMPOSITION, IN PARTICULAR FOR MAKING INFALSIFIABLE PAPER

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Publication number Priority date Publication date Assignee Title
FR2943074B1 (en) * 2009-03-13 2011-05-20 Arjowiggins Security LASER MARKABLE SUBSTRATE AND METHOD FOR MANUFACTURING THE SAME

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FR2410702A1 (en) * 1977-12-05 1979-06-29 Tullis Russell Co Ltd Sized paper for documents comprising erasure indicator - contg. cpd. colourless at paper pH and coloured at higher pH
EP0027529A1 (en) * 1979-09-15 1981-04-29 BASF Aktiengesellschaft Cumarin derivatives and their use in dyeing synthetic fibres or plastics

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US2673186A (en) * 1948-01-15 1954-03-23 Procter & Gamble Alkaline detergent composition
US3886083A (en) * 1974-05-09 1975-05-27 American Bank Note Co Safety inks and documents
FR2365656A1 (en) * 1976-05-25 1978-04-21 Arjomari Prioux SECURITY PAPER

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Publication number Priority date Publication date Assignee Title
FR2410702A1 (en) * 1977-12-05 1979-06-29 Tullis Russell Co Ltd Sized paper for documents comprising erasure indicator - contg. cpd. colourless at paper pH and coloured at higher pH
EP0027529A1 (en) * 1979-09-15 1981-04-29 BASF Aktiengesellschaft Cumarin derivatives and their use in dyeing synthetic fibres or plastics

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2647820A1 (en) * 1989-06-01 1990-12-07 Aussedat Rey INFALSIFIABLE SAFETY PAPER AND USEFUL AQUEOUS OR ORGANIC COMPOSITION, IN PARTICULAR FOR MAKING INFALSIFIABLE PAPER

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DE3170783D1 (en) 1985-07-04
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EP0056157B1 (en) 1985-05-29

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