EP0056157B1 - Utilisation de composés 7-hydroxy-coumarine pour l'imprégnation du papier - Google Patents

Utilisation de composés 7-hydroxy-coumarine pour l'imprégnation du papier Download PDF

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Publication number
EP0056157B1
EP0056157B1 EP81110811A EP81110811A EP0056157B1 EP 0056157 B1 EP0056157 B1 EP 0056157B1 EP 81110811 A EP81110811 A EP 81110811A EP 81110811 A EP81110811 A EP 81110811A EP 0056157 B1 EP0056157 B1 EP 0056157B1
Authority
EP
European Patent Office
Prior art keywords
phenyl
alkyl
hydroxy
coumarin compounds
chlorine
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP81110811A
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German (de)
English (en)
Other versions
EP0056157A1 (fr
Inventor
Horst Dr. Harnisch
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer AG
Original Assignee
Bayer AG
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Filing date
Publication date
Application filed by Bayer AG filed Critical Bayer AG
Publication of EP0056157A1 publication Critical patent/EP0056157A1/fr
Application granted granted Critical
Publication of EP0056157B1 publication Critical patent/EP0056157B1/fr
Expired legal-status Critical Current

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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

  • DE-A-2 747 349 emphasizes the superiority of pyranine for impregnating counterfeit-proof papers over previously used indicators.
  • compounds of the formula can advantageously be used to impregnate such papers, despite the absence of sulfonic acid groups which make water soluble.
  • 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 can also be fused.
  • Preferred heterocyclic radicals A are those of the benzothiazole, benzoxazole, benzimidazole, quinazol-4-one, benzo [b] furan, benzo [b] thiophene, 5-phenyl-1,3,4-oxadiazole -, 5-Phenyl-1,3,4-thiadiazole or pyridine series.
  • Suitable substituents customary in dye chemistry are, for example, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, phenyl-C 1 -C 3 -alkyl, cyclohexyl, optionally by 1-2 C 1 -C 4- alkyl, C 1 - to C 2 -alkoxy and / or chlorine-substituted phenyl, trifluoromethyl, chlorine, C 1 - to C 4 -alkoxycarbonyl, carboxyl, carbamoyl- optionally substituted by 1-2 C 1 - to C 4 -alkyl radicals 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.
  • 'As a functionally modified carboxyl group are, in particular C 1 - to C 4 -alkyl, optionally substituted by 1-2C 1 - to C 4 -alkyl-substituted carboxamides, Carbopiperidid, Carbopyrrolidid, Carbomorpholid, Carbothiomorpholid, Carbopiperazid and the nitrile group into consideration.
  • an aqueous mineral acid such as hydrochloric acid or sulfuric acid
  • the 7-hydroxy-coumarin compounds of the formula are expediently 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 from below 6, in particular from 5 to 1, used.
  • a very fine distribution can advantageously be achieved by adding 1-10% 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 size 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 2 is.
  • 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 a 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), with 10 g of oxidized starch 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 approximately 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.

Landscapes

  • Plural Heterocyclic Compounds (AREA)
  • Paper (AREA)

Claims (4)

1. Utilisation de dérivés de 7-hydroxy-coumarine de formule générale:
Figure imgb0014
dans laquelle
A représente un reste hétérocyclique, qui peut contenir des substituants non ionogènes habituels dans la chimie des colorants,
R représente l'hydrogène ou un groupe cyano et
Z représente l'oxygène ou un groupe NH et

le noyau B peut encore porter d'autres substituants non ioniques pour l'imprégnation de papier.
2. Utilisation de dérivés de 7-hydroxy-coumarine selon la revendication 1, caractérisée en ce que le reste hétérocyclique A appartient à la série du benzothiazole, du benzoxazole, du benzimidazole, de la quinoxazole-4-one, du benzo(b)thiophène, du benzo(b)furanne, du 5-phényl-1,3,4-oxadiazole, du 5- phényl-1,3,4-thiadiazole ou de la pyridine, et
les substituants dans A sont choisis parmi les groupes alkyle en C1-C4, alcoxy en C1-C4, phényl-alkyle en C1-C3, cyclohexyle, phényle éventuellement substitué par un ou deux groupes alkyle en C1-C4 ou alcoxy en Ci ou C2 et/ou atomes de chlore, les groupestrifluorométhyles, les atomes de chlore, les groupes (alcoxy en C1-C4)carbonyle, carboxyle, les groupes carbamoyle ou sulfamoyle éventuellement substitués par un ou deux restes alkyles en C1-C4, des groupes alkylsulfonyle en C1-C4, phényl-(alkyl en C1-C3)sulfonyle, phénylsulfonyle, alkylmercapto en C1-C4 et phénylmercapto, et le noyau B contient éventuellement encore un groupe alkyle en C1-C3 ou un atome de chlore.
3. Utilisation de dérivés de 7-hydroxy-coumarine de formule
Figure imgb0015
dans laquelle
Z représente l'oxygène ou NH,
R représente l'hydrogène ou cyano,
X représente -0-, -S- ou -N(R1)-,
Rl représente l'hydrogène, alkyle en Cl-C4, benzyle ou phényle, et
D représente les chaînons restants d'un reste benzoxazole-2-yle,benzothiazole-2-yle, benzimidazole-2-yle, quinazole-4-one-2-yle, 5-phényl-1,3,4-oxadiazole -2-yle ou 5-phényl-1,3,4-thiadiazo- le-2-yle, le reste
D pouvant éventuellement être substitué par un ou deux groupes alkyles en C1-C4, un ou deux atomes de chlore, par alcoxy en C1 ou C2, phényle, cyclohexyle, alkylsulfonyle en Cl-C4, carboxy ou (alkyl en Ci ou C2)carbonyle,

pour l'imprégnation du papier.
4. Utilisation de dérivés de 7-hydroxy-coumarine selon la revendication 3, caractérisée en ce que
Z représente l'oxygène et
R représente l'hydrogène et
X et D forment ensemble un système cyclique benzoxazole éventuellement substitué comme indiqué à la revendication 3.
EP81110811A 1981-01-08 1981-12-29 Utilisation de composés 7-hydroxy-coumarine pour l'imprégnation du papier Expired EP0056157B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19813100295 DE3100295A1 (de) 1981-01-08 1981-01-08 Verwendung von 7-hydroxy-cumarin-verbindungen zum impraegnieren von papier
DE3100295 1981-01-08

Publications (2)

Publication Number Publication Date
EP0056157A1 EP0056157A1 (fr) 1982-07-21
EP0056157B1 true EP0056157B1 (fr) 1985-05-29

Family

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Family Applications (1)

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EP81110811A Expired EP0056157B1 (fr) 1981-01-08 1981-12-29 Utilisation de composés 7-hydroxy-coumarine pour l'imprégnation du papier

Country Status (3)

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US (1) US4411946A (fr)
EP (1) EP0056157B1 (fr)
DE (2) DE3100295A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2647820B1 (fr) * 1989-06-01 1991-09-20 Aussedat Rey Papier de securite infalsifiable et composition aqueuse ou organique utile, notamment pour rendre un papier infalsifiable
FR2943074B1 (fr) * 2009-03-13 2011-05-20 Arjowiggins Security Substrat marquable au laser et procede de fabrication associe

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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 (fr) * 1976-05-25 1978-04-21 Arjomari Prioux Papier de securite
FR2410702A1 (fr) * 1977-12-05 1979-06-29 Tullis Russell Co Ltd Papier de securite renfermant un indicateur de produit effaceur
DE2937422A1 (de) * 1979-09-15 1981-04-09 Basf Ag, 6700 Ludwigshafen Heterocyclische verbindungen

Also Published As

Publication number Publication date
US4411946A (en) 1983-10-25
DE3170783D1 (en) 1985-07-04
DE3100295A1 (de) 1982-08-05
EP0056157A1 (fr) 1982-07-21

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