EP0000900B1 - Spirobipyrannes, leur utilisation et matériaux de reproduction sensibles à la pression les contenant - Google Patents

Spirobipyrannes, leur utilisation et matériaux de reproduction sensibles à la pression les contenant Download PDF

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Publication number
EP0000900B1
EP0000900B1 EP78100629A EP78100629A EP0000900B1 EP 0000900 B1 EP0000900 B1 EP 0000900B1 EP 78100629 A EP78100629 A EP 78100629A EP 78100629 A EP78100629 A EP 78100629A EP 0000900 B1 EP0000900 B1 EP 0000900B1
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EP
European Patent Office
Prior art keywords
methyl
color
spirodipyrans
formula
pressure
Prior art date
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Expired
Application number
EP78100629A
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German (de)
English (en)
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EP0000900A1 (fr
Inventor
Hans Dr. Baumann
Andreas Dr. Oberlinner
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BASF SE
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BASF SE
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
    • C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
    • C07D493/10—Spiro-condensed systems
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/124—Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components
    • B41M5/132—Chemical colour-forming components; Additives or binders therefor
    • B41M5/136—Organic colour formers, e.g. leuco dyes
    • B41M5/15—Spiro-pyrans

Definitions

  • the spirodipyrans of the formula are weakly colored to colorless compounds, the solutions of which give red-violet to blue colorations in an inert, organic solvent in contact with electro-attracting substances.
  • electron acceptor substances are carbon or mineral acids, kaolin, bentonite, activated clay, aluminum silicate, attapulgite or any clay, acidic polymeric materials such as condensation products from phenols and / or phenolsulfonic acids, also metal oxides or salts such as zinc oxide, aluminum oxide, zinc chloride, Iron stearate or cobalt naphthenate.
  • the new spirodipyrans of formula 1 are suitable as color formers for pressure-sensitive recording materials or copying materials.
  • the spirodipyrans of formula 1 according to the invention have the advantage in pressure-sensitive copying systems that the color formers show practically no tendency towards color formation on uncoated coating base paper. When copying, there is therefore no mirror writing on the back of the cover sheet coated with the color former. For the same reason, if the capsules are inadvertently destroyed, the side of the sheet carrying the microcapsule layer is not soiled (stained).
  • the spirodipyrans according to the invention have the advantage over the spirodipyrans known from DE-OS 22 32 364, 23 23 803 and 24 30 568, which carry a dialkylamino group in the 7-position, that the spirodipyrans of the present invention are on coating base paper and not on Give practically no coloring to active clay coated paper.
  • the color former known from Example 1 of DE-OS 22 32 364 stains coating base paper about 12.5 times as strongly as the dye of Example 8 of the present invention.
  • the spirodipyrans Compared to the spirodipyran known from Example 15 of DE-OS 26 11 600, which bears a morpholine group in the 7-position and a diethylamino group in the 7'-position and which is the closest to the spirodipyrans of the present invention, the spirodipyrans have the present invention with the same behavior on coating base paper and a significantly higher color strength.
  • the color strength of the color former known from Example 15 of DE-OS 26 11 600 is only 29% of that of the color former from Example 2 of the present invention.
  • spirodipyrans in a known manner in organic solvents such as chlorinated paraffins, halogenated or partially hydrogenated biphenyl, alkylbenzene, alkylnaphthalene, alkylated dibenzylbenzene, paraffin oil, mineral oil or else in customary solvents such as toluene, xylene, in the form of a solution or suspension in microcapsules and thus to coat the paper surface with the use of binders and other aids such as spacers.
  • Organic solvents such as chlorinated paraffins, halogenated or partially hydrogenated biphenyl, alkylbenzene, alkylnaphthalene, alkylated dibenzylbenzene, paraffin oil, mineral oil or else in customary solvents such as toluene, xylene, in the form of a solution or suspension in microcapsules and thus to coat the paper surface with the use of binders and other aids such as spacers.
  • Pressure-sensitive papers
  • Suitable methods for producing microcapsules are e.g. in US-PS 2,800,457 and 2,800,458 and in DE-PS 21 19 933.
  • spirodipyrans (I) according to the invention are more stable in aqueous suspension than color formers which contain dialkylamino groups (DE-OS 22 32 364, 23 23 803 and 24 30 568), practically colorless microcapsule dispersions are obtained with the former.
  • the spirodipyrans of the general formula I according to the invention can also be finely divided into wax or oil-wax mixtures by the process described in US Pat. No. 3,103,404 and carriers, such as foils or paper, coated with these mixtures.
  • Pressure-sensitive materials are obtained which are suitable for copying on papers coated with electron acceptor substances and which are removed after use like carbon paper.
  • C 1 to C 16 alkyl for example: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec. Butyl, isobutyl, tert. Butyl, n-pentyl, isopentyl, n-hexyl, n-nonyl, i-nonyl, n-octyl, i-octyl, n-decyl, i-decyl, n-dodecyl, i-dodecyl, n-hexadecyl.
  • the color formers are synthesized according to the following reaction scheme in a manner known per se by cyclization of the o-hydroxylaryl-styryl compounds of the formula IV.
  • the latter are obtained, for example, by condensation of benzopyrylium salts of the formula II with N-substituted p-aminosalicylaldehydes of the formula III:
  • the condensation is expediently carried out in inert organic solvents, such as alcohols, carboxylic acids, carboxylic anhydrides, carboxamides, hydrocarbons or acetonitrile, optionally in the presence of acidic or basic condensing agents, such as zinc chloride, phosphoric acid, hydrogen chloride, toluenesulfonic acid, boric acid, pyridine, piperidine, triethylamine, ammonium acetate, under the usual condensation conditions .
  • inert organic solvents such as alcohols, carboxylic acids, carboxylic anhydrides, carboxamides, hydrocarbons or acetonitrile
  • acidic or basic condensing agents such as zinc chloride, phosphoric acid, hydrogen chloride, toluenesulfonic acid, boric acid, pyridine, piperidine, triethylamine, ammonium acetate, under the usual condensation conditions .
  • the condensation is carried out at temperatures in the range from 20 to 120 ° C.
  • the ring closure to the pyran derivative can take place together with the condensation or subsequent to it in the same or in a separate operation.
  • the ring closure is carried out in the presence of bases, such as sodium or potassium hydroxide, sodium or potassium carbonate, sodium or potassium acetate, ammonia, aliphatic amines, pyridine, in a conventional manner.
  • bases such as sodium or potassium hydroxide, sodium or potassium carbonate, sodium or potassium acetate, ammonia, aliphatic amines, pyridine, in a conventional manner.
  • bases such as sodium or potassium hydroxide, sodium or potassium carbonate, sodium or potassium acetate, ammonia, aliphatic amines, pyridine, in a conventional manner.
  • the crystallized spirodipyran compounds which precipitate out of this solution are, e.g. usable as color formers for copying processes by recrystallization or reprecipitation.
  • the color former also shows this slight tendency to form when writing on uncoated paper, where there is almost no color development, while a color former with a diethylamino group instead of the morpholine ring develops a clearly visible blue copy.
  • the compound develops a blue color in contact with acidic substances.
  • the color former melts at 101 to 102 ° C and develops a blue color with electron acceptor substances.

Claims (4)

1. Spirodipyrannes de formule générale
Figure imgb0012
dans laquelle R1 représente un alcoyle à 1-16 atomes de carbone et A le radical d'un noyau benzénique ou 2,1-naphtalénique fixé par condensation.
2. Spirodipyrannes selon la revendication 1, caractérisés en ce que, dans la formule, RI est mis pour un alcoyle à 1-4 atomes de carbone.
3. Utilisation des spirodipyrannes selon la revendication 1 ou 2 comme chromogène pour des matériels graphiques sensibles à l'effet de la pression.
4. Matériels graphiques sensibles à l'effet de la pression, caractérisés en ce qu'ils contiennent, en tant que chromogènes, des spirodipyrannes selon la revendication 1 ou 2.
EP78100629A 1977-08-18 1978-08-09 Spirobipyrannes, leur utilisation et matériaux de reproduction sensibles à la pression les contenant Expired EP0000900B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19772737207 DE2737207A1 (de) 1977-08-18 1977-08-18 Farbbildner fuer kopierverfahren
DE2737207 1977-08-18

Publications (2)

Publication Number Publication Date
EP0000900A1 EP0000900A1 (fr) 1979-03-07
EP0000900B1 true EP0000900B1 (fr) 1981-01-14

Family

ID=6016689

Family Applications (1)

Application Number Title Priority Date Filing Date
EP78100629A Expired EP0000900B1 (fr) 1977-08-18 1978-08-09 Spirobipyrannes, leur utilisation et matériaux de reproduction sensibles à la pression les contenant

Country Status (4)

Country Link
US (1) US4161589A (fr)
EP (1) EP0000900B1 (fr)
JP (1) JPS5441880A (fr)
DE (2) DE2737207A1 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2611600C2 (de) * 1976-03-19 1986-12-18 Basf Ag, 6700 Ludwigshafen Spirodipyrane und deren Verwendung
JPS5545713A (en) * 1978-09-27 1980-03-31 Hodogaya Chem Co Ltd 7-substituted-spiropyran derivative
DE2847690A1 (de) * 1978-11-03 1980-05-22 Basf Ag Farbbildner fuer kopierverfahren
AT385272B (de) * 1986-04-02 1988-03-10 Koreska Licensing Ges M B H Verfahren zur herstellung von neuen zweifach basisch substituierten spirodipyranen
US7179912B2 (en) 2000-09-01 2007-02-20 Icos Corporation Materials and methods to potentiate cancer treatment

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL252815A (fr) * 1959-06-19
NL125655C (fr) * 1959-07-15
FR2046319A5 (en) * 1969-04-23 1971-03-05 Fuji Photo Film Co Ltd Colour forming printing ink
DE2323803C3 (de) * 1973-05-11 1983-12-01 Basf Ag, 6700 Ludwigshafen Spirodipyrane und deren Verwendung als Farbbildner für Kopierverfahren
DE2363702A1 (de) * 1973-12-21 1975-07-10 Licentia Gmbh Spiropyranverbindung
DE2430568C3 (de) * 1974-06-26 1979-02-08 Basf Ag, 6700 Ludwigshafen Spirodipyrane und deren Verwendung als Farbbildner für druckempfindliche Aufzeichnungsmaterialien
DE2611600C2 (de) * 1976-03-19 1986-12-18 Basf Ag, 6700 Ludwigshafen Spirodipyrane und deren Verwendung

Also Published As

Publication number Publication date
EP0000900A1 (fr) 1979-03-07
DE2860328D1 (en) 1981-03-12
JPS5441880A (en) 1979-04-03
DE2737207A1 (de) 1979-03-01
US4161589A (en) 1979-07-17

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