EP0266311B1 - Mélange de colorants fluoranes et matériaux pour l'enregistrement l'utilisant - Google Patents

Mélange de colorants fluoranes et matériaux pour l'enregistrement l'utilisant Download PDF

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Publication number
EP0266311B1
EP0266311B1 EP87810616A EP87810616A EP0266311B1 EP 0266311 B1 EP0266311 B1 EP 0266311B1 EP 87810616 A EP87810616 A EP 87810616A EP 87810616 A EP87810616 A EP 87810616A EP 0266311 B1 EP0266311 B1 EP 0266311B1
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Prior art keywords
halogen
colour former
fluoran
methyl
mixture according
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EP87810616A
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German (de)
English (en)
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EP0266311A2 (fr
EP0266311A3 (en
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Rudolf Zink
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Novartis AG
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Ciba Geigy AG
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Classifications

    • 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
    • B41M5/145—Organic colour formers, e.g. leuco dyes with a lactone or lactam ring
    • B41M5/1455—Organic colour formers, e.g. leuco dyes with a lactone or lactam ring characterised by fluoran compounds
    • 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
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • B41M5/323—Organic colour formers, e.g. leuco dyes
    • B41M5/327—Organic colour formers, e.g. leuco dyes with a lactone or lactam ring
    • B41M5/3275—Fluoran compounds

Definitions

  • the present invention relates to a fluoran color former mixture and its use in a pressure-sensitive or particularly heat-sensitive recording material.
  • the fluorine color former mixture has a nuance structure that is uniform at all response temperatures.
  • the components of the formulas (1) and (2) can be present as individual compounds or as mixtures.
  • Lower alkyl and lower alkoxy in the definition of the radicals of the fluoranes are generally groups or group components which have 1 to 5, in particular 1 to 3, carbon atoms, such as, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec. -Butyl, tert-butyl or amyl or methoxy, ethoxy, isopropoxy, tert-butoxy or tert. Amyloxy.
  • X and Y substituents are alkyl groups, they can be straight-chain or branched alkyl radicals.
  • alkyl radicals are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, amyl, n-hexyl, 2-ethyl-hexyl, n-heptyl, n-octyl, isooctyl, n-nonyl, Isononyl or n-dodecyl.
  • alkyl radicals in the X and Y substituents are primarily cyanoalkyl, haloalkyl, hydroxyalkyl or alkoxyalkyl, each preferably with a total of 2 to 6 carbon atoms, such as e.g. ⁇ -cyanoethyl, ⁇ -chloroethyl, ⁇ -chloropropyl, ⁇ -hydroxyethyl, ⁇ -hydroxypropyl, ⁇ -methoxyethyl or ⁇ -ethoxyethyl.
  • cycloalkyl in the meaning of the X and Y substituents are cyclopentyl or preferably cyclohexyl.
  • X1-X4 and Y1-Y4 in the meaning of aralkyl are usually phenylethyl, phenylisopropyl or primarily benzyl, while aryl for X1, X2, X3, Y1, Y2 and Y3 expediently means naphthyl, diphenyl and especially phenyl .
  • the aralkyl and aryl radicals can be substituted by halogen, trifluoromethyl, cyano, nitro, lower alkyl, lower alkoxy, lower alkoxycarbonyl or lower alkylcarbonyl.
  • Preferred substituents in the benzyl and phenyl group of the X and Y radicals are e.g. Halogen, trifluoromethyl, cyano, methyl, methoxy or carbomethoxy.
  • Examples of such araliphatic or aromatic radicals are methylbenzyl, 2,4- or 2,5-dimethylbenzyl, chlorobenzyl, dichlorobenzyl, cyanophenyl, tolyl, xylyl, chlorophenyl, trifluoromethylphenyl, methoxyphenyl or carbomethoxyphenyl.
  • substituents (X1 and X2), (X3 and X4), (Y1 and Y2) and (Y3 and Y4) together with the common nitrogen atom represent a heterocyclic radical
  • this is, for example, pyrrolidino, piperidino, pipecolino, morpholino, thiomorpholino or Piperazino such as methylpiperazino.
  • Preferred saturated heterocyclic radicals for -NX1X2, -NX3X4, -NY1Y2 and -NY3Y4 are pyrrolidino, piperidino or morpholino.
  • DE-A-3 300 229 discloses heat-sensitive recording sheets whose heat-sensitive layer contains dyes in which fluoran compounds corresponding to the above formulas (1) or (2) are used. Nevertheless, the fluoran colorant mixtures according to the invention are not disclosed in this publication.
  • X1 and Y1 are preferably C1-C8 alkyl, cyclohexyl, phenyl, tolyl, benzyl or especially lower alkyl.
  • X2 and Y2 are preferably lower alkyl or benzyl and especially methyl or ethyl.
  • Both -NX1X2 and -NY1Y2 can preferably also be pyrrolidino.
  • N-substituents X3, X4, Y3 and Y4 are preferably C1-C8-alkyl, phenylethyl, phenylisopropyl, cyclohexyl or especially benzyl, which is unsubstituted or substituted by 1 to 5 methyl or halogen.
  • aryl radicals X3 and Y3 mean in particular phenyl, 2-chlorophenyl or tolyl.
  • Particularly preferred amino groups -NX3X4 and -NY3Y4 are diethylamino, n-octylamino, benzylamino, phenylethylamino, di (phenylethyl) amino, phenylisopropylamino, N-phenyl-N-methylamino and especially di- (2- or 4-methylbenzyl) amino or dibenzylamino .
  • R1, R3 and R4 are preferably hydrogen, halogen or methyl.
  • R2 is especially ethyl and especially methyl.
  • Rings A and B are preferably not further substituted. If they have substituents, they are primarily substituted by halogen, nitro or di-lower alkylamino.
  • Halogen means for example fluorine, bromine, iodine or preferably chlorine.
  • the new fluoran color former mixtures can be prepared by simple mixing and, if necessary, grinding the components (a) and (b) mentioned, homogeneous powder mixtures being obtained which are stable in storage at room temperature.
  • Components (a) and (b) can be used both in the crystalline form and in the amorphous state.
  • the amorphous form can be created before or after mixing.
  • the color former components (a) and (b) are generally present in a weight ratio of 1: 5 to 1: 1, preferably 1: 3 to 1: 2 and in particular 1: 2 to 1: 1. This allows the desired color shades to be set.
  • the color former mixtures according to the invention are very well suited for the production of pressure-sensitive and especially heat-sensitive recording systems.
  • components (a) and (b) can also be used separately.
  • the color former mixtures are usually colorless or at most weakly colored. If these color formers are brought into contact with a preferably acidic developer, ie an electron acceptor, they result in intense gray to black shades which are outstandingly lightfast. They can also be mixed with one or more other known color formers, for example 3,3- (bis-aminophenyl) phthalides, 3-indolyl-3-aminophenyl-azaphthalides, 3,3- (bis-indolyl) phthalides, 3- Aminofluoranes, 2-amino-6-arylaminofluoranes, Leucoauramines, spiropyrans, dispiropyans, phenoxazines, phenothiazines, carbazolylmethanes and other triarylmethane leuco dyes can be used.
  • a preferably acidic developer ie an electron acceptor
  • the color former mixtures from components (a) and (b) show excellent color intensity and lightfastness both on phenolic substrates and on clays and substituted zinc salicylates. They are particularly suitable as very rapidly developing color formers for use in a pressure-sensitive or, in particular, heat-sensitive recording material, which can be both copying and registration material. They are characterized by the fact that they are extremely soluble in the capsule oils and have a slight decrease in color strength (CB deactivation) due to exposure in the CB leaf. Black records that are produced on clays with the color former mixture according to the invention are distinguished by a single component, e.g. Recordings obtained from 2-phenylamino-3-methyl-6-diethylaminofluoran are characterized by an improved, constant-shade storage stability.
  • a pressure-sensitive material consists, for example, of at least one pair of sheets which contain at least one color former mixture of components (a) and (b) dissolved in an organic solvent and an electron acceptor as developer.
  • Typical examples of such developers are active clay substances, such as attapulgus clay, acid clay, bentonite, montmorillonite, activated clay, such as, for example, acid-activated bentonite or montmorillonite, furthermore zeolite, halloysite, silicon dioxide, aluminum oxide, aluminum sulfate, aluminum phosphate, zinc chloride, zinc nitrate, kaolin or any clay or acidic organic compound, such as optionally ring-substituted phenols, salicylic acid or salicylic acid esters and their metal salts, and also an acidic polymeric material, such as a phenolic polymer, an alkylphenol acetylene resin, a maleic acid rosin resin or a partial or fully hydrolyzed polymer of Maleic anhydride with styrene, ethylene or vinyl methyl ether, or carboxypolymethylene. Mixtures of the polymeric compounds mentioned can also be used.
  • Preferred developers are acid-activated bentonite
  • the developers can also be mixed with per se unreactive or less reactive pigments or other auxiliaries such as silica gel or UV absorbers, such as 2- (2-hydroxyphenyl) benzotriazoles.
  • pigments are: Talc, titanium oxide, zinc oxide, chalk; Clays such as kaolin and organic pigments, eg urea-formaldehyde condensates (BET surface 2-75 m2 / g) or melamine-formaldehyde condensation products.
  • the color former mixture provides a colored marking at the points where it comes into contact with the electron acceptor.
  • these are generally separated from the electron acceptor. This can conveniently be achieved by incorporating the color formers into foam, sponge or honeycomb structures.
  • the color formers are preferably enclosed in microcapsules which can usually be broken by pressure.
  • the color former solution When the capsules are broken by pressure, for example using a pencil, the color former solution is transferred to an adjacent sheet coated with an electron acceptor, thereby producing a colored area. The color results from the dye formed, which absorbs in the visible range of the electromagnetic spectrum.
  • the color former mixtures are preferably encapsulated in the form of solutions in organic solvents.
  • suitable solvents are preferably non-volatile solvents, for example polyhalogenated paraffin or diphenyl, such as chlorinated paraffin, monochlorodiphenyl or trichlorodiphenyl, also tricresyl phosphate, di-n-butyl phthalate, dioctyl phthalate, trichlorobenzene, trichloroethyl phosphate, aromatic ethers, such as benzylphenyl ether, hydrocarbon oils, such as paraffin or keropropyl, e.g.
  • the capsule walls can be formed evenly around the droplets of the color former solution by coacervation forces, the encapsulation material e.g. may consist of gelatin and gum arabic, such as e.g. in U.S. Patent 2,800,457.
  • the capsules can preferably also be formed from an aminoplast or modified aminoplast by polycondensation, as described in British Patents 989,264, 1 156 725, 1 301 052 and 1 355 124.
  • Microcapsules formed by interfacial polymerization such as e.g. Capsules made of polyester, polycarbonate, polysulfonamide, polysulfonate, but especially made of polyamide or polyurethane.
  • the microcapsules containing color former mixtures can be used to produce pressure-sensitive copying materials of the most varied types known.
  • the different systems differ essentially from each other in the arrangement of the capsules, the color reactants and the carrier material.
  • An arrangement is preferred in which the encapsulated color former in the form of a layer on the back of a transfer sheet and the electron acceptor in the form of a layer on the front of a receiver sheet.
  • microcapsules containing the color former and the developer are present in or on the same sheet in the form of one or more individual layers or in the paper pulp.
  • the capsules are preferably attached to the carrier by means of a suitable binder.
  • this binder is primarily paper coating agents, such as gum arabic, polyvinyl alcohol, hydroxymethyl cellulose, casein, methyl cellulose, dextrin, starch or starch derivatives or polymer latices.
  • the latter are, for example, optionally carboxylated butadiene-styrene copolymers or acrylic homo or copolymers.
  • the paper used is not only normal paper made from cellulose fibers, but also papers in which the cellulose fibers are (partially or completely) replaced by fibers made from synthetic polymers.
  • the color former mixtures of components (a) and (b) can also be used as color former in a thermoreactive recording material.
  • the mixture according to the invention is characterized in that components (a) and (b) develop almost the same color intensity at the same temperature, in particular at 110 to 200 ° C.
  • the thermoreactive recording material generally contains at least one layer support, the color former mixture, an electron acceptor and optionally also a binder and / or wax.
  • Thermoreactive recording systems include, for example, heat sensitive recording and copying materials and papers. These systems are used, for example, to record information, For example, used in electronic computers, remote printers, teletypes or in recording devices and measuring instruments, such as electrocardiographs.
  • the imaging (marking) can also be done manually with a heated spring.
  • Another device for producing markings by means of heat is laser beams.
  • thermoreactive recording material can be constructed such that the color former is dissolved or dispersed in a binder layer and the developer is dissolved and dispersed in the binder in a second layer. Another possibility is that both the color former and the developer are dispersed in one layer.
  • the binder is softened by heat in specific areas and at these points where heat is applied the color former comes into contact with the electron acceptor and the desired color develops immediately.
  • developers are the clay minerals and phenolic resins already mentioned, or also phenolic compounds, as described, for example, in DE-PS 12 51 348, for example 4-tert-butylphenol, 4-phenylphenol, methylene-bis (p-phenylphenol), 4-Hydroxydiphenyl ether, ⁇ -naphthol, ⁇ -naphthol, 4-hydroxy-diphenyl sulfone, 4-hydroxy-4 ⁇ -methyl-diphenyl sulfone, 4-hydroxybenzoic acid methyl ester or benzyl ester, 4-hydroxyacetophenone, 2,2 ⁇ -dihydroxydiphenyl, 4,4 ⁇ -isopropyl , 4,4 ⁇ -isopropylidene-bis- (2-methylphenol), an antipyrine complex of zinc thiocyanate, a pyridine complex of zinc thiocyanate, 4,4-bis- (4-hydroxyphenyl
  • Fusible, film-forming binders are preferably used to produce the thermoreactive recording material. These binders are usually water soluble, while the color former mixture and developer are sparingly soluble or insoluble in water. The binder should be able to disperse and fix the color former mixture and the developer at room temperature.
  • Water-soluble or at least water-swellable binders are e.g. hydrophilic polymers, such as polyvinyl alcohol, polyacrylic acid, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, polyacrylamide, polyvinyl pyrrolidone, butadiene-styrene copolymers, carboxylated butadiene styrene copolymers, gelatin, starch or etherified corn starch.
  • hydrophilic polymers such as polyvinyl alcohol, polyacrylic acid, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, polyacrylamide, polyvinyl pyrrolidone, butadiene-styrene copolymers, carboxylated butadiene styrene copolymers, gelatin, starch or etherified corn starch.
  • water-insoluble binders i.e. binders soluble in non-polar or only weakly polar solvents, e.g. Natural rubber, synthetic rubber, chlorinated rubber, alkyd resins, polystyrene, styrene / butadiene copolymers, polymethacrylates, ethyl cellulose, nitrocellulose e.g. Polyvinyl carbazole.
  • binders soluble in non-polar or only weakly polar solvents
  • non-polar or only weakly polar solvents e.g. Natural rubber, synthetic rubber, chlorinated rubber, alkyd resins, polystyrene, styrene / butadiene copolymers, polymethacrylates, ethyl cellulose, nitrocellulose e.g. Polyvinyl carbazole.
  • the preferred arrangement is one in which the color former and the developer are contained in one layer in an water-soluble binder.
  • thermoreactive layers can contain further additives.
  • these layers can contain, for example, talc, titanium dioxide, zinc oxide, aluminum oxide, aluminum hydroxide, calcium carbonate, clays or else organic pigments, such as, for example, urea-formaldehyde polymers.
  • substances such as urea, thiourea, Diphenylthiourea, acetamide, acetanilide, benzenesulfanilide, stearic acid amide, phthalic anhydride, metal stearates such as zinc stearate, phthalic nitrile, dimethyl terephthalate or other corresponding meltable products which induce the simultaneous melting of the color former and the developer, are added.
  • Thermographic recording materials preferably contain waxes, for example carnauba wax, montan wax, paraffin wax, polyethylene wax, condensates of higher fatty acid amides and formaldehyde and condensates of higher fatty acids and ethylenediamine.
  • waxes for example carnauba wax, montan wax, paraffin wax, polyethylene wax, condensates of higher fatty acid amides and formaldehyde and condensates of higher fatty acids and ethylenediamine.
  • This solution is microencapsulated in a manner known per se with gelatin and gum arabic by coacervation, whereupon the microcapsules are mixed with starch solution and spread on a sheet of paper.
  • the second sheet of paper is coated on the front with a clay that is customary as a color developer.
  • the first sheet and the paper coated with the color developer are placed on top of each other with the coatings adjacent. Writing by hand or with the typewriter on the first sheet exerts pressure, and a very intense black copy develops immediately on the sheet coated with the developer, which has excellent storage stability.
  • Example 1 Corresponding intensive and storage-stable black colorations are obtained if, in Example 1, the following components (a) and (b) are used as the color former mixture instead of the components used, which accordingly replace either component (a) or component (b) or both components.
  • dispersion A 9 g of 4,4′-isopropylidenediphenol (bisphenol A), 13.5 g of a 10% aqueous solution of polyvinyl alcohol VO3 / 140 and 18 g of water with spheres up to a grain size of 2-4 ⁇ m are used within 2 -4 hours ground.
  • bisphenol A 4,4′-isopropylidenediphenol
  • 13.5 g of a 10% aqueous solution of polyvinyl alcohol VO3 / 140 and 18 g of water with spheres up to a grain size of 2-4 ⁇ m are used within 2 -4 hours ground.
  • dispersion B To prepare dispersion B, 1 g of 2-dibenzylamino-3-methyl-6-pyrrolidinofluorane, 2 g of 2-dibenzylamino-6-pyrrolidinofluoron, 10.5 g of a 10% strength aqueous solution of polyvinyl alcohol VO3 / 140 and 6 g of water ground with balls up to a grain size of 2-4 ⁇ m.
  • the two dispersions are then mixed.
  • the mixture is applied to paper with a basis weight of 50 g / m2 using a doctor blade.
  • the proportion of the applied material is 3 g / m2 (dry weight). From 110 ° C a black color develops quickly, the full color strength of which is reached at about 170 ° C. The nuance is stable over the entire temperature range and when stored.
  • Example 2 Corresponding intensive and stable black colorations are obtained if, in Example 2, components (a) and (b) according to Example 1 are used as the color former mixture instead of the components used, correspondingly either component (a) or component (b) or both by these fluoran compounds be replaced.
  • This solution is microencapsulated in a manner known per se with gelatin and gum arabic by coacervation, whereupon the microcapsules are mixed with starch solution and spread on a sheet of paper.
  • a second sheet of paper is coated on the front with a phenolic resin commonly used as a color developer.
  • the first sheet and the paper coated with the color developer are placed on top of each other with the coatings. Typing on the first sheet by hand or typewriter exerts pressure and an intense black copy with good lightfastness immediately develops on the sheet coated with the developer.
  • the two dispersions C and D are then mixed.
  • the mixture is applied to paper with a basis weight of 50 g / m2 using a doctor knife.
  • the proportion of the applied material is 3 g / m2 (dry weight). From 100 ° C a black color develops quickly, the full color strength of which is reached at about 170 ° C. The nuance is stable over the entire temperature range and when stored.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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Claims (14)

  1. Mélange de composés chromogènes de type fluoranne, contenant au moins
    (a) un composé fluoranne de formule
    Figure imgb0014
     et
    (b) un composé fluoranne de formule
    Figure imgb0015
     formules dans lesquelles
    R₁, R₃ et R₄   représentent chacun, indépendamment les uns des autres, un atome d'hydrogène ou d'halogène, ou un groupe alkyle inférieur ou alcoxy inférieur;
    R₂   représente un atome d'halogène ou un groupe alkyle inférieur ou alcoxy inférieur;
    X₁, X₂, Y₁ et Y₂   représentent chacun, indépendamment les uns des autres, un atome d'hydrogène ou un radical alkyle ayant au maximum 12 atomes de carbone, cycloalkyle, aryle ou aralkyle, non substitué ou substitué par un atome d'halogène ou par un groupe hydroxy, cyano ou alcoxy inférieur;
    X₃ et Y₃   représentent chacun, indépendamment l'un de l'autre, un atome d'hydrogène ou un radical alkyle ayant au maximum 12 atomes de carbone, cycloalkyle, aryle ou aralkyle, non substitué ou substitué par un atome d'halogène ou par un groupe hydroxy, cyano ou alcoxy inférieur;
    X₄ et Y₄   représentent, indépendamment l'un de l'autre, un radical alkyle ayant au maximum 12 atomes de carbone, cycloalkyle ou aralkyle, non substitué ou substitué par un atome d'halogène ou par un groupe hydroxy, cyano ou alcoxy inférieur; ou
    (X₁ et X₂), (X₃ et X₄), (Y₁ et Y₂) et (Y₃ et Y₄)
        représentent, indépendamment les uns des autres, conjointement avec l'atome d'azote commun, un radical hétérocyclique à 5 ou 6 chaînons; et
    les cycles A et B sont,   indépendamment l'un de l'autre, chacun non substitué ou substitué par un atome d'halogène ou par un groupe nitro, amino, mono(alkyl inférieur)-amino ou di(alkyl inférieur)-amino.
  2. Melange de composés chromogènes selon la revendication 1, caractérisé en ce qu'il contient des composants (a) et (b) dans lesquels, dans les formules (1) et (2),
    X₁ et Y₁   représentent un radical alkyle en C₁-C₈, cyclohexyle, phényle, tolyle ou benzyle, et
    X₂ et Y₂   représentent un radical alkyle inférieur ou benzyle.
  3. Mélange de composés chromogènes selon la revendication 1, caractérisé en ce qu'il contient des composants (a) et (b) dans lesquels, dans les formules (1) et (2), -NX₁X₂ ou -NY₁Y₂ représente le radical pyrrolidino.
  4. Mélange de composés chromogènes selon l'une des revendications 1 à 3, caractérisé en ce qu'il contient des composants (a) et (b) dans lesquels, dans les formules (1) et (2), R₁, R₃ et R₄ représentent un atome d'hydrogène ou d'halogène ou le groupe méthyle, et R₂ est le groupe méthyle ou éthyle.
  5. Mélange de composés chromogènes selon la revendication 1, caractérisé en ce qu'il contient, en tant que composant (a), un composé fluoranne de formule
    Figure imgb0016
     dans laquelle
    R₁'   représente un atome d'hydrogène ou le groupe méthyle;
    R₂'   représente un atome d'halogène ou le groupe méthyle ou éthyle;
    X₁'   représente un radical alkyle en C₁-C₆, cycloalkyle en C₅-C₆, phénylalkyle en C₇-C₉, phényle ou un radical phényle substitué par un atome d'halogène ou par un groupe alkyle en C₁-C₄ ou alcoxy en C₁-C₄;
    X₂'   représente un radical alkyle en C₁-C₆ ou phénylalkyle en C₇-C₉, ou NX₁'X₂' représente le radical pyrrolidinyle, pipéridinyle ou morpholinyle;
    X₃' et X₄'   représentent chacun un radical phénylalkyle en C₇-C₉, chlorobenzyle ou alkyl(C₁-C₄)-benzyle.
  6. Mélange de composés chromogènes selon la revendication 1 ou 5, caractérisé en ce qu'il contient, en tant que composant (b), un composé fluoranne de formule
    Figure imgb0017
     dans laquelle
    R₄'   représente un atome d'hydrogène ou d'halogène, ou le groupe méthyle;
    Y₁'   représente un radical alkyle en C₁-C₆, cycloalkyle en C₅-C₆, phénylalkyle en C₇-C₉, phényle ou un radical phényle substitué par un atome d'halogène ou par un groupe alkyle en C₁-C₄ ou alcoxy en C₁-C₄;
    Y₂'   représente un radical alkyle en C₁-C₆ ou phénylalkyle en C₇-C₉, ou -NY₁'Y₂ représente le radical pyrrolidinyle, pipéridinyle ou morpholinyle;
    Y₃'   représente un atome d'hydrogène ou un radical alkyle en C₁-C₈, phényle, phénylalkyle en C₇-C₉, chlorobenzyle ou alkyl(C₁-C₄)-benzyle; et
    Y₄'   représente un radical alkyle en C₁-C₈, phénylalkyle en C₇-C₉, chlorobenzyle ou alkyl(C₁-C₄)-benzyle.
  7. Mélange de composés chromogènes selon la revendication 5 ou 6, caractérisé en ce qu'il contient, en tant que composants (a) et (b), des composés fluoranne de formules (3) et (4), dans lesquelles
    X₁' et Y₁'   représentent chacun un radical alkyle en C₁-C₄, cyclohexyle, phényle ou tolyle;
    X₂' et Y₂'   représentent chacun un radical alkyle en C₁-C₄, ou -NX₁'X₂' ou -NY₁'Y₂' représente le radical pyrrolidino; et
    X₃', X₄', Y₃' et Y₄   ' représentent chacun un radical phénylalkyle en C₇-C₉ ou un radical benzyle substitué au noyau par un atome de chlore ou par le groupe méthyle.
  8. Mélange de composés chromogènes selon l'une des revendications 1 à 7, caractérisé en ce que le rapport pondéral (a):(b) va de 1:5 à 1:1, de préférence de 1:3 à 1:2.
  9. Mélange de composés chromogènes selon l'une des revendications 1 à 8, caractérisé en ce que les composants (a) et (b) se trouvent à l'état amorphe.
  10. Solution de mélange de composés chromogènes, contenant un composé fluoranne de formule (1) et un composé fluoranne de formule (2) selon l'une des revendications 1 à 9, microencapsulée.
  11. Matériau d'enregistrement sensible à la pression, contenant un mélange de composés chromogènes selon l'une des revendications 1 à 9.
  12. Matériau d'enregistrement sensible à la pression, selon la revendication 11, caractérisé en ce que le mélange de composés chromogènes est présent sous forme d'une couche au verso d'une feuille de transfert et le révélateur chromogène est présent sous forme d'une couche au recto de la feuille de réception.
  13. Matériau d'enregistrement sensible à la chaleur, contenant un mélange de composés chromogènes selon l'une des revendications 1 à 9.
  14. Matériau d'enregistrement sensible à la chaleur, selon la revendication 13, comportant une couche thermosensible qui contient un composé chromogène et un révélateur chromogène pour le composé chromogène, caractérisé en ce que le composé chromogène est un mélange de composés chromogènes selon l'une des revendications 1 à 9.
EP87810616A 1986-10-31 1987-10-26 Mélange de colorants fluoranes et matériaux pour l'enregistrement l'utilisant Expired - Lifetime EP0266311B1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
CH4313/86 1986-10-31
CH431386 1986-10-31
CH158/87 1987-01-16
CH15887 1987-01-16

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EP0266311A2 EP0266311A2 (fr) 1988-05-04
EP0266311A3 EP0266311A3 (en) 1989-08-30
EP0266311B1 true EP0266311B1 (fr) 1992-06-17

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EP87810616A Expired - Lifetime EP0266311B1 (fr) 1986-10-31 1987-10-26 Mélange de colorants fluoranes et matériaux pour l'enregistrement l'utilisant

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US (1) US5071480A (fr)
EP (1) EP0266311B1 (fr)
DE (1) DE3779866D1 (fr)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2081360T3 (es) * 1989-02-24 1996-03-01 Ciba Geigy Ag Compuestos 2- o 3-dicarboximida-fluorano, procedimiento para su obtencion y utilizacion de los mismos en materiales de artes graficas.
EP0466040B1 (fr) * 1990-07-12 1996-11-06 MITSUI TOATSU CHEMICALS, Inc. Cristaux de composé fluorane, solvates cristallins, leur méthode de préparation et matériau d'enregistrement contenant ledit cristal ou ledit solvate
EP0591106B1 (fr) * 1992-09-30 1998-01-14 Ciba SC Holding AG Compositions liquides aqueuses concentrées de formateurs de couleurs
US5681791A (en) * 1993-09-30 1997-10-28 Ciba-Geigy Corporation Color former mixture
DE59404879D1 (de) * 1993-09-30 1998-02-05 Ciba Geigy Ag Farbbildnergemisch
US6899507B2 (en) * 2002-02-08 2005-05-31 Asm Japan K.K. Semiconductor processing apparatus comprising chamber partitioned into reaction and transfer sections
US7700258B2 (en) * 2003-01-24 2010-04-20 Hewlett-Packard Development Company, L.P. Color forming compositions with improved marking sensitivity and image contrast and associated methods

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1192938A (en) * 1966-11-18 1970-05-28 Fuji Photo Film Co Ltd Improvements in or relating to Pressure-Sensitive Copying Paper
FR1546851A (fr) * 1966-11-18 1968-11-22 Fuji Photo Film Co Ltd Papier copiant sensibilisé à la pression
JPS5416863B1 (fr) * 1970-03-10 1979-06-26
JPS4835492B1 (fr) * 1970-04-02 1973-10-29
US3998846A (en) * 1970-07-08 1976-12-21 Yamamoto Kagaku Gosei Kabushiki Kaisha Process for preparing dibenzylamino fluoran compounds
SE385010B (sv) * 1970-07-08 1976-05-31 Yamamoto Kagaku Gosei Kk Dibensylaminofluoranforening till anvendning som fergbildare i tryckkensligt kopieringspapper samt sett att framstella foreningen ifraga
US3857675A (en) * 1970-11-16 1974-12-31 H Schwab Mixtures of two chromogenic compounds
CA969960A (en) * 1970-12-15 1975-06-24 Kenji Yamamoto Pressure sensitive copying paper
JPS5138245B2 (fr) * 1973-05-22 1976-10-20
JPS56164890A (en) * 1980-05-23 1981-12-18 Kanzaki Paper Mfg Co Ltd Heat-sensitive recording material
JPS57178792A (en) * 1981-04-27 1982-11-04 Kohjin Co Ltd Black color heat sensitive recording medium
JPS58119892A (ja) * 1982-01-08 1983-07-16 Fuji Photo Film Co Ltd 感熱記録紙
JPS58208092A (ja) * 1982-05-28 1983-12-03 Fuji Xerox Co Ltd 感熱記録紙
JPS592890A (ja) * 1982-06-30 1984-01-09 Mita Ind Co Ltd 黒色感熱記録体

Also Published As

Publication number Publication date
EP0266311A2 (fr) 1988-05-04
DE3779866D1 (de) 1992-07-23
US5071480A (en) 1991-12-10
EP0266311A3 (en) 1989-08-30

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