EP0317825B1 - Colour-photographic recording material - Google Patents

Colour-photographic recording material Download PDF

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Publication number
EP0317825B1
EP0317825B1 EP88118632A EP88118632A EP0317825B1 EP 0317825 B1 EP0317825 B1 EP 0317825B1 EP 88118632 A EP88118632 A EP 88118632A EP 88118632 A EP88118632 A EP 88118632A EP 0317825 B1 EP0317825 B1 EP 0317825B1
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Prior art keywords
alkyl
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mol
aryl
recording material
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German (de)
French (fr)
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EP0317825A3 (en
EP0317825A2 (en
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Walter Dr. Pätzold
Armin Dr. Voigt
Helmut Dr. Mäder
Sieghart Dipl.-Ing. Klötzer
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Agfa Gevaert AG
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Agfa Gevaert AG
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/10—Organic substances
    • G03C1/12—Methine and polymethine dyes
    • G03C1/127—Methine and polymethine dyes the polymethine chain forming part of a carbocyclic ring

Definitions

  • the invention relates to a color photographic recording material which contains at least one blue-sensitive, at least one green-sensitive and at least one red-sensitive silver halide emulsion layer on a reflective layer support and optionally further non-light-sensitive binder layers, the binder of which is hardened with an instant hardener.
  • the hardeners generally react with free amino, imino or hydroxyl groups of the proteinaceous binder with crosslinking thereof.
  • slow-reacting hardeners are disadvantageous in that, for example, important parameters of the cast layers in photographic recording materials remain over a longer period of time change.
  • sensitometric data such as sensitivity, gradation and maximum density can change slowly, and the final properties of the layer or layer structure are often only achieved after a considerable period of storage. This necessitates increased testing effort during production.
  • fast-acting curing agents because with them the final properties are achieved within a short time after the casting, so that the required storage or waiting times can be shortened and the test effort can be reduced.
  • Very useful fast-acting curing agents hereinafter also called instant hardeners, are described in DE-A-22 25 230, DE-A-23 17 677 and DE-A-24 39 551.
  • Immediate hardeners are understood to mean compounds which crosslink suitable binders in such a way that the hardening is completed immediately after casting or at the latest after 24 hours, preferably after 8 hours, to the extent that no further change in the sensitometry caused by the crosslinking reaction and the swelling of the layer structure occurs.
  • Swelling is understood to mean the difference between the wet layer thickness and the dry layer thickness during the aqueous processing of the film (Photogr. Sci. Eng. 8 (1964), 275; Photogr. Sci. Eng. 16 (1972), 449).
  • hardening agents which react very quickly with gelatin are, for example, carbamoylpyridinium salts which presumably are able to react with free carboxyl groups of the proteinaceous binder, so that the latter can react with free amino groups to form peptide bonds and crosslink the binder.
  • carbamoylpyridinium salts which presumably are able to react with free carboxyl groups of the proteinaceous binder, so that the latter can react with free amino groups to form peptide bonds and crosslink the binder.
  • the instant hardeners mentioned may generally only be added to casting solutions containing gelatin shortly before the casting, since otherwise the casting properties, in particular the viscosity of the casting solutions, would be changed quickly and sustainably by premature reaction.
  • the immediate hardener is added to the top layer (protective layer). By diffusion, it reaches the other gelatin-containing layers to be hardened and crosslinks the gelatin so quickly that the hardening is almost complete immediately after drying and the parameters characteristic of the physical and photographic properties have reached their final values
  • red-sensitive silver halide emulsion layers of which are sensitized with the usual sulfo-containing sensitizers have a decrease in sensitivity if moisture acts on these materials before exposure (moisture defects).
  • the invention was based on the object of providing a color photographic recording material which is produced using instant hardeners but does not show any moisture defects.
  • red-sensitive Layers sensitized with at least one special sensitizer and at least one special potentizer.
  • the sensitizer I is preferably used in an amount of 0.05 to 0.25, in particular 0.075 to 0.20 mmol / mol Ag, the potentizer II in an amount of 0.45 to 3.00, in particular 0.70 to 1 , 40 mmol / mol Ag used.
  • the instant hardener is preferably used in an amount of 0.1 to 5 mmol / m2, preferably 0.5 to 1.7 mmol / m2.
  • alkyl is in particular C1-C2 Hydrox-alkyl optionally substituted by halogen, hydroxy, sulfo, C1-C20-alkoxy.
  • Aryl unless otherwise defined, is in particular optionally substituted by halogen, sulfo, C1-C20-alkoxy or C1-C20-alkyl C6-C14-aryl.
  • Aralkyl unless otherwise defined, is in particular C Halogen-C20-aralkyl substituted by halogen, C1-C20-alkoxy, sulfo or C1-C20-alkyl.
  • Alkoxy unless otherwise defined, is in particular C1-C20 alkoxy.
  • X ⁇ is preferably a halide ion such as Cl ⁇ , Br ⁇ or BF4 ⁇ , NO3 ⁇ , (SO42 ⁇ ) 1/2 , ClO4 ⁇ , CH3OSO3 ⁇ , PF6 ⁇ , CF3SO3 ⁇ and in particular a -SO3 ⁇ - covalently linked to the hardener molecule Group, where the -SO3 ⁇ group can be directly connected to the heterocycle via a substituent (see definitions alkyl, aryl, aralkyl) or in the formulas (a), (b), (c).
  • a substituent see definitions alkyl, aryl, aralkyl
  • Alkenyl is especially C2-C20 alkenyl.
  • Alkylene is especially C2-C20 alkylene; Arylene especially phenylene, aralkylene especially benzylene and alkaralkylene especially xylylene.
  • Suitable N-containing ring systems that can represent Z are shown on the previous page.
  • the pyridine ring is preferred.
  • R36 and R37 together with the nitrogen atom to which they are bonded, in particular form a pyrrolidine or piperidine ring substituted by 2 oxo groups bonded in the o- and o'-position, and the benzo, cyclohexeno- or [2.1.1] -bicyclohexeno-condensed can.
  • Acyl is especially C1-C10 alkylcarbonyl or benzoyl; Carbalkoxy is especially C1-C10 alkoxycarbonyl; Carbamoyl is especially mono- or di-C1-C4 alkylaminocarbonyl; Carbaroxy is especially phenoxycarbonyl.
  • Groups R24 which can be split off by nucleophilic agents are, for example, halogen atoms, C1-C15 alkylsulfonyloxy groups, C7-C15 aralkylsulfonyloxy groups, C6-C15 arylsulfonyloxy groups and 1-pyridinyl radicals.
  • the compounds can be prepared in a simple manner known from the literature.
  • the secondary amines are e.g. with phosgene the carbamic acid chlorides, which are then reacted with aromatic, heterocyclic nitrogen-containing compounds in the dark.
  • the preparation of compound 3 is described in Chemical Reports 40, (1907), page 1831. Further information on the synthesis can be found in DE-OS 2 225 230, DE-OS 2 317 677 and DE-OS 2 439 551.
  • JP-OSs 44 140/82 and 46 538/82 and JP-PS 50 669/83 Methods for the synthesis of these compounds are described in more detail in JP-OSs 44 140/82 and 46 538/82 and JP-PS 50 669/83.
  • the binder to be cured used in the layers which are subjected to the curing process according to the invention is a porten-like binder which contains free amino groups and free carboxyl groups.
  • Gelatin is a preferred example. Gelatin is mainly used in photographic recording materials as a binder for the light-sensitive substances, the coloring compounds and, if appropriate, other additives. Such recording materials often have a large number of different layers.
  • the hardening by means of an instant hardener is usually carried out in such a way that the hardening agent is applied in excess as the last layer on the layers to be hardened is, wherein the hardening coating solution further substances such as UV absorbers, antistatic agents, matting agents and polymeric organic particles can be added.
  • the layer containing the hardening agent can be applied simultaneously with or after the casting of the remaining layers by means of cascade or curtain coaters.
  • the casting temperature can be varied over a wide range, e.g. B. between 45 and 5 ° C, preferably between 38 and 18 ° C.
  • the layer thickness of the hardening casting is, for example, between 0.2 and 2.5 ⁇ m.
  • Other additives such as UV absorbers, color correction dyes, antistatic agents and inorganic or organic solid particles, which are used, for example, as matting agents or spacers, can be added to the hardener-containing layer.
  • Suitable UV absorbers are described, for example, in US Pat. No. 3,253,921, DE-C-20 36 719 and EP-A-0 057 160.
  • suitable inorganic solid particles are silicon dioxide, magnesium dioxide, titanium dioxide and calcium carbonate. Such materials are widely used to matt the outermost layers of photographic recording materials and thus reduce their stickiness.
  • solid particles Organic in nature which can be alkali-soluble or alkali-insoluble, are suitable for this purpose. Such particles, also referred to as spacers, generally roughen the surface, so that the surface properties, in particular the adhesive or sliding properties, can be modified thereby.
  • Polymethyl methacrylate is an example of alkali-insoluble spacers. Alkali-soluble spacers are described, for example, in DE-A-34 24 893.
  • Particulate organic polymers with reactive groups in particular those reactive groups which react with the binder, as described, for example, in DE-A-35 44 212, can also be added as so-called hardeners.
  • the hardener-containing partial layer which contains comparatively little or no binding agent
  • its thickening agent such as polystyrene sulfonic acid or hydroxyethyl cellulose.
  • the color photographic recording materials according to the present invention are multilayer materials which have a plurality of silver halide emulsion layers or emulsion layer units with different spectral sensitivity.
  • the emulsion layer unit is understood to mean layer packages of 2 or more silver halide emulsion layers of the same spectral sensitivity. Layers of the same However, spectral sensitivity does not necessarily have to be arranged adjacent to one another, but can also be separated from one another by other layers, in particular also by layers of different spectral sensitivity.
  • the binder in these layers is usually a protein-like binder with free carboxyl groups and free amino groups, preferably gelatin.
  • the layered binder can contain up to 50% by weight of non-proteinaceous binders such as polyvinyl alcohol, N-vinylpyrrolidone, polyacrylic acid and their derivatives, in particular copolymers, or cellulose derivatives and gelatin derivatives.
  • non-proteinaceous binders such as polyvinyl alcohol, N-vinylpyrrolidone, polyacrylic acid and their derivatives, in particular copolymers, or cellulose derivatives and gelatin derivatives.
  • each of the light-sensitive silver halide emulsion layers or emulsion layer units mentioned is assigned at least one color-imparting compound, usually a color coupler, which can react with color developer oxidation products to form a non-diffusing dye.
  • the color couplers are expediently non-diffusing and accommodated in the light-sensitive layer itself or in close proximity to it.
  • the color couplers assigned to the two or more partial layers of an emulsion layer unit do not necessarily have to be identical. They are only intended to give the same color in color development, usually a color that is complementary to the color of the light to which the photosensitive silver halide emulsion layers are sensitive.
  • the red-sensitive silver halide emulsion layers are assigned at least one non-diffusing color coupler for producing the blue-green partial color image, usually a coupler of the phenol or ⁇ -naphthol type.
  • a coupler of the phenol or ⁇ -naphthol type is particularly noteworthy.
  • cyan couplers as described in US-A-2,474,293, US-A-2,367,531, US-A-2,895,826, US-A-3,772,002, EP-A-0 028 099 , EP-A-0 112 514.
  • the green-sensitive silver halide emulsion layers are generally assigned at least one non-diffusing color coupler for producing the purple partial color image, color couplers of the 5-pyrazolone or indazolone type usually being used. Cyanoacetyl compounds, oxazolones and pyrazoloazoles are also suitable as magenta couplers. Particularly noteworthy are, for example, purple couplers, as described in US Pat. Nos. 2,600,788, 4,383,027, 1,547,803, 1,810,464, 24,066,665, DE -A-32 26 163 are described.
  • the blue-sensitive silver halide emulsion layers are normally assigned at least one non-diffusing color coupler to produce the yellow partial color image, usually a color coupler with an open-chain ketomethylene grouping.
  • a color coupler with an open-chain ketomethylene grouping are particularly noteworthy.
  • yellow couplers as described in US Pat. No. 3,408,194, US Pat. No. 3,933,501, DE-A-23 29 587, DE-A-24 56 976.
  • Color couplers of these types are known in large numbers and are described in a large number of patents. Examples include the publications “Color Coupler” by W. Pelz, "Messages from the research laboratories of Agfa, Leverkusen / Kunststoff", Volume III (1961) p. 111, and by K. Venkataraman in “The Chemistry of Synthetic Dyes” , Vol. 4., 341 to 387, Academic Press (1971).
  • the color couplers can be 4-equivalent couplers, but also 2-equivalent couplers.
  • the latter are derived from the 4-equivalent couplers in that they contain a substituent in the coupling site which is split off during the coupling.
  • the 2-equivalent couplers include both those that are practically colorless and those that have an intense intrinsic color that disappears when the color is coupled or is replaced by the color of the image dye produced (mask coupler).
  • the known white couplers are also to be counted among the 2-equivalent couplers, but they essentially result in colorless products on reaction with color developer oxidation products.
  • the 2-equivalent couplers also include those couplers which contain a cleavable residue in the coupling site, which is released upon reaction with color developer oxidation products and thereby either directly or after one or more further groups have been cleaved from the primarily cleaved residue (e.g. DE-A-27 03 145, DE-A-28 55 697, DE-A-31 05 026, DE-A-33 19 428), a develops certain desired photographic effectiveness, for example as a development inhibitor or accelerator.
  • Examples of such 2-equivalent couplers are the known DIR couplers as well as DAR and FAR couplers.
  • Suitable DIR couplers are described, for example, in GB-A-953 454, DE-A-1 800 420, DE-A-20 15 867, DE-A-24 14 006, DE-A-28 42 063, DE-A- 34 27 235.
  • Suitable DAR or FAR couplers are described, for example, in DE-A-32 09 110, EP-A-0 089 834, EP-A-0 117 511, EP-A-0 118 087.
  • DIR, DAR or FAR couplers Since with DIR, DAR or FAR couplers the effectiveness of the residue released during coupling is mainly desired and the color-forming properties of these couplers are less important, such DIR, DAR or FAR couplers are also suitable, the products which are essentially colorless upon coupling, as described, for example, in DE-A-1 547 640.
  • the cleavable residue can also be a ballast residue, so that when reacting with color developer oxidation products coupling products e.g. Dyes can be obtained which are diffusible or at least have a weak or restricted mobility, as described, for example, in US Pat. No. 4,420,556.
  • High molecular weight color couplers are described, for example, in DE-C-1 297 417, DE-A-24 07 569, DE-A-31 48 125, DE-A-32 17 200, DE-A-33 20 079, DE-A-33 24 932, DE-A-33 31 743, DE-A-33 40 376, EP-A-0 027 284, US-A-4 080 211.
  • the high molecular color coupler are usually produced by polymerizing ethylenically unsaturated monomeric color couplers. However, they can also be obtained by polyaddition or polycondensation.
  • the layers of the color photographic recording material to be hardened by the process according to the invention may contain further additives, for example antioxidants, dye-stabilizing agents and agents for influencing the mechanical and electrostatic properties.
  • the layers to be hardened can also contain compounds which absorb UV light.
  • the silver halide present as a light-sensitive component in the photographic material can contain chloride, bromide or iodide or mixtures thereof as the halide.
  • the silver halide preferably consists of 15 to 100 mol% of chloride, 0 to 85 mol% of bromide and 0 to 2 mol% of iodide.
  • the average particle diameter is preferably 0.2 to 0.6 ⁇ m.
  • the silver halides can be doped with Rh, Ir, Cd or Pb and ripened with sulfur compounds or a combination of sulfur and gold compounds.
  • the silver halide emulsions can also contain at least 80 mol% of chloride, preferably 95 to 100 mol% of chloride, 0 to 5 mol% of bromide and 0 to 1 mol% of iodide.
  • Example 1 corresponded to Example 1 with the difference that a silver chloride emulsion (100 mol% chloride) was used in the 3rd layer.
  • the emulsion was prepared by double inlet with a grain size of 0.40 ⁇ m, flocculated in the usual way, washed and redispersed with gelatin.
  • the weight ratio gelatin-silver (as AgNO3) was 0.5.
  • the emulsion was then ripened with 20 ⁇ mol thiosulfate, 1.5 ⁇ mol HAuCl4 and 15 ⁇ mol NH4SCN per mol Ag for optimal sensitivity, sensitized to the blue spectral range and stabilized.
  • the same emulsion was used in the 5th and 7th layers, but sensitized to the green and red spectral range.
  • Example 1 The samples were then exposed through a step wedge.
  • the samples of Example 1 and the comparison to Example 1 were developed in the EP2 process, samples of Example 2 and the comparison to 2 in the RA-4 process.

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Description

Die Erfindung betrifft ein farbfotografisches Aufzeichnungsmaterial, das auf einem reflektierenden Schichtträger mindestens eine blauempfindliche, mindestens eine grünempfindliche und mindestens eine rotempfindliche Silberhalogenidemulsionsschicht und gegebenenfalls weitere nicht lichtempfindliche Bindemittelschichten enthält, deren Bindemittel mit einen Soforthärtungsmittel gehärtert ist.The invention relates to a color photographic recording material which contains at least one blue-sensitive, at least one green-sensitive and at least one red-sensitive silver halide emulsion layer on a reflective layer support and optionally further non-light-sensitive binder layers, the binder of which is hardened with an instant hardener.

Für die Härtung der Bindemittelschichten farbfotografische Aufzeichungsmaterialien sind eine Vielzahl von Härtungsmitteln bekannt geworden. Die Härtungsmittel reagieren in der Regel mit freien Amino-, Imino- oder Hydroxylgruppen des proteinartigen Bindemittels unter Vernetzung desselben.A large number of hardening agents have become known for the hardening of the binder layers of color photographic recording materials. The hardeners generally react with free amino, imino or hydroxyl groups of the proteinaceous binder with crosslinking thereof.

Die Verwendung langsam reagierender Härtungsmittel ist insofern nachteilig als beispielsweise in fotografischen Aufzeichnungsmaterialien wichtige Parameter der gegossenen Schichten sich über einen längeren Zeitraum noch verändern. Insbesondere können sensitometrische Daten wie Empfindlichkeit, Gradation und Maximaldichte sich langsam verändern, und die endgültigen Eigenschaften der Schicht oder des Schichtverbandes werden oft erst nach einer beträchtlichen Lagerungsdauer erreicht. Dies macht bei der Produktion einen erhöhten Prüfaufwand erforderlich. Es ist daher sehr erwünscht, schnell wirkende Härtungsmittel zu verwenden, weil mit ihnen die endgültigen Eigenschaften innerhalb kurzer Zeit nach dem Beguß erreicht sind, so daß die erforderlichen Lagerungs- bzw. Wartezeiten abgekürzt werden können und der Prüfaufwand reduziert werden kann. Sehr brauchbare schnellwirkende Härtungsmittel, im folgenden auch Soforthärter genannt, sind in DE-A-22 25 230, DE-A-23 17 677 und DE-A-24 39 551 beschrieben.The use of slow-reacting hardeners is disadvantageous in that, for example, important parameters of the cast layers in photographic recording materials remain over a longer period of time change. In particular, sensitometric data such as sensitivity, gradation and maximum density can change slowly, and the final properties of the layer or layer structure are often only achieved after a considerable period of storage. This necessitates increased testing effort during production. It is therefore very desirable to use fast-acting curing agents, because with them the final properties are achieved within a short time after the casting, so that the required storage or waiting times can be shortened and the test effort can be reduced. Very useful fast-acting curing agents, hereinafter also called instant hardeners, are described in DE-A-22 25 230, DE-A-23 17 677 and DE-A-24 39 551.

Unter Soforthärtern werden Verbindungen verstanden, die geeignete Bindemittel so vernetzen, daß unmittelbar nach Beguß bzw. spätestens nach 24 Stunden, vorzugsweise nach 8 Stunden die Härtung soweit abgeschlossen ist, daß keine weitere durch die Vernetzungsreaktion bedingte Änderung der Sensitometrie und der Quellung des Schichtverbandes auftritt. Unter Quellung wird die Differenz von Naßschichtdicke und Trockenschichtdicke bei der wäßrigen Verarbeitung des Films verstanden (Photogr. Sci. Eng. 8 (1964), 275; Photogr. Sci. Eng. 16 (1972), 449).Immediate hardeners are understood to mean compounds which crosslink suitable binders in such a way that the hardening is completed immediately after casting or at the latest after 24 hours, preferably after 8 hours, to the extent that no further change in the sensitometry caused by the crosslinking reaction and the swelling of the layer structure occurs. Swelling is understood to mean the difference between the wet layer thickness and the dry layer thickness during the aqueous processing of the film (Photogr. Sci. Eng. 8 (1964), 275; Photogr. Sci. Eng. 16 (1972), 449).

Bei diesen mit Gelatine sehr schnell reagierenden Härtungsmitteln handelt es sich z.B. um Carbamoylpyridiniumsalze, die vermutlich mit freien Carboxylgruppen des proteinartigen Bindemittels zu reagieren vermögen, so daß letztere mit freien Aminogruppen unter Ausbildung von Peptidbindungen und Vernetzung des Bindemittels reagieren können. Wegen dieser schnellen Wirkung dürfen die erwähnten Soforthärter gelatinehaltigen Gießlösungen im allgemeinen erst kurz vor dem Beguß zugesetzt werden, da anderenfalls durch vorzeitige Reaktion die Gießeigenschaften inbesondere die Viskosität der Gießlösungen rasch und nachhaltig verändert würden. Im allgemeinen wird der Soforthärter der obersten Schicht (Schutzschicht) zugesetzt. Durch Diffusion gelangt er in die anderen zu härtenden gelatinehaltigen Schichten und vernetzt darin die Gelatine so schnell, daß bereits unmittelbar nach der Trocknung die Härtung nahezu abgeschlossen ist und die für die physikalischen und fotografischen Eigenschaften charakteristischen Parameter ihre endgültigen Werte erreicht haben.These hardening agents which react very quickly with gelatin are, for example, carbamoylpyridinium salts which presumably are able to react with free carboxyl groups of the proteinaceous binder, so that the latter can react with free amino groups to form peptide bonds and crosslink the binder. Because of this rapid action, the instant hardeners mentioned may generally only be added to casting solutions containing gelatin shortly before the casting, since otherwise the casting properties, in particular the viscosity of the casting solutions, would be changed quickly and sustainably by premature reaction. In general, the immediate hardener is added to the top layer (protective layer). By diffusion, it reaches the other gelatin-containing layers to be hardened and crosslinks the gelatin so quickly that the hardening is almost complete immediately after drying and the parameters characteristic of the physical and photographic properties have reached their final values.

Solche Materialien, deren rotempfindliche Silberhalogenidemulsionsschichten mit den üblichen sulfogruppenhaltigen Sensibilisatoren sensibilisiert sind, weisen einen Empfindlichkeitsrückgang auf, wenn vor der Belichtung Feuchtigkeit auf diese Materialien einwirkt (Feuchtefehler).Such materials, the red-sensitive silver halide emulsion layers of which are sensitized with the usual sulfo-containing sensitizers, have a decrease in sensitivity if moisture acts on these materials before exposure (moisture defects).

Der Erfindung lag die Aufgabe zugrunde, ein farbfotografisches Aufzeichnungsmaterial bereitzustellen, das unter Einsatz von Soforthärtern hergestellt wird, aber keinen Feuchtefehler zeigt.The invention was based on the object of providing a color photographic recording material which is produced using instant hardeners but does not show any moisture defects.

Es wurde nun überraschenderweise gefunden, daß sich diese Aufgabe dadurch lösen läßt, daß man die rotempfindlichen Schichten mit wenigstens einem speziellen Sensibilisator und wenigstens einem speziellen Potenzator sensibilisiert.It has now surprisingly been found that this problem can be solved by the red-sensitive Layers sensitized with at least one special sensitizer and at least one special potentizer.

Gegenstand der Erfindung ist daher ein farbfotographisches Aufzeichnungsmaterial der eingangs genannten Art, dessen wenigstens eine rotempfindliche Schicht mit wenigstens einer Verbindung der Formel I

Figure imgb0001

worin

R₅₃ und R₅₄
Alkyl, insbesondere C₁-C₄-Alkyl,
R₅₅, R₅₆, R₅₇ und R₅₈
Wasserstoff, Halogen Alkyl, insbesondere C₁-C₄-Alkyl, Alkoxy, insbesondere C₁-C₄-Alkoxy, einen Rest der Formel
Figure imgb0002
 Aryl, insbesondere Phenyl oder R₅₅ und R₅₆ gemeinsam, bzw. R₅₇ und R₅₈ gemeinsam eine Methylendioxygruppe oder die restlichen Glieder eines ankondensierten Benzolrings
R₅₉ und R₆₀
Alkyl, insbesondere C₁-C₄-Alkyl,
R₆₁
Wasserstoff oder Methyl,
X⊖
ein Anion, insbesondere Chlorid, Bromid, Iodid, Perchlorat oder p-Toluolsulfonat und
n
eine Zahl von 1 bis 5 bedeuten und
das Kation keine Sulfonsäuregruppen kovalent gebunden enthält,
und wenigstens einer Mercaptoverbindung des Oxazins, Oxazols, Thiazols, Thiadiazols, Imidazols oder Tetrazols, die durch ein Halogenatom, eine Sulfonsäure-, Sulfonamid-, Carboxyl-, Alkylsulfon- oder Phenylgruppe oder einen anellierten Benzolrest, der seinerseits durch die genannten Gruppen substituiert sein kann, substituiert sein kann (II), sensibilisiert sind.The invention therefore relates to a color photographic recording material of the type mentioned, the at least one red-sensitive layer with at least one compound of the formula I.
Figure imgb0001
wherein
R₅₃ and R₅₄
Alkyl, in particular C₁-C₄-alkyl,
R₅₅, R₅₆, R₅₇ and R₅₈
Hydrogen, halogen alkyl, especially C₁-C₄-alkyl, alkoxy, especially C₁-C₄-alkoxy, a radical of the formula
Figure imgb0002
 Aryl, especially phenyl or R₅₅ and R₅₆ together, or R₅₇ and R₅₈ together a methylenedioxy group or the remaining members of a fused benzene ring
R₅₉ and R₆₀
Alkyl, in particular C₁-C₄-alkyl,
R₆₁
Hydrogen or methyl,
X ⊖
an anion, in particular chloride, bromide, iodide, perchlorate or p-toluenesulfonate and
n
represent a number from 1 to 5 and
the cation does not contain any sulfonic acid groups covalently bound,
and at least one mercapto compound of oxazine, oxazole, thiazole, thiadiazole, imidazole or tetrazole, which can be substituted by a halogen atom, a sulfonic acid, sulfonamide, carboxyl, alkylsulfone or phenyl group or a fused benzene residue, which in turn can be substituted by the groups mentioned , may be substituted (II), are sensitized.

Die Verbindungen I (z.B. aus DE-A-35 10 968) und II (z.B. aus GB-A-1 108 745) sind bekannt. Bevorzugte Verbindungen II sind solche der Formel

Figure imgb0003

worin

Y
N-R₆₃, O oder S
R₆₂
Wasserstoff oder Halogen und
R₆₃
Wasserstoff oder C₁-C₄-Alkyl bedeuten.
The compounds I (for example from DE-A-35 10 968) and II (for example from GB-A-1 108 745) are known. Preferred compounds II are those of the formula
Figure imgb0003
wherein
Y
N-R₆₃, O or S
R₆₂
Hydrogen or halogen and
R₆₃
Is hydrogen or C₁-C₄ alkyl.

Der Sensibilisator I wird vorzugsweise in einer Menge von 0,05 bis 0,25, insbesondere 0,075 bis 0,20 mMol/Mol Ag, der Potenzator II vorzugsweise in einer Menge von 0,45 bis 3,00, insbesondere 0,70 bis 1,40 mMol/Mol Ag eingesetzt.The sensitizer I is preferably used in an amount of 0.05 to 0.25, in particular 0.075 to 0.20 mmol / mol Ag, the potentizer II in an amount of 0.45 to 3.00, in particular 0.70 to 1 , 40 mmol / mol Ag used.

Der Soforthärter wird bevorzugt in einer Menge von 0,1 bis 5 mMol/m², vorzugsweise von 0,5 bis 1,7 mMol/m² eingesetzt.The instant hardener is preferably used in an amount of 0.1 to 5 mmol / m², preferably 0.5 to 1.7 mmol / m².

Geeignete Beispiele für Sofort-Härtungsmittel sind Verbindungen der folgenden allgemeinen Formeln:

  • (a)
    Figure imgb0004
     worin
    R₁
    Alkyl, Aryl oder Aralkyl bedeutet,
    R₂
    die gleiche Bedeutung wie R₁ hat oder Alkylen, Arylen, Aralkylen oder Alkaralkylen bedeutet, wobei die zweite Bindung mit einer Gruppe der Formel
    Figure imgb0005
     verknüpft ist, oder
    R₁ und R₂
    zusammen die zur Vervollständigung eines gegebenenfalls substituierten heterocyclischen Ringes, beispielsweise eines Piperidin-, Piperazin- oder Morpholinringes erforderlichen Atome bedeuten, wobei der Ring z.B. durch C₁-C₃-Alkyl oder Halogen substituiert sein kann,
    R₃
    für Wasserstoff, Alkyl, Aryl, Alkoxy, -NR₄-COR₅, -(CH₂)m-NR₈R₉, -(CH₂)n-CONR₁₃R₁₄ oder
    Figure imgb0006
     oder ein Brückenglied oder eine direkte Bindung an eine Polymerkette steht, wobei
    R₄, R₆, R₇, R₉, R₁₄, R₁₅, R₁₇, R₁₈, und R₁₉
    Wasserstoff oder C₁-C₄-Alkyl,
    R₅
    Wasserstoff, C₁-C₄-Alkyl oder NR₆R₇,
    R₈
    -COR₁₀
    R₁₀
    NR₁₁R₁₂
    R₁₁
    C₁-C₄-Alkyl oder Aryl, insbesondere Phenyl,
    R₁₂
    Wasserstoff, C₁-C₄-Alkyl oder Aryl, insbesondere Phenyl,
    R₁₃
    Wasserstoff, C₁-C₄-Alkyl oder Aryl, insbesondere Phenyl,
    R₁₆
    Wasserstoff, C₁-C₄-Alkyl, COR₁₈ oder CONHR₁₉,
    m
    eine Zahl 1 bis 3
    n
    eine Zahl 0 bis 3
    o
    eine Zahl 1 oder 2
    p
    eine Zahl 2 bis 3 und
    Y
    0 oder NR₁₇ bedeuten oder
    R₁₃ und R₁₄
    gemeinsam die zur Vervollständigung eines gegebenenfalls substituierten heterocyclischen Ringes, beispielsweise eines Piperidin-, Piperazin- oder Morpholinringes erforderlichen Atome darstellen, wobei der Ring z.B. durch C₁-C₃-Alkyl oder Halogen substituiert sein kann,
    Z
    die zur Vervollständigung eines 5- oder 6-gliedrigen aromatischen heterocyclischen Ringes, gegebenenfalls mit anelliertem Benzolring, erforderlichen C-Atome und
    X⊖
    ein Anion bedeuten, das mit dem übrigen Molekül über eine kovalente Bindung verknüpft sein kann;
  • (b)
    Figure imgb0007
     worin
    R₁, R₂, R₃ und X⊖
    die für Formel (a) angegebene Bedeutung besitzen;
  • (c)
    Figure imgb0008
     worin
    R₂₀, R₂₁, R₂₂, R₂₃
    C₁-C₂₀-Alkyl, C₆-C₂₀-Aralkyl, C₅-C₂₀-Aryl, jeweils unsubstituiert oder durch Halogen, Sulfo, C₁-C₂₀-Alkoxy, N,N-Di-C₁-C₄-alkyl-substituiertes Carbamoyl und, im Falle von Aralkyl und Aryl durch C₁-C₂₀-Alkyl substituiert,
    R₂₄
    eine durch ein nucleophiles Agens abspaltbare Gruppe bedeuten und
    X⊖
    die für Formel (a) angegebene Bedeutung besitzt, wobei
    2 oder 4 der Substituenten R₂₀, R₂₁, R₂₂ und R₂₃ zusammen mit einem Stickstoffatom oder der Gruppe
    Figure imgb0009
     gegebenenfalls unter Einschluß weiterer Heteroatome wie O oder N auch zu einem oder zwei gesättigten, 5 - 7-gliedrigen Ringen vereint sein können;
  • (d)



            R₂₅―N=C=N―R₂₆



    worin
    R₂₅
    C₁-C₁₀-Alkyl, C₅-C₈-Cycloalkyl, C₃-C₁₀-Alkoxyalkyl oder C₇-C₁₅-Aralkyl bedeutet,
    R₂₆
    die Bedeutung von R₂₅ besitzt oder für einen Rest der Formel
    Figure imgb0010
     steht, wobei
    R₂₇
    C₂-C₄-Alkylen und
    R₂₈, R₂₉ und R₃₀
    C₁-C₆-Alkyl bedeuten, wobei einer der Reste R₂₈, R₂₉ und R₃₀ durch eine Carbamoylgruppe oder eine Sulfogruppe substituiert sein kann und zwei der Reste R₂₈, R₂₉ und R₃₀ zusammen mit dem Stickstoffatom zu einem gegebenenfalls substituierten heterocyclischen Ring, beispielsweise einen Pyrrolidin-, Piperazin- oder Morpholinring verknüpft sein können, wobei der Ring z.B. durch C₁-C₃-Alkyl oder Halogen substituiert sein kann, und
    X⊖
    die für Formel (a) angegebene Bedeutung besitzt;
  • (e)
    Figure imgb0011
     worin
    X⊖
    die für Formel (a) angegebene Bedeutung hat,
    R₂₄
    die für Formel (c) angegebene Bedeutung besitzt,
    R₃₁
    C₁-C₁₀-Alkyl, C₆-C₁₅-Aryl oder C₇-C₁₅-Aralkyl, jeweils unsubstituiert oder durch Carbamoyl, Sulfamoyl oder Sulfo substituiert,
    R₃₂ und R₃₃
    Wasserstoff, Halogen, Acylamino, Nitro, Carbamoyl, Ureido, Alkoxy, Alkyl, Alkenyl, Aryl oder Aralkyl oder gemeinsam die restlichen Glieder eines mit dem Pyridiniumring kondensierten Ringes, insbesondere eines Benzoringes, bedeuten,
    wobei
    R₂₄ und R₃₁ miteinander verknüpft sein können, wenn R₂₄ eine Sulfonyloxygruppe ist;
  • (f)
    Figure imgb0012
     worin
    R₁, R₂ und X⊖
    die für Formel (a) angegebene Bedeutung besitzen und
    R₃₄
    C₁-C₁₀-Alkyl, C₆-C₁₄-Aryl oder C₇-C₁₅-Aralkyl bedeutet;
  • (g)
    Figure imgb0013
     worin
    R₁, R₂ und X⊖
    die für Formel (a) angegebene Bedeutung besitzen,
    R₃₅
    Wasserstoff, Alkyl, Aralkyl, Aryl, Alkenyl, R₃₈O-, R₃₉R₄₀N, R₄₁R₄₂C=N- oder R₃₈S-,
    R₃₆ und R₃₇
    Alkyl,Aralkyl, Aryl, Alkenyl,
    Figure imgb0014
     R₄₄-SO₂ oder R₄₅-N=N- oder gemeinsam mit dem Stickstoffatom die restlichen Glieder eines heterocyclischen Ringes oder die Gruppierung
    Figure imgb0015
    R₃₈, R₃₉, R₄₀, R₄₁, R₄₂, R₄₃, R₄₄ und R₄₅
    Alkyl, Aralkyl, Alkenyl, R₄₁ und R₄₂ darüberhinaus Wasserstoff, R₃₉ und R₄₀ bzw. R₄₁ und R₄₂ darüberhinaus die restlichen Glieder eines 5-oder 6-gliedrigen, gesättigten carbocyclischen oder heterocyclischen Ringes bedeuten;
  • (h)
    Figure imgb0016
     worin
    R₄₆
    Wasserstoff, Alkyl oder Aryl
    R₄₇
    Acyl, Carbalkoxy, Carbamoyl oder Aryloxycarbonyl;
    R₄₈
    Wasserstoff oder R₄₇
    R₄₉ und R₅₀
    Alkyl, Aryl, Aralkyl oder gemeinsam mit dem Stickstoffatom die restlichen Glieder eines gegebenenfalls substituierten heterocyclischen Ringes, beispielsweise eines Piperidin-, Piperazin- oder Morpholinringes bedeuten, wobei der Ring z.B. durch C₁-C₃-Alkyl oder Halogen substituiert sein kann, und
    X⊖
    die für Formel (a) angegebene Bedeutung besitzt;
  • (i)
    Figure imgb0017
     worin
    R₅₁
    einen gegebenenfalls substituierten heteroaromatischen Ring, der mindestens q Ring-C-Atome und mindestens ein Ring-O-, Ring-S- oder Ring-N-Atom enthält, und
    q
    eine ganze Zahl ≧ 2 bedeuten.
Suitable examples of instant hardeners are compounds of the following general formulas:
  • (a)
    Figure imgb0004
     wherein
    R₁
    Means alkyl, aryl or aralkyl,
    R₂
    has the same meaning as R₁ or means alkylene, arylene, aralkylene or alkaralkylene, the second bond having a group of the formula
    Figure imgb0005
     is linked, or
    R₁ and R₂
    together those to complete an optionally substituted heterocyclic Ring, for example a piperidine, piperazine or morpholine ring mean necessary atoms, which ring can be substituted, for example by C₁-C₃-alkyl or halogen,
    R₃
    for hydrogen, alkyl, aryl, alkoxy, -NR₄-COR₅, - (CH₂) m -NR₈R₉, - (CH₂) n -CONR₁₃R₁₄ or
    Figure imgb0006
     or a bridge link or a direct bond to a polymer chain, wherein
    R₄, R₆, R₇, R₉, R₁₄, R₁₅, R₁₇, R₁₈, and R₁₉
    Hydrogen or C₁-C₄-alkyl,
    R₅
    Hydrogen, C₁-C₄-alkyl or NR₆R₇,
    R₈
    -COR₁₀
    R₁₀
    NR₁₁R₁₂
    R₁₁
    C₁-C₄ alkyl or aryl, especially phenyl,
    R₁₂
    Hydrogen, C₁-C₄ alkyl or aryl, especially phenyl,
    R₁₃
    Hydrogen, C₁-C₄ alkyl or aryl, especially phenyl,
    R₁₆
    Hydrogen, C₁-C₄-alkyl, COR₁₈ or CONHR₁₉,
    m
    a number 1 to 3
    n
    a number 0 to 3
    O
    a number 1 or 2
    p
    a number 2 to 3 and
    Y
    0 or NR₁₇ mean or
    R₁₃ and R₁₄
    together represent the atoms required to complete an optionally substituted heterocyclic ring, for example a piperidine, piperazine or morpholine ring, which ring may be substituted, for example, by C₁-C₃alkyl or halogen,
    Z
    the carbon atoms required to complete a 5- or 6-membered aromatic heterocyclic ring, optionally with a fused benzene ring, and
    X ⊖
    mean an anion which can be linked to the rest of the molecule via a covalent bond;
  • (b)
    Figure imgb0007
     wherein
    R₁, R₂, R₃ and X ⊖
    have the meaning given for formula (a);
  • (c)
    Figure imgb0008
     wherein
    R₂₀, R₂₁, R₂₂, R₂₃
    C₁-C₂₀-alkyl, C₆-C₂₀-aralkyl, C₅-C₂₀-aryl, each unsubstituted or by halogen, sulfo, C₁-C₂₀-alkoxy, N, N-di-C₁-C₄-alkyl-substituted carbamoyl and, in the case of aralkyl and aryl substituted by C₁-C₂₀ alkyl,
    R₂₄
    mean a group which can be split off by a nucleophilic agent and
    X ⊖
    has the meaning given for formula (a), where
    2 or 4 of the substituents R₂₀, R₂₁, R₂₂ and R₂₃ together with a nitrogen atom or the group
    Figure imgb0009
     optionally including other heteroatoms such as O or N, can also be combined to form one or two saturated, 5- to 7-membered rings;
  • (d)



    R₂₅ ― N = C = N ― R₂₆



    wherein
    R₂₅
    Is C₁-C₁₀ alkyl, C₅-C₈ cycloalkyl, C₃-C₁₀ alkoxyalkyl or C₇-C₁₅ aralkyl,
    R₂₆
    has the meaning of R₂₅ or for a radical of the formula
    Figure imgb0010
     stands where
    R₂₇
    C₂-C₄ alkylene and
    R₂₈, R₂₉ and R₃₀
    C₁-C₆-alkyl, where one of the radicals R₂₈, R₂₉ and R₃₀ can be substituted by a carbamoyl group or a sulfo group and two of the radicals R₂₈, R₂₉ and R₃₀ together with the nitrogen atom to form an optionally substituted heterocyclic ring, for example a pyrrolidine, Piperazine or morpholine ring can be linked, the ring can be substituted, for example, by C₁-C₃-alkyl or halogen, and
    X ⊖
    has the meaning given for formula (a);
  • (e)
    Figure imgb0011
     wherein
    X ⊖
    has the meaning given for formula (a),
    R₂₄
    has the meaning given for formula (c),
    R₃₁
    C₁-C₁₀-alkyl, C₆-C₁₅-aryl or C₇-C₁₅-aralkyl, in each case unsubstituted or substituted by carbamoyl, sulfamoyl or sulfo,
    R₃₂ and R₃₃
    Are hydrogen, halogen, acylamino, nitro, carbamoyl, ureido, alkoxy, alkyl, alkenyl, aryl or aralkyl or together the remaining members of a ring condensed with the pyridinium ring, in particular a benzo ring,
    in which
    R₂₄ and R₃₁ can be linked when R₂₄ is a sulfonyloxy group;
  • (f)
    Figure imgb0012
     wherein
    R₁, R₂ and X ⊖
    have the meaning given for formula (a) and
    R₃₄
    Is C₁-C₁₀ alkyl, C₆-C₁₄ aryl or C₇-C₁₅ aralkyl;
  • (G)
    Figure imgb0013
     wherein
    R₁, R₂ and X ⊖
    have the meaning given for formula (a),
    R₃₅
    Hydrogen, alkyl, aralkyl, aryl, alkenyl, R₃₈O-, R₃₉R₄₀N, R₄₁R₄₂C = N- or R₃₈S-,
    R₃₆ and R₃₇
    Alkyl, aralkyl, aryl, alkenyl,
    Figure imgb0014
     R₄₄-SO₂ or R₄₅-N = N- or together with the nitrogen atom the remaining members of a heterocyclic ring or the grouping
    Figure imgb0015
    R₃₈, R₃₉, R₄₀, R₄₁, R₄₂, R₄₃, R₄₄ and R₄₅
    Alkyl, aralkyl, alkenyl, R₄₁ and R₄₂ furthermore represent hydrogen, R₃₉ and R₄₀ or R₄₁ and R₄₂ furthermore the remaining members of a 5-or 6-membered, saturated carbocyclic or heterocyclic ring;
  • (H)
    Figure imgb0016
     wherein
    R₄₆
    Hydrogen, alkyl or aryl
    R₄₇
    Acyl, carbalkoxy, carbamoyl or aryloxycarbonyl;
    R₄₈
    Hydrogen or R₄₇
    R₄₉ and R₅₀
    Alkyl, aryl, aralkyl or together with the nitrogen atom mean the remaining members of an optionally substituted heterocyclic ring, for example a piperidine, piperazine or morpholine ring, which ring can be substituted, for example, by C₁-C₃-alkyl or halogen, and
    X ⊖
    has the meaning given for formula (a);
  • (i)
    Figure imgb0017
     wherein
    R₅₁
    an optionally substituted heteroaromatic ring which contains at least q ring C atoms and at least one ring O, ring S or ring N atom, and
    q
    is an integer ≧ 2.

Der durch R₅₁ dargestellte heteroaromatische Ring ist beispielsweise ein Triazol-, Thiadiazol-, Oxadiazol-, Pyridin-, Pyrrol-, Chinoxalin-, Thiophen-, Furan-, Pyrimidin- oder Triazinring. Er kann außer den mindestens zwei Vinylsulfonylgruppen gegebenenfalls weitere Substituenten sowie gegebenenfalls ankondensierte Benzolringe enthalten, die ihrerseits ebenfalls substituiert sein können. Beispiele von heteroaromatischen Ringen (R₅₁) sind im folgenden aufgeführt.

Figure imgb0018

worin

r
eine Zahl 0 bis 3 und
R₅₂
C₁-C₄-Alkyl, C₁-C₄-Alkoxy oder Phenyl bedeutet.
The heteroaromatic ring represented by R₅₁ is, for example, a triazole, thiadiazole, oxadiazole, pyridine, pyrrole, quinoxaline, thiophene, furan, pyrimidine or triazine ring. In addition to the at least two vinylsulfonyl groups, it may optionally contain further substituents and optionally fused-on benzene rings, which in turn may also be substituted. Examples of heteroaromatic rings (R₅₁) are listed below.
Figure imgb0018
wherein
r
a number 0 to 3 and
R₅₂
C₁-C₄ alkyl, C₁-C₄ alkoxy or phenyl.

Als Soforthärtungsmittel eignen sich schließlich die in den japanischen Offenlegungsschriften 38 540/75, 93 470/77, 43 353/81 und 113 929/83 sowie in der US-PS 3 321 313 beschriebenen Verbindungen.Finally, the compounds described in Japanese Patent Laid-Open Nos. 38 540/75, 93 470/77, 43 353/81 and 113 929/83 and in US Pat. No. 3,321,313 are suitable as immediate hardening agents.

Alkyl, sofern nicht anders definiert, ist insbesondere gegebenenfalls durch Halogen, Hydroxy, Sulfo, C₁-C₂₀-Alkoxy substituiertes C₁-C₂₀-Alkyl.Unless otherwise defined, alkyl is in particular C₁-C₂ Hydrox-alkyl optionally substituted by halogen, hydroxy, sulfo, C₁-C₂₀-alkoxy.

Aryl, sofern nicht anders definiert, ist insbesondere gegebenenfalls durch Halogen, Sulfo, C₁-C₂₀-Alkoxy oder C₁-C₂₀-Alkyl substituiertes C₆-C₁₄-Aryl. Aralkyl, sofern nicht anders definiert, ist insbesondere durch Halogen, C₁-C₂₀-Alkoxy, Sulfo oder C₁-C₂₀-Alkyl substituiertes C₇-C₂₀-Aralkyl. Alkoxy, sofern nicht anders definiert, ist insbesondere C₁-C₂₀-Alkoxy.Aryl, unless otherwise defined, is in particular optionally substituted by halogen, sulfo, C₁-C₂₀-alkoxy or C₁-C₂₀-alkyl C₆-C₁₄-aryl. Aralkyl, unless otherwise defined, is in particular C Halogen-C₂₀-aralkyl substituted by halogen, C₁-C₂₀-alkoxy, sulfo or C₁-C₂₀-alkyl. Alkoxy, unless otherwise defined, is in particular C₁-C₂₀ alkoxy.

X⊖ ist vorzugsweise ein Halogenidion wie Cl⊖, Br⊖ oder BF₄⊖, NO₃⊖, (SO₄²⊖)1/2, ClO₄⊖, CH₃OSO₃⊖, PF₆⊖, CF₃SO₃⊖ und insbesondere eine mit dem Härtermolekül kovalent verknüpfte -SO₃⊖-Gruppe, wobei die -SO₃⊖-Gruppe über einen Substituenten (s. Definitionen Alkyl, Aryl, Aralkyl) oder in den Formeln (a), (b), (c) mit dem Heterocyclus direkt verbunden sein kann.X ⊖ is preferably a halide ion such as Cl ⊖ , Br ⊖ or BF₄ ⊖ , NO₃ ⊖ , (SO₄² ⊖ ) 1/2 , ClO₄ ⊖ , CH₃OSO₃ ⊖ , PF₆ ⊖ , CF₃SO₃ ⊖ and in particular a -SO₃ ⊖ - covalently linked to the hardener molecule Group, where the -SO₃ ⊖ group can be directly connected to the heterocycle via a substituent (see definitions alkyl, aryl, aralkyl) or in the formulas (a), (b), (c).

Alkenyl ist insbesondere C₂-C₂₀-Alkenyl. Alkylen ist insbesondere C₂-C₂₀-Alkylen; Arylen insbesondere Phenylen, Aralkylen insbesondere Benzylen und Alkaralkylen insbesondere Xylylen.Alkenyl is especially C₂-C₂₀ alkenyl. Alkylene is especially C₂-C₂₀ alkylene; Arylene especially phenylene, aralkylene especially benzylene and alkaralkylene especially xylylene.

Geeignete N-haltige Ringsysteme, die für Z stehen können, sind auf der vorigen Seite dargestellt. Bevorzugt ist der Pyridinring.Suitable N-containing ring systems that can represent Z are shown on the previous page. The pyridine ring is preferred.

R₃₆ und R₃₇ bilden zusammen mit dem Stickstoffatom, an das sie gebunden sind, insbesondere einen durch 2 in o-und o′-Stellung gebundene Oxogruppen substituierten Pyrrolidin- oder Piperidinring, der benzo-, cyclohexeno- oder [2.1.1]-bicyclohexenokondensiert sein kann.R₃₆ and R₃₇ together with the nitrogen atom to which they are bonded, in particular form a pyrrolidine or piperidine ring substituted by 2 oxo groups bonded in the o- and o'-position, and the benzo, cyclohexeno- or [2.1.1] -bicyclohexeno-condensed can.

Acyl ist insbesondere C₁-C₁₀-Alkylcarbonyl oder Benzoyl; Carbalkoxy ist insbesondere C₁-C₁₀-Alkoxycarbonyl; Carbamoyl ist insbesondere Mono- oder Di-C₁-C₄-Alkylaminocarbonyl; Carbaroxy ist insbesondere Phenoxycarbonyl.Acyl is especially C₁-C₁₀ alkylcarbonyl or benzoyl; Carbalkoxy is especially C₁-C₁₀ alkoxycarbonyl; Carbamoyl is especially mono- or di-C₁-C₄ alkylaminocarbonyl; Carbaroxy is especially phenoxycarbonyl.

Durch nucleophile Agentien abspaltbare Gruppen R₂₄ sind beispielsweise Halogenatome, C₁-C₁₅-Alkylsulfonyloxygruppen, C₇-C₁₅-Aralkylsulfonyloxygruppen, C₆-C₁₅-Arylsulfonyloxygruppen und 1-Pyridinylreste.Groups R₂₄ which can be split off by nucleophilic agents are, for example, halogen atoms, C₁-C₁₅ alkylsulfonyloxy groups, C₇-C₁₅ aralkylsulfonyloxy groups, C₆-C₁₅ arylsulfonyloxy groups and 1-pyridinyl radicals.

Nachfolgend sind bevorzugte Härter aufgeführt:Preferred hardeners are listed below:

Verbindungen der Formel (a)Compounds of formula (a)

Figure imgb0019
Figure imgb0019
Figure imgb0020
Figure imgb0020
Figure imgb0021
Figure imgb0021
Figure imgb0022
Figure imgb0022
Figure imgb0023
Figure imgb0023
Figure imgb0024
Figure imgb0024
Figure imgb0025
Figure imgb0025
Figure imgb0026
Figure imgb0026
Figure imgb0027
Figure imgb0027
Figure imgb0028
Figure imgb0028
Figure imgb0029
Figure imgb0029

Die Verbindungen sind in einfacher und aus der Literatur bekannter Weise darstellbar. Aus den sekundären Aminen stellt man z.B. mit Phosgen die Carbaminsäurechloride her, die dann unter Lichtabschluß mit aromatischen, heterocyclischen stickstoffhaltigen Verbindungen umgesetzt werden. Die Herstellung der Verbindung 3 wird in den Chemischen Berichten 40, (1907), Seite 1831, beschrieben. Weitere Angaben zur Synthese finden sich in DE-OS 2 225 230, DE-OS 2 317 677 und DE-OS 2 439 551.The compounds can be prepared in a simple manner known from the literature. The secondary amines are e.g. with phosgene the carbamic acid chlorides, which are then reacted with aromatic, heterocyclic nitrogen-containing compounds in the dark. The preparation of compound 3 is described in Chemical Reports 40, (1907), page 1831. Further information on the synthesis can be found in DE-OS 2 225 230, DE-OS 2 317 677 and DE-OS 2 439 551.

Verbindungen der Formel (b)Compounds of formula (b)

Verfahren zur Synthese dieser Verbindungen sind beispielsweise in der DE-A 2 408 814 beschrieben:

Figure imgb0030
Figure imgb0031
 Methods for the synthesis of these compounds are described, for example, in DE-A 2 408 814:
Figure imgb0030
Figure imgb0031

Verbindungen der Formel (c)Compounds of formula (c)

Methoden zur Synthese dieser Verbindungen werden genauer beschrieben in Chemistry Letters (The Chemical Society of Japan), Seite 1891-1984 (1982). Weitere Angaben zur Synthese finden sich auch in der EP-A-162 308.

Figure imgb0032
Figure imgb0033
 Methods for the synthesis of these compounds are described in more detail in Chemistry Letters (The Chemical Society of Japan), pages 1891-1984 (1982). Further information on the synthesis can also be found in EP-A-162 308.
Figure imgb0032
Figure imgb0033

Verbindungen der Formel (d)Compounds of formula (d)

Methoden zur Synthese dieser Verbindungen werden genauer beschrieben in den JP-OS'en 126 125/76 und 48 311/77.

Figure imgb0034
Figure imgb0035
 Methods for the synthesis of these compounds are described in more detail in JP-OSs 126 125/76 and 48 311/77.
Figure imgb0034
Figure imgb0035

Verbindungen der Formel (e)Compounds of formula (e)

Methoden zur Synthese dieser Verbindungen werden genauer beschrieben in den JP-OS'en 44 140/82 und 46 538/82 und der JP-PS 50 669/83.

Figure imgb0036
Figure imgb0037
 Methods for the synthesis of these compounds are described in more detail in JP-OSs 44 140/82 and 46 538/82 and JP-PS 50 669/83.
Figure imgb0036
Figure imgb0037

Verbindungen der Formel (f)Compounds of formula (f)

Methode zur Synthese dieser Verbindungen werden genauer beschrieben in der JP-OS 54 427/77.

Figure imgb0038
Methods for the synthesis of these compounds are described in more detail in JP-OS 54 427/77.
Figure imgb0038

Verbindungen der Formel (g)Compounds of formula (g)

Die Synthese dieser Verbindungen ist in US-PS 4 612 280 beschrieben.

Figure imgb0039
Figure imgb0040
Figure imgb0041
Figure imgb0042
Figure imgb0043
 The synthesis of these compounds is described in U.S. Patent 4,612,280.
Figure imgb0039
Figure imgb0040
Figure imgb0041
Figure imgb0042
Figure imgb0043

Verbindungen der Formeln (h)Compounds of the formulas (h)

Die Herstellung dieser Verbindungen ist in der DD 232 564 A 1 beschrieben.

Figure imgb0044
Figure imgb0045
 The preparation of these compounds is described in DD 232 564 A1.
Figure imgb0044
Figure imgb0045

Verbindungen der Formel (i)Compounds of formula (i)

Methoden zur Herstellung dieser Verbindungen sind in DE-OS 35 23 360 beschrieben.

Figure imgb0046
Methods for the preparation of these compounds are described in DE-OS 35 23 360.
Figure imgb0046

Weitere geeignete Soforthärtungsmittel entsprechen folgenden Formeln

Figure imgb0047
Figure imgb0048
Figure imgb0049
Figure imgb0050
Die Verbindungen (a) sind besonders bevorzugt.Other suitable instant hardeners correspond to the following formulas
Figure imgb0047
Figure imgb0048
Figure imgb0049
Figure imgb0050
The compounds (a) are particularly preferred.

Das verwendete zu härtende Bindemittel in den Schichten, die dem erfindungsgemäßen Härtungsverfahren unterworfen werden, ist ein porteinartiges Bindemittel, das freie Aminogruppen und freie Carboxylgruppen enthält. Gelatine ist ein bevorzugtes Beispiel. In fotografischen Aufzeichnungsmaterialien wird hauptsächlich Gelatine als Bindemittel für die lichtempfindlichen Substanzen, die farbgebenden Verbindungen und gegebenenfalls weitere Zusätze verwendet. Häufig weisen solche Aufzeichnungsmaterialien eine Vielzahl verschiedener Schichten auf. Die Härtung mittels Soforthärter wird meist in der Weise durchgeführt, daß das Härtungsmittel im Überschuß als letzte Schicht auf die zu härtenden Schichten aufgetragen wird, wobei der Härtungsbeschichtungslösung weitere Substanzen, wie UV-Absorber, Antistatika, Mattierungsmittel und polymere organische Teilchen zugesetzt werden können.The binder to be cured used in the layers which are subjected to the curing process according to the invention is a porten-like binder which contains free amino groups and free carboxyl groups. Gelatin is a preferred example. Gelatin is mainly used in photographic recording materials as a binder for the light-sensitive substances, the coloring compounds and, if appropriate, other additives. Such recording materials often have a large number of different layers. The hardening by means of an instant hardener is usually carried out in such a way that the hardening agent is applied in excess as the last layer on the layers to be hardened is, wherein the hardening coating solution further substances such as UV absorbers, antistatic agents, matting agents and polymeric organic particles can be added.

Das Auftragen der das Härtungsmittel enthaltenden Schicht kann gleichzeitig mit oder nach dem Guß der übrigen Schichten mittels Kaskaden- oder Vorhanggießern erfolgen. Die Gießtemperatur kann dabei in weiten Bereichen variiert werden, z. B. zwischen 45 und 5°C vorzugsweise zwischen 38 und 18°C.The layer containing the hardening agent can be applied simultaneously with or after the casting of the remaining layers by means of cascade or curtain coaters. The casting temperature can be varied over a wide range, e.g. B. between 45 and 5 ° C, preferably between 38 and 18 ° C.

Die Schichtdicke des Härtungsbegusses liegt beispielsweise zwischen 0,2 und 2,5 µm. Weiter Zusätze wie UV-Absorber, Farbkorrekturfarbstoffe, Antistatika und anorganische oder organische feste Teilchen, die beispielsweise als Mattierungsmittel oder Abstandshalter verwendet werden, können der härtungsmittelhaltigen Schicht zugesetzt sein. Geeignete UV-Absorber sind beispielsweise in US-A-3 253 921, DE-C-20 36 719 und EP-A-0 057 160 beschrieben.The layer thickness of the hardening casting is, for example, between 0.2 and 2.5 µm. Other additives such as UV absorbers, color correction dyes, antistatic agents and inorganic or organic solid particles, which are used, for example, as matting agents or spacers, can be added to the hardener-containing layer. Suitable UV absorbers are described, for example, in US Pat. No. 3,253,921, DE-C-20 36 719 and EP-A-0 057 160.

Als anorganische feste Teilchen eignen sich beispielsweise Siliziumdioxid, Magnesiumdioxid, Titandioxid und Calciumcarbonat. Solche Materialien werden vielfach verwendet um die äußersten Schichten von fotografischen Aufzeichnungsmaterialien zu mattieren und auf diese Weise ihre Klebrigkeit zu vermindern. Auch fest Teilchen organischer Natur, die alkalilöslich oder alkaliunlöslich sein können, eignen sich für diesen Zweck. Durch solche Teilchen, auch als Abstandshalter bezeichnet, wird in der Regel die Oberfläche aufgerauht, so daß hierdurch die Oberflächeneigenschaften, insbesondere die Haft- bzw. Gleiteigenschaften modifiziert werden können. Polymethylmethacrylat ist ein Beispiel für alkaliunlösliche Abstandshalter. Alkalilösliche Abstandshalter sind beispielsweise in DE-A-34 24 893 beschrieben. Auch teilchenförmige organische Polymere mit reaktiven Gruppen, insbesondere solchen reaktiven Gruppen, die mit dem Bindemittel reagieren, wie beispielsweise in DE-A-35 44 212 beschrieben, können als sogenannte Hartmacher zugefügt werden.Examples of suitable inorganic solid particles are silicon dioxide, magnesium dioxide, titanium dioxide and calcium carbonate. Such materials are widely used to matt the outermost layers of photographic recording materials and thus reduce their stickiness. Also solid particles Organic in nature, which can be alkali-soluble or alkali-insoluble, are suitable for this purpose. Such particles, also referred to as spacers, generally roughen the surface, so that the surface properties, in particular the adhesive or sliding properties, can be modified thereby. Polymethyl methacrylate is an example of alkali-insoluble spacers. Alkali-soluble spacers are described, for example, in DE-A-34 24 893. Particulate organic polymers with reactive groups, in particular those reactive groups which react with the binder, as described, for example, in DE-A-35 44 212, can also be added as so-called hardeners.

Um der Gießlösung für die härtungsmittelhaltige Teilschicht, die vergleichsweise wenig oder gar kein Bindemittel enthält, die erforderliche Gießviskosität zu verleihen, ist es zweckmäßig ihr Verdickungsmittel wie Polystyrolsulfonsäure oder Hydroxyethylcellulose zuzusetzen.In order to impart the required casting viscosity to the casting solution for the hardener-containing partial layer, which contains comparatively little or no binding agent, it is expedient to add its thickening agent, such as polystyrene sulfonic acid or hydroxyethyl cellulose.

Bei den farbfotografischen Aufzeichnungsmaterialien, gemäß vorliegender Erfindung handelt es sich um mehrschichtige Materialien, die mehrere Silberhalogenidemulsionsschichten oder Emulsionsschichteneinheiten mit unterschiedlicher Spektralempfindlichkeit aufweisen. Als Emulsionsschichteneinheit werden dabei Schichtpakete von 2 oder mehr Silberhalogenidemulsionsschichten gleicher Spektralempfindlichkeit verstanden. Schichten gleicher Spektralempfindlichkeit müssen aber nicht notwendigerweise benachbart zueinander angeordnet sein, sondern können auch durch andere Schichten, insbesondere auch durch Schichten anderer Spektralempfindlichkeit voneinander getrennt sein. Das Bindemittel in diesen Schichten ist in der Regel ein proteinartiges Bindemittel mit freien Carboxylgruppen und freien Aminogruppen, bevorzugt Gelatine. Das Schichtbindemittel kann aber neben dem proteinartigen Bindemittel bis zu 50 Gew.-% nicht proteinartige Bindemittel wie Polyvinylalkohol, N-Vinylpyrrolidon, Polyacrylsäure und deren Derivate, insbesondere Mischpolymerisate, oder Cellulosederivate sowie Gelatinederivate enthalten.The color photographic recording materials according to the present invention are multilayer materials which have a plurality of silver halide emulsion layers or emulsion layer units with different spectral sensitivity. In this case, the emulsion layer unit is understood to mean layer packages of 2 or more silver halide emulsion layers of the same spectral sensitivity. Layers of the same However, spectral sensitivity does not necessarily have to be arranged adjacent to one another, but can also be separated from one another by other layers, in particular also by layers of different spectral sensitivity. The binder in these layers is usually a protein-like binder with free carboxyl groups and free amino groups, preferably gelatin. In addition to the proteinaceous binder, the layered binder can contain up to 50% by weight of non-proteinaceous binders such as polyvinyl alcohol, N-vinylpyrrolidone, polyacrylic acid and their derivatives, in particular copolymers, or cellulose derivatives and gelatin derivatives.

In farbfotografischen Aufzeichungsmaterialien ist jeder der genannten lichtempfindlichen Silberhalogenidemulsionsschichten bzw. Emulsionsschichteneinheiten mindestens eine farbgebende Verbindung, in der Regel ein Farbkuppler, zugeordnet, die mit Farbentwickleroxidationsprodukten unter Bildung eines nichtdiffundierenden Farbstoffes zu reagieren vermag. Zweckmäßigerweise sind die Farbkuppler nichtdiffundierend und in der lichtempfindlichen Schicht selbst oder in enger Nachbarschaft hierzu untergebracht. Die den zwei oder mehr Teilschichten einer Emulsionsschichteneinheit zugeordneten Farbkuppler brauchen nicht notwendigerweise identisch zu sein. Sie sollen lediglich bei der Farbentwicklung die gleiche Farbe ergeben, normalerweise eine Farbe, die komplementär ist zu der Farbe des Lichtes, gegen das die lichtempfindlichen Silberhalogenidemulsionsschichten empfindlich sind.In color photographic recording materials, each of the light-sensitive silver halide emulsion layers or emulsion layer units mentioned is assigned at least one color-imparting compound, usually a color coupler, which can react with color developer oxidation products to form a non-diffusing dye. The color couplers are expediently non-diffusing and accommodated in the light-sensitive layer itself or in close proximity to it. The color couplers assigned to the two or more partial layers of an emulsion layer unit do not necessarily have to be identical. They are only intended to give the same color in color development, usually a color that is complementary to the color of the light to which the photosensitive silver halide emulsion layers are sensitive.

Den rotempfindlichen Silberhalgenidemulsionsschichten ist folglich mindestens ein nichtdiffundierender Farbkuppler zur Erzeugung des blaugrünen Teilfarbenbildes zugeordnet, in der Regel ein Kuppler vom Phenol- oder α-Naphtholtyp. Besonders hervorzuheben sind beispielsweise Blaugrünkuppler, wie sie beschrieben sind in US-A-2 474 293, US-A-2 367 531, US-A-2 895 826, US-A-3 772 002, EP-A-0 028 099, EP-A-0 112 514.Consequently, the red-sensitive silver halide emulsion layers are assigned at least one non-diffusing color coupler for producing the blue-green partial color image, usually a coupler of the phenol or α-naphthol type. Particularly noteworthy are, for example, cyan couplers as described in US-A-2,474,293, US-A-2,367,531, US-A-2,895,826, US-A-3,772,002, EP-A-0 028 099 , EP-A-0 112 514.

Den grünempfindlichen Silberhalogenidemulsionsschichten ist in der Regel mindestens ein nichtdiffundierender Farbkuppler zur Erzeugung des purpurnen Teilfarbbildes zugeordnet, wobei üblicherweise Farbkuppler vom Typ des 5-Pyrazolons oder des Indazolons Verwendung finden. Weiter kommen als Purpurkuppler auch Cyanacetylverbindungen, Oxazolone, und Pyrazoloazole in Frage. Besonders hervorzuheben sind beispielsweise Purpurkuppler, wie sie in US-A-2 600 788, US-A-4 383 027, DE-A-1 547 803, DE-A-1 810 464, DE-A-24 08 665, DE-A-32 26 163 beschrieben sind.The green-sensitive silver halide emulsion layers are generally assigned at least one non-diffusing color coupler for producing the purple partial color image, color couplers of the 5-pyrazolone or indazolone type usually being used. Cyanoacetyl compounds, oxazolones and pyrazoloazoles are also suitable as magenta couplers. Particularly noteworthy are, for example, purple couplers, as described in US Pat. Nos. 2,600,788, 4,383,027, 1,547,803, 1,810,464, 24,066,665, DE -A-32 26 163 are described.

Den blauempfindlichen Silberhalogenidemulsionschichten schließlich ist normalerweise mindestens ein nichtdiffundierender Farbkuppler zur Erzeugung des gelben Teilfarbenbildes zugeordnet, in der Regel ein Farbkuppler mit einer offenkettigen Ketomethylengruppierung. Besonders hervorzuheben sind beispielsweise Gelbkuppler, wie sie in US-A-3 408 194, US-A-3 933 501, DE-A-23 29 587, DE-A-24 56 976 beschrieben sind.Finally, the blue-sensitive silver halide emulsion layers are normally assigned at least one non-diffusing color coupler to produce the yellow partial color image, usually a color coupler with an open-chain ketomethylene grouping. Particularly noteworthy are, for example, yellow couplers as described in US Pat. No. 3,408,194, US Pat. No. 3,933,501, DE-A-23 29 587, DE-A-24 56 976.

Farbkuppler dieser Arten sind in großer Zahl bekannt und in einer Vielzahl von Patentschriften beschrieben. Beispielhaft sei hier ferner auf die Veröffentlichungen "Farbkuppler" von W. Pelz, "Mitteilungen aus den Forschungslaboratorien der Agfa, Leverkusen/München", Band III (1961) S. 111, und von K. Venkataraman in "The Chemistry of Synthetic Dyes", Vol. 4., 341 bis 387, Academic Press (1971), verwiesen.Color couplers of these types are known in large numbers and are described in a large number of patents. Examples include the publications "Color Coupler" by W. Pelz, "Messages from the research laboratories of Agfa, Leverkusen / Munich", Volume III (1961) p. 111, and by K. Venkataraman in "The Chemistry of Synthetic Dyes" , Vol. 4., 341 to 387, Academic Press (1971).

Bei den Farbkupplern kann es sich um 4-Äquivalentkuppler, aber auch um 2-Äquivalentkuppler handeln. Letztere leiten sich bekanntlich von den 4-Äquivalentkupplern dadurch ab, daß sie in der Kupplungsstelle einen Substituenten enthalten, der bei der Kupplung abgespalten wird. Zu den 2-Äquivalentkupplern sind sowohl solche zu rechnen, die praktisch farblos sind, als auch solche, die eine intensive Eigenfarbe aufweisen, die bei der Farbkupplung verschwindet bzw. durch die Farbe des erzeugten Bildfarbstoffes ersetzt wird (Maskenkuppler). Zu den 2-Äquivalentkupplern sind im Prinzip auch die bekannten Weißkuppler zu rechnen, die jedoch bei Reaktion mit Farbentwickleroxidationsprodukten im wesentlichen farblose Produkte ergeben. Zu den 2-Äquvivalentkupplern sind ferner solche Kuppler zu rechnen, die in der Kupplungsstelle einen abspaltbaren Rest enthalten, der bei Reaktion mit Farbentwickleroxidationsprodukten in Freiheit gesetzt wird und dabei entweder direkt oder nachdem aus dem primär abgespaltenen Rest eine oder mehrere weitere Gruppen abgespalten worden sind (z.B. DE-A-27 03 145, DE-A-28 55 697, DE-A-31 05 026, DE-A-33 19 428), eine bestimmte erwünschte fotografische Wirksamkeit entfaltet, z.B. als Entwicklungsinhibitor oder -accelerator. Beispiele für solche 2-Äquivalentkuppler sind die bekannten DIR-Kuppler wie auch DAR- bzw. FAR-Kuppler.The color couplers can be 4-equivalent couplers, but also 2-equivalent couplers. As is known, the latter are derived from the 4-equivalent couplers in that they contain a substituent in the coupling site which is split off during the coupling. The 2-equivalent couplers include both those that are practically colorless and those that have an intense intrinsic color that disappears when the color is coupled or is replaced by the color of the image dye produced (mask coupler). In principle, the known white couplers are also to be counted among the 2-equivalent couplers, but they essentially result in colorless products on reaction with color developer oxidation products. The 2-equivalent couplers also include those couplers which contain a cleavable residue in the coupling site, which is released upon reaction with color developer oxidation products and thereby either directly or after one or more further groups have been cleaved from the primarily cleaved residue ( e.g. DE-A-27 03 145, DE-A-28 55 697, DE-A-31 05 026, DE-A-33 19 428), a develops certain desired photographic effectiveness, for example as a development inhibitor or accelerator. Examples of such 2-equivalent couplers are the known DIR couplers as well as DAR and FAR couplers.

Geeignete DIR-Kuppler sind beispielsweise in GB-A-953 454, DE-A-1 800 420, DE-A-20 15 867, DE-A-24 14 006, DE-A-28 42 063, DE-A-34 27 235 beschrieben.Suitable DIR couplers are described, for example, in GB-A-953 454, DE-A-1 800 420, DE-A-20 15 867, DE-A-24 14 006, DE-A-28 42 063, DE-A- 34 27 235.

Geeignete DAR- bzw. FAR-Kuppler sind beispielsweise in DE-A-32 09 110, EP-A-0 089 834, EP-A-0 117 511, EP-A-0 118 087 beschrieben.Suitable DAR or FAR couplers are described, for example, in DE-A-32 09 110, EP-A-0 089 834, EP-A-0 117 511, EP-A-0 118 087.

Da bei den DIR-, DAR- bzw. FAR-Kupplern hauptsächlich die Wirksamkeit des bei der Kupplung freigesetzten Restes erwünscht ist und es weniger auf die farbbildenden Eigenschaften dieser Kuppler ankommt, sind auch solche DIR-, DAR- bzw. FAR-Kuppler geeignet, die bei der Kupplung im wesentlichen farblose Produkte ergeben wie beispielsweise in DE-A-1 547 640 beschrieben.Since with DIR, DAR or FAR couplers the effectiveness of the residue released during coupling is mainly desired and the color-forming properties of these couplers are less important, such DIR, DAR or FAR couplers are also suitable, the products which are essentially colorless upon coupling, as described, for example, in DE-A-1 547 640.

Der abspaltbare Rest kann auch ein Ballastrest sein, so daß bei der Reaktion mit Farbentwickleroxidationsprodukten Kupplungsprodukte z.B. Farbstoffe erhalten werden können, die diffusionsfähig sind oder zumindest eine schwache bzw. eingeschränkte Beweglichkeit aufweisen wie beispielsweise in US-A-4 420 556 beschrieben.The cleavable residue can also be a ballast residue, so that when reacting with color developer oxidation products coupling products e.g. Dyes can be obtained which are diffusible or at least have a weak or restricted mobility, as described, for example, in US Pat. No. 4,420,556.

Hochmolekulare Farbkuppler sind beispielsweise in DE-C-1 297 417, DE-A-24 07 569, DE-A-31 48 125, DE-A-32 17 200, DE-A-33 20 079, DE-A-33 24 932, DE-A-33 31 743, DE-A-33 40 376, EP-A-0 027 284, US-A-4 080 211 beschrieben. Die hochmolekularen Farbkuppler werden in der Regel durch Polymerisation von ethylenisch ungesättigten monomeren Farbkupplern hergestellt. Sie können aber auch durch Polyaddition oder Polykondensation erhalten werden.High molecular weight color couplers are described, for example, in DE-C-1 297 417, DE-A-24 07 569, DE-A-31 48 125, DE-A-32 17 200, DE-A-33 20 079, DE-A-33 24 932, DE-A-33 31 743, DE-A-33 40 376, EP-A-0 027 284, US-A-4 080 211. The high molecular color coupler are usually produced by polymerizing ethylenically unsaturated monomeric color couplers. However, they can also be obtained by polyaddition or polycondensation.

Über die genannten Bestandteile hinaus können die Schichten des nach dem erfindungsgemäßen Verfahren zu härtenden farbfotografischen Aufzeichnungsmaterials weitere Zusätze enthalten, zum Beispiel Antioxidantien, farbstoffstabilisierende Mittel und Mittel zur Beeinflussung der mechanischen und elektrostatischen Eigenschaften. Um die nachteilige Einwirkung von UV-Licht auf die mit dem erfindungsgemäßen farbfotografischen Aufzeichnungsmaterial hergestellten Farbbilder zu vermindern oder zu vermeiden, können auch die zu härtenden Schichten UV-Licht absorbierende Verbindungen enthalten.In addition to the constituents mentioned, the layers of the color photographic recording material to be hardened by the process according to the invention may contain further additives, for example antioxidants, dye-stabilizing agents and agents for influencing the mechanical and electrostatic properties. In order to reduce or avoid the disadvantageous effect of UV light on the color images produced with the color photographic recording material according to the invention, the layers to be hardened can also contain compounds which absorb UV light.

Das als lichtempfindlicher Bestandteil in dem fotografischen Material befindliche Silberhalogenid kann als Halogenid Chlorid, Bromid oder Iodid bzw. Mischungen davon enthalten. Vorzugsweise besteht das Silberhalogenid aus 15 bis 100 Mol-% Chlorid, 0 bis 85 Mol-% Bromid und 0 bis 2 Mol-% Iodid. Der mittlere Teilchendurchmesser beträgt vorzugsweise 0,2 bis 0,6 µm. Die Silberhalogenide können mit Rh, Ir, Cd oder Pb dotiert und mit Schwefelverbindungen oder einer Kombination von Schwefel- und Goldverbindungen gereift sein.The silver halide present as a light-sensitive component in the photographic material can contain chloride, bromide or iodide or mixtures thereof as the halide. The silver halide preferably consists of 15 to 100 mol% of chloride, 0 to 85 mol% of bromide and 0 to 2 mol% of iodide. The average particle diameter is preferably 0.2 to 0.6 μm. The silver halides can be doped with Rh, Ir, Cd or Pb and ripened with sulfur compounds or a combination of sulfur and gold compounds.

Die Silberhalogenidemulsionen können aber auch mindestens 80 Mol-% Chlorid, vorzugsweise 95 bis 100 Mol-% Chlorid, 0 bis 5 Mol-% Bromid und 0 bis 1 Mol-% Iodid enthalten.However, the silver halide emulsions can also contain at least 80 mol% of chloride, preferably 95 to 100 mol% of chloride, 0 to 5 mol% of bromide and 0 to 1 mol% of iodide.

Beispiel 1example 1

Ein Schichtträger aus beidseitig mit Polyethylen beschichtetem Papier wurde mit folgenden Schichten versehen. Die Mengenangaben beziehen sich auf 1 m².

  • 1. Eine Substratschicht aus 200 mg Gelatine mit KNO₃-und Chromalaunzusatz.
  • 2. Eine Haftschicht aus 320 mg Gelatine.
  • 3. Eine blauempfindliche Silberbromidchloridemulsionsschicht (20 mol-% Chlorid) aus 450 mg AgNO₃ mit 1600 mg Gelatine, 1,0 mmol Gelbkuppler, 27,7 mg 2,5-Dioctylhydrochinon und 650 mg Trikresylphosphat.
    Die Emulsion wurde durch Doppeleinlauf mit einer Korngröße von 0,8 µm hergestellt, in der üblichen Weise geflockt, gewaschen und mit Gelatine redispergiert. Das Gewichtsverhältnis Gelatine-Silber (als AgNO₃) betrug 0,5. Die Emulsion wurde anschließend mit 60 µmol Thiosulfat pro mol Ag zur optimalen Empfindlichkeit gereift, für den blauen Spektralbereich mit einer Verbindung der Formel
    Figure imgb0051
     sensibilisiert und stabilisiert.
  • 4. Eine Zwischenschicht aus 1200 mg Gelatine, 80 mg 2,5-Dioctylhydrochinon und 100 mg Trikresylphosphat.
  • 5. Eine grünempfindliche Silberbromidchloridemulsionsschicht (20 mol-% Chlorid) aus 530 mg AgNO₃ mit 750 mg Gelatine sensibilisiert mit der Verbindung der Formel
    Figure imgb0052
     0,625 mmol Purpurkuppler, 118 mg α-(3-t-Butyl-4-hydroxyphenoxy)-myristinsäureethylester, 43 mg 2,5-Dioctylhydrochinon, 343 mg Dibutylphthalat und 43 mg Trikresylphosphat.
  • 6. Eine Zwischenschicht aus 1550 mg Gelatine, 285 mg eines UV-Absorbers der Formel
    Figure imgb0053
     80 mg Dioctylhydrochinon und 650 mg Trikresylphosphat.
  • 7. Eine rotempfindliche Silberbromidchloridemulsionsschicht (20 mol-% Chlorid) aus 400 mg AgNO₃ mit 1470 mg Gelatine mit den in der nachfolgenden Tabelle angegebenen Verbindungen sensibilisiert, 0,780 mmol Blaugrünkuppler, 285 mg Dibutylphthalat und 122 mg Trikresylphosphat.
  • 8. Eine Schutzschicht aus 1200 mg Gelatine, 134 mg eines UV-Absorbers gemäß 6. Schicht und 240 mg Trikresylphosphat.
  • 9. Eine Härtungsschicht aus 400 mg Gelatine und 400 mg Härtungsmittel der Formel
Figure imgb0054
 A layer support made of paper coated on both sides with polyethylene was provided with the following layers. The quantities refer to 1 m².
  • 1. A substrate layer of 200 mg of gelatin with KNO₃ and Chromalaunzusatz.
  • 2. An adhesive layer made of 320 mg of gelatin.
  • 3. A blue-sensitive silver bromide chloride emulsion layer (20 mol% chloride) from 450 mg AgNO₃ with 1600 mg gelatin, 1.0 mmol yellow coupler, 27.7 mg 2,5-dioctylhydroquinone and 650 mg tricresyl phosphate.
    The emulsion was prepared by double inlet with a grain size of 0.8 μm, flocculated in the usual way, washed and redispersed with gelatin. The weight ratio gelatin-silver (as AgNO₃) was 0.5. The emulsion was then ripened with 60 μmol thiosulfate per mol Ag for optimal sensitivity, for the blue spectral range with a compound of the formula
    Figure imgb0051
     sensitized and stabilized.
  • 4. An intermediate layer of 1200 mg gelatin, 80 mg 2,5-dioctylhydroquinone and 100 mg tricresyl phosphate.
  • 5. A green-sensitive silver bromide chloride emulsion layer (20 mol% chloride) from 530 mg AgNO₃ with 750 mg gelatin sensitized with the compound of the formula
    Figure imgb0052
     0.625 mmol of purple coupler, 118 mg of ethyl α- (3-t-butyl-4-hydroxyphenoxy) myristic acid, 43 mg of 2,5-dioctylhydroquinone, 343 mg of dibutyl phthalate and 43 mg of tricresyl phosphate.
  • 6. An intermediate layer of 1550 mg gelatin, 285 mg of a UV absorber of the formula
    Figure imgb0053
     80 mg dioctyl hydroquinone and 650 mg tricresyl phosphate.
  • 7. A red-sensitive silver bromide chloride emulsion layer (20 mol% chloride) from 400 mg AgNO₃ with 1470 mg gelatin sensitized with the compounds listed in the table below, 0.780 mmol cyan coupler, 285 mg dibutyl phthalate and 122 mg tricresyl phosphate.
  • 8. A protective layer of 1200 mg of gelatin, 134 mg of a UV absorber according to the 6th layer and 240 mg of tricresyl phosphate.
  • 9. A hardening layer of 400 mg gelatin and 400 mg hardening agent of the formula
Figure imgb0054

Als Farbkuppler wurden folgende Verbindungen verwendet:
Gelbkuppler:

Figure imgb0055

Purpurkuppler:
Figure imgb0056
Blaugrünkuppler;
Figure imgb0057
 The following connections were used as color couplers:
Yellow coupler:
Figure imgb0055
Purple coupler:
Figure imgb0056
Cyan coupler;
Figure imgb0057

Beispiel 2Example 2

Das Beispiel entsprach Beispiel 1 mit dem Unterschied, daß in der 3. Schicht eine Silberchloridemulsion (100 mol-% Chlorid) eingesetzt wurde.The example corresponded to Example 1 with the difference that a silver chloride emulsion (100 mol% chloride) was used in the 3rd layer.

Die Emulsion wurde durch Doppeleinlauf mit einer Korngröße von 0,40 µm hergestellt, in der üblichen Weise geflockt, gewaschen und mit Gelatine redispergiert. Das Gewichtsverhältnis Gelatine-Silber (als AgNO₃) betrug 0,5. Die Emulsion wurde anschließend mit 20 µmol Thiosulfat, 1,5 µmol HAuCl₄ und 15 µmol NH₄SCN pro mol Ag zur optimalen Empfindlichkeit gereift, für den blauen Spektralbereich sensibilisiert und stabilisiert.The emulsion was prepared by double inlet with a grain size of 0.40 μm, flocculated in the usual way, washed and redispersed with gelatin. The weight ratio gelatin-silver (as AgNO₃) was 0.5. The emulsion was then ripened with 20 µmol thiosulfate, 1.5 µmol HAuCl₄ and 15 µmol NH₄SCN per mol Ag for optimal sensitivity, sensitized to the blue spectral range and stabilized.

In der 5. und 7. Schicht wurde die gleiche Emulsion eingesetzt, allerdings für den grünen bzw. roten Spektralbereich sensibilisiert.The same emulsion was used in the 5th and 7th layers, but sensitized to the green and red spectral range.

Sensitometrische AuswertungSensitometric evaluation

Probe 1:Sample 1:
unbehandeltuntreated
Probe 2:Sample 2:
24 Stunden bei 80 % r.F. und 23°C gelagert.24 hours at 80% RH and stored at 23 ° C.

Anschließend wurden die Proben durch einen Stufenkeil belichtet. Die Proben des Beispiels 1 und des Vergleichs zu Beispiel 1 wurden im EP2-Prozess, Proben des Beispiels 2 und des Vergleichs zu 2 im RA-4-Prozess entwickelt.The samples were then exposed through a step wedge. The samples of Example 1 and the comparison to Example 1 were developed in the EP2 process, samples of Example 2 and the comparison to 2 in the RA-4 process.

Die Dichtemessung erfolgte hinter Rotfilter, die Empfindlichkeit wurde bei D = 0,6 bestimmt.

Figure imgb0058
Figure imgb0059
Verbindung 1
Figure imgb0060
Verbindung 2
Figure imgb0061
Verbindung 3The density was measured behind a red filter, the sensitivity was determined at D = 0.6.
Figure imgb0058
Figure imgb0059
Connection 1
Figure imgb0060
Connection 2
Figure imgb0061
Connection 3

Es zeigt sich, daß bei Verwendung der erfindungsgemäßen Rotsensibilisatoren durch Zusatz des "Potenzators" ein Abfallen der Empfindlichkeit bei Lagerung vermieden wird. Eine Kombination nicht-erfindungsgemäßer Sensibilisatoren mit dem "Potenzator" zeigt dieses Ergebnis nicht und zudem auch im ungelagerten Zustand eine niedrige Empfindlichkeit und dadurch bedingt eine unerwünscht flache Gradution.It turns out that when using the red sensitizers according to the invention, a drop in sensitivity during storage is avoided by adding the "potentiator". A combination of sensitizers not according to the invention with the "potentiator" does not show this result and, moreover, a low sensitivity even in the unstored state and therefore causes an undesirably flat graduation.

Claims (8)

  1. Colour photographic recording material containing, on a reflective layer support, at least one blue-sensitive, at least one green-sensitive and at least one red-sensitive silver halide emulsion layer and optionally other layers of binder which are not light-sensitive and in which the binder is hardened with an instant hardener, the at least one red-sensitive layer being sensitized with at least one compound Corresponding to the formula
    Figure imgb0067
     wherein
    R₅₃ and R₅₄   denote alkyl,
    R₅₅, R₅₆, R₅₇ and R₅₈   denote hydrogen, halogen, alkyl, alkoxy, a radical corresponding to the formula
    Figure imgb0068
     or aryl or R₅₅ and R₅₆ together and R₅₇ and R₅₈ together denote a methylenedioxy group or the remaining members of a condensed benzene ring,
    R₅₉ and R₆₀   denote alkyl,
    R₆₁   denotes hydrogen or methyl,
    X⊖   denotes an anion and
    n   stands for a number from 1 to 5 and
    the cation contains no covalently bound sulphonic acid groups,
    and with at least one mercapto compound (compound II) of oxazine, oxazole, thiazole, thiadiazole, imidazole or tetrazole which may be substituted by a halogen atom, a sulphonic acid group, a sulphonamide group, a carboxyl group, an alkylsulphone group or a phenyl group or a condensed benzene group, which may in turn be substituted by the aforesaid groups.
  2. Colour photographic recording material according to Claim 1, characterised in that the instant hardener is used in a quantity of from 0.1 to 5 mmol/m².
  3. Colour photographic recording material according to Claim 1, characterised in that the instant hardener is used in a quantity of from 0.5 to 1.7 mmol/m².
  4. Colour photographic recording material according to Claim 1, characterised in that the silver halide consists of from 15 to 100 mol-% of chloride, from 0 to 85 mol-% of bromide and from 0 to 2 mol-% of iodide and has an average particle diameter of from 0.2 to 0.6 µm.
  5. Colour photographic recording material according to Claim 1, characterised in that the instant hardener corresponds to the following formula
    Figure imgb0069
     wherein
    R₁   denotes alkyl, aryl or aralkyl,
    R₂   has the same meaning as R₁ or denotes alkylene, arylene, aralkylene or alkaralkylene in which the second bond is linked to a group of the formula
    Figure imgb0070
     or
    R₁ and R₂   together may stand for the atoms required for completing an optionally substituted heterocyclic ring, for example a piperidine, piperazine or morpholine ring, which ring may be substituted, e.g. by C₁-C₃-alkyl or halogen,
    R₃   denotes hydrogen, alkyl, aryl, alkoxy, -NR₄-COR₅, -(CH₂)m-NR₈R₉, -(CH₂)n-CONR₁₃R₁₄ or
    Figure imgb0071
     or a bridging member or a direct link to a polymer chain, wherein
    R₄, R₆, R₇, R₉, R₁₄, R₁₅, R₁₇, R₁₈ and R₁₉   stand for hydrogen or C₁-C₄-alkyl,
    R₅   denotes hydrogen, C₁-C₄-alkyl or NR₆R₇,
    R₈   denotes -COR₁₀,
    R₁₀   denotes NR₁₁R₁₂,
    R₁₁   denotes C₁-C₄-alkyl or aryl, in particular phenyl,
    R₁₂   denotes hydrogen, C₁-C₄-alkyl or aryl, in particular phenyl,
    R₁₃   denotes hydrogen, C₁-C₄-alkyl or aryl, in particular phenyl,
    R₁₆   denotes hydrogen, C₁-C₄-alkyl, COR₁₈ or CONHR₁₉,
    m   stands for a number from 1 to 3,
    n   stands for a number from 0 to 3,
    o   stands for the number 1 or 2,
    p   stands for a number from 2 to 3 and
    Y   denotes O or NR₁₇ or
    R₁₃ and R₁₄   together represent the atoms required for completing an optionally substituted heterocyclic ring, for example a piperidine, piperazine or morpholine ring, which ring may be substituted, e.g. by C₁-C₃-alkyl or by halogen,
    Z   denotes the carbon atoms required for completing a 5-membered or 6-membered aromatic heterocyclic ring optionally having a condensed benzene ring attached and
    X⊖   denotes an anion which may be linked to the rest of the molecule by a covalent bond.
  6. Colour photographic recording material according to Claim 1, characterised in that compound I is used in a quantity of from 0.05 to 0.25 µmol/mol of Ag and compound II is used in a quantity of from 0.45 to 3.00 µmol/mol of Ag.
  7. Colour photographic recording material according to Claim 1, characterised in that the silver halide consists of at least 80 mol-% of chloride.
  8. Colour photographic recording material according to Claim 7, characterised in that the silver halide consists of from 95 to 100 mol-% of chloride, from 0 to 5 mol-% of bromide and from 0 to 1 mol-% of iodide.
EP88118632A 1987-11-21 1988-11-09 Colour-photographic recording material Expired - Lifetime EP0317825B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19873739474 DE3739474A1 (en) 1987-11-21 1987-11-21 COLOR PHOTOGRAPHIC RECORDING MATERIAL
DE3739474 1987-11-21

Publications (3)

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EP0317825A2 EP0317825A2 (en) 1989-05-31
EP0317825A3 EP0317825A3 (en) 1990-05-16
EP0317825B1 true EP0317825B1 (en) 1993-07-21

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DE (2) DE3739474A1 (en)

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Publication number Priority date Publication date Assignee Title
EP0605917B1 (en) * 1992-12-16 1996-06-26 Eastman Kodak Company Red sensitizers for high silver chloride emulsions

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1447577B1 (en) * 1964-03-11 1970-05-14 Agfa Ag Stabilized supersensitization of halogen silver emulsions
US4618570A (en) * 1984-03-27 1986-10-21 Konishiroku Photo Industry Co., Ltd. Silver halide photographic materials
DE3606086A1 (en) * 1986-02-26 1987-08-27 Agfa Gevaert Ag COLOR PHOTOGRAPHIC RECORDING MATERIAL

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DE3882492D1 (en) 1993-08-26
DE3739474A1 (en) 1989-06-01
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EP0317825A2 (en) 1989-05-31
JPH01155334A (en) 1989-06-19

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