EP0364807A2 - Colour-photographic recording material - Google Patents

Colour-photographic recording material Download PDF

Info

Publication number
EP0364807A2
EP0364807A2 EP89118297A EP89118297A EP0364807A2 EP 0364807 A2 EP0364807 A2 EP 0364807A2 EP 89118297 A EP89118297 A EP 89118297A EP 89118297 A EP89118297 A EP 89118297A EP 0364807 A2 EP0364807 A2 EP 0364807A2
Authority
EP
European Patent Office
Prior art keywords
color
layer
recording material
coupler
photographic recording
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP89118297A
Other languages
German (de)
French (fr)
Other versions
EP0364807A3 (en
Inventor
Günter Dr. Junkers
Klaus Dr. Wagner
Gerald Dr. Karich
Friedhelm Dipl.-Chem. Sommer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Agfa Gevaert AG
Original Assignee
Agfa Gevaert AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Agfa Gevaert AG filed Critical Agfa Gevaert AG
Publication of EP0364807A2 publication Critical patent/EP0364807A2/en
Publication of EP0364807A3 publication Critical patent/EP0364807A3/en
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/305—Substances liberating photographically active agents, e.g. development-inhibiting releasing couplers
    • G03C7/30511—Substances liberating photographically active agents, e.g. development-inhibiting releasing couplers characterised by the releasing group
    • G03C7/30517—2-equivalent couplers, i.e. with a substitution on the coupling site being compulsory with the exception of halogen-substitution
    • G03C7/30535—2-equivalent couplers, i.e. with a substitution on the coupling site being compulsory with the exception of halogen-substitution having the coupling site not in rings of cyclic compounds
    • 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
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/388—Processes for the incorporation in the emulsion of substances liberating photographically active agents or colour-coupling substances; Solvents therefor
    • G03C7/3882—Processes for the incorporation in the emulsion of substances liberating photographically active agents or colour-coupling substances; Solvents therefor characterised by the use of a specific polymer or latex

Definitions

  • the invention relates to a color photographic recording material with at least one light-sensitive silver halide emulsion layer, which is associated with a yellow coupler dissolved in a special oil former, which is characterized by greater color purity and better dark fading stability.
  • color photographic images by chromogenic development, that is to say by developing an image-wise exposed recording material with at least one silver halide emulsion layer in the presence of suitable color couplers by means of suitable color-forming developer substances - so-called color developers - with the oxidation product of the developer substances resulting in accordance with the silver image the color coupler reacts to form a dye image.
  • suitable color-forming developer substances - so-called color developers - with the oxidation product of the developer substances resulting in accordance with the silver image the color coupler reacts to form a dye image.
  • Aromatic compounds containing primary amino groups are usually used as color developers those of the p-phenylenediamine type are used.
  • the color couplers are generally contained in one or more layers of the color photographic material.
  • couplers are dissolved in a solvent, for example tricresyl phosphate, and the solution is emulsified in an aqueous gelatin solution.
  • a solvent for example tricresyl phosphate
  • the disadvantage is that the yellow couplers produced by these couplers and the oxidation products of the color developers have an undesirable purple shim density and inadequate dark fading stability (ie stability against the fading of the dye when stored in the dark).
  • the object of the invention was therefore to find means which overcome these disadvantages without dispensing with the couplers mentioned.
  • Suitable diols are alkanediols with 2 to 10 C atoms, the carbon chain of which can be interrupted by 1 to 3 ether oxygen atoms.
  • the weight ratio of coupler to oil former is preferably 1: 0.1-2.
  • the degree of polymerization is adjusted so that the esters are of low viscosity.
  • the viscosity is preferably in a range from 50 to 5000 mPa.s.
  • the cleavage group of the yellow coupler identified by R2 is, for example, a halogen atom, for example Cl, or an organic group which is generally linked to the coupling point of the coupler molecule via an oxygen, sulfur or nitrogen atom. If the cleavable group is a cyclic group, the coupling to the coupling point of the coupler molecule can either take place directly via an atom which is part of a ring, for example a nitrogen atom, or indirectly via an intermediate link. Such cleavable groups are known in large numbers, for example as escape groups of 2-equivalent magenta couplers.
  • cleavable groups linked via oxygen correspond to the formula -O-R4, where R4 represents an acyclic or cyclic organic radical, for example alkyl, aryl, a heterocyclic group or acyl, which is derived, for example, from an organic carbon or sulfonic acid.
  • R4 represents an optionally substituted phenyl group.
  • heterocyclic rings which are connected to the coupling site of the yellow coupler via a ring nitrogen atom.
  • the heterocyclic rings often contain groups adjacent to the nitrogen atom which activates the bond to the coupler molecule, e.g. B. carbonyl or sulfonyl groups or double bonds.
  • the cleavable group is attached to the coupling site of the coupler via a sulfur atom, it can be the remainder of a diffusible mercapto compound which is able to inhibit the development of silver halide.
  • inhibitor residues have been described many times as cleavable group bound to the coupling point of couplers, also yellow couplers, e.g. See, for example, US-A-3,227,554.
  • the yellow coupler used according to the invention can also be a polymeric purple coupler, for example obtained by homo- or copolymerization of monomeric couplers according to the formula which contain an ethylenically unsaturated copolymerizable double bond in one of the substituents. Couplers of this type are described, for example, in DE-A-31 48 125, DE-A-33 00 665, DE-A-33 05 718 and Research Disclosure 25 724 (September 1985).
  • the color photographic recording material according to the invention contains at least one light-sensitive silver halide emulsion layer and preferably a sequence of several such light-sensitive silver halide emulsion layers and, if appropriate, non-light-sensitive binder layers arranged between them.
  • the oil-forming agent according to the invention can be used alone or together with other known oil-forming agents, but if the yellow coupler is dissolved in a mixture of oil-forming agents, such a mixture preferably consists of at least 50% by weight of an oil-forming agent of the present invention.
  • the oil formers are generally high-boiling substances which have a good dissolving power for the couplers to be dispersed and which are therefore also referred to as coupler solvents.
  • the light-sensitive silver halide emulsions used in the light-sensitive layers can contain chloride, bromide and iodide or mixtures thereof as the halide.
  • the halide content of at least one layer can consist of 0 to 12 mol% of iodide, 0 to 50 mol% of chloride and 50 to 100 mol% of bromide.
  • the crystals are predominantly compact, for example cubic or octahedral or have transition forms. They can be characterized in that they essentially have a thickness of more than 0.2 ⁇ m.
  • the average ratio of diameter to thickness is preferably less than 8: 1, it being true that the diameter of a grain is defined as the diameter of a circle with a circle content corresponding to the projected area of the grain. In other embodiments, however, all or individual emulsions can also have essentially tabular silver halide crystals in which the ratio of diameter to thickness is greater than 8: 1.
  • the emulsions can be heterodisperse, or also act as monodisperse emulsions, which preferably have an average grain size of 0.3 ⁇ m to 1.2 ⁇ m.
  • the silver halide grains can also have a layered grain structure.
  • the emulsions can be chemically and or spectrally sensitized in the usual way; they can also be stabilized by suitable additives. Suitable chemical sensitizers, spectral sensitizing dyes and stabilizers are described, for example, in Research Disclosure 17643 (December 1978); Reference is made in particular to chapters III, IV and VI.
  • the color photographic recording material according to the invention preferably contains at least one silver halide emulsion layer for the recording of light from each of the three spectral ranges red, green and blue.
  • the light-sensitive layers are spectrally sensitized in a known manner by means of suitable sensitizing dyes.
  • Blue-sensitive silver halide emulsion layers do not necessarily have to contain a spectral sensitizer, since in many cases the intrinsic sensitivity of the silver halide is sufficient for the recording of blue light.
  • Each of the light-sensitive layers mentioned can consist of a single layer or, in a known manner, for example in the case of the so-called double-layer arrangement, can also comprise two or more silver halide emulsion partial layers (DE-C-1 121 470).
  • Red-sensitive silver halide emulsion layers are usually the support arranged closer than green-sensitive silver halide emulsion layers and these, in turn, closer than blue-sensitive layers, a non-light-sensitive yellow filter layer generally being located between green-sensitive layers and blue-sensitive layers.
  • a layer which is not sensitive to light is generally arranged between layers of different spectral sensitivity and can contain means for preventing the incorrect diffusion of developer oxidation products.
  • silver halide emulsion layers of the same spectral sensitivity they can be directly adjacent to one another or be arranged such that a light-sensitive layer with a different spectral sensitivity is located between them (DE-A-1 958 709, DE-A-2 530 645, DE-A -2 622 922).
  • Color photographic recording materials according to the invention usually contain, in spatial and spectral assignment to the silver halide emulsion layers of different spectral sensitivity, color couplers for producing the different partial color images cyan, purple and yellow, the yellow couplers dispersed with the oil former of the present invention being assigned to a blue-sensitive silver halide emulsion layer.
  • Color coupler is in such a spatial relationship with the silver halide emulsion layer that an interaction between them is possible, which is an image according agreement between the silver image formed during development and the color image generated from the color coupler. This is usually achieved by the fact that the color coupler is contained in the silver halide emulsion layer itself or in a possibly non-light-sensitive binder layer adjacent to it.
  • Spectral assignment is understood to mean that the spectral sensitivity of each of the light-sensitive silver halide emulsion layers and the color of the partial color image generated from the spatially assigned color coupler are in a specific relationship to one another, with each of the spectral sensitivities (red, green, blue) having a different color of the relevant partial color image (in general, for example, the colors cyan, purple or yellow in this order).
  • One or more color couplers can be assigned to each of the differently spectrally sensitized silver halide emulsion layers. If there are several silver halide emulsion layers of the same spectral sensitivity, each of them can contain a color coupler, which color couplers need not necessarily be identical. They should only result in at least approximately the same color during color development, normally a color that is complementary to the color of the light, for which the silver halide emulsion layers in question are predominantly sensitive.
  • red-sensitive silver halide emulsion layers are therefore assigned at least one non-diffusing color coupler for producing the blue-green partial color image, as a rule a coupler of the phenol or ⁇ -naphthol type, green-sensitive silver halide emulsion layers are assigned at least one non-diffusing color coupler for generating the purple partial color image in the regular color image of the indazolone or pyrazoloazole type. Finally, blue-sensitive silver halide emulsion layers are assigned at least one non-diffusing color coupler for generating the yellow partial color image. Color couplers of this type are known in large numbers and are described in a large number of patents.
  • the color couplers according to the invention can be both conventional 4-equivalent couplers and 2-equivalent couplers, in which a smaller amount of silver halide is required to produce the color.
  • 2-equivalent couplers are derived from the 4-equivalent couplers in that they contain a substituent in the coupling site, which is split off during the coupling.
  • To the 2- Equivalent couplers are to be counted 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.
  • the latter couplers can also be present in the light-sensitive silver halide emulsion layers and serve there as mask couplers to compensate for the undesired secondary densities of the image dyes.
  • the known white couplers are also to be counted among the 2-equivalent couplers, but they do not give any dye on reaction with color developer oxidation products.
  • the 2-equivalent couplers also include those couplers which contain a detachable residue in the coupling point, which is released when reacting with color developer oxidation products and thereby develops a certain desired photographic activity, 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.
  • the cleavable residue can also be a ballast residue, so that in the reaction with color developer oxidation products coupling products, for example dyes, can be obtained which are diffusible or at least have a weak or restricted mobility.
  • Weak or restricted mobility means mobility that is dimensioned such that the contours of the discrete dye spots formed in the chromogenic development run and are smeared into one another.
  • this degree of mobility is to be distinguished from the usual case of complete immobility in photographic layers, which is sought in the conventional photographic recording materials for the color couplers or the dyes produced therefrom in order to achieve the highest possible sharpness, and on the other hand the case of complete mobility of the dyes, which is sought, for example, in color diffusion processes.
  • the extent of the weak mobility sought according to the invention can be controlled by varying substituents in order to influence, for example, the solubility in the organic medium of the oil former or the affinity for the binder matrix in a targeted manner.
  • the usual supports e.g. Cellulose ester supports, e.g. Cellulose acetate and polyester.
  • paper supports which can optionally be coated, e.g. with polyolefins, especially with polyethylene or polypropylene.
  • polyolefins especially with polyethylene or polypropylene.
  • hydrophilic film-forming agents for example proteins, in particular gelatin, are suitable as protective colloids or binders for the layers of the recording material.
  • Casting aids and plasticizers can be used. Reference is made to Research Disclosure 17643, Chapter IX, XI and XII.
  • the layers of the photographic material can be hardened in the usual way, for example with hardeners which contain at least two reactive oxirane, aziridine or acryloyl groups. Furthermore, it is also possible to harden the layers in accordance with the process described in DE-A-22 18 009. It is also possible to harden the photographic layers or the color photographic multilayer materials with hardnesses of the diazine, triazine or 1,2-dihydroquinoline series or with hardeners of the vinyl sulfone type. Other suitable curing agents are known from DE-A-22 25 230, DE-A-23 17 677, DE-A-24 39 551, and also from Research Disclosure 17 643, Chapter X. The stabilizing effect of the oil formers according to the invention is particularly pronounced when hardening agents which activate carboxyl groups, e.g. Carbamoylpyridinium or carbamoyloxypyridinium salts can be used.
  • hardening agents which activate carboxyl groups e.g. Carbamo
  • Suitable color developer substances for the material according to the invention are in particular those of the p-phenylenediamine type, for example 4-amino-N, N-diethyl-aniline hydrochloride, 4-amino-3-methyl-N-ethyl-N- ⁇ - (methanesulfonamido) ethyl-aniline sulfate hydrate , 4-amino-3-methyl-N-ethyl-N- ⁇ -hydroxyethylaniline sulfate, 4-amino-N-ethyl-N- (2-methoxyethyl) -m-toluidine-di-p-toluenesulfonic acid and N-ethyl-N - ⁇ -hydroxyethyl-p-phenylenediamine.
  • Other useful color developers are described, for example, in J.Amer.Chem.Soc. 73 , 3100 (1951) and in G. Haist, Modern Photographic Processing, 1979
  • the material is usually bleached and fixed. Bleaching and fixing can be carried out separately or together.
  • the usual compounds can be used as bleaching agents, e.g. Fe3+ salts and Fe3+ complex salts such as ferricyanides, dichromates, water-soluble cobalt complexes etc.
  • Particularly preferred are iron III complexes of aminopolycarboxylic acids, especially e.g. Ethylenediaminetetraacetic acid, nitrilotriacetic acid, iminodiacetic acid, N-hydroxyethylethylenediaminetriacetic acid, alkyliminodicarboxylic acids and corresponding phosphonic acids.
  • Persulphates are also suitable as bleaching agents.
  • the color development is preceded by a black and white development and a diffuse second exposure or chemical fogging.
  • a color photographic recording material was prepared by applying the following layers in the order given to a transparent cellulose triacetate support. The quantities given relate to 1 m2. For the silver halide application, the corresponding amounts of AgNO3 are given. All silver halide emulsions were stabilized per 100 g of AgNO3 with 0.5 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene.
  • Samples 2 and 3 show a clearly narrower flank spacing of the absorption curve and do not extend as far into the long-wave, green absorption area as sample 1. They therefore show a purer, less purple yellow than sample 1.
  • a color photographic recording material for reverse color development was prepared by applying the following layers in the order given on a transparent cellulose triacetate support. The quantities given relate to 1 m2. For the silver halide application, the corresponding amounts of AgNO3 are given. All silver halide emulsions were stabilized per 100 g of AgNO3 with 0.5 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene.
  • Blue-sensitized silver bromide iodide emulsion (4 mol% iodide; average grain diameter 0.25 ⁇ m) from 0.5 g AgNO3, with 0.6 g yellow coupler GB 19, emulsified with 0.3 g CPM and 0.75 g gelatin.
  • Blue-sensitized silver bromide iodide emulsion (3 mol% iodide; average grain diameter 0.8 ⁇ m) from 1.15 g AgNO3, with 1.35 g yellow coupler GB 19, emulsified with 0.7 g CPM and 1.6 g gelatin.
  • Blue-sensitized silver bromide iodide emulsion (4 mol% iodide; average grain diameter 0.03 ⁇ m) from 0.2 g AgNO3, with 0.8 g of a conventional UV absorber and 0.8 g gelatin.
  • the oil former consisted of 100% by weight of CPM.
  • the oil formers each consisted of 50% by weight of CPM and I-2.
  • the oil former consisted of 100% by weight of I-2.
  • a color photographic recording material for reverse color development was prepared by applying the following layers in the order given on a transparent cellulose triacetate support. The quantities given relate to 1 m2. For the silver halide application, the corresponding amounts of AgNO3 are given. All silver halide emulsions were stabilized per 100 g of AgNO3 with 0.5 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene.
  • red-sensitized silver bromide iodide emulsion (4 mol% iodide; average grain diameter 0.25 ⁇ m) from 1.3 g AgNO3, with 0.38 g compound cyan coupler C-1, emulsified in 0.19 g CPM, and 1.3 g gelatin.
  • red-sensitized silver bromide iodide emulsion (3 mol% iodide; average grain diameter 0.8 ⁇ m) from 2.0 g AgNO3, with 1.2 g cyan coupler C-1 emulsified in 0.6 g CPM, and 1.8 gelatin.
  • Green-sensitized silver bromide iodide emulsion (4 mol% iodide; average grain diameter 0.25 ⁇ m) from 1.3 g AgNO3, with 0.32 g purple coupler M-1, emulsified with 0.16 g CPM and 1.0 g gelatin.
  • green-sensitized silver bromide iodide emulsion (3 mol% iodide, average grain diameter 0.8 ⁇ m) from 1.4 g AgNO3, with 1.16 g purple coupler M-1, emulsified in 0.58 g CPM and 1.35 g gelatin.
  • Blue-sensitized silver bromide iodide emulsion (4 mol% iodide; average grain diameter 0.25 ⁇ m) from 0.5 g AgNO3, with 0.6 g yellow coupler GB 19, emulsified with 0.3 oil former I-2 and 0.75 g gelatin.
  • Blue-sensitized silver bromide iodide emulsion (3 mol% iodide; average grain diameter 0.8 ⁇ m) from 1.15 g AgNO3, with 1.35 g yellow coupler GB 19, emulsified with 0.3 g oil former I-2 and 1.6 g gelatin.
  • Blue-sensitized silver bromide iodide emulsion (4 mol% iodide; average grain diameter 0.03 ⁇ m) from 0.2 g AgNO3, with 0.8 g of a conventional UV absorber and 0.8 g gelatin.
  • Example 2 The treatment and processing were the same as in Example 1.
  • the image obtained shows pure colors, in particular a pure yellow, and very good dark fading stability.

Abstract

Colour-photographic recording material with a base and at least one light-sensitive silver halide emulsion layer associated with a yellow coupler of the pivaloyl- or benzoyl-acetanilide type, dissolved in a polymeric ester of aromatic or aliphatic dicarboxylic acids, is distinguished by higher colour purity and improved dark-fading stability.

Description

Die Erfindung betrift ein farbfotografisches Aufzeich­nungsmaterial mit mindestens einer lichtempfindlichen Silberhalogenidemulsionsschicht, der ein Gelbkuppler ge­löst in einem speziellen Ölbildner zugeordnet ist, das sich durch größere Farbreinheit und bessere dark-fading-­Stabilität auszeichnet.The invention relates to a color photographic recording material with at least one light-sensitive silver halide emulsion layer, which is associated with a yellow coupler dissolved in a special oil former, which is characterized by greater color purity and better dark fading stability.

Es ist bekannt, farbfotografische Bilder durch chromogene Entwicklung herzustellen, d.h. dadurch, daß man ein bild­mäßig belichtetes Aufzeichnungsmaterial mit mindestens einer Silberhalogenidemulsionsschicht in Gegenwart ge­eigneter Farbkuppler mittels geeigneter farbbildender Ent­wicklersubstanzen - sogenannter Farbentwickler - ent­wickelt, wobei das in Übereinstimmung mit dem Silberbild entstehende Oxidationsprodukt der Entwicklersubstanzen mit dem Farbkuppler unter Bildung eines Farbstoffbildes rea­giert. Als Farbentwickler werden gewöhnlich aromatische, primäre Aminogruppen enthaltende Verbindungen, insbeson­ dere solche vom p-Phenylendiamintyp, verwendet. Die Farb­kuppler sind im allgemeinen in einer oder mehrern Schichten des farbfotografischen Materials enthalten.It is known to produce color photographic images by chromogenic development, that is to say by developing an image-wise exposed recording material with at least one silver halide emulsion layer in the presence of suitable color couplers by means of suitable color-forming developer substances - so-called color developers - with the oxidation product of the developer substances resulting in accordance with the silver image the color coupler reacts to form a dye image. Aromatic compounds containing primary amino groups, in particular, are usually used as color developers those of the p-phenylenediamine type are used. The color couplers are generally contained in one or more layers of the color photographic material.

Als Gelbkuppler werden im allgemeinen Verbindungen der Formel

Figure imgb0001
verwendet, wobei
R₁ tert.-Butyl oder gegebenenfalls substituiertes Phenyl,
R₂ Wasserstoff oder eine Abspaltgruppe,
R₃ Wasserstoff, Alkoxy oder Halogen
R₄ Wasserstoff, Alkoxy oder Dialkylaminosulfonyl und
R₅ Wasserstoff, Alkoxy oder einen Ballastrest
bedeuten, wobei das Kupplermolekül wenigstens einen Ballastrest enthält.Compounds of the formula are generally used as yellow couplers
Figure imgb0001
 used, where
R₁ tert-butyl or optionally substituted phenyl,
R₂ is hydrogen or a splitting group,
R₃ is hydrogen, alkoxy or halogen
R₄ is hydrogen, alkoxy or dialkylaminosulfonyl and
R₅ is hydrogen, alkoxy or a ballast residue
mean, wherein the coupler molecule contains at least one ballast residue.

Diese Kuppler werden in einem Lösungsmittel, z.B. Tri­kresylphosphat gelöst und die Lösung in einer wäßrigen Gelatinelösung emulgiert. Nachteilig ist, daß die aus diesen Kupplern und den Oxidationsprodukten der Farbent­wickler erzeugten Gelbfarbstoffe eine unerwünschte Pur­purnebendichte und eine unzureichende dark-fading-Sta­bilität (d.h. Stabilität gegen das Verblassen des Farb­stoffs bei Dunkellagerung) aufweisen.These couplers are dissolved in a solvent, for example tricresyl phosphate, and the solution is emulsified in an aqueous gelatin solution. The disadvantage is that the yellow couplers produced by these couplers and the oxidation products of the color developers have an undesirable purple shim density and inadequate dark fading stability (ie stability against the fading of the dye when stored in the dark).

Aufgabe der Erfindung war daher, Mittel zu finden, die diese Nachteile beseitigen, ohne auf die genannten Kuppler zu verzichten.The object of the invention was therefore to find means which overcome these disadvantages without dispensing with the couplers mentioned.

Es wurde nun gefunden, daß diese Aufgabe dadurch gelöst werden kann, daß man als Ölbildner polymere Ester von aro­matischen oder aliphatischen Dicarbonsäuren, insbesondere polymere Phthalsäure-oder Adipinsäureester einsetzt.It has now been found that this object can be achieved by using polymeric esters of aromatic or aliphatic dicarboxylic acids, in particular polymeric phthalic or adipic acid esters, as oil formers.

Als Diole kommen Alkandiole mit 2 bis 10 C-Atomen in Frage, deren Kohlenstoffkette durch 1 bis 3 Ethersauer­stoffatome unterbrochen sein kann.Suitable diols are alkanediols with 2 to 10 C atoms, the carbon chain of which can be interrupted by 1 to 3 ether oxygen atoms.

Das Gewichtsverhältnis Kuppler zu Ölbildner beträgt vor­zugsweise 1:0,1-2.The weight ratio of coupler to oil former is preferably 1: 0.1-2.

Der Polymerisationsgrad wird so eingestellt, daß die Ester niedrigviskos sind. Die Viskosität liegt vorzugsweise in einem Bereich von 50 bis 5000 mPa.s.The degree of polymerization is adjusted so that the esters are of low viscosity. The viscosity is preferably in a range from 50 to 5000 mPa.s.

Geeignet Verbindungen sind:

  • I-1 Poly-triethylenglykol-nonylphthalat
  • I-2 Poly-hexandiol-isodecylphthalat
  • I-3 Poly-propylenglykoladipat
  • I-4 Poly-(1,3- und 1,4-)-butandiol-2-ethylpropan­dioladipat
  • I-5 Poly-1,3-butylenglykol-1,6-hexandioladipat
  • I-6 Poly-butandioladipat
  • I-7 Poly-pentandioladipat
Suitable connections are:
  • I-1 poly-triethylene glycol nonyl phthalate
  • I-2 poly hexanediol isodecyl phthalate
  • I-3 polypropylene glycol adipate
  • I-4 poly- (1,3- and 1,4-) - butanediol-2-ethylpropanediol adipate
  • I-5 poly-1,3-butylene glycol 1,6-hexanediol adipate
  • I-6 poly-butanediol adipate
  • I-7 poly-pentanediol adipate

Die Herstellung dieser Verbindungen erfolgt in bekannter Weise durch Verestern der Säureanhydride bzw. Säuren mit den Diolen.These compounds are prepared in a known manner by esterifying the acid anhydrides or acids with the diols.

Lit.: I. Mellan, Industrial Plasticisers, Pergamon Press 1963
Gnamm, Sommer "Die Lösungs- und Weichmachungs­mittel", Stuttgart 1958, S. 708 ff.Lit .: I. Mellan, Industrial Plasticisers, Pergamon Press 1963
Gnamm, Sommer "The solvents and plasticizers", Stuttgart 1958, p. 708 ff.

Bei der durch R₂ gekennzeichneten Abspaltgruppe des Gelb­kupplers handelt es sich beispielsweise um ein Halogenatom z.B. Cl oder um eine organische Gruppe, die in der Regel über ein Sauerstoff-, Schwefel- oder Stickstoffatom an die Kupplungsstelle des Kupplermoleküls angeknüpft ist. Falls es sich bei der abspaltbaren Gruppe um einen cyclische Gruppe handelt, kann die Anknüpfung an die Kupplungsstelle des Kupplermoleküls entweder direkt über ein Atom, das Bestandteil eines Ringes ist, z.B. ein Stickstoffatom, oder indirekt über ein zwischengeschaltetes Bindeglied erfolgt sein. Derartige abspaltbare Gruppen sind in großer Zahl bekannt, z.B. als Fluchtgruppen von 2-Äquivalent-­purpurkupplern.The cleavage group of the yellow coupler identified by R₂ is, for example, a halogen atom, for example Cl, or an organic group which is generally linked to the coupling point of the coupler molecule via an oxygen, sulfur or nitrogen atom. If the cleavable group is a cyclic group, the coupling to the coupling point of the coupler molecule can either take place directly via an atom which is part of a ring, for example a nitrogen atom, or indirectly via an intermediate link. Such cleavable groups are known in large numbers, for example as escape groups of 2-equivalent magenta couplers.

Beispiele von über Sauerstoff angeknüpften abspaltbaren Gruppen entsprechen der Formel
-O-R⁴,
worin R⁴ für einen acyclischen oder cyclischen organischen Rest steht, z.B. für Alkyl, Aryl, eine heterocyclische Gruppe oder Acyl, das sich beispielsweise ableitet von einer organischen Carbon- oder Sulfonsäure. Bei besonders bevorzugten abspaltbaren Gruppen dieser Art bedeutet R⁴ eine gegebenenfalls substituierte Phenylgruppe.Examples of cleavable groups linked via oxygen correspond to the formula
-O-R⁴,
where R⁴ represents an acyclic or cyclic organic radical, for example alkyl, aryl, a heterocyclic group or acyl, which is derived, for example, from an organic carbon or sulfonic acid. In particularly preferred cleavable groups of this type, R⁴ represents an optionally substituted phenyl group.

Beispiele von über Stickstoff angeknüpften abspaltbaren Gruppen sind in den folgenden deutschen Offenlegungs­schriften (DE-A-) beschrieben:
25 36 191, 27 03 589, 28 13 522, 33 39 201.Examples of cleavable groups linked via nitrogen are described in the following German Offenlegungsschriften (DE-A-):
25 36 191, 27 03 589, 28 13 522, 33 39 201.

Hierbei handelt es sich vielfach um 5-gliedrige hetero­cyclische Ringe, die über ein Ringstickstoffatom mit der Kupplungsstelle des Gelbkupplers verbunden sind. Die heterocyclischen Ringe enthalten vielfach benachbart zu dem die Bindung an das Kupplermolekül vermittelnden Stick­stoffatom aktivierende Gruppen, z. B. Carbonyl- oder Sul­fonylgruppen oder Doppelbindungen.These are often 5-membered heterocyclic rings which are connected to the coupling site of the yellow coupler via a ring nitrogen atom. The heterocyclic rings often contain groups adjacent to the nitrogen atom which activates the bond to the coupler molecule, e.g. B. carbonyl or sulfonyl groups or double bonds.

Wenn die abspaltbare Gruppe über ein Schwefelatom an die Kupplungsstelle des Kupplers gebunden ist, kann es sich bei ihr um den Rest einer diffusionsfähigen Mercaptover­bindung handeln, die die Entwicklung von Silberhalogenid zu inhibieren vermag. Derartige Inhibitorreste sind viel­fach als an die Kupplungsstelle von Kupplern, auch Gelb­kupplern gebundene abspaltbare Gruppe beschrieben worden, z. B. in US-A-3 227 554.If the cleavable group is attached to the coupling site of the coupler via a sulfur atom, it can be the remainder of a diffusible mercapto compound which is able to inhibit the development of silver halide. Such inhibitor residues have been described many times as cleavable group bound to the coupling point of couplers, also yellow couplers, e.g. See, for example, US-A-3,227,554.

Der erfindungsgemäß verwendete Gelbkuppler kann auch ein polymerer Purpurkuppler sein, beispielsweise erhalten durch Homo- oder Copolymerisation von monomeren Kupplern gemäß Formel, die in einem der Substituenten eine ethyle­nisch ungesättigte copolymerisierbare Doppelbindung ent­halten. Derartige Kuppler sind beispielsweise in DE-A-­31 48 125, DE-A-33 00 665, DE-A-33 05 718 und Research Disclosure 25 724 (September 1985) beschrieben.The yellow coupler used according to the invention can also be a polymeric purple coupler, for example obtained by homo- or copolymerization of monomeric couplers according to the formula which contain an ethylenically unsaturated copolymerizable double bond in one of the substituents. Couplers of this type are described, for example, in DE-A-31 48 125, DE-A-33 00 665, DE-A-33 05 718 and Research Disclosure 25 724 (September 1985).

Nachstehend sind Beispiele für geeignete Gelbkuppler ange­geben.

Figure imgb0002
Figure imgb0003
Figure imgb0004
Figure imgb0005
Figure imgb0006
Figure imgb0007
 Examples of suitable yellow couplers are given below.
Figure imgb0002
Figure imgb0003
Figure imgb0004
Figure imgb0005
Figure imgb0006
Figure imgb0007

Das erfindungsgemäße farbfotografische Aufzeichnungsma­terial enthält mindestens eine lichtempfindliche Silber­halogenidemulsionsschicht und vorzugsweise eine Abfolge mehrerer solcher lichtempfindlichen Silberhalogenidemul­sionsschichten und gegebenenfalls dazwischen angeordneten nicht lichtempfindlichen Bindemittelschichten, wobei nach vorliegender Erfindung mindestens einer der vorhandenen lichtempfindlichen Silberhalogenidemulsionsschichten ein Gelbkuppler der angegebenen Formel emulgiert mit einem Ölbildner gemäß vorliegender Erfindung zugeordnet ist.The color photographic recording material according to the invention contains at least one light-sensitive silver halide emulsion layer and preferably a sequence of several such light-sensitive silver halide emulsion layers and, if appropriate, non-light-sensitive binder layers arranged between them.

Der erfindungsgemäße Ölbildner kann alleine oder zusammen mit anderen bekannten Ölbildnern verwendet werden, wobei jedoch, falls der Gelbkuppler in einem Gemisch von Öl­bildnern gelöst wird, ein solches Gemisch vorzugsweise zu wenigstens 50 Gew.-% aus einem Ölbildner der vorliegenden Erfindung besteht.The oil-forming agent according to the invention can be used alone or together with other known oil-forming agents, but if the yellow coupler is dissolved in a mixture of oil-forming agents, such a mixture preferably consists of at least 50% by weight of an oil-forming agent of the present invention.

Bei den Ölbildnern handelt es sich allgemein um hochsie­dende Substanzen, die für die zu dispergierenden Kuppler ein gutes Lösungsvermögen haben und die daher auch als Kupplerlösungsmittel bezeichnet werden.The oil formers are generally high-boiling substances which have a good dissolving power for the couplers to be dispersed and which are therefore also referred to as coupler solvents.

Die in den lichtempfindlichen Schichten verwendeten licht­empfindlichen Silberhalogenidemulsionen können als Haloge­nid Chlorid, Bromid und Iodid bzw. Mischungen davon ent­halten. Beispielsweise kann der Halogenidanteil wenigstens einer Schicht zu 0 bis 12 mol-% aus Iodid, zu 0 bis 50 mol-% aus Chlorid und zu 50 bis 100 mol-% aus Bromid bestehen. In bestimmten Ausführungsformen handelt es sich um überwiegend kompakte Kristalle, die z.B. kubisch oder oktaedrisch sind oder Übergangsformen aufweisen. Sie las­sen sich dadurch kennzeichnen, daß sie im wesentlichen eine Dicke von mehr als 0,2 µm aufweisen. Das durch­schnittliche Verhältnis von Durchmesser zu Dicke ist be­vorzugt kleiner als 8:1, wobei gilt, daß der Durchmesser eines Kornes definiert ist als der Durchmesser eines Krei­ses mit einem Kreisinhalt entsprechend der projizierten Fläche des Kornes. In anderen Ausführungsformen können alle oder einzelne Emulsionen aber auch im wesentlichen tafelförmige Silberhalogenidkristalle aufweisen, bei denen das Verhältnis von Durchmesser zu Dicke größer als 8:1 ist. Bei den Emulsionen kann es sich um heterodisperse, oder auch um monodisperse Emulsionen handeln, die bevor­zugt eine mittlere Korngröße von 0,3 µm bis 1,2 µm auf­weisen. Die Silberhalogenidkörner können auch einen ge­schichteten Kornaufbau aufweisen.The light-sensitive silver halide emulsions used in the light-sensitive layers can contain chloride, bromide and iodide or mixtures thereof as the halide. For example, the halide content of at least one layer can consist of 0 to 12 mol% of iodide, 0 to 50 mol% of chloride and 50 to 100 mol% of bromide. In certain embodiments, the crystals are predominantly compact, for example cubic or octahedral or have transition forms. They can be characterized in that they essentially have a thickness of more than 0.2 μm. The average ratio of diameter to thickness is preferably less than 8: 1, it being true that the diameter of a grain is defined as the diameter of a circle with a circle content corresponding to the projected area of the grain. In other embodiments, however, all or individual emulsions can also have essentially tabular silver halide crystals in which the ratio of diameter to thickness is greater than 8: 1. The emulsions can be heterodisperse, or also act as monodisperse emulsions, which preferably have an average grain size of 0.3 μm to 1.2 μm. The silver halide grains can also have a layered grain structure.

Die Emulsionen können in der üblichen Weise chemisch und oder spektral sensibilisiert sein; sie können auch durch geeignete Zusätze stabilisiert sein. Geeignete chemische Sensibilisatoren, spektrale Sensibilisierungsfarbstoffe und Stabilisatoren sind beispielsweise in Research Disclo­sure 17643 (Dezember 1978) beschrieben; verwiesen wird insbesondere auf die Kapitel III, IV und VI.The emulsions can be chemically and or spectrally sensitized in the usual way; they can also be stabilized by suitable additives. Suitable chemical sensitizers, spectral sensitizing dyes and stabilizers are described, for example, in Research Disclosure 17643 (December 1978); Reference is made in particular to chapters III, IV and VI.

Das erfindungsgemäße farbfotografische Aufzeichnungsma­terial enthält bevorzugt mindestens je eine Silberhaloge­nidemulsionsschicht für die Aufzeichnung von Licht jedes der drei Spektralbereiche Rot, Grün und Blau. Zu diesem Zweck sind die lichtempfindlichen Schichten in bekannter Weise durch geeignete Sensibilisierungsfarbstoffe spektral sensibilisiert. Blauempfindliche Silberhalogenidemulsions­schichten müssen nicht notwendigerweise einen Spektralsen­sibilisator enthalten, da für die Aufzeichnung von blauem Licht in vielen Fällen die Eigenempfindlichkeit des Sil­berhalogenids ausreicht.The color photographic recording material according to the invention preferably contains at least one silver halide emulsion layer for the recording of light from each of the three spectral ranges red, green and blue. For this purpose, the light-sensitive layers are spectrally sensitized in a known manner by means of suitable sensitizing dyes. Blue-sensitive silver halide emulsion layers do not necessarily have to contain a spectral sensitizer, since in many cases the intrinsic sensitivity of the silver halide is sufficient for the recording of blue light.

Jede der genannten lichtempfindlichen Schichten kann aus einer einzigen Schicht bestehen oder in bekannter Weise, z.B. bei der sogenannten Doppelschichtanordnung, auch zwei oder auch mehr Silberhalogenidemulsionsteilschichten um­fassen (DE-C-1 121 470). Üblicherweise sind rotempfind­liche Silberhalogenidemulsionsschichten dem Schichtträger näher angeordnet als grünempfindliche Silberhalogenid­emulsionsschichten und diese wiederum näher als blau­empfindliche, wobei sich im allgemeinen zwischen grün­empfindlichen Schichten und blauempfindlichen Schichten eine nicht lichtempfindliche gelbe Filterschicht befindet. Es sind aber auch andere Anordnungen denkbar. Zwischen Schichten unterschiedlicher Spektralempfindlichkeit ist in der Regel eine nicht lichtempfindliche Zwischenschicht angeordnet, die Mittel zur Unterbindung der Fehldiffusion von Entwickleroxidationsprodukten enthalten kann. Falls mehrere Silberhalogenidemulsionsschichten gleicher Spek­tralempfindlichkeit vorhanden sind, können diese einander unmittelbar benachbart sein oder so angeordnet sein, daß sich zwischen ihnen eine lichtempfindliche Schicht mit anderer Spektralempfindlichkeit befindet (DE-A-1 958 709, DE-A-2 530 645, DE-A-2 622 922).Each of the light-sensitive layers mentioned can consist of a single layer or, in a known manner, for example in the case of the so-called double-layer arrangement, can also comprise two or more silver halide emulsion partial layers (DE-C-1 121 470). Red-sensitive silver halide emulsion layers are usually the support arranged closer than green-sensitive silver halide emulsion layers and these, in turn, closer than blue-sensitive layers, a non-light-sensitive yellow filter layer generally being located between green-sensitive layers and blue-sensitive layers. However, other arrangements are also conceivable. A layer which is not sensitive to light is generally arranged between layers of different spectral sensitivity and can contain means for preventing the incorrect diffusion of developer oxidation products. If there are several silver halide emulsion layers of the same spectral sensitivity, they can be directly adjacent to one another or be arranged such that a light-sensitive layer with a different spectral sensitivity is located between them (DE-A-1 958 709, DE-A-2 530 645, DE-A -2 622 922).

Erfindungsgemäße farbfotografische Aufzeichnungsmateriali­en enthalten üblicherweise in räumlicher und spektraler Zuordnung zu den Silberhalogenidemulsionsschichten un­terschiedlicher Spektralempfindlichkeit Farbkuppler zur Erzeugung der unterschiedlichen Teilfarbenbilder Cyan, Purpur und Gelb, wobei die mit dem Ölbildner der vorlie­genden Erfindung dispergierten Gelbkuppler einer blau­empfindlichen Silberhalogenidemulsionsschicht zugeordnet sind.Color photographic recording materials according to the invention usually contain, in spatial and spectral assignment to the silver halide emulsion layers of different spectral sensitivity, color couplers for producing the different partial color images cyan, purple and yellow, the yellow couplers dispersed with the oil former of the present invention being assigned to a blue-sensitive silver halide emulsion layer.

Unter räumlicher Zuordnung ist dabei zu verstehen, daß der Farbkuppler sich in einer solchen räumlichen Beziehung zu der Silberhalogenidemulsionsschicht befindet, daß eine Wechselwirkung zwischen ihnen möglich ist, die eine bild­ gemäße Übereinstimmung zwischen dem bei der Entwicklung gebildeten Silberbild und dem aus dem Farbkuppler erzeug­ten Farbbild zuläßt. Dies wird in der Regel dadurch er­reicht, daß der Farbkuppler in der Silberhalogenidemul­sionsschicht selbst enthalten ist oder in einer hierzu benachbarten gegebenenfalls nichtlichtempfindlichen Binde­mittelschicht.Spatial assignment is to be understood to mean that the color coupler is in such a spatial relationship with the silver halide emulsion layer that an interaction between them is possible, which is an image according agreement between the silver image formed during development and the color image generated from the color coupler. This is usually achieved by the fact that the color coupler is contained in the silver halide emulsion layer itself or in a possibly non-light-sensitive binder layer adjacent to it.

Unter spektraler Zuordnung ist zu verstehen, daß die Spek­tralempfindlichkeit jeder der lichtempfindlichen Silberha­logenidemulsionsschichten und die Farbe des aus dem jeweils räumlich zugeordneten Farbkuppler erzeugten Teilfarbenbildes in einer bestimmten Beziehung zueinander stehen, wobei jeder der Spektralempfindlichkeiten (Rot, Grün, Blau) eine andere Farbe des betreffenden Teilfarbenbildes (im allgemeinen z.B. die Farben Cyan, Purpur bzw. Gelb in dieser Reihenfolge) zugeordnet ist.Spectral assignment is understood to mean that the spectral sensitivity of each of the light-sensitive silver halide emulsion layers and the color of the partial color image generated from the spatially assigned color coupler are in a specific relationship to one another, with each of the spectral sensitivities (red, green, blue) having a different color of the relevant partial color image (in general, for example, the colors cyan, purple or yellow in this order).

Jeder der unterschiedlich spektral sensibilisierten Sil­berhalogenidemulsionsschichten kann ein oder können auch mehrere Farbkuppler zugeordnet sein. Wenn mehrere Silber­halogenidemulsionsschichten gleicher Spektralempfindlich­keit vorhanden sind, kann jede von ihnen einen Farbkuppler enthalten, wobei diese Farbkuppler nicht notwendigerweise identisch zu sein brauchen. Sie sollen lediglich bei der Farbentwicklung wenigstens annähernd die gleiche Farbe er­geben, normalerweise eine Farbe, die komplementär ist zu der Farbe des Lichtes, für das die betreffenden Silberha­logenidemulsionsschichten überwiegend empfindlich sind.One or more color couplers can be assigned to each of the differently spectrally sensitized silver halide emulsion layers. If there are several silver halide emulsion layers of the same spectral sensitivity, each of them can contain a color coupler, which color couplers need not necessarily be identical. They should only result in at least approximately the same color during color development, normally a color that is complementary to the color of the light, for which the silver halide emulsion layers in question are predominantly sensitive.

Rotempfindlichen Silberhalogenidemulsionsschichten ist folglich bei bevorzugten Ausführungsformen mindestens ein nichtdifundierender Farbkuppler zur Erzeugung des blau­grünen Teilfarbenbildes zugeordnet, in der Regel ein Kupp­ler vom Phenol- oder α-Naphtholtyp, Grünempfindlichen Silberhalogenidemulsionsschichten ist mindestens ein nichtdiffundierender Farbkuppler zur Erzeugung des pur­purnen Teilfarbenbildes zugeordnet, in der Regel ein Kuppler vom Indazolon- oder Pyrazoloazoltyp. Blauempfind­lichen Silberhalogenidemulsionsschichten schließlich ist mindestens ein nichtdiffundierender Farbkuppler zur Er­zeugung des gelben Teilfarbenbildes zugeordnet. Farb­kuppler dieser Art sind in großer Zahl bekannt und in einer Vielzahl von Patentschriften beschrieben. Bei­spielhaft sei hier auf die Veröffentlichungen "Farb­kuppler" von W. PELZ in "Mitteilungen aus den For­schungslaboratorien der Agfa, Leverkusen/München", Band III, Seite 111 (1961) und von K. VENKATARAMAN in "The Chemistry of Synthetic Dyes", Vol. 4, 341 bis 387, Academic Press (1971), verwiesen.In preferred embodiments, red-sensitive silver halide emulsion layers are therefore assigned at least one non-diffusing color coupler for producing the blue-green partial color image, as a rule a coupler of the phenol or α-naphthol type, green-sensitive silver halide emulsion layers are assigned at least one non-diffusing color coupler for generating the purple partial color image in the regular color image of the indazolone or pyrazoloazole type. Finally, blue-sensitive silver halide emulsion layers are assigned at least one non-diffusing color coupler for generating the yellow partial color image. Color couplers of this type are known in large numbers and are described in a large number of patents. Examples include the publications "Farbkuppler" by W. PELZ in "Mitteilungen aus den Forschungslaboratorien der Agfa, Leverkusen / München", Volume III, page 111 (1961) and by K. VENKATARAMAN in "The Chemistry of Synthetic Dyes", Vol 4, 341 to 387, Academic Press (1971).

Bei den erfindungsgemäßen Farbkupplern wie auch bei den übrigen im farbfotografischen Aufzeichnungsmaterial vor­handenen Farbkupplern kann es sich sowohl um übliche 4-­Äquivalentkuppler handeln als auch um 2-Äquivalentkuppler, bei denen zur Farberzeugung eine geringere Menge Silber­halogenid erforderlich ist. 2-Äquivalentkuppler 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. Letztere Kuppler können ebenfalls zusätzlich in den lichtempfindlichen Silberhalogenid­emulsionsschichten vorhanden sein und dort als Masken­kuppler zur Kompensierung der unerwünschten Nebendichten der Bildfarbstoffe dienen. Zu den 2-Äquivalenkupplern sind aber auch die bekannten Weißkuppler zu rechnen, die jedoch bei Reaktion mit Farbentwickleroxidationsprodukten keinen Farbstoff ergeben. Zu den 2-Äquivalentkupplern 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 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. Der abgespaltbare 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.The color couplers according to the invention, as well as the other color couplers present in the color photographic recording material, can be both conventional 4-equivalent couplers and 2-equivalent couplers, in which a smaller amount of silver halide is required to produce the color. As is well known, 2-equivalent couplers are derived from the 4-equivalent couplers in that they contain a substituent in the coupling site, which is split off during the coupling. To the 2- Equivalent couplers are to be counted 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. The latter couplers can also be present in the light-sensitive silver halide emulsion layers and serve there as mask couplers to compensate for the undesired secondary densities of the image dyes. However, the known white couplers are also to be counted among the 2-equivalent couplers, but they do not give any dye on reaction with color developer oxidation products. The 2-equivalent couplers also include those couplers which contain a detachable residue in the coupling point, which is released when reacting with color developer oxidation products and thereby develops a certain desired photographic activity, 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. The cleavable residue can also be a ballast residue, so that in the reaction with color developer oxidation products coupling products, for example dyes, can be obtained which are diffusible or at least have a weak or restricted mobility.

Unter einer schwachen bzw. eingeschränkten Beweglichkeit ist eine Beweglichkeit zu verstehen, die so bemessen ist, daß die Konturen der bei der chromogenen Entwicklung ge­bildeten diskreten Farbstoffflecken verlaufen und inein­ander verschmiert werden. Dieses Ausmaß der Beweglichkeit ist einerseits zu unterscheiden von dem üblichen Fall der völligen Unbeweglichkeit in fotografischen Schichten, der in der herkömmlichen fotografischen Aufzeichnungsmateri­alien für die Farbkuppler bzw. die daraus hergestellten Farbstoffe angestrebt wird um eine möglichst hohe Schärfe zu erzielen, und andererseits von dem Fall der völligen Beweglichkeit der Farbstoffe, der beispielsweise bei Farb­diffusionsverfahren angestrebt wird. Das Ausmaß der erfindungsgemäß angestrebten schwachen Beweglichkeit kann gesteuert werden durch Variation von Substituenten um beispielsweise die Löslichkeit im organischen Medium des Ölbildners oder die Affinität zur Bindemittelmatrix in gezielter Weise zu beeinflussen.Weak or restricted mobility means mobility that is dimensioned such that the contours of the discrete dye spots formed in the chromogenic development run and are smeared into one another. On the one hand, this degree of mobility is to be distinguished from the usual case of complete immobility in photographic layers, which is sought in the conventional photographic recording materials for the color couplers or the dyes produced therefrom in order to achieve the highest possible sharpness, and on the other hand the case of complete mobility of the dyes, which is sought, for example, in color diffusion processes. The extent of the weak mobility sought according to the invention can be controlled by varying substituents in order to influence, for example, the solubility in the organic medium of the oil former or the affinity for the binder matrix in a targeted manner.

Für die erfindungsgemäßen Aufzeichnungsmaterialien eignen sich die üblichen Schichtträger, z.B. Träger aus Cellulo­seestern, z.B. Celluloseacetat und aus Polyestern. Geeig­net sind ferner Papierträger, die gegebenenfalls beschich­tet sein können z.B. mit Polyolefinen, insbesondere mit Polyethylen oder Polypropylen. Verwiesen wird diesbezüg­lich auf Research Disclosure 17643, Kapitel XVII.The usual supports, e.g. Cellulose ester supports, e.g. Cellulose acetate and polyester. Also suitable are paper supports, which can optionally be coated, e.g. with polyolefins, especially with polyethylene or polypropylene. In this regard, reference is made to Research Disclosure 17643, Chapter XVII.

Als Schutzkolloid bzw. Bindemittel für die Schichten des Aufzeichnungsmaterials sind die üblichen hydrophilen film­bildenden Mittel geeignet, z.B. Proteine, insbesondere Ge­latine. Begußhilfsmittel und Weichmacher können verwendet werden. Verwiesen wird auf Research Disclosure 17643, Kapitel IX, XI und XII.The usual hydrophilic film-forming agents, for example proteins, in particular gelatin, are suitable as protective colloids or binders for the layers of the recording material. Casting aids and plasticizers can be used. Reference is made to Research Disclosure 17643, Chapter IX, XI and XII.

Die Schichten des fotografischen Materials können in der üblichen Weise gehärtet sein, beispielsweise mit Härtern, die mindestens zwei reaktive Oxiran-, Aziridin- oder Acry­loylgruppen enthalten. Weiterhin ist es auch möglich, die Schichten gemäß dem in DE-A-22 18 009 beschriebenen Ver­fahren zu härten. Es ist ferner möglich, die fotografi­schen Schichten bzw. die farbfotografischen Mehrschichten­materialien mit Härten der Diazin-, Triazin- oder 1,2-­Dihydrochinolin-Reihe zu härten oder mit Härtern vom Vinylsulfon-Typ. Weitere geeignete Härtungsmittel sind aus DE-A-22 25 230, DE-A-23 17 677, DE-A-24 39 551, wie auch aus Research Disclosure 17 643, Kapitel X bekannt. Beson­ders ausgeprägt ist die stabilisierende Wirkung der er­findungsgemäßen Ölbildner, wenn Carboxylgruppen akti­vierende Härtungsmittel, z.B. Carbamoylpyridinium- oder Carbamoyloxypyridiniumsalze verwendet werden.The layers of the photographic material can be hardened in the usual way, for example with hardeners which contain at least two reactive oxirane, aziridine or acryloyl groups. Furthermore, it is also possible to harden the layers in accordance with the process described in DE-A-22 18 009. It is also possible to harden the photographic layers or the color photographic multilayer materials with hardnesses of the diazine, triazine or 1,2-dihydroquinoline series or with hardeners of the vinyl sulfone type. Other suitable curing agents are known from DE-A-22 25 230, DE-A-23 17 677, DE-A-24 39 551, and also from Research Disclosure 17 643, Chapter X. The stabilizing effect of the oil formers according to the invention is particularly pronounced when hardening agents which activate carboxyl groups, e.g. Carbamoylpyridinium or carbamoyloxypyridinium salts can be used.

Weitere geeignete Zusätze werden in der Research Disclo­sure 17 643 und in "Product Licensing Index" von Dezember 1971, Seiten 107-110, angegeben.Further suitable additives are given in Research Disclosure 17 643 and in "Product Licensing Index" from December 1971, pages 107-110.

Geeignete Farbentwicklersubstanzen für das erfindungs­gemäße Material sind insbesondere solche vom p-Phenylen­diamintyp, z.B. 4-Amino-N,N-diethyl-anilinhydrochlorid, 4-Amino-3-methyl-N-ethyl-N-β-(methansulfonamido)-ethyl-­anilinsulfathydrat, 4-Amino-3-methyl-N-ethyl-N-β-hy­droxyethylanilinsulfat, 4-Amino-N-ethyl-N-(2-methoxy­ethyl)-m-toluidin-di-p-toluolsulfonsäure und N-Ethyl-­N-β-hydroxyethyl-p-phenylendiamin. Weitere brauchbare Farbentwickler sind beispielsweise beschrieben in J.Amer.Chem.Soc. 73, 3100 (1951) und in G. Haist, Modern Photographic Processing, 1979, John Wiley and Sons, New York, Seiten 545 ff.Suitable color developer substances for the material according to the invention are in particular those of the p-phenylenediamine type, for example 4-amino-N, N-diethyl-aniline hydrochloride, 4-amino-3-methyl-N-ethyl-N-β- (methanesulfonamido) ethyl-aniline sulfate hydrate , 4-amino-3-methyl-N-ethyl-N-β-hydroxyethylaniline sulfate, 4-amino-N-ethyl-N- (2-methoxyethyl) -m-toluidine-di-p-toluenesulfonic acid and N-ethyl-N -β-hydroxyethyl-p-phenylenediamine. Other useful color developers are described, for example, in J.Amer.Chem.Soc. 73 , 3100 (1951) and in G. Haist, Modern Photographic Processing, 1979, John Wiley and Sons, New York, pages 545 ff.

Nach der Farbentwicklung wird das Material üblicherweise gebleicht und fixiert. Bleichung und Fixierung können ge­trennt voneinander oder auch zusammen durchgeführt werden. Als Bleichmittel können die üblichen Verbindungen verwen­det werden, z.B. Fe³⁺-Salze und Fe³⁺-Komplexsalze wie Ferricyanide, Dichromate, wasserlösliche Kobaltkomplexe usw. Besonders bevorzugt sind Eisen-III-Komplexe von Aminopolycarbonsäuren, insbesondere z.B. Ethylendiamin­tetraessigsäure, Nitrilotriessigsäure, Iminodiessigsäure, N-Hydroxyethylethylendiamintriessigsäure, Alkylimino­dicarbonsäuren und von entsprechenden Phosphonsäuren. Geeignet als Bleichmittel sind weiterhin Persulfate.After color development, the material is usually bleached and fixed. Bleaching and fixing can be carried out separately or together. The usual compounds can be used as bleaching agents, e.g. Fe³⁺ salts and Fe³⁺ complex salts such as ferricyanides, dichromates, water-soluble cobalt complexes etc. Particularly preferred are iron III complexes of aminopolycarboxylic acids, especially e.g. Ethylenediaminetetraacetic acid, nitrilotriacetic acid, iminodiacetic acid, N-hydroxyethylethylenediaminetriacetic acid, alkyliminodicarboxylic acids and corresponding phosphonic acids. Persulphates are also suitable as bleaching agents.

Im Falle von - hier bevorzugten - Farbumkehrmaterialien geht der Farbentwicklung eine Schwarz-Weißentwicklung und eine diffuse Zweitbelichtung oder chemische Verschleierung voraus.In the case of - here preferred - color reversal materials, the color development is preceded by a black and white development and a diffuse second exposure or chemical fogging.

Beispiel 1 (Einzelschicht) Example 1 (single layer)

Ein farbfotografisches Aufzeichnungsmaterial wurde herge­stellt, indem auf einen transparenten Schichtträger aus Cellulosetriacetat die folgenden Schichten in der ange­gebenen Reihenfolge aufgetragen wurden. Die Mengenangaben beziehen sich jeweils auf 1 m². Für den Silberhalogenid­auftrag werden die entsprechenden Mengen AgNO₃ angegeben. Alle Silberhalogenidemulsionen waren pro 100 g AgNO₃ mit 0,5 g 4-Hydroxy-6-methyl-1,3,3a,7-tetraazainden stabili­siert.A color photographic recording material was prepared by applying the following layers in the order given to a transparent cellulose triacetate support. The quantities given relate to 1 m². For the silver halide application, the corresponding amounts of AgNO₃ are given. All silver halide emulsions were stabilized per 100 g of AgNO₃ with 0.5 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene.

Schicht 1 (Antihaloschicht)Layer 1 (antihalo layer)

Schwarzes kolloidales Silbersol mit 1,5 g Gelatine und 0,33 g Ag.Black colloidal silver sol with 1.5 g gelatin and 0.33 g Ag.

Schicht 2 (Zwischenschicht)Layer 2 (intermediate layer)

0,6 g Gelatine0.6 g gelatin

Schicht 3 (blauempfindliche Schicht)Layer 3 (blue sensitive layer)

blausensibilisierte Silberbromidiodidemul­sion (4 mol-% Iodid;
mittlerer Korndurchmesser 0,3 µm) aus 2,0 g AgNO₃, mit 2,3 g Gelbkuppler GB 19 emul­giert in 1,15 g Ölbildner, und 2,8 g Gelatine.blue-sensitized silver bromide iodide emulsion (4 mol% iodide;
average grain diameter 0.3 µm) from 2.0 g of AgNO₃, with 2.3 g of yellow coupler GB 19 emulsified in 1.15 g of oil former, and 2.8 g of gelatin.

Schicht 4 (Schutzschicht)Layer 4 (protective layer)

1,2 g Gelatine.1.2 g gelatin.

Schicht 5 (Härtungsschicht)Layer 5 (hardening layer)

1,3 g Gelatine und 0,5 g Härtungsmittel der folgenden Formel

Figure imgb0008
1.3 g gelatin and 0.5 g hardening agent of the following formula
Figure imgb0008

Von dem Aufzeichnungsmaterial wurden drei verschiedene Versionen hergestellt (Proben 1, 2 und 3), die sich nur durch die Art des in Schicht 3 verwendeten Ölbildners unterschieden.

  • In Probe 1 bestand der Ölbildner zu 100 % aus Trikresyl­phosphat (TKP).
  • In Probe 2 bestand der Ölbildner zu je 50 Gew.-% aus TKP und I-2.
  • In Probe 3 bestand der Ölbildner zu 100 % aus I-2.
Three different versions of the recording material were produced (samples 1, 2 and 3), which differed only in the type of oil former used in layer 3.
  • In sample 1, the oil generator consisted of 100% tricresyl phosphate (TKP).
  • In sample 2, the oil former consisted of 50% by weight of CPM and I-2.
  • In sample 3, the oil generator was 100% I-2.

Die so hergestellten Proben wurden belichtet und in einer üblichen Color-Umkehrentwicklung, siehe Beispiel 2 der EP-A-62 202, entwickelt.The samples produced in this way were exposed and developed in a customary color reversal development, see Example 2 of EP-A-62 202.

Die Absorptionskurven der entwickelten Proben wurde je­weils für Dichte 1,0 vermessen und daraus der Flanken­abstand bei 50 % Absorption sowie die auf der langwelligen Flanke bei 30 % Absorption ereichte Wellenlänge bestimmt. Die Ergebnisse sind der Tabelle 1 zu entnehmen.The absorption curves of the developed samples were measured for density 1.0 and the flank spacing at 50% absorption and the wavelength reached on the long-wave flank at 30% absorption were determined. The results are shown in Table 1.

Die Proben 2 und 3 zeigen einen deutlich engeren Flanken­abstand der Absorptionskurve und reichen nicht soweit in den langwelligen, grünen Absorptionsbereich hinein wie die Probe 1. Sie zeigen somit ein farbreineres, weniger pur­purnes Gelb als Probe 1.Samples 2 and 3 show a clearly narrower flank spacing of the absorption curve and do not extend as far into the long-wave, green absorption area as sample 1. They therefore show a purer, less purple yellow than sample 1.

Zur Überprüfung der Farbstoffstabilität bei Dunkellagerung werden die entwickelten Proben bei 80°C und 40 % relat. Feuchte 14, 28 und 42 Tage gelagert und die Änderung der Maximaldichte gemessen. Die in Tabelle 1 angegebenen rela­tiven Maximaldichten Dt/Dto · 100 zeigen eine deutlich höhere dark-fading-Stabilität für die Proben 2 und 3.To check the dye stability in dark storage, the developed samples are at 80 ° C and 40% relat. Moisture stored for 14, 28 and 42 days and the change in maximum density measured. The relative maximum densities D t / D to · 100 shown in Table 1 show a significantly higher dark fading stability for samples 2 and 3.

Beispiel 2 (Doppelschicht) Example 2 (double layer)

Ein farbfotografisches Aufzeichnungsmaterial für die Um­kehrfarbentwicklung wurde hergestellt, indem auf einen transparenten Schichtträger aus Cellulosetriacetat die folgenden Schichten in der angegebenen Reihenfolge aufge­tragen wurden. Die Mengenangaben beziehen sich jeweils auf 1 m². Für den Silberhalogenidauftrag werden die ent­sprechenden Mengen AgNO₃ angegeben. Alle Silberhalogenid­emulsionen waren pro 100 g AgNO₃ mit 0,5 g 4-Hydroxy-6-­methyl-1,3,3a,7-tetraazainden stabilisiert.A color photographic recording material for reverse color development was prepared by applying the following layers in the order given on a transparent cellulose triacetate support. The quantities given relate to 1 m². For the silver halide application, the corresponding amounts of AgNO₃ are given. All silver halide emulsions were stabilized per 100 g of AgNO₃ with 0.5 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene.

Schicht 1 (Antihaloschicht)Layer 1 (antihalo layer)

schwarzes kolloidales Silbersol mit 1,5 g Gelatine und 0,33 g Ag.black colloidal silver sol with 1.5 g gelatin and 0.33 g Ag.

Schicht 2 (Zwischenschicht)Layer 2 (intermediate layer)

0,6 g Gelatine0.6 g gelatin

Schicht 3 (1. blauempfindliche Schicht)Layer 3 (1st blue sensitive layer)

blausensibilisierte Silberbromidiodidemul­sion (4 mol-% Iodid; mittlerer Korndurch­messer 0,25 µm) aus 0,5 g AgNO₃, mit 0,6 g Gelbkuppler GB 19, emulgiert mit 0,3 g TKP und 0,75 g Gelatine.Blue-sensitized silver bromide iodide emulsion (4 mol% iodide; average grain diameter 0.25 µm) from 0.5 g AgNO₃, with 0.6 g yellow coupler GB 19, emulsified with 0.3 g CPM and 0.75 g gelatin.

Schicht 4 (2. blauempfindliche Schicht)Layer 4 (2nd blue sensitive layer)

blausensibilisierte Silberbromidiodidemul­sion (3 mol-% Iodid; mittlerer Korndurch­messer 0,8 µm) aus 1,15 g AgNO₃, mit 1,35 g Gelbkuppler GB 19, emulgiert mit 0,7 g TKP und 1,6 g Gelatine.Blue-sensitized silver bromide iodide emulsion (3 mol% iodide; average grain diameter 0.8 µm) from 1.15 g AgNO₃, with 1.35 g yellow coupler GB 19, emulsified with 0.7 g CPM and 1.6 g gelatin.

Schicht 5 (3. blauempfindliche Schicht)Layer 5 (3rd blue-sensitive layer)

blausensibilisierte Silberbromidiodidemul­sion (4 mol-% Iodid; mittlerer Korndurch­messer 0,03 µm) aus 0,2 g AgNO₃, mit 0,8 g eines üblichen UV-Absorbers und 0,8 g Gela­tine.Blue-sensitized silver bromide iodide emulsion (4 mol% iodide; average grain diameter 0.03 µm) from 0.2 g AgNO₃, with 0.8 g of a conventional UV absorber and 0.8 g gelatin.

Schicht 6 (Schutzschicht)Layer 6 (protective layer)

0,7 g Gelatine.0.7 g gelatin.

Schicht 7 (Härtungsschicht)Layer 7 (hardening layer)

1,5 g Gelatine und 0,7 g des in Beispiel 1 beschriebenen Härtungsmittels.1.5 g of gelatin and 0.7 g of the hardening agent described in Example 1.

Von diesem Aufzeichnungsmaterial wurden drei verschiedene Versionen hergestellt, (Proben 4, 5 und 6) die sich nur durch die Art des in den Schichten 3 und 4 verwendeten Ölformers unterscheiden.Three different versions of this recording material were produced (samples 4, 5 and 6) which differ only in the type of oil former used in layers 3 and 4.

In Probe 4 bestand der Ölbildner zu 100 Gew.-% aus TKP. In Probe 5 bestanden die Ölformer zu je 50 Gew.-% aus TKP und I-2. In Probe 6 bestand der Ölformer zu 100 Gew.-% aus I-2.In sample 4, the oil former consisted of 100% by weight of CPM. In sample 5, the oil formers each consisted of 50% by weight of CPM and I-2. In sample 6, the oil former consisted of 100% by weight of I-2.

Die Verarbeitung und Auswertung war die gleiche wie in Beispiel 1. Die Ergebnisse (Farbeinheit und dark-fading-­Stabilität) sind in Tabelle 1 angegeben. Wieder zeigen die erfindungsgemäßen Varianten 5 und 6 eine höhere Farbrein­heit und bessere dark-fading-Stabilität. Tabelle 1 Probe Nr. Flankenabstand der Absorptionskurve in nm bei halber Dichte Absorptionswellenlänge bei 30 % Dichte der langwelligen Flanke Darkfading-Stabilität Anfangsdichte Restdichte [%] 14d 28d 42d 1 Vergleich 89 507 3,10 95 83 69 2 erfindungsgemäß 84 499 3,05 96 87 77 3 erfindungsgemäß 80 492 3,08 98 92 82 4 Vergleich 92 510 3,14 96 85 71 5 erfindungsgemäß 86 501 3,18 97 90 79 6 erfindungsgemäß 81 494 3,12 100 96 86 The processing and evaluation was the same as in Example 1. The results (color unit and dark fading stability) are given in Table 1. Again, variants 5 and 6 according to the invention show higher color purity and better dark fading stability. Table 1 Sample No. Edge distance of the absorption curve in nm at half density Absorption wavelength at 30% density of the long-wave flank Darkfading stability Initial density Residual density [%] 14d 28d 42d 1 comparison 89 507 3.10 95 83 69 2 according to the invention 84 499 3.05 96 87 77 3 according to the invention 80 492 3.08 98 92 82 4 comparison 92 510 3.14 96 85 71 5 according to the invention 86 501 3.18 97 90 79 6 according to the invention 81 494 3.12 100 96 86

Beispiel 3Example 3

Ein farbfotografisches Aufzeichnungsmaterial für die Um­kehrfarbentwicklung wurde hergestellt, indem auf einen transparenten Schichtträger aus Cellulosetriacetat die folgenden Schichten in der angegebenen Reihenfolge aufge­tragen wurden. Die Mengenangaben beziehen sich jeweils auf 1 m². Für den Silberhalogenidauftrag werden die ent­sprechenden Mengen AgNO₃ angegeben. Alle Silberhalogenid­emulsionen waren pro 100 g AgNO₃ mit 0,5 g 4-Hydroxy-6-­methyl-1,3,3a,7-tetraazainden stabilisiert.A color photographic recording material for reverse color development was prepared by applying the following layers in the order given on a transparent cellulose triacetate support. The quantities given relate to 1 m². For the silver halide application, the corresponding amounts of AgNO₃ are given. All silver halide emulsions were stabilized per 100 g of AgNO₃ with 0.5 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene.

Schicht 1 (Antihaloschicht)Layer 1 (antihalo layer)

schwarzes kolloidales Silbersol mit 1,5 g Gelatine und 0,33 g Ag.black colloidal silver sol with 1.5 g gelatin and 0.33 g Ag.

Schicht 2 (Zwischenschicht)Layer 2 (intermediate layer)

0,6 g Gelatine.0.6 g gelatin.

Schicht 3 (1. rotsensibilisierte Schicht)Layer 3 (1st red-sensitized layer)

rotsensibilisierte Silberbromidiodidemulsion (4 mol-% Iodid; mittlerer Korndurchmesser 0,25 µm) aus 1,3 g AgNO₃, mit 0,38 g Verbindung Blaugrünkuppler C-1, emulgiert in 0,19 g TKP, und 1,3 g Gelatine.red-sensitized silver bromide iodide emulsion (4 mol% iodide; average grain diameter 0.25 µm) from 1.3 g AgNO₃, with 0.38 g compound cyan coupler C-1, emulsified in 0.19 g CPM, and 1.3 g gelatin.

Schicht 4 (2. rotsensibilisierte Schicht)Layer 4 (2nd red-sensitized layer)

rotsensibilisierte Silberbromidiodidemulsion (3 mol-% Iodid; mittlerer Korndurchmesser 0,8 µm) aus 2,0 g AgNO₃, mit 1,2 g Blaugrün­kuppler C-1 emulgiert in 0,6 g TKP, und 1,8 Gelatine.red-sensitized silver bromide iodide emulsion (3 mol% iodide; average grain diameter 0.8 µm) from 2.0 g AgNO₃, with 1.2 g cyan coupler C-1 emulsified in 0.6 g CPM, and 1.8 gelatin.

Schicht 5 (Zwischenschicht)Layer 5 (intermediate layer)

1,1 g Gelatine und 0,5 g 2,5-Diisooctyl­hydrochinon.1.1 g gelatin and 0.5 g 2,5-diisooctylhydroquinone.

Schicht 6 (1. grünsensibilisierte Schicht)Layer 6 (1st green-sensitized layer)

grünsensibilisierte Silberbromidiodidemul­sion (4 mol-% Iodid; mittlerer Korndurch­messer 0,25 µm) aus 1,3 g AgNO₃, mit 0,32 g Purpurkuppler M-1, emulgiert mit 0,16 g TKP und 1,0 g Gelatine.Green-sensitized silver bromide iodide emulsion (4 mol% iodide; average grain diameter 0.25 µm) from 1.3 g AgNO₃, with 0.32 g purple coupler M-1, emulsified with 0.16 g CPM and 1.0 g gelatin.

Schicht 7 (2. grünsensibilisierte Schicht)Layer 7 (2nd green-sensitized layer)

grünsensibilisierte Silberbromidiodidemul­sion (3 mol-% Iodid, mittlerer Korndurch­messer 0,8 µm) aus 1,4 g AgNO₃, mit 1,16 g Purpurkuppler M-1, emulgiert in 0,58 g TKP und 1,35 g Gelatine.green-sensitized silver bromide iodide emulsion (3 mol% iodide, average grain diameter 0.8 µm) from 1.4 g AgNO₃, with 1.16 g purple coupler M-1, emulsified in 0.58 g CPM and 1.35 g gelatin.

Schicht 8 (Gelbfilterschicht)Layer 8 (yellow filter layer)

gelbes kolloidales Silbersol mit 0,18 g Ag, 1,0 g Gelatine und 0,3 g 2,5-Diisooctylhy­drochinon.yellow colloidal silver sol with 0.18 g Ag, 1.0 g gelatin and 0.3 g 2,5-diisooctylhydroquinone.

Schicht 9 (1. blauempfindliche Schicht)Layer 9 (1st blue sensitive layer)

blausensibilisierte Silberbromidiodidemul­sion (4 mol-% Iodid; mittlerer Korndurch­messer 0,25 µm) aus 0,5 g AgNO₃, mit 0,6 g Gelbkuppler GB 19, emulgiert mit 0,3 Ölbild­ner I-2 und 0,75 g Gelatine.Blue-sensitized silver bromide iodide emulsion (4 mol% iodide; average grain diameter 0.25 µm) from 0.5 g AgNO₃, with 0.6 g yellow coupler GB 19, emulsified with 0.3 oil former I-2 and 0.75 g gelatin.

Schicht 10 (2. blauempfindliche Schicht)Layer 10 (2nd blue sensitive layer)

blausensibilisierte Silberbromidiodidemul­sion (3 mol-% Iodid; mittlerer Korndurch­messer 0,8 µm) aus 1,15 g AgNO₃, mit 1,35 g Gelbkuppler GB 19, emulgiert mit 0,3 g Öl­bildner I-2 und 1,6 g Gelatine.Blue-sensitized silver bromide iodide emulsion (3 mol% iodide; average grain diameter 0.8 µm) from 1.15 g AgNO₃, with 1.35 g yellow coupler GB 19, emulsified with 0.3 g oil former I-2 and 1.6 g gelatin.

Schicht 11 (3. blauempfindliche Schicht)Layer 11 (3rd blue-sensitive layer)

blausensibilisierte Silberbromidiodidemul­sion (4 mol-% Iodid; mittlerer Korndurch­messer 0,03 µm) aus 0,2 g AgNO₃, mit 0,8 g eines üblichen UV-Absorbers und 0,8 g Gelatine.Blue-sensitized silver bromide iodide emulsion (4 mol% iodide; average grain diameter 0.03 µm) from 0.2 g AgNO₃, with 0.8 g of a conventional UV absorber and 0.8 g gelatin.

Schicht 12 (Schutzschicht)Layer 12 (protective layer)

0,7 g Gelatine.0.7 g gelatin.

Schicht 13 (Härtungsschicht)Layer 13 (hardening layer)

1,5 g Gelatine und 0,7 g des in Beispiel 1 beschriebenen Härtungsmittels.1.5 g of gelatin and 0.7 g of the hardening agent described in Example 1.

Die Behandlung und Verarbeitung war die gleiche wie in Beispiel 1. Das erhaltene Bild zeigt reine Farben, insbesondere ein reines gelb, und sehr gute dark-fading-­Stabilität.The treatment and processing were the same as in Example 1. The image obtained shows pure colors, in particular a pure yellow, and very good dark fading stability.

Folgende Kuppler wurden verwendet

Figure imgb0009
The following couplers were used
Figure imgb0009

Claims (5)

1. Farbfotografisches Aufzeichnungsmaterial mit einem Träger und mindestens einer lichtempfindlichen Silberhalogenidemulsionsschicht, der ein Gelbkuppler gelöst in einem Ölbildner zugeordnet ist, dadurch gekennzeichnet, daß der Gelbkuppler der Formel
Figure imgb0010
 entspricht, worin
R₁ tert.-Butyl oder gegebenenfalls substitu­iertes Phenyl,
R₂ Wasserstoff oder eine Abspaltgruppe,
R₃ Wasserstoff, Alkoxy oder Halogen
R₄ Wasserstoff, Alkoxy oder Dialkylaminosulfonyl und
R₅ Wasserstoff, Alkoxy oder einen Ballastrest bedeuten und wobei das Kupplermolekül wenigstens einen Ballastrest enthält,
und als Ölbildner ein polymerer Ester von aroma­tischen oder aliphatischen Dicarbonsäuren verwendet wird.1. Color photographic recording material with a support and at least one light-sensitive silver halide emulsion layer, which is assigned a yellow coupler dissolved in an oil former, characterized in that the yellow coupler of the formula
Figure imgb0010
 corresponds to what
R₁ tert-butyl or optionally substituted phenyl,
R₂ is hydrogen or a splitting group,
R₃ is hydrogen, alkoxy or halogen
R₄ is hydrogen, alkoxy or dialkylaminosulfonyl and
R₅ is hydrogen, alkoxy or a ballast residue mean and wherein the coupler molecule contains at least one ballast residue,
and a polymeric ester of aromatic or aliphatic dicarboxylic acids is used as the oil former. 2. Farbfotografisches Aufzeichnungsmaterial nach An­spruch 1, dadurch gekennzeichnet, daß als Ölbildner ein polymerer Phthalsäure- oder Adipinsäureester verwendet wird.2. Color photographic recording material according to claim 1, characterized in that a polymeric phthalic or adipic acid ester is used as the oil former. 3. Farbfotografisches Aufzeichnungsmaterial nach An­spruch 1, dadurch gekennzeichnet, daß der Ölbildner eine Viskosität von 50 bis 5000 mPa.s aufweist.3. Color photographic recording material according to claim 1, characterized in that the oil former has a viscosity of 50 to 5000 mPa.s. 4. Farbfotografisches Aufzeichnungsmaterial nach An­spruch 1, dadurch gekennzeichnet, daß als Diole der polymeren Ester Alkandiole mit 2 bis 10 C-Atomen ver­wendet werden, deren Kohlenstoffkette durch 1 bis 3 Ethersauerstoffatome unterbrochen sein kann.4. Color photographic recording material according to claim 1, characterized in that alkane diols having 2 to 10 carbon atoms are used as diols of the polymeric esters, the carbon chain of which can be interrupted by 1 to 3 ether oxygen atoms. 5. Farbfotografisches Aufzeichnungsmaterial nach An­spruch 1, dadurch gekennzeichnet, daß das Gewichts­verhältnis Kuppler zu Ölbildner 1:0,1-2 beträgt.5. Color photographic recording material according to claim 1, characterized in that the weight ratio of coupler to oil former is 1: 0.1-2.
EP19890118297 1988-10-15 1989-10-03 Colour-photographic recording material Withdrawn EP0364807A3 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3835202A DE3835202A1 (en) 1988-10-15 1988-10-15 COLOR PHOTOGRAPHIC RECORDING MATERIAL
DE3835202 1988-10-15

Publications (2)

Publication Number Publication Date
EP0364807A2 true EP0364807A2 (en) 1990-04-25
EP0364807A3 EP0364807A3 (en) 1990-12-05

Family

ID=6365219

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19890118297 Withdrawn EP0364807A3 (en) 1988-10-15 1989-10-03 Colour-photographic recording material

Country Status (4)

Country Link
US (1) US5043255A (en)
EP (1) EP0364807A3 (en)
JP (1) JPH02150839A (en)
DE (1) DE3835202A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0437818A2 (en) * 1990-01-13 1991-07-24 Agfa-Gevaert AG Colour photographic recording material
EP0632325A1 (en) * 1993-07-02 1995-01-04 Agfa-Gevaert AG Colour photographic material

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5441861A (en) * 1992-09-08 1995-08-15 Agfa-Gevaert Ab Color photographic silver halide material
US5451497A (en) * 1993-12-30 1995-09-19 Eastman Kodak Company Photographic dispersion having improved stability
US5426019A (en) * 1993-12-30 1995-06-20 Eastman Kodak Company Color photographic element
JP2001100379A (en) * 1999-09-28 2001-04-13 Fuji Photo Film Co Ltd Silver halide color photographic sensitive material

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2535497A1 (en) * 1974-08-09 1976-02-26 Fuji Photo Film Co Ltd Photographic organic colloid coating compsn. - contg. hydrophobic additive in disperse phase of water-immiscible polyester resin
EP0069671A2 (en) * 1981-07-07 1983-01-12 EASTMAN KODAK COMPANY (a New Jersey corporation) Latex compositions for water resistant coating applications
EP0256531A2 (en) * 1986-08-13 1988-02-24 Fuji Photo Film Co., Ltd. Silver halide color photographic material
EP0280238A2 (en) * 1987-02-23 1988-08-31 Fuji Photo Film Co., Ltd. Silver halide color photographic photosensitive materials

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4201589A (en) * 1974-08-26 1980-05-06 Fuji Photo Film Co., Ltd. Silver halide photo-sensitive material prepared with solvent and solvent soluble polymer
DE3024881A1 (en) * 1980-07-01 1982-01-28 Agfa-Gevaert Ag, 5090 Leverkusen DISPERSING PROCEDURE
EP0293190B1 (en) * 1987-05-26 1994-04-13 Konica Corporation Silver halide light-sensitive photographic material

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2535497A1 (en) * 1974-08-09 1976-02-26 Fuji Photo Film Co Ltd Photographic organic colloid coating compsn. - contg. hydrophobic additive in disperse phase of water-immiscible polyester resin
EP0069671A2 (en) * 1981-07-07 1983-01-12 EASTMAN KODAK COMPANY (a New Jersey corporation) Latex compositions for water resistant coating applications
EP0256531A2 (en) * 1986-08-13 1988-02-24 Fuji Photo Film Co., Ltd. Silver halide color photographic material
EP0280238A2 (en) * 1987-02-23 1988-08-31 Fuji Photo Film Co., Ltd. Silver halide color photographic photosensitive materials

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0437818A2 (en) * 1990-01-13 1991-07-24 Agfa-Gevaert AG Colour photographic recording material
EP0437818B1 (en) * 1990-01-13 1995-09-06 Agfa-Gevaert AG Colour photographic recording material
EP0632325A1 (en) * 1993-07-02 1995-01-04 Agfa-Gevaert AG Colour photographic material

Also Published As

Publication number Publication date
DE3835202A1 (en) 1990-04-19
JPH02150839A (en) 1990-06-11
EP0364807A3 (en) 1990-12-05
US5043255A (en) 1991-08-27

Similar Documents

Publication Publication Date Title
EP0213569B1 (en) Photographic recording material with a uv-absorber, and uv-absorber
DE4323512A1 (en) Photographic recording material
DE3633364C2 (en)
EP0257451B1 (en) Colour-photographic recording material
EP0415056B1 (en) Colour photographic recording material with a coupler liberating a photographically useful compound
EP0364807A2 (en) Colour-photographic recording material
EP0255892B1 (en) Colour-photographic recording material for making colour control images
EP0254151B1 (en) Colour photographic material containing couplers
DE3626219A1 (en) COLOR PHOTOGRAPHIC RECORDING MATERIAL WITH A YELLOW DIR COUPLER
EP0421221A2 (en) Colour photographic recording material with a DIR coupler
EP0401613A2 (en) Colour photographic recording material with a DIR coupler
DE3819051A1 (en) COLOR PHOTOGRAPHIC RECORDING MATERIAL
DE3636824A1 (en) COLOR PHOTOGRAPHIC RECORDING MATERIAL WITH A YELLOW DIR COUPLER
EP0309819B1 (en) Colour-photographic recording material
DE3700570C2 (en) Color photographic recording material
DE3706202C2 (en) Color photographic recording material
DE3730557A1 (en) Process for the production of colour photographs (prints), and colour-photographic recording material suitable for this purpose
DE3613974C2 (en) Color photographic recording material
EP0394762B1 (en) Colour photographic recording material with a colour coupling substance of the pyrazoloazole type
DE3936300A1 (en) Photographic material giving stable cyan image - contg. phenyl-ureido-phenol coupler in hydroxy or alkoxy phenyl sulphonyl or sulphonamido phenol oil former
DE3823049A1 (en) Colour-photographic recording material
DE3608744A1 (en) POLYMER PURPLE COUPLER AND COLOR PHOTOGRAPHIC RECORDING MATERIAL CONTAINING THIS POLYMER PURPLE COUPLER
DE19525666A1 (en) Silver halide colour photographic material with new magenta coupler
EP0318799B1 (en) Color photographic recording material with a cyan phenolic coupler
DE4326647A1 (en) Photographic recording material

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19891003

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): BE DE FR GB

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): BE DE FR GB

17Q First examination report despatched

Effective date: 19940210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN WITHDRAWN

18W Application withdrawn

Withdrawal date: 19940524