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.

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• 1988
  • 1988-10-15 DE DE3835202A patent/DE3835202A1/de not_active Withdrawn
• 1989
  • 1989-09-29 US US07/415,098 patent/US5043255A/en not_active Expired - Fee Related
  • 1989-10-03 EP EP19890118297 patent/EP0364807A3/de not_active Withdrawn
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