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
  • G03C7/392—Additives
  • G03C7/39208—Organic compounds
  • G03C7/39212—Carbocyclic
• • 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
  • G03C7/3029—Materials characterised by a specific arrangement of layers, e.g. unit layers, or layers having a specific function
• • 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
  • G03C7/392—Additives
  • G03C7/39208—Organic compounds
  • G03C7/39212—Carbocyclic
  • G03C7/39216—Carbocyclic with OH groups

Definitions

• the invention relates to a color photographic recording material with at least six pairs of colors sensitized in the additive primary colors Silver halide layers and at least three of the individual layers according to the complementary color principle assigned color couplers, the improved Grainy.
• the excess color developer oxidation product is known to be by rapidly destroys the quinone diimine stage deamination reaction. It is in the first Line the higher redox potential of the immediate environment of the developed Silver halide grain caused by the accumulation of developer oxidation products development inhibits.
• the low-sensitivity layers contain on the other hand, such high proportions of couplers that they account for most of the developing color density contribute.
• the unused silver halide of the highly sensitive layers represents not only from an economic point of view, but also from a photographic point of view an avoidable ballast. It increases the layer thickness and the light scattering in the layer and it diminishes the possibilities by saving of layer colloid the diffusion paths between the top layer and the shorten the bottom light-sensitive layers. It is therefore desirable To find procedures by which good graininess even at relatively high Coupler / silver ratio can be achieved.
• the granularity developed contains color couplers Layers by using limited diffusible couplers or such Couplers that form a limited diffusible dye is improved.
• the proposal known from DE-A-31 35 938, EP-A-0 109 831 and DE-A-35 41 858 is to use 2-equivalent couplers that have an azomethine dye result, which is initially still limited diffusible after development and can no longer migrate in the shift after the process has been completed. This principle is known to the person skilled in the art under the name "smearing coupler".
• the second proposed solution is based on the developer oxidation product in a relatively hydrophobic soft polymer matrix apparently undamaged for longer survive and can even diffuse over long distances. It can it is assumed that the developer oxidation products present in the polymer matrix are not cationic, but are electrically neutral. This one The main shortcoming of the concept lies in the higher shift load, but also in that the dye can migrate in the polymer matrix.
• the invention relates to a color photographic recording material at least one red sensitive silver halide emulsion layer unit, the a cyan coupler is assigned to at least one green-sensitive silver halide emulsion layer unit, to which a magenta coupler is assigned, at least a blue sensitive silver halide emulsion layer unit, the one Yellow coupler is assigned, and possibly other non-photosensitive Layers, wherein at least one of said silver halide emulsion layer units at least two adjacent silver halide emulsion sublayers with the spectral sensitivity concerned, one of which is more sensitive and one less sensitive, characterized in that it is in reactive assignment to at least one more sensitive, based on the silver halide content comparatively low color coupler silver halide emulsion partial layer contains a compound (or a precursor compound thereof) that is able, under the conditions of chromogenic development with the Oxidation product of the color developer is essentially non-colored to form diffusible coupling product, which under the conditions of chrom
• a relatively low color coupler silver halide emulsion partial layer is one Layer that is not based on the amount of silver halide contained therein contains more than 1/5 of the equivalent amount of color coupler.
• the invention is characterized by the use of an EOPTA connection Formula I in a reactive assignment to a more sensitive, relatively low-color coupler Silver halide emulsion sublayer. If it is the color photographic Recording materials around those with three-layer silver halide emulsion sub-layer units acts, consisting of high, medium and less sensitive sublayers, the EOPTA compound according to the invention is located preferably in reactive assignment to a highly sensitive or a medium sensitive silver halide emulsion sublayer. With reactive assignment is to be understood that the EOPTA connection is in such a Arrangement to the relevant silver halide emulsion sublayer is that it is able to react at least with part of the resulting EOP. For this purpose, the EOPTA connection is either in the sensitive silver halide emulsion sublayer itself or in one of these immediately adjacent color coupler poor or color coupler-free layer.
• the EOPTA connection is able to display the image information from the more sensitive one comparatively low color coupler silver halide emulsion partial layer an adjacent layer containing color coupler, e.g. on a less sensitive silver halide emulsion partial layer containing color coupler of the same silver halide emulsion partial layer unit, to transfer and thus by transfer of the color developer residue on the color coupler contained therein to the total color density to contribute.
• the additives according to the invention can be water-soluble, limited water-soluble or be water-insoluble. As such, they can be found in the color photographic recording material be included or in the form of an alkaline cleavage Precursor compound exist. After processing, you can use the processed recording material to be washed out or in undiminished Share in the emulsified droplets or in the binder phase.
• the additives according to the invention are further characterized in that their Coupling products with EOP are essentially colorless.
• the totality of the substituents R 1 to R 18 of the compounds according to the invention contains, depending on the respective basic structure (formulas II to VIII), no more than 15 carbon atoms, preferably no more than 12 carbon atoms and even more preferably 2 to 10 carbon atoms. Atoms.
• hydrophilic or solubilizing groups can be useful in achieving the required diffusibility. Examples of such groups are phenolic hydroxyl groups, carboxyl groups, sulfo groups and N-phenylsulfamoyl groups which still bear an unsubstituted H atom on the N atom.
• An alkyl group represented by one of the radicals R 1 to R 18 preferably contains no more than 4 carbon atoms. Preferred examples are methyl, ethyl and t-butyl.
• the alkyl groups, in particular a methyl group, can also be substituted, for example with carboxyl, sulfo, phenylsulfonyl, hydroximino or phenyl (benzyl).
• An alkoxy group (R 4 , R 5 ) is preferably methoxy or ethoxy.
• An acyl group (R 5 , R 6 ) or the acyl radical of an acylamino group (R 1 to R 4 , R 8 , R 9 , R 14 ) is derived from an aliphatic or aromatic carboxylic or sulfonic acid, a carbamic acid or a carbonic acid half-ester. Examples are acetyl, succinoyl, -CO-CF 3 , methoxycarbonyl, N-methylcarbamoyl, benzoyl and phenylsulfonyl.
• An aryl group is especially phenyl, optionally substituted, e.g. With - OH, alkyl, carboxyl and / or sulfo.
• R 12 or R 18 examples of substituents represented by R 12 or R 18 are halogen, alkyl, sulfone and sulfonamide.
• the additives according to the invention are the casting solutions for the respective Layer added in the usual way, e.g. if it is limited water soluble or water-insoluble compounds, in emulsified form.
• the molar ratio between the EOPTA compound and that in the layer occurring concentration of color developers lies between the Values 1: 5 and 5: 1; an approximately equimolar ratio is preferred.
• the Proportion of the EOPTA compound preferably between 20 mol% and 200 mol%.
• the EOPTA compound of the invention is assigned a maximum of 20% of the color coupler equivalent, based on the amount of developable silver halide in the more sensitive silver halide emulsion sublayer, while at least 80% of the color coupler equivalent are contained in at least one adjacent layer.
• one neighboring layer may be a non-light sensitive layer or is a less sensitive silver halide emulsion sublayer.
• Examples of recording materials according to the invention are in particular color photographs Color negative films and color reversal films.
• the photographic materials consist of a support on which the photosensitive Silver halide emulsion layers are applied.
• a carrier thin films and foils are particularly suitable.
• An overview of carrier materials and on the front and back of the auxiliary layers is in Research Disclosure 37254, Part 1 (1995), p. 285.
• Color photographic films such as color negative films and color reversal films show in in the following order on the carrier 2 or 3 sensitive to red, cyan-coupling silver halide emulsion layers, 2 or 3 green-sensitive, purple-coupling silver halide emulsion layers and 2 or 3 blue-sensitive, yellow-coupling silver halide emulsion layers.
• the layers same spectral sensitivity differ in their photographic sensitivity, with the less sensitive sub-layers usually closer arranged to the carrier than the higher sensitive sub-layers.
• a yellow filter layer is applied, which prevents blue light from entering the to get layers below.
• Deviations in the number and arrangement of the photosensitive layers can occur to achieve certain results. For example, you can all highly sensitive layers in one layer package and all low-sensitive layers Layers to another layer package in a photographic film be summarized to increase the sensitivity (DE 25 30 645).
• Essential components of the photographic emulsion layers are binders, Silver halide grains and color couplers.
• Photographic materials with camera sensitivity usually contain silver bromoiodide emulsions, which may also contain small amounts of silver chloride can contain.
• the maximum absorption of that from the couplers and the color developer oxidation product Dyes formed are preferably in the following areas: Yellow coupler 430 to 460 nm, purple coupler 540 to 560 nm, cyan coupler 630 up to 700 nm.
• hydrophobic color couplers but also other hydrophobic components of the layers, are usually in high-boiling organic solvents dissolved or dispersed. These solutions or dispersions are then in one emulsified aqueous binder solution (usually gelatin solution) and lie after drying the layers as fine droplets (0.05 to 0.8 ⁇ m diameter) in the layers before.
• aqueous binder solution usually gelatin solution
• the usually between layers of different spectral sensitivity arranged non-light-sensitive intermediate layers can contain agents which an undesirable diffusion of developer oxidation products from a photosensitive to another photosensitive layer with different prevent spectral sensitization.
• Suitable connections can be found in Research Disclosure 37254, Part 7 (1995), p. 292 and in Research Disclosure 37038, Part III (1995), p. 84.
• the photographic material can also contain UV light-absorbing compounds, whiteners, spacers, filter dyes, formalin scavengers, light stabilizers, antioxidants, D min dyes, additives to improve the stability of dyes, couplers and whites as well as to reduce the color fog, plasticizers (latices), Contain biocides and others.
• Suitable compounds can be found in Research Disclosure 37254, Part 8 (1995), P. 292 and in Research Disclosure 37038, parts IV, V, VI, VII, X, XI and XIII (1995), p. 84 ff.
• the layers of color photographic materials are usually hardened, i.e. the binder used, preferably gelatin, is by suitable cross-linked chemical processes.
• Suitable hardener substances can be found in Research Disclosure 37254, Part 9 (1995), p. 294 and in Research Disclosure 37038, Part XII (1995), page 86.
• a three-layer test set-up (magenta casting) of a color photographic recording material for color negative development was produced by applying the following layers in the order given to a transparent layer support made of cellulose triacetate with a thickness of 120 ⁇ m and having an adhesive layer. The amounts are given in g / m 2 . The corresponding amounts of AgNO 3 are given for the silver halide application.
• Layer 1 green-sensitized silver bromide emulsion 1.1 gelatin 2.1 Magenta coupler XM-1 0.85 Tricresyl phosphate (CPM) 0.85
• Layer 2 gelatin 0.5
• Layer 3 gelatin 0.5 Instant hardener XH-1 0.035
• EOPTA compound according to the invention being used in layer 2
• Table 1 Layer 1: gelatin 1.65 Magenta coupler XM-1 0.83 Tricresyl phosphate (CPM) 0.83
• Layer 2 gelatin 1.0 additive according to the invention (EOPTA compound) (1 mmol) Dibutyl phthalate (DBP) 0.4
• Layer 3 medium sensitive green sensitized silver bromide emulsion 1.1 gelatin 0.85
• Layer 4 gelatin 0.5
• Data 5 gelatin 0.5 Instant hardener XH-1 0.040
• the curing is set so that a swelling factor of 3 results.
• the layer thickness of the intermediate layer in the swollen state is then approx. 3.2 ⁇ m.
• the density resulting in material 3.1 comes exclusively by transferring development oxidation product over the intermediate layer conditions. It provides a grainless picture.
• a four-layer magenta cast of a color photographic recording material for color negative development was produced (material 2.1. - comparison) by applying the following layers in the order given to a transparent layer support made of cellulose triacetate with a thickness of 120 ⁇ m and having an adhesive layer. The amounts are given in g / m 2 . The corresponding amounts of AgNO 3 are given for the silver halide application. The silver halide emulsions were stabilized per 100 g of AgNO 3 with 0.1 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene.
• d v is given below in ⁇ m.
• Layer 4 (Yellow filter layer) gelatin 1.20 yellow filter dye XF-1 0.07
• Example 2 The materials described were processed immediately after casting, as in Example 1. The sensitivity was determined after densitometric measurement behind a green filter (pp) at a density of 0.2 and 1.0 (relative DIN units). The granularity was determined at density 0.4 and 1.0 ( ⁇ D values). The results are shown in Table 2. material sensitivity ⁇ 1 ⁇ 2 ⁇ D (0.4) ⁇ D (1.0) 2.1 35.8 0.5 0.8 9.0 10.1 2.2 35.9 0.45 0.7 8.75 9.5

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• Physics & Mathematics (AREA)
• General Physics & Mathematics (AREA)
• Spectroscopy & Molecular Physics (AREA)
• Silver Salt Photography Or Processing Solution Therefor (AREA)

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Citations (2)

• 1996
  • 1996-08-12 DE DE19632428A patent/DE19632428A1/de not_active Withdrawn
• 1997
  • 1997-07-30 EP EP97113080A patent/EP0824220A1/fr not_active Withdrawn
  • 1997-08-05 US US08/906,388 patent/US5885760A/en not_active Expired - Fee Related

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