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
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
  • Y10S430/156—Precursor compound
  • Y10S430/158—Development inhibitor releaser, DIR

Definitions

• the invention relates to a color photographic recording material having at least one light-sensitive silver halide emulsion layer which contains a coupler which releases a development inhibitor when color develops.
• DIR development inhibitor releasing
• the DIR compounds can be those which release an inhibitor the rest react with the oxidation product of a color developer to form a dye (DIR coupler), or those which release the inhibitor without simultaneously forming a dye. The latter are also referred to as DIR compounds in the narrower sense.
• DIR couplers are known, for example, from US-A-3 148 062, US-A-3 227 554, US-A-3 615 506, US-A-3 617 291 and DE-A-24 14 006.
• Development inhibitors released are usually heterocyclic mercapto compounds or derivatives of benzotriazole.
• DIR couplers which release monocyclic triazoles as development inhibitors are described, for example, in DE-A-28 42 063 and EP-A-0 272 573.
• essentially colorless coupling DIR compounds reference is made, for example, to US Pat. No. 3,632 345, DE-A-23 59 295 and DE-A-25 40 959.
• Such effects are, for example, the lowering of the gradation, the achievement of a finer grain of color, the improvement of the sharpness through the so-called edge effect and the improvement of the color purity and the color brilliance through so-called interimage effects.
• DIR Development-Inhibitor-Releasing
• the colorless coupling DIR compounds have the advantage over the color coupling DIR couplers that they can be used universally, so that the same connection can be used in all light-sensitive layers of a color photographic recording material regardless of the color to be produced.
• DIR couplers on the other hand, can usually only be used in part of the light-sensitive layers because of the color they produce, unless the color secondary density to be attributed to them is tolerable in the other layers. This advantage of the DIR compounds is offset by the disadvantage that they are generally less reactive than the DIR couplers.
• the invention has for its object to provide a color photographic recording material, the coupler with a triazole ring bound to the coupling point contains from which the triazole ring is released as a highly effective silver halide development inhibitor during development.
• the invention relates to a color photographic recording material having at least one light-sensitive silver halide emulsion layer and a coupler assigned to it, which carries a removable triazolyl radical bonded to its coupling point, characterized in that the coupler corresponds to the following formula I.
• A- (TIME) n -Z I in what mean A is the rest of a coupler which couples under the conditions of photographic development with the oxidation product of a silver halide developing agent and thereby the rest of the formula - (TIME) n -Z releases;
• TIME is a link which, when the coupler reacts with the oxidation product of a silver halide developing agent, is released together with the radical Z (a triazole ring) bound to it and in turn releases the radical Z with a delay under the development conditions;
• Z is a triazole residue of one of the formulas R1 alkylthio; R2 H, alkyl, alkylthio, aryl or a heterocyclic group, at least one of the radicals R1 and R2 at a distance of 2 to 4 atoms from the triazole ring a group saponifiable in aqueous alkali -CO-OR3, -O-CO-OR3 or -
• the rest of a coupler represented by A in Formula I can be the rest of a coupler which gives a cyan, purple or yellow dye upon color development, or the rest of a coupler which gives essentially colorless or only slightly colored products. It is essentially known coupler remains. Teal couplers generally have a phenolic or naphtholic structure. Examples of these are described, for example, in US-A-2 369 929, US-A-2 772 162, EP-A-0 067 689, GB-A-519 208. Purple couplers are derived from 5-pyrazolone, indazolone or various pyrazoloazoles . Examples are described, for example, in DE-A-25 36 191, DE-A-27 03 589 and DE-A-28 13 522, GB-A-1 247 493.
• Yellow couplers are derived, for example, from ⁇ -acylacetanilides such as pivaloylacetanilides or benzoylacetanilides or malondianilides. Examples are described, for example, in US-A-2,875,057, US-A-3,265,506, US-A-4,359,521 and DE-A-2,655,871. Couplers which provide essentially colorless products and at the same time are photographically effective Release of connection are described, for example, in US-A-3,632,345, US-A-3,928,041, US-A-3,958,993, US-A-3,961,959, US-A-4,052,213, US-A -4 088 491.
• a link represented in formula I by TIME is a group which, after being split off from the coupling point of the coupler when it is coupled with the oxidation product of the silver halide developing agent, is capable, in a subsequent reaction, of releasing a photographically active radical bound to it, in the present case a monocyclic triazole radical.
• the group TIME is also referred to as a timing control element because, in the presence of such a group, a photographically active residue attached to it, for example an inhibitor residue, is released in many cases with a delay and can take effect.
• Timing elements are, for example, a group -O- H-, the O atom being bonded to the coupling point of the coupler and the C atom being bound to an N atom of a photographically active compound (for example DE-A-27 03 145), a group which after cleavage from the coupler undergoes an intramolecular nucleophilic displacement reaction and thereby releases the photographically active compound (for example DE-A-28 55 697), a group in which electron transfer along a conjugate system can take place after being split off from the coupler, thereby releasing the photographically active compound (eg DE-A-31 05 026), or a group -X- , in which X (for example -O-) is bonded to the coupling point of the coupler and the C atom is bound to an atom of the photographically active compound and in which R is, for example, aryl (for example EP-A-0 127 063).
• a photographically active compound for example DE-A-27 03 145
• An alkylthio radical represented by R 1 or R 2 in formula I preferably contains 1 to 7 C atoms; it can also be substituted, e.g. with one of the saponifiable groups mentioned.
• An alkyl radical represented by R2 or R3 in formula I preferably contains 1 to 7 C atoms; it can also be substituted, in particular by halogen, such as Cl or F, or by -CN.
• a heterocyclic group (R2) is, for example, a furyl group.
• An aryl group represented by R3 is, for example, phenyl, optionally substituted, e.g. with alkyl or halogen.
• the 2 to 4 atoms that define the distance between the group saponifiable in aqueous alkali -CO-OR3, -O-CO-OR3 or -O-CO-R3 and the triazole ring can be carbon atoms and / or heteroatoms. They can in turn contain a group -CO-O-, which in this case cannot be saponified in aqueous alkali or can be saponified to a much lesser extent, cf. INH-1.
• the advantageous properties of the couplers according to the invention are presumably due, among other things, to the fact that the triazole ring is apparently not only a good leaving group (escape group), so that the couplers are very reactive, but apparently also has a certain tendency to adsorb on the silver halide grain and thereby the development to inhibit the silver halide.
• Suitable inhibitors are the following:
• DIR couplers are the following:
• the imino ether hydrochloride obtained is added in portions to a solution of 45 g of 2-amino-4-chlorobenzamide heated to 85 ° C. in 300 ml of propionic acid. The mixture is then held at 100 ° C. for 1 hour, under reflux for 1 hour and is discharged onto 1,500 g of ice. After standing overnight, the residue is decanted and stirred with methanol. 65 g of the compound crystallize out overnight. After drying mp 184 ° C to 186 ° C.
• 19.5 g (0.04 ml) of the compound obtained in stage 2 are brominated in 200 ml of acetic acid with 6.4 g of bromine in 20 ml of acetic acid at 25 ° C. After adding 5 g of sodium acetate, it is poured onto 400 ml of ice and until stirred to complete crystallization. It is suctioned off, digested with 100 ml of methanol and suctioned off again. After drying 17.5 g with decomposition melting point 160 ° C to 170 ° C.
• the purification is carried out by column chromatography on silica gel with toluene-ethyl acetate 8: 2 as the eluent. 5 g of compound with a melting point of 125 ° C. to 131 ° C. (two isomers! Are obtained.
• the compounds of the present invention are suitable for use as DIR couplers in color photographic, in particular multilayer, recording materials. If they are yellow couplers, they are preferably used in or associated with a light-sensitive silver halide emulsion layer with a predominant sensitivity to the blue spectral range of visible light.
• the couplers according to the invention namely a comparatively low development inhibition in the layer to which such a compound is assigned, in addition to a comparatively high development inhibition in adjacent unassigned layers, naturally comes into play particularly when it is a multi-layer color photographic recording material which, in addition to a predominantly blue-sensitive silver halide emulsion layer, contains further light-sensitive silver halide emulsion layers with predominant sensitivity for the green or red spectral range of the visible light.
• the DIR couplers according to the invention are preferably assigned to a green-sensitive layer as purple couplers or preferably to a red-sensitive layer as cyan-green couplers. Couplers which give only a little color during development can be assigned to a blue-sensitive, a green-sensitive or a red-sensitive layer or also several of these layers without fear of color falsification.
• the DIR couplers according to the invention can also be used as color couplers in comparatively small amounts in order to produce the desired effects, in particular the interimage effects.
• the DIR couplers according to the invention can thus advantageously also be used as yellow couplers in purple layers as well as in blue-green layers. The same applies to the purple couplers and the cyan couplers.
• the diffusion-resistant DIR couplers of the present invention can optionally be incorporated together with other couplers in a known manner into the casting solution of the silver halide emulsion layers or other colloid layers.
• oil-soluble or hydrophobic couplers can be added to a hydrophilic colloid solution, preferably from a solution in a suitable coupler solvent (oil former), optionally in the presence of a wetting or dispersing agent.
• the hydrophilic casting solution can of course contain other conventional additives in addition to the binder.
• the solution of the coupler need not be directly dispersed in the casting solution for the silver halide emulsion layer or other water permeable layer; rather, it can also advantageously first be dispersed in an aqueous, non-photosensitive solution of a hydrophilic colloid whereupon the mixture obtained, optionally after removal of the low-boiling organic solvents used, is mixed with the casting solution for the light-sensitive silver halide emulsion layer or another water-permeable layer before application.
• Suitable light-sensitive silver halide emulsions are emulsions of silver chloride, silver bromide or mixtures thereof, possibly with a low silver iodide content of up to 15 mol% in one of the commonly used hydrophilic binders.
• Gelatin is preferably used as a binder for the photographic layers. However, this can be replaced in whole or in part by other natural or synthetic binders.
• the emulsions can be chemically and spectrally sensitized in the usual way, and the emulsion layers as well as other non-light-sensitive layers can be hardened in the usual way with known hardening agents.
• Color photographic recording materials usually contain at least one silver halide emulsion layer for the recording of light in 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 need a spectral sensitizer included, since the intrinsic sensitivity of the silver halide is sufficient for the recording of blue light in many cases.
• Each of the said photosensitive layers can consist of a single layer or in a known manner, e.g. in the case of the so-called double-layer arrangement, also comprise two or more silver halide emulsion partial layers (DE-C-1 121 470).
• red-sensitive silver halide emulsion layers are arranged closer to the layer support than green-sensitive silver halide emulsion layers and these are in turn closer than blue-sensitive layers, a yellow filter layer which is not sensitive to light generally being located between green-sensitive layers and blue-sensitive layers.
• a non-light-sensitive intermediate layer 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 can be directly adjacent to one another or be arranged in such a way that a light-sensitive layer with a different spectral sensitivity is located between them (DE-A-1 958 709, DE-A-25 30 645, DE-A -26 22 922).
• Color photographic recording materials for producing multicolored images usually contain spatial and spectral assignment to the silver halo Genide emulsion layers of different spectral sensitivity coloring compounds, here especially color couplers, for the generation of the different partial color images teal, purple and yellow.
• Spatial assignment is 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 allows an image-wise match 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 (e.g. teal, purple, yellow) is assigned.
• One or more color couplers can be assigned to each of the differently spectrally sensitized silver halide emulsion layers. If several silver halide emulsion layers of the same spectral sensitivity is present, each of them may contain its color coupler, although these 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 at least one non-diffusing color coupler for producing the blue-green partial color image
• green-sensitive silver halide emulsion layers at least one non-diffusing color coupler for producing the purple partial color image
• blue-sensitive silver halide emulsion layers for generating the yellow partial color coupler for producing the partial color image.
• other assignments are also known.
• Color couplers for producing the blue-green partial color image are usually couplers of the phenol or ⁇ -naphthol type; suitable examples are
• Color couplers for producing the purple partial color image are generally couplers of the 5-pyrazolone, indazolone or pyrazoloazole type; suitable examples are
• Color couplers for producing the yellow partial color image are generally couplers with an open-chain ketomethylene group, in particular couplers of the ⁇ -acylacetamide type; suitable examples of this are ⁇ -benzoylacetanilide couplers and ⁇ -pivaloylacetanilide couplers of the formulas
• the color couplers can be 4-equivalent couplers, but also 2-equivalent couplers.
• the latter are derived from the 4-equivalent couplers in that they contain a substituent in the coupling site which is split off during the coupling.
• the 2-equivalent couplers include those that are colorless, as well as those that have an intense intrinsic color that disappears when the color is coupled or is replaced by the color of the image dye produced (mask coupler), and the white couplers that react with color developer oxidation products yield essentially colorless products.
• the 2-equivalent couplers also include those couplers which contain a cleavable residue in the coupling site, which is released upon reaction with color developer oxidation products, either directly or after one or more further groups have been cleaved from the primarily cleaved residue (e.g. DE-A-27 03 145, DE-A-28 55 697, DE-A-31 05 026, DE-A-33 19 428), a certain desired photographic effectiveness unfolds, for example as a development inhibitor or accelerator.
• Examples of such 2-equivalent couplers are the known DIR couplers as well as DAR or. FAR coupler.
• DAR or FAR couplers Since in the DIR, DAR or FAR couplers the effectiveness of the residue released during the coupling is mainly desired and the color-forming properties of these couplers are less important, such DIR, DAR or FAR couplers are also suitable which give essentially colorless products on coupling (DE-A-15 47 640).
• the cleavable residue can also be a ballast residue, so that upon reaction with color developer oxidation products coupling products are obtained which are diffusible or at least have a weak or restricted mobility (US Pat. No. 4,420,556).
• the color photographic recording material additionally contains at least one DIR coupler of the formula I, which coupler contains not only in the yellow layer but also in the purple layer and / or also in the blue-green layer and also in a non-light-sensitive layer adjacent to one of the layers mentioned can be.
• the color photographic recording material of the present invention can contain further additives, for example antioxidants, dye-stabilizing agents and agents for influencing the mechanical and electrostatic properties.
• antioxidants for example antioxidants, dye-stabilizing agents and agents for influencing the mechanical and electrostatic properties.
• dye-stabilizing agents for influencing the mechanical and electrostatic properties.
• the adverse effects of UV light on the color images produced with the color photographic recording material according to the invention To reduce or avoid, it is advantageous to use UV-absorbing compounds in one or more of the layers contained in the recording material, preferably in one of the upper layers. Suitable UV absorbers are described for example in US-A-3 253 921, DE-C-2 036 719 and EP-A-0 057 160.
• hydrophilic film-forming agents are suitable as protective colloid or binder for the layers of the recording material, e.g. Proteins, especially gelatin. Casting aids and plasticizers can be used. Reference is made to the compounds specified in Research Disclosure No. 17,643 in Sections IX, XI and XII.
• the layers of the photographic material can be hardened in the usual manner, for example with hardeners of the epoxy type, the heterocyclic ethylene imine and the acryloyl type. Furthermore, it is also possible to harden the layers according to the process of DE-A-22 18 009 in order to obtain color photographic materials which are suitable for high-temperature processing. It is also possible to harden the photographic layers with hardeners of the diazine, triazine or 1,2-dihydroquinoline series or with hardeners of the vinyl sulfone type.
• the color photographic recording material according to the invention is developed with a color developer compound.
• All developer compounds which have the ability to react in the form of their oxidation product with color couplers to form azomethine dyes can be used as the color developer compound.
• Suitable color developer compounds are aromatic compounds of the p-phenylenediamine type containing at least one primary amino group, for example N, N-dialkyl-p-phenylenediamines, such as N, N-diethyl-p-phenylenediamine, 1- (N-ethyl-N-methyl-sulfonamidoethyl) -3-methyl-p-phenylenediamine, 1- (N-ethyl-N-hydroxyethyl-3-methyl-p-phenylenediamine and 1- (N-ethyl-N-methoxyethyl) -3-methyl-p-phenylenediamine.
• N, N-dialkyl-p-phenylenediamines such as N, N-diethyl-p-phenylenediamine, 1- (N-ethyl-N-methyl-sulfonamidoethyl) -3-methyl-p-phenylenediamine, 1- (N-eth
• 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, for example Fe3+ salts and Fe3+ complex salts such as ferricyanides, dichromates, water-soluble cobalt complexes, etc.
• Particularly preferred are iron III complexes of aminopolycarboxylic acids, in particular, for example, ethylenediaminetetraacetic acid, N-hydroxyethylethylenediamine triacetic acid, alkyliminodicarboxylic acids and alkyliminodicarboxylic acids and Phosphonic acids.
• Persulphates are also suitable as bleaching agents.
• a color photographic recording material for color negative color development was produced (layer structure 1A comparison) by applying the following layers in the order given to a transparent cellulose triacetate support.
• the quantities given relate to 1 m2.
• the corresponding amounts of AgNO3 are given. All silver halide emulsions were stabilized per 100 g of AgNO3 with 0.1 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene.
• Example 1 the following compounds are used in addition to the couplers already mentioned:
• KE bg KE in the red-sensitized layer KE pp KE in the green-sensitized layer
• Table 1 Layer structure DIR coupler IIE pp IIE bg KE pp KE bg 1A DIR-A 37 40 0.49 0.62 1B DIR-6 75 45 0.80 1.15 1C DIR-12 76 65 1) 1) 1D DIR-21 76 49 0.80 0.85 1E DIR-22 63 35 0.63 0.58 1F DIR-23 133 62 1) 1) 1) Value above the measurement limit

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• 1989
  • 1989-06-06 DE DE3918394A patent/DE3918394A1/de not_active Withdrawn
• 1990
  • 1990-05-23 US US07/528,043 patent/US5021331A/en not_active Expired - Lifetime
  • 1990-05-24 EP EP90109914A patent/EP0401612B1/fr not_active Expired - Lifetime
  • 1990-05-24 DE DE59009272T patent/DE59009272D1/de not_active Expired - Fee Related
  • 1990-06-04 JP JP2144576A patent/JPH0318844A/ja active Pending

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