EP0148441A2 - Colour-photographic recording material and developing process - Google Patents
Colour-photographic recording material and developing process Download PDFInfo
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- EP0148441A2 EP0148441A2 EP84115219A EP84115219A EP0148441A2 EP 0148441 A2 EP0148441 A2 EP 0148441A2 EP 84115219 A EP84115219 A EP 84115219A EP 84115219 A EP84115219 A EP 84115219A EP 0148441 A2 EP0148441 A2 EP 0148441A2
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- silver halide
- recording material
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Classifications
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- 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
- G03C7/32—Colour coupling substances
- G03C7/3225—Combination of couplers of different kinds, e.g. yellow and magenta couplers in a same layer or in different layers of the photographic material
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- 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
- G03C7/3003—Materials characterised by the use of combinations of photographic compounds known as such, or by a particular location in the photographic element
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
- G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
- G03C2001/03511—Bromide content
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
- G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
- G03C2001/03517—Chloride content
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- 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
- G03C7/30541—Substances liberating photographically active agents, e.g. development-inhibiting releasing couplers characterised by the released group
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- 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 with at least one more sensitive silver halide emulsion layer and a comparatively less sensitive silver halide emulsion layer, but which are sensitive in the same spectral range, color layers and DIR compounds being assigned to these layers.
- the invention further relates to a method for developing an exposed photographic recording material.
- DIR couplers known from GB 953 454, which carry a substituent in the coupling point which is split off during the coupling with the release of a diffusing compound, which inhibits the development of the silver halide.
- US Pat. No. 3,620,747 and DE-OS 2 322 165 disclose photographic materials with two differently sensitive silver halide emulsion layers with the same spectral sensitivity, color couplers being contained in both layers and a DIR compound additionally being present in the less sensitive layer.
- the combination of at least two DIR compounds of different reactivity is known from DE-OS 2 509 722 and GB-PS 1 536 341.
- a silver halide emulsion layer can then be divided into two sub-layers of different sensitivity, the more sensitive silver halide sub-layer containing the more reactive and the less sensitive silver halide sub-layer containing the less reactive DIR compound or vice versa.
- dir Compounds in stronger and less sensitive sub-layers are also given in DE-OS 2 600 524 and US 4 170 479. From DE-OS 2 707 489 and US Pat. No. 4 183 752 photographic recording materials with DIR compounds are lower Known reactivity, which are particularly suitable for mixing with more reactive DIR compounds. You can combine a coarse-grained, highly sensitive layer with a color coupler deficit with a less sensitive layer in a so-called double-layer structure. To achieve better sensitometric properties, the DIR compounds can either be added to one of the two layers or to each of the layers, but addition to the lower fine-grained layer of a double-layer dressing is preferred.
- DIR compounds of particularly high reactivity are known from DE-OS 2 853 362 and US Pat. No. 4,315,040. According to European patent application 00 70 183, DIR compounds are preferably contained in less sensitive sub-layers of a double-layer structure. According to EP 00 86 654, a DIR connection with a so-called "timing group” is introduced into a highly sensitive layer and a DIR connection without a "timing group” into a less sensitive layer.
- the object of the invention is to improve the sensitometric properties of color recording materials.
- the color granularity of such recording materials should also be improved in the range of low color density without impairing the sensitivity.
- the ratio k Ku / k DIR of the effective reaction rate constants of the color coupler k KU and the DIR compound k DIR in layer I is greater than in layer II.
- the effective reaction rate constants relate to the reaction with the developer oxidation product. This is formed by oxidation of the p-phenylenediamines usually used as color developer substances by silver halide.
- reaction rate constants The measurement of reaction rate constants is described, for example, by J. Eggers in "Messages from the Agfa Research Laboratories", Leverkusen / Kunststoff, Volume III, 1961, pages 81 ff. Since it has been shown that the reaction rate constants of a DIR compound are influenced by the surrounding medium is raised to the effective reaction rate constant according to the invention. This takes into account the type of surrounding medium, for example the use of an oil generator.
- the effective reaction rate constant can be determined electrochemically by the method known from DE-OS 2 853 632 and US 4,315,070.
- the effective reaction rate constant k eff then has the dimension LI x mol x sek. ] on.
- the ratio of the effective reaction rate constants in the more sensitive layer I is preferably between 2: 1 and 20: 1 and the ratio of the reaction rate constants of color coupler and DIR compounds of the less sensitive layer II is preferably between 0.03: 1 and 6: 1.
- DIR compounds and couplers are each assigned to specific silver halide emulsion layers. Your further reaction in photographic development is therefore controlled by the development of the respective silver halide emulsion layer.
- color coupler and DIR compound are contained in the respective silver halide emulsion layer itself, but they can also be present in an adjacent layer.
- the photographic material itself contains the usual color couplers, which can react with the oxidation product of developers, generally p-phenylenediamines, to form dyes.
- the red-sensitive layer can contain a non-diffusing color coupler for producing the blue-green partial color image, generally a coupler of the phenol or ⁇ -naphthol type.
- the green-sensitive layer can contain, for example, at least one non-diffusing color coupler for producing the purple partial color image, usually color couplers of the 5-pyrazolone or layer type can contain, for example, a non-diffusing color coupler for producing the yellow partial color image, usually a color coupler with a open chain ketomethylene grouping included.
- the color couplers can be, for example, 6-, 4- and 2-equivalent couplers, including the so-called white couplers, which do not produce any dye when reacted with color developer oxidation products.
- Suitable couplers are known, for example, from the publications "Color Couplers” by W. Pelz in “Messages from the Research Laboratories of Agfa, Leverkusen / Kunststoff", Volume III, page 111 (1961, K. Venkataraman in “The Chemistry of Synthetic Dyes", Vol. 4, 341 to 387, Academic Press (1971) and TH James, “The Theory of the Photographic Process", 4th Ed., P. 353 -362, as well as from Research Disclosure No. 17643 of December 1978, Section VII, published by Industrial Opportunities Ltd., Homewell Havant, Hampshire, P09 1 EF in Great Britain.
- the DIR compounds to be used according to the invention are substances which are able to react with the oxidized color developer and thereby free up imagewise substances which inhibit the development of the neighboring silver halide.
- the inhibitory substances released are preferably mercapto compounds, e.g. 1-phenyl-5-mercaptotetrazole.
- the inhibitory substances are released directly by reaction of the DIR compound with the developer oxidation product.
- Very particularly suitable compounds for use in sensitive layer I according to the present invention are listed in Table 1 below.
- the keff values refer to a solution in the specified solvent:
- Particularly useful DIR compounds for use in the relatively less sensitive layer II are known for example from the D E -OS 2,853,362 and U.S. Patents 3,227,554 and 4 315 070.
- Particularly preferred DIR compounds are shown in the following Table 2 (k eff values for the solution in the specified solvent).
- the color couplers and DIR compounds to be used according to the invention can be incorporated into the materials according to the invention by customary, known methods.
- the compounds are soluble in water or alkali, they can be added in the form of aqueous solutions, optionally with the addition of water-miscible organic solvents such as ethanol, acetone or dimethylformamide.
- water-miscible organic solvents such as ethanol, acetone or dimethylformamide.
- the color couplers and DIR compounds are insoluble in water or alkali, they can be incorporated into the recording materials in dispersed form in a manner known per se. For example, a solution of these compounds in a low-boiling organic solvent can be mixed directly with the silver halide emulsion or initially with an aqueous gelatin solution and the organic solvent can then be removed. The dispersion of the respective compound thus obtained can then be mixed with the silver halide emulsion.
- oil formers generally higher-boiling organic compounds
- DIR compounds to be dispersed in the form of oily droplets.
- the recording materials according to the invention contain at least one silver halide emulsion layer unit for recording blue, green and red light.
- the ratio of the reaction rate constants to be used according to the invention can be used in all, but possibly also only in one or two, layer units.
- the silver halide emulsions used can contain chloride, bromide and iodide or mixtures thereof as the halide.
- the halide content of at least one layer consists of 0 to 10 mol% AgI, 0 to 10 mol% AgCl and 0 to 100% AgBr, the sum of these proportions being 100% complementary.
- the halide portion can also consist predominantly of chloride.
- the silver halide horns can e.g. B. cubic, octahedral or tabular.
- the emulsions can be chemically sensitized.
- the usual sensitizers are suitable for chemical sensitization of the silver halide grains.
- Sulfur-containing compounds for example allyl isothiocyanate, allyl thiourea and thiosulfates, are particularly preferred.
- Reducing agents e.g. B. the tin compounds described in Belgian patents 493 464 or 568 687, further polyamines such as diethylenetriamine or aminomethylsulfinic acid derivatives, for. IF. according to Belgian patent 547 323.
- Suitable as a chemical Noble metals or noble metal compounds such as gold, platinum, palladium, iridium, ruthenium or rhodium are also sensitizers. This method of chemical sensitization is described in the article by R. Koslowsky, Z.Wiss.Phot. 46, 65-72 (1951). It is also possible to sensitize the emulsions with polyalkylene oxide derivatives, e.g. B.
- condensation products of alkylene oxides and aliphatic alcohols, glycols, cyclic dehydration products of hexitols, with alkyl-substituted phenols, aliphatic carboxylic acids, aliphatic amines, aliphatic diamines and amides.
- the condensation products have a molecular weight of at least 700, preferably more than 1000.
- these sensitizers can of course be used in combination, as described in Belgian patent 537 278 and British patent 727 982. Reference is also made to Research Disclosure No. 17 643, section III.
- the emulsions can be optically sensitized in a manner known per se, e.g. with the usual polymethine dyes, such as neutrocyanines, basic or acidic carbocyanines, rhodacyanines, hemicyanines, styryl dyes, oxonols and the like.
- polymethine dyes such as neutrocyanines, basic or acidic carbocyanines, rhodacyanines, hemicyanines, styryl dyes, oxonols and the like.
- Such sensitizers are from F.M. Hamer in "The Cyanine Dyes and related Compounds", (1964). In this regard, reference is made in particular to Ullmann's Encyclopedia of Industrial Chemistry, 4th edition. Volume 18, pages 431 ff and on the above-mentioned Research Disclosure No. 17643, Section IV.
- antifoggants In addition to the antifoggants to be used in the present invention, commonly used antifoggants and stabilizers can be used.
- Suitable stabilizers are azaindenes, preferably tetra- or penta-azaindenes, in particular those which are substituted by hydroxyl or amino groups. Such connections are e.g. in the article by Birr, Z.Wiss.Phot. 47, 1952), pp. 2-58.
- Other suitable stabilizers and antifoggants are given in Research Disclosure No. 17643 above in Section IV.
- the usual substrates can be used for the materials according to the invention, 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.
- 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 are suitable as protective colloid or binder for the layers of the recording material, for example proteins, in particular gelatin, alginic acid or their derivatives such as esters, amides or salts, cellulose derivatives such as carboxymethyl cellulose and cellulose sulfates, starch or their derivatives or hydrophilic synthetic Binders like Polyvinyl alcohol, partially saponified polyvinyl acetate, polyvinyl pyrrolidone and others.
- the layers can also contain other synthetic binders in dissolved or dispersed form, such as homopolymers or copolymers of acrylic or methacrylic acid or their derivatives, such as esters, amides or nitriles, and also vinyl polymers, such as vinyl esters or vinyl ethers.
- binders specified in Research Disclosure 17643 above in Section IX.
- 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 in accordance with the process of German laid-open specification 2 218 009 in order to obtain color photographic materials which are suitable for high-temperature processing. It is also possible to harden the photographic layers or the color photographic multilayer materials with hardeners of the diazine, triazine or 1,2-dihydroquinoline series or with hardeners of the vinyl sulfone type. Further suitable hardening agents are known from German laid-open documents 2 439 551, 2 225 230, 2 317 672 and from Research Disclosure 17643, section XI given above.
- Suitable color developer substances for the material according to the invention are in particular those of the p-phenylenediamine type, e.g. 4-amino-N, N-diethyl-aniline hydrochloride; 4-amino-3-methyl-N-ethyl-N- ⁇ - (methanesulfonamido) ethylaniline 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-ß-hydroxyethyl-p-phenylenediamine.
- the p-phenylenediamine type e.g. 4-amino-N, N-diethyl-aniline hydrochloride; 4-amino-3-methyl
- 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 Fe 3+ salts and Fe 3+ complex salts such as ferricyanides, dichromates, water-soluble cobalt complexes etc.
- Iron-III complexes of aminopolycarboxylic acids in particular for example ethylenediaminetetraacetic acid, nitrilotriacetic acid, iminodiacetic acid, N, are particularly preferred -Hydroxyethylethylenediamintriessigkla, alkyliminodicarboxylic acids and corresponding phosphonic acids.
- Persulphates are also suitable as bleaching agents.
- the color couplers given in the examples have the following structure:
- the top layer consists of gelatin.
- Table 3 shows that when a DIR compound is used alone in the less sensitive layer, good sensitivity is obtained, but only moderate graininess is obtained.
- the reactive DIR compound 2.1 also in the highly sensitive layer, an improvement in the granularity is obtained, however, a significant loss in sensitivity has to be accepted (structure II). It is only when a suitable DIR compound with lower reactivity is used that an improvement in granularity is achieved with the same sensitivity (structure III, invention).
- a color photographic recording material with double layers, which are combined according to their sensitivity, is produced. It corresponds, except for the Changes given below, essentially the structure specified from the example of DE-OS 2 704 797 and US Pat. No. 4,173,479. For this purpose, the following layers are applied to a carrier in the order given.
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Abstract
Verbesserte fotografische Aufzeichnungsmaterialien enthalten wenigstens eine Silberhalogenidemulsionsschicht vergleichsweise hoher und wenigstens eine Silberhalogenidemulsionsschicht vergleichsweise niedrigerer Empfindlichkeit. Diesen Schichten sind Farbkuppler und DIR-Verbindungen unterschiedlicher Reaktivität zugeordnet.Improved photographic recording materials contain at least one silver halide emulsion layer of comparatively high sensitivity and at least one silver halide emulsion layer of comparatively lower sensitivity. Color couplers and DIR compounds of different reactivity are assigned to these layers.
Description
Die Erfindung betrifft ein farbfotografisches Aufzeichnungsmaterial mit wenigstens einer empfindlicheren Silberhalogenidemulsionsschicht und einer vergleichsweise geringer empfindlichen Silberhalogenidemulsionsschicht, die aber im gleichen Spektralbereich empfindlich sind, wobei diesen Schichten Farbkuppler und DIR-Verbindungen zugeordnet sind. Die Erfindung betrifft weiterhin ein Verfahren zur Entwicklung eines belichteten fotografischen Aufzeichnungsmaterials.The invention relates to a color photographic recording material with at least one more sensitive silver halide emulsion layer and a comparatively less sensitive silver halide emulsion layer, but which are sensitive in the same spectral range, color layers and DIR compounds being assigned to these layers. The invention further relates to a method for developing an exposed photographic recording material.
Es ist bekannt, die sensitometrischen Eigenschaften eines Aufzeichnungsmaterials durch derartige Verbindungen zu steuern, aus denen bei der Entwicklung diffundierende Substanzen in Freiheit gesetzt werden, die die Entwicklung des Silberhalogenids zu inhibieren vermögen. Hierzu zählen die aus der GB 953 454 bekannten DIR-Kuppler, die in der Kupplungsstelle einen Substituenten tragen, der bei der Kupplung abgespalten wird unter Freisetzung einer diffundierenden Verbindung, die die Entwicklung des Silberhalogenids hemmt. Durch die Verwendung von DIR-Kupplern läßt sich die Farbkörnigkeit verbessern und der Interimage-Effekt gezielt beeinflussen.It is known to control the sensitometric properties of a recording material by means of compounds of this type, from which diffusing substances are released during development which are capable of inhibiting the development of the silver halide. These include the DIR couplers known from GB 953 454, which carry a substituent in the coupling point which is split off during the coupling with the release of a diffusing compound, which inhibits the development of the silver halide. By using DIR couplers, the color granularity can be improved and the interimage effect can be influenced in a targeted manner.
Gleichartige Effekte lassen sich auch mit derartigen Verbindungen erzeugen, die keinen dauerhaften Farbstoff erzeugen, verwiesen wird auf die US 3 632 345 und die DE-OS 2 359 295. Im folgenden werden alle Verbindungen, die bei der Reaktion mit FarbentwicklerOxidationsprodukten diffundierende, organische, die Entwicklung des Silberhalogenids inhibierende Substanzen in Freiheit setzen, als DIR-Verbindungen bezeichnet.Similar effects can also be produced with compounds of this type which do not produce a permanent dye, reference is made to US Pat. No. 3,632,345 and DE-OS 2,359,295. In the following, all compounds which diffuse in the reaction with color developer oxidation products are organic, which Release the development of silver halide inhibiting substances, referred to as DIR compounds.
Aus der US-PS 3 620 747 und der DE-OS 2 322 165 sind fotografische Materialien mit zwei unterschiedlich empfindlichen Silberhalogenidemulsionsschichten gleicher spektraler Empfindlichkeit bekannt, wobei in beiden Schichten Farbkuppler enthalten sind und wobei in der unempfindlicheren Schicht zusätzlich eine DIR-Verbindung vorliegt. Aus der DE-OS 2 509 722 und der GB-PS 1 536 341 ist die Kombination von wenigstens zwei DIR-Verbindungen unterschiedlicher Reaktivität bekannt. Danach kann eine Silberhalogenidemulsionsschicht in zwei Teilschichten unterschiedlicher Empfindlichkeit aufgeteilt werden, wobei die empfindlichere Silberhalogenidteilschicht die reaktivere und die weniger empfindliche Silberhalogenidteilschicht die weniger reaktive DIR-Verbindung enthalten kann oder umgekehrt. Die Verwendung von DIR-Verbindungen in stärker und in weniger empfindlichen Teilschichten ist ebenfalls angegeben in der DE-OS 2 600 524 und der US 4 170 479. Aus der DE-OS 2 707 489 und der US-PS 4 183 752 sind fotografische Aufzeichnungsmaterialien mit DIR-Verbindungen geringer Reaktivität bekannt, die sich insbesondere zur Abmischung mit reaktiveren DIR-Verbindungen eignen. Dabei kann man eine grobkörnige hochempfindliche Schicht mit einem Farbkupplerunterschuß mit einer geringer empfindlichen Schicht in einem sogenannten Doppelschichtverband kombinieren. Zur Erzielung besserer sensitometrischer Eigenschaften können die DIR-Verbindungen dabei entweder einer der beiden Schichten oder auch jeder der Schichten zugesetzt werden, bevorzugt ist jedoch die Zugabe zu der unteren feinkörnigen Schicht eines Doppelschichtverbandes. Aus der DE-OS 2 853 362 und der US-PS 4 315 040 sind DIR-Verbindungen besonders hoher Reaktivität bekannt. Gemäß der europäischen Patentanmeldung 00 70 183 sind DIR-Verbindungen vorzugsweise in weniger empfindlichen Teilschichten eines Doppelschichtverbandes enthalten. Gemäß der EP 00 86 654 wird eine DIR-Verbindung mit einer sogenannten "Timing-Gruppe" in eine hochempfindliche Schicht und eine DIR-Verbindung ohne "Timing-Gruppe" in eine weniger empfindliche Schicht eingebracht.US Pat. No. 3,620,747 and DE-OS 2 322 165 disclose photographic materials with two differently sensitive silver halide emulsion layers with the same spectral sensitivity, color couplers being contained in both layers and a DIR compound additionally being present in the less sensitive layer. The combination of at least two DIR compounds of different reactivity is known from DE-OS 2 509 722 and GB-PS 1 536 341. A silver halide emulsion layer can then be divided into two sub-layers of different sensitivity, the more sensitive silver halide sub-layer containing the more reactive and the less sensitive silver halide sub-layer containing the less reactive DIR compound or vice versa. The use of dir Compounds in stronger and less sensitive sub-layers are also given in DE-OS 2 600 524 and US 4 170 479. From DE-OS 2 707 489 and US Pat. No. 4 183 752 photographic recording materials with DIR compounds are lower Known reactivity, which are particularly suitable for mixing with more reactive DIR compounds. You can combine a coarse-grained, highly sensitive layer with a color coupler deficit with a less sensitive layer in a so-called double-layer structure. To achieve better sensitometric properties, the DIR compounds can either be added to one of the two layers or to each of the layers, but addition to the lower fine-grained layer of a double-layer dressing is preferred. DIR compounds of particularly high reactivity are known from DE-OS 2 853 362 and US Pat. No. 4,315,040. According to European patent application 00 70 183, DIR compounds are preferably contained in less sensitive sub-layers of a double-layer structure. According to EP 00 86 654, a DIR connection with a so-called "timing group" is introduced into a highly sensitive layer and a DIR connection without a "timing group" into a less sensitive layer.
Bei Doppelschichtanordnungen führt die Verwendung von DIR-Verbindungen in höher empfindlichen Teilschichten leicht zu nicht tolerierbaren Empfindlichkeitsverlusten. Andererseits ist die Verwendung von DIR-Verbindungen auch in den höher empfindlichen Teilschichten zur Verbesserung der Farbkörnigkeit erwünscht.In the case of double-layer arrangements, the use of DIR connections leads to more sensitive sub-layers easily to intolerable loss of sensitivity. On the other hand, the use of DIR compounds is also desirable in the more sensitive sub-layers to improve the color grain.
Der Erfindung liegt die Aufgabe zugrunde, die sensitometrischen Eigenschaften von Farbaufzeichnungsmaterialien zu verbessern. Insbesondere soll die Farbkörnigkeit derartiger Aufzeichnungsmaterialien auch im Bereich geringer Farbdichte verbessert werden, ohne die Empfindlichkeit zu beeinträchtigen.The object of the invention is to improve the sensitometric properties of color recording materials. In particular, the color granularity of such recording materials should also be improved in the range of low color density without impairing the sensitivity.
Es wurde nun ein fotografisches Aufzeichnungsmaterial mit wenigstens einer vergleichsweise empfindlicheren Silberhalogenidemulsionsschicht I und einer vergleichsweise weniger empfindlichen Silberhalogenidemulsionsschicht II, die beide im gleichen Spektralbereich empfindlich sind, gefunden, wobei den Schichten I und II DIR-Verbindungen unterschiedlicher Reaktivität und Farbkuppler zugeordnet sind. Erfindungsgemäß ist das Verhältnis kKu/kDIR der effektiven Reaktionsgeschwindigkeitskonstanten des Farbkupplers kKU und der DIR-Verbindung kDIR in Schicht I größer als in Schicht II.We have now found a photographic recording material with at least one comparatively more sensitive silver halide emulsion layer I and one comparatively less sensitive silver halide emulsion layer II, both of which are sensitive in the same spectral range, with layers I and II being assigned DIR compounds of different reactivity and color couplers. According to the invention, the ratio k Ku / k DIR of the effective reaction rate constants of the color coupler k KU and the DIR compound k DIR in layer I is greater than in layer II.
Die effektiven Reaktionsgeschwindigkeitskonstanten beziehen sich dabei auf die Reaktion mit dem Entwickleroxidationsprodukt. Dieses wird durch Oxidation der üblicherweise als Farbentwicklersubstanzen verwendeten p-Phenylendiamine durch Silberhalogenid gebildet.The effective reaction rate constants relate to the reaction with the developer oxidation product. This is formed by oxidation of the p-phenylenediamines usually used as color developer substances by silver halide.
Die Messung von Reaktionsgeschwindigkeitskonstanten wird beispielsweise von J. Eggers beschrieben in "Mitteilungen aus den Forschungslaboratorien der Agfa", Leverkusen/ München, Band III, 1961, Seiten 81 ff. Da sich gezeigt hat, daß die Reaktionsgeschwindigkeitskonstanten einer DIR-Verbindung vom umgebenden Medium beeinflußt wird, ist erfindungsgemäß auf die effektive Reaktionsgeschwindigkeitskonstante abgehoben. Diese berücksichtigt die Art des umgebenden Mediums, beispielsweise die Verwendung eines ölbildners. Die effektive Reaktionsgeschwindigkeitskonstante läßt sich nach dem aus der DE-OS 2 853 632 und der US 4 315 070 bekannten Methode elektrochemisch bestimmen. Danach weist die effektive Reaktionsgeschwindigkeitskonstante keff die Dimension LI x mol x sek. ] auf.The measurement of reaction rate constants is described, for example, by J. Eggers in "Messages from the Agfa Research Laboratories", Leverkusen / Munich, Volume III, 1961, pages 81 ff. Since it has been shown that the reaction rate constants of a DIR compound are influenced by the surrounding medium is raised to the effective reaction rate constant according to the invention. This takes into account the type of surrounding medium, for example the use of an oil generator. The effective reaction rate constant can be determined electrochemically by the method known from DE-OS 2 853 632 and US 4,315,070. The effective reaction rate constant k eff then has the dimension LI x mol x sek. ] on.
Das Verhältnis der effektiven Reaktionsgeschwindigkeitskonstanten in der empfindlicheren Schicht I liegt vorzugsweise zwischen 2:1 und 20:1 und das Verhältnis der Reaktionsgeschwindigkeitskonstanten von Farbkuppler und DIR-Verbindungen der weniger empfindlichen Schicht II liegt vorzugsweise zwischen 0,03:1 und 6:1. DIR-Verbindungen und Kuppler sind jeweils bestimmten Silberhalogenidemulsionsschichten zugeordnet. Ihre weitere Reaktion bei der fotografischen Entwicklung wird deshalb durch die Entwicklung der jeweiligen Silberhalogenidemulsionsschicht gesteuert. Im einfachsten Falle sind Farbkuppler und DIR-Verbindung in der jeweiligen Silberhalogenidemulsionsschicht selbst enthalten, sie können aber auch in einer benachbarten Schicht vorliegen.The ratio of the effective reaction rate constants in the more sensitive layer I is preferably between 2: 1 and 20: 1 and the ratio of the reaction rate constants of color coupler and DIR compounds of the less sensitive layer II is preferably between 0.03: 1 and 6: 1. DIR compounds and couplers are each assigned to specific silver halide emulsion layers. Your further reaction in photographic development is therefore controlled by the development of the respective silver halide emulsion layer. In the simplest case, color coupler and DIR compound are contained in the respective silver halide emulsion layer itself, but they can also be present in an adjacent layer.
Gegebenenfalls ist es aber auch möglich, den Farbkuppler erst bei der Entwicklung in das Aufzeichnungsmaterial eindiffundieren zu lassen.If necessary, it is also possible to let the color coupler diffuse into the recording material only during development.
In einer bevorzugten Ausführungsform enthält aber das fotografische Material selbst die üblichen Farbkuppler, die mit dem Oxidationsprodukt von Entwicklern, im allgemeinen p-Phenylendiaminen, unter Bildung von Farbstoffen reagieren können.In a preferred embodiment, however, the photographic material itself contains the usual color couplers, which can react with the oxidation product of developers, generally p-phenylenediamines, to form dyes.
So kann die rotempfindliche Schicht beispielsweise einen nicht-diffundierenden Farbkuppler zur Erzeugung des blaugrünen Teilfarbenbildes enthalten, in der Regel einen Kuppler vom Phenol- oder α-Naphtholtyp. Die grünempfindliche Schicht kann beispielsweise mindestens einen nicht-diffundierenden Farbkuppler zur Erzeugung des purpurnen Teilfarbenbildes enthalten, wobei üblicherweise Farbkuppler vom Typ des 5-Pyrazolons oder des Schicht kann beispielsweise einen nicht-diffundierenden Farbkuppler zur Erzeugung des gelben Teilfarbenbildes, in der Regel einen Farbkuppler mit einer offenkettigen Ketomethylengruppierung enthalten. Bei den Farbkupplern kann es sich z.B. um 6-, 4- und um 2-Äquivalentkupplern handeln, darunter die sogenannten Weißkuppler, die bei Reaktion mit Farbentwickleroxidationsprodukten keinen Farbstoff ergeben. Geeignete Kuppler sind beispielsweise bekannt aus den Veröffentlichungen "Farbkuppler" von W. Pelz in "Mitteilungen aus den Forschungslaboratorien der Agfa, Leverkusen/München", Band III, Seite 111 (1961, K. Venkataraman in "The Chemistry of Synthetic Dyes", Vol. 4, 341 bis 387, Academic Press (1971) und T.H. James, "The Theory of the Photographic Process", 4. Ed., S. 353-362, sowie aus der Zeitschrift Research Disclosure Nr. 17643 vom Dezember 1978, Abschnitt VII, veröffentlicht von Industrial Opportunities Ltd., Homewell Havant, Hampshire, P09 1 EF in Großbritannien.For example, the red-sensitive layer can contain a non-diffusing color coupler for producing the blue-green partial color image, generally a coupler of the phenol or α-naphthol type. The green-sensitive layer can contain, for example, at least one non-diffusing color coupler for producing the purple partial color image, usually color couplers of the 5-pyrazolone or layer type can contain, for example, a non-diffusing color coupler for producing the yellow partial color image, usually a color coupler with a open chain ketomethylene grouping included. The color couplers can be, for example, 6-, 4- and 2-equivalent couplers, including the so-called white couplers, which do not produce any dye when reacted with color developer oxidation products. Suitable couplers are known, for example, from the publications "Color Couplers" by W. Pelz in "Messages from the Research Laboratories of Agfa, Leverkusen / Munich", Volume III, page 111 (1961, K. Venkataraman in "The Chemistry of Synthetic Dyes", Vol. 4, 341 to 387, Academic Press (1971) and TH James, "The Theory of the Photographic Process", 4th Ed., P. 353 -362, as well as from Research Disclosure No. 17643 of December 1978, Section VII, published by Industrial Opportunities Ltd., Homewell Havant, Hampshire, P09 1 EF in Great Britain.
Bei den erfindungsgemäß zu verwendenden DIR-Verbindungen handelt es sich um Substanzen, die mit dem oxidierten Farbentwickler zu reagieren vermögen und dabei bildmäßig Substanzen in Freiheit setzen, die die Entwicklung des benachbarten Silberhalogenids inhibieren. Bei den freigesetzen Hemmsubstanzen handelt es sich vorzugsweise um Mercapto-Verbindungen, z.B. 1-Phenyl-5-mercaptotetrazol. Bei den erfindungsgemäß zu verwendenden DIR-Verbindungen werden die Hemmsubstanzen unmittelbar durch Reaktion der DIR-Verbindung mit dem Entwickleroxidationsprodukt in Freiheit gesetzt.The DIR compounds to be used according to the invention are substances which are able to react with the oxidized color developer and thereby free up imagewise substances which inhibit the development of the neighboring silver halide. The inhibitory substances released are preferably mercapto compounds, e.g. 1-phenyl-5-mercaptotetrazole. In the DIR compounds to be used according to the invention, the inhibitory substances are released directly by reaction of the DIR compound with the developer oxidation product.
Besonders geeignete DIR-Verbindungen zum Einsatz in der vergleichsweise empfindlichen Schicht I sind beispielsweise aus der DE-OS 2 707 489 bekannt und weisen folgende Formel auf
- R 1 einen gegebenenfalls substituierten Hydrocarbylrest
- Y -S- oder -NR 2 worin R 2 für Wasserstoff, einen gegebenenfalls substituierten Hydrocarbylrest, eine über ein Ringkohlenstoffatom angeknüpfte heterocyclische Gruppe oder einen Elektronen anziehenden Substituenten steht
- X eine aliphatische Gruppe, eine aromatische Gruppe oder insbesondere eine heterocyclische Gruppe, die bei der Abspaltung mit dem Schwefelatom der Thioetherbrücke eine diffundierende, die Entwicklung des Silberhalogenids inhibierende Mercaptoverbindung bildet.
- R 1 is an optionally substituted hydrocarbyl radical
- Y -S- or - NR 2 wherein R 2 represents hydrogen, an optionally substituted hydrocarbyl radical, a heterocyclic group linked via a ring carbon atom or an electron-attracting substituent
- X is an aliphatic group, an aromatic group or, in particular, a heterocyclic group which, when cleaved off with the sulfur atom of the thioether bridge, forms a diffusing mercapto compound which inhibits the development of the silver halide.
Besonders geeignet sind die in der DE-OS 2 707 489 und der US-PS 4 183 752 unter 1 bis 30 angegebenen speziellen Verbindungen vom Thiazol-Typ und Imidazol-Typ.The special compounds of the thiazole type and imidazole type specified in DE-OS 2 707 489 and US Pat. No. 4 183 752 under 1 to 30 are particularly suitable.
Ganz besonders geeignete Verbindungen für die Verwendung in der empfindlichen Schicht I gemäß der vorliegenden Erfindung sind in folgender Tabelle 1 aufgeführt. Die keff-werte beziehen sich auf eine Lösung in dem angegebenen Lösungsmittel:
Die erfindungsgemäßen Aufzeichnungsmaterialien enthalten mindestens eine Silberhalogenidemulsionsschichten-Einheit für die Aufzeichnung von blauem, grünem und rotem Licht.The recording materials according to the invention contain at least one silver halide emulsion layer unit for recording blue, green and red light.
üblicherweise ist die rotempfindliche Silberhalogenidemulsionsschichten-Einheit dem Schichtträger näher angeordnet als die grünempfindliche Silberhalogenidemulsionsschichten-Einheit und diese wiederum näher als die blauempfindliche. Wenigstens eine Silberhalogenidemulsionsschichten-Einheit besteht aus wenigstens zwei Teilschichten unterschiedlicher Empfindlichkeit. In einer bevorzugten Ausführungsform besteht wenigstens eine der Einheiten für die Aufzeichnung von grünem, rotem und blauem Licht aus wenigstens zwei Teilschichten. Ein besonders bevorzugter Aufbau dieses Typs setzt sich aus folgenden Schichten zusammen:
- blauempfindliche Schicht(en)
- Gelbfilter
- höher grünempfindliche Schicht
- geringer grünempfindliche Schicht
- höher rotempfindliche Schicht
- geringer rotempfindliche Schicht Träger.
- blue sensitive layer (s)
- Yellow filter
- higher green sensitive layer
- less green sensitive layer
- higher red sensitive layer
- less red-sensitive layer of support.
Zwischenschichten sind hierbei nicht angegeben, können selbstverständlich aber enthalten sein.Intermediate layers are not specified here, but can of course be included.
Es ist auch möglich, Teilschichten unterschiedlicher spektraler Empfindlichkeit nach ihrer Empfindlichkeit zusammenzufassen. In einer besonders bevorzugten Ausführungsform liegt - ohne Berücksichtigung von Zwischenschichten - folgender Aufbau vor:
- blauempfindliche Schicht(ten)
- Gelbfilterschicht
- höher grünempfindliche Schicht
- höher rotempfindliche Schicht
- geringer grünempfindliche Schicht geringer rotempfindliche Schicht
- Träger.
- blue-sensitive layer (s)
- Yellow filter layer
- higher green sensitive layer
- higher red sensitive layer
- less green sensitive layer less red sensitive layer
- Carrier.
Das erfindungsgemäß anzuwendende Verhältnis der Reaktionsgeschwindigkeitskonstanten kann in allen, gegebenenfalls aber auch nur in einer oder zwei Schichteinheiten angewandt werden.The ratio of the reaction rate constants to be used according to the invention can be used in all, but possibly also only in one or two, layer units.
Die verwendeten Silberhalogenidemulsionen können als Halogenid Chlorid, Bromid und Iodid bzw. Mischungen davon enthalten. In einer bevorzugten Ausführungsform besteht der Halogenidanteil wenigstens einer Schicht zu 0 bis 10 Mol-% aus AgI, zu 0 bis 10 Mol-% aus AgCl und zu 0 bis 100 % aus AgBr, wobei sich die Summe dieser Anteile zu 100 % ergänzt. In einer weiteren Ausführungsform kann der Halogenidanteil auch überwiegend aus Chlorid bestehen. Die Silberhalogenidhörner können z. B. kubisch, oktaedrisch oder tafelförmig sein.The silver halide emulsions used can contain chloride, bromide and iodide or mixtures thereof as the halide. In a preferred embodiment, the halide content of at least one layer consists of 0 to 10 mol% AgI, 0 to 10 mol% AgCl and 0 to 100% AgBr, the sum of these proportions being 100% complementary. In a further embodiment, the halide portion can also consist predominantly of chloride. The silver halide horns can e.g. B. cubic, octahedral or tabular.
Die Emulsionen können chemisch sensibilisiert sein. Zur chemischen Sensibilisierung der Silberhalogenidkörner sind die üblichen Sensibilisierungsmittel geeignet. Besonders bevorzugt sind schwefelhaltige Verbindungen, beispielsweise Allylisothiocyanat, Allylthioharnstoff und Thiosulfate.The emulsions can be chemically sensitized. The usual sensitizers are suitable for chemical sensitization of the silver halide grains. Sulfur-containing compounds, for example allyl isothiocyanate, allyl thiourea and thiosulfates, are particularly preferred.
Als chemische Sensibilisatoren können ferner auch Reduktionsmittel, z. B. die in den belgischen Patentschriften 493 464 oder 568 687 beschriebenen Zinnverbindungen, ferner Polyamine wie Diethylentriamin oder Aminomethylsulfinsäure-Derivate, z. OB. gemäß der belgischen Patentschrift 547 323, verwendet werden. Geeignet als chemische Sensibilisatoren sind auch Edelmetalle bzw. Edelmetallverbindungen wie Gold, Platin, Palladium, Iridium, Ruthenium oder Rhodium. Diese Methode der chemischen Sensibilisierung ist in dem Artikel von R. Koslowsky, Z.Wiss.Phot. 46, 65-72 (1951), beschrieben. Es ist ferner möglich, die Emulsionen mit Polyalkylenoxid-Derivaten zu sensibilisieren, z. B. mit Polyethylenoxid eines Molekulargewichts zwischen 1000 und 20 000, ferner mit Kondensationsprodukten von Alkylenoxiden und aliphatischen Alkoholen, Glykolen, cyclischen dehydratisierungsprodukten von Hexitolen, mit alkylsubstituierten Phenolen, aliphatischen Carbonsäuren, aliphatischen Aminen, aliphatischen Diaminen und Amiden. Die Kondensationsprodukte haben ein Molekulargewicht von mindestens 700, vorzugsweise von mehr als 1000. Zur Erzielung besonderer Effekte kann man diese Sensibilisatoren selbstverständlich kombiniert verwenden, wie in der belgischen Patentschrift 537 278 und in der britischen Patentschrift 727 982 beschrieben. Verwiesen wird weiter auf die oben angegebene Research Disclosure Nr. 17 643, Abschnitt III.Reducing agents, e.g. B. the tin compounds described in Belgian patents 493 464 or 568 687, further polyamines such as diethylenetriamine or aminomethylsulfinic acid derivatives, for. IF. according to Belgian patent 547 323. Suitable as a chemical Noble metals or noble metal compounds such as gold, platinum, palladium, iridium, ruthenium or rhodium are also sensitizers. This method of chemical sensitization is described in the article by R. Koslowsky, Z.Wiss.Phot. 46, 65-72 (1951). It is also possible to sensitize the emulsions with polyalkylene oxide derivatives, e.g. B. with polyethylene oxide having a molecular weight between 1000 and 20,000, also with condensation products of alkylene oxides and aliphatic alcohols, glycols, cyclic dehydration products of hexitols, with alkyl-substituted phenols, aliphatic carboxylic acids, aliphatic amines, aliphatic diamines and amides. The condensation products have a molecular weight of at least 700, preferably more than 1000. To achieve special effects, these sensitizers can of course be used in combination, as described in Belgian patent 537 278 and British patent 727 982. Reference is also made to Research Disclosure No. 17 643, section III.
Die Emulsionen können in an sich bekannter Weise optisch sensibilisiert werden, z.B. mit den üblichen Polymethinfarbstoffen, wie Neutrocyaninen, basischen oder sauren Carbocyaninen, Rhodacyaninen, Hemicyaninen, Styrylfarbstoffen, Oxonolen und ähnlichen. Derartige Sensibilisatoren sind von F.M. Hamer in "The Cyanine Dyes and related Compounds", (1964), beschrieben. Verwiesen sei diesbezüglich insbesondere auf Ullmanns Enzyklopädie der technischen Chemie, 4. Auflage. Band 18, Seiten 431 ff und auf die oben angegebene Research Disclosure Nr. 17643, Abschnitt IV.The emulsions can be optically sensitized in a manner known per se, e.g. with the usual polymethine dyes, such as neutrocyanines, basic or acidic carbocyanines, rhodacyanines, hemicyanines, styryl dyes, oxonols and the like. Such sensitizers are from F.M. Hamer in "The Cyanine Dyes and related Compounds", (1964). In this regard, reference is made in particular to Ullmann's Encyclopedia of Industrial Chemistry, 4th edition. Volume 18, pages 431 ff and on the above-mentioned Research Disclosure No. 17643, Section IV.
Zusätzlich zu den erfindungsgemäß zu verwendenden Antischleiermittel können üblicherweise verwendete Antischleiermittel und Stabilisatoren verwendet werden.In addition to the antifoggants to be used in the present invention, commonly used antifoggants and stabilizers can be used.
Als Stabilisatoren sind besonders geeignet Azaindene, vorzugsweise Tetra- oder Pentaazaindene, insbesondere solche, die mit Hydroxyl- oder Aminogruppen substituiert sind. Derartige Verbindungen sind z.B. in dem Artikel von Birr, Z.Wiss.Phot. 47, 1952), S. 2-58, beschrieben. Weitere geeignete Stabilisatoren und Antischleiermittel sind in der oben angegebenen Research Disclosure Nr. 17643 in Abschnitt IV angegeben.Particularly suitable stabilizers are azaindenes, preferably tetra- or penta-azaindenes, in particular those which are substituted by hydroxyl or amino groups. Such connections are e.g. in the article by Birr, Z.Wiss.Phot. 47, 1952), pp. 2-58. Other suitable stabilizers and antifoggants are given in Research Disclosure No. 17643 above in Section IV.
Für die erfindungsgemäßen Materialien können die üblichen Schichtträger verwendet werden, 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 die oben angegebene Research Disclosure Nr. 17643 Abschnitt XVII.The usual substrates can be used for the materials according to the invention, 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 No. 17643 section XVII indicated above.
Als Schutzkolloid bzw. Bindemittel für die Schichten des Aufzeichnungsmaterials sind die üblichen hydrophilen filmbildenden Mittel geeignet, z.B. Proteine, insbesondere Gelatine, Alginsäure oder deren Derivate wie Ester, Amide oder Salze, Cellulose-Derivate wie Carboxymethylcellulose und Cellulosesulfate, Stärke oder deren Derivate oder hydrophile synthetische Bindemittel wie Polyvinylalkohol, teilweise verseiftes Polyvinylacetat, Polyvinylpyrrolidon und andere. Die Schichten können im Gemisch mit den hydrophilen Bindemitteln auch andere synthetische Bindemittel in gelöster oder dispergierter Form enthalten wie Homo- oder Copolymerisate von Acryl-oder Methacrylsäure oder deren Derivaten wie Estern, Amiden oder Nitrilen, ferner Vinylpolymerisate wie Vinylester oder Vinylether. Verwiesen wird weiterhin auf die in der oben angegebenen Research Disclosure 17643 in Abschnitt IX angegebenen Bindemittel.The usual hydrophilic film-forming agents are suitable as protective colloid or binder for the layers of the recording material, for example proteins, in particular gelatin, alginic acid or their derivatives such as esters, amides or salts, cellulose derivatives such as carboxymethyl cellulose and cellulose sulfates, starch or their derivatives or hydrophilic synthetic Binders like Polyvinyl alcohol, partially saponified polyvinyl acetate, polyvinyl pyrrolidone and others. In a mixture with the hydrophilic binders, the layers can also contain other synthetic binders in dissolved or dispersed form, such as homopolymers or copolymers of acrylic or methacrylic acid or their derivatives, such as esters, amides or nitriles, and also vinyl polymers, such as vinyl esters or vinyl ethers. Reference is also made to the binders specified in Research Disclosure 17643 above in Section IX.
Die Schichten des fotografischen Materials können in der üblichen Weise gehärtet sein, beispielsweise mit Härtern des Epoxidtyps, des heterocyclischen Ethylenimins und des Acryloyltyps. Weiterhin ist es auch möglich, die Schichten gemäß dem Verfahren der deutschen Offenlegungsschrift 2 218 009 zu härten, um farbfotografische Materialien zu erzielen, die für eine Hochtemperaturverarbeitung geeignet sind. Es ist ferner möglich, die fotografischen Schichten bzw. die farbfotografischen Mehrschichtenmaterialien mit Härtern der Diazin-, Triazin- oder 1,2-Dihydrochinolin-Reihe zu härten oder mit Härtern vom Vinylsulfon-Typ. Weitere geeignete Härtungsmittel sind aus den deutschen Offenlegungsschriften 2 439 551, 2 225 230, 2 317 672 und aus der oben angegebenen Research Disclosure 17643, Abschnitt XI bekannt.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 in accordance with the process of German laid-open specification 2 218 009 in order to obtain color photographic materials which are suitable for high-temperature processing. It is also possible to harden the photographic layers or the color photographic multilayer materials with hardeners of the diazine, triazine or 1,2-dihydroquinoline series or with hardeners of the vinyl sulfone type. Further suitable hardening agents are known from German laid-open documents 2 439 551, 2 225 230, 2 317 672 and from Research Disclosure 17643, section XI given above.
Weitere geeignete Zusätze werden in der Research Disclosure 17643 und in "Product Licensing Index" von Dezember 1971, Seiten 107 - 110 angegeben.Further suitable additives are described in Research Dis closure 17643 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-anilinhydrochlo- rid; 4-Amino-3-methyl-N-ethyl-N-ß-(methansulfonamido)-ethylanilinsulfathydrat; 4-Amino-3-methyl-N-ethyl-N-ß- hydroxyethylanilinsulfat; 4-Amino-N-ethyl-N-(2-methoxyethyl)-m-toluidin-di-p-toluolsulfonsäure und N-Ethyl-N-ß-hydroxyethyl-p-phenylendiamin.Suitable color developer substances for the material according to the invention are in particular those of the p-phenylenediamine type, e.g. 4-amino-N, N-diethyl-aniline hydrochloride; 4-amino-3-methyl-N-ethyl-N-β- (methanesulfonamido) ethylaniline 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-ß-hydroxyethyl-p-phenylenediamine.
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.Further 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, for example Fe 3+ salts and Fe 3+ complex salts such as ferricyanides, dichromates, water-soluble cobalt complexes etc. Iron-III complexes of aminopolycarboxylic acids, in particular for example ethylenediaminetetraacetic acid, nitrilotriacetic acid, iminodiacetic acid, N, are particularly preferred -Hydroxyethylethylenediamintriessigsäure, alkyliminodicarboxylic acids and corresponding phosphonic acids. Persulphates are also suitable as bleaching agents.
Die in den Beispielen angegebenen Farbkuppler entsprechen folgender Struktur:
Auf einen mit einer Lichthofschutzschicht und einer Haftschicht versehenen Cellulosetriacetatträger werden nacheinander die im folgenden angegebenen Schichten aufgetragen. Angegebene Mengenangaben beziehen sich jeweils auf 1m2. Der Silberauftrag wird durch die Angabe der äquimolaren Mengen Silbernitrat ausgewiesen:
- 1. Rotempfindliche Schicht geringer Empfindlichkeit Die Schicht enthält eine rotempfindliche Silberbromidiodidemulsion vergleichsweise geringer Empfindlichkeit (5 Mol % Silberiodid), 600 mg Blaugrünkuppler A, 30 mg DIR-Verbindung 2.1 sowie einen Maskenkuppler. Farbkuppler A wird hierbei in 600 mg n-Dibutylphthalat und die DIR-Verbindung 2.1 in 60 mg Trikresylphosphat als ölformer dispergiert. Silberauftrag: 3,5 g.
- 2. Rotempfindliche Schicht hoher Empfindlichkeit Die Schicht enthält eine rotempfindliche Silberbromidiodidemulsion hoher Empfindlichkeit mit 8 Mol % Silberiodid, 200 mg des unter 1.) angegebenen Blaugrünkupplers A in 200 mg n-Dibutylphthalat sowie nach Maßgabe der Tabelle 3 eine DIR-Verbindung. Silberauftrag: 3,0 g.
- 3. Zwischenschicht Die Zwischenschicht enthält 0,7 g Gelatine, 0,09 g eines darin dispergierten Fängers für Entwickleroxidationsprodukte der folgenden Formel:
- 4. Grünempfindliche Schicht geringer Empfindlichkeit Die Schicht enthält eine grünempfindliche Silberbromidiodidemulsion vergleichsweise geringer Empfindlichkeit (6 Mol % Silberiodid) sowie einen Purpurkuppler vom Pyrazolontyp, eine DIR-Verbindung und einen Gelbmaskenkuppler. Silberauftrag: 2,2 g.
- 5. Grünempfindliche Schicht hoher Empfindlichkeit Die Schicht enthält eine grünempfindliche Silberbromidiodidemulsion hoher Empfindlichkeit (10 Mol % Silberiodid) sowie einen darin dispergierten Purpurkuppler vom Pyrazolontyp.
- 6. Zwischenschicht Die Zwischenschicht enthält 0,5 g Gelatine und darin dispergiert den unter Schicht 3 angegebenen Fänger für Entwickleroxidationsprodukte.
- 7. Gelbfilterschicht Die Gelbfilterschicht enthält kolloidales Silber. Dichte: 0,7.
- 8. Blauempfindliche Schicht niedriger Empfindlichkeit Die Schicht enthält eine blauempfindliche Silberbromidiodidemulsion vergleichsweise geringer Empfindlichkeit (5 Mol % Silberiodid) und darin dispergiert eine Abmischung von Gelbkupplern vom Benzoylacetanilid-Typ.
- 9. Blauempfindliche Schicht hoher Empfindlichkeit Die Schicht enthält eine blauempfindliche Schicht hoher Empfindlichkeit mit 6 Mol % Silberiodid sowie eine Mischung der unter Schicht 8 angegebenen Gelbkuppler.
- 10. UV-Absorberschicht Die Schicht enthält in Gelatine dispergiert 0,8 g eines UV-Absorbers vom Benzotriazol-Typ.
- 11. Deckschicht
- 1. Red-sensitive layer of low sensitivity The layer contains a red-sensitive silver bromide iodide emulsion of comparatively low sensitivity (5 mol% silver iodide), 600 mg of cyan coupler A, 30 mg of DIR compound 2.1 and a mask coupler. Color coupler A is dispersed in 600 mg of n-dibutyl phthalate and the DIR compound 2.1 in 60 mg of tricresyl phosphate as an oil former. Silver application: 3.5 g.
- 2. Red-sensitive layer of high sensitivity The layer contains a red-sensitive silver bromide iodide emulsion with high sensitivity with 8 mol% of silver iodide, 200 mg of the cyan coupler A specified in 1.) in 200 mg of n-dibutyl phthalate and, in accordance with Table 3, a DIR compound. Silver application: 3.0 g.
- 3. Interlayer The intermediate layer contains 0.7 g of gelatin, 0.09 g of a scavenger for developer oxidation products of the following formula dispersed therein:
- 4. Green-sensitive layer of low sensitivity The layer contains a green-sensitive silver bromide iodide emulsion of comparatively low sensitivity (6 mol% silver iodide) as well as a purple coupler of the pyrazolone type, a DIR compound and a yellow mask coupler. Silver application: 2.2 g.
- 5. Green Sensitive Layer of High Sensitivity The layer contains a green sensitive silver bromide iodide emulsion of high sensitivity (10 mol% silver iodide) and a magenta coupler of the pyrazolone type dispersed therein.
- 6. Intermediate layer The intermediate layer contains 0.5 g of gelatin and disperses therein the scavenger for developer oxidation products specified under layer 3.
- 7. Yellow filter layer The yellow filter layer contains colloidal silver. Density: 0.7.
- 8. Blue Sensitive Layer of Low Sensitivity The layer contains a blue sensitive silver bromide iodide emulsion of comparatively low sensitivity (5 mol% silver iodide) and disperses therein a mixture of yellow couplers of the benzoylacetanilide type.
- 9. Blue-sensitive layer of high sensitivity The layer contains a blue-sensitive layer of high sensitivity with 6 mol% silver iodide and a mixture of the yellow couplers indicated under layer 8.
- 10. UV absorber layer The layer contains 0.8 g of a benzotriazole-type UV absorber dispersed in gelatin.
- 11. Top layer
Proben derart aufgebauter Materialien werden hinter einem Stufenkeil belichtet und der aus British Journal of Photography, 1974, Seite 597 bekannten Farbnegativverarbeitung unterworfen. Es werden die in folgender Tabelle 3 angegebenen Ergebnisse erhalten.
- Die Empfindlichkeit wird angegeben in DIN; eine Steigerung um 3,0 Einheiten entspricht einer Verdoppelung der Empfindlichkeit.
- The sensitivity is given in DIN; an increase of 3.0 units corresponds to a doubling of the sensitivity.
Körnigkeit:
- Die Körnigkeit wird angegeben in Form des δD-Wertes x 102. Er ergibt sich aus den Dichteschwankungen, die beim Abtasten einer möglichst langen Spur des Materials registriert werden. Zur Meßmethodik wird verwiesen auf Ullmann Encyclopädie der technischen Chemie, 4. Auflage, Verlag Chemie, Weinheim 1979, Seite 412 ff.
- The granularity is given in the form of the δ D value x 10 2 . It results from the density fluctuations that are registered when scanning the longest possible track of the material. Regarding the measuring methodology, reference is made to Ullmann Encyclopedia of Technical Chemistry, 4th edition, Verlag Chemie, Weinheim 1979, page 412 ff.
Tabelle 3 zeigt, daß bei alleiniger Verwendung einer DIR-Verbindung in der weniger empfindlichen Schicht zwar eine gute Empfindlichkeit, jedoch nur eine mäßige Körnigkeit erhalten wird. Durch Verwendung der reaktiven DIR-Verbindung 2.1 auch in der hochempfindlichen Schicht wird zwar eine Verbesserung der Körnigkeit erhalten jedoch muß eine deutliche Einbuße an Empfindlichkeit in Kauf genommen werden (Aufbau II). Erst bei Verwendung einer geeigneten DIR-Verbindung niedrigerer Reaktivität wird eine Verbesserung der Körnigkeit bei gleicher Empfindlichkeit erzielt (Aufbau III, Erfindung).Table 3 shows that when a DIR compound is used alone in the less sensitive layer, good sensitivity is obtained, but only moderate graininess is obtained. By using the reactive DIR compound 2.1 also in the highly sensitive layer, an improvement in the granularity is obtained, however, a significant loss in sensitivity has to be accepted (structure II). It is only when a suitable DIR compound with lower reactivity is used that an improvement in granularity is achieved with the same sensitivity (structure III, invention).
Ein farbfotografisches Aufzeichnungsmaterial mit Doppelschichten, die gemäß ihrer Empfindlichkeit zusammengefaßt sind, wird hergestellt. Es entspricht, bis auf die im folgenden angegebenen Änderungen, im wesentlichen dem aus dem Beispiel der DE-OS 2 704 797 und der US-PS 4 173 479 angegebenen Aufbau. Hierzu werden auf einen Träger in der angegebenen Reihenfolge folgende Schichten aufgetragen.A color photographic recording material with double layers, which are combined according to their sensitivity, is produced. It corresponds, except for the Changes given below, essentially the structure specified from the example of DE-OS 2 704 797 and US Pat. No. 4,173,479. For this purpose, the following layers are applied to a carrier in the order given.
- 1. Rotempfindliche Schicht geringer Empfindlichkeit mit einem Blaugrünkuppler.1. Red sensitive layer of low sensitivity with a cyan coupler.
- 2. Eine Gelatinezwischenschicht.2. An intermediate layer of gelatin.
- 3. Eine grünempfindliche Schicht geringer Empfindlichkeit. Die Schicht enthält eine Silberbromidiodidemulsion vergleichsweise geringer Empfindlichkeit mit 7 Mol % Silberiodid und ist grün sensibilisiert. Sie enthält weiter 1000 mg des Farbkupplers B dispergiert in 1000 mg Trikresylphosphat und 35 mg der DIR-Verbindung 2.2 in 35 mg Trikresylphosphat dispergiert. Der Silberauftrag beträgt 3,8 g.3. A green sensitive layer of low sensitivity. The layer contains a silver bromide iodide emulsion of comparatively low sensitivity with 7 mol% silver iodide and is green-sensitized. It also contains 1000 mg of color coupler B dispersed in 1000 mg of tricresyl phosphate and 35 mg of DIR compound 2.2 dispersed in 35 mg of tricresyl phosphate. The silver coating is 3.8 g.
- 4. Eine Gelatinezwischenschicht.4. An intermediate layer of gelatin.
- 5. Eine rotempfindliche Schicht hoher Empfindlichkeit.5. A red sensitive layer of high sensitivity.
- 6. Eine Gelatinezwischenschicht,6. An intermediate layer of gelatin,
- 7. Eine grünempfindliche Schicht hoher Empfindlichkeit. Die Schicht enthält eine Silberbromidiodidemulsion hoher Empfindlichkeit mit 10 Mol % Iodid, die grün sensibilisiert ist. Sie enthält weiterhin 250 mg des in 250 mg Trikresylphosphat dispergierten Farbkupplers B sowie nach Maßgabe der folgenden Tabelle 4 gegebenenfalls eine DIR-Verbindung. Der Silberauftrag beträgt 2,2 g.7. A green sensitive layer of high sensitivity. The layer contains a high sensitivity silver bromide iodide emulsion with 10 mol% iodide which is green sensitized. It also contains 250 mg the color coupler B dispersed in 250 mg of tricresyl phosphate and, in accordance with the following Table 4, if appropriate a DIR compound. The silver coating is 2.2 g.
- 8. Eine Gelatinezwischenschicht.8. An intermediate layer of gelatin.
- 9. Eine Gelbfilterschicht aus kolloidalem Silber.9. A yellow filter layer made of colloidal silver.
- 10. Eine blauempfindliche Schicht geringer Empfindlichkeit mit einem Gelbkuppler.10. A low sensitivity blue sensitive layer with a yellow coupler.
- 11. Eine blauempfindliche Schicht hoher Empfindlichkeit mit einem Gelbkuppler.11. A high sensitivity blue sensitive layer with a yellow coupler.
- 12. Eine Gelatineschutzschicht.12. A protective layer of gelatin.
Proben derart aufgebauter Materialien werden hinter einem Stufenkeil belichtet und der aus dem British Journal of Photography, 1974, Seite 597 beschriebenen Farbnegativverarbeitung unterworfen. Hierbei werden die in folgender Tabelle 4 angegebenen Ergebnisse erhalten.
Claims (8)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19833346621 DE3346621A1 (en) | 1983-12-23 | 1983-12-23 | COLOR PHOTOGRAPHIC RECORDING MATERIAL AND DEVELOPMENT METHOD |
DE3346621 | 1983-12-23 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0148441A2 true EP0148441A2 (en) | 1985-07-17 |
EP0148441A3 EP0148441A3 (en) | 1986-06-25 |
EP0148441B1 EP0148441B1 (en) | 1988-02-17 |
Family
ID=6217827
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP84115219A Expired EP0148441B1 (en) | 1983-12-23 | 1984-12-12 | Colour-photographic recording material and developing process |
Country Status (4)
Country | Link |
---|---|
US (1) | US4571378A (en) |
EP (1) | EP0148441B1 (en) |
JP (1) | JPS60227256A (en) |
DE (2) | DE3346621A1 (en) |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0220052A2 (en) * | 1985-10-17 | 1987-04-29 | Konica Corporation | Silver halide color photographic light-sensitive material |
EP0231870A2 (en) * | 1986-01-29 | 1987-08-12 | Fuji Photo Film Co., Ltd. | Method for color image formation |
EP0269740A1 (en) * | 1986-03-26 | 1988-06-08 | Konica Corporation | Process for processing silver halide color photographic material involving rapid development |
EP0317826A2 (en) * | 1987-11-21 | 1989-05-31 | Agfa-Gevaert AG | Negative colour-photographic recording material with DIR compounds |
EP0329016A2 (en) * | 1988-02-19 | 1989-08-23 | Agfa-Gevaert AG | Colour-photographic recording material |
EP0377910A2 (en) * | 1989-01-12 | 1990-07-18 | Agfa-Gevaert AG | Colour-photographic negative-recording material |
US5354646A (en) * | 1986-03-26 | 1994-10-11 | Konishiroku Photo Industry Co., Ltd. | Method capable of rapidly processing a silver halide color photographic light-sensitive material |
EP0631181A1 (en) * | 1993-06-24 | 1994-12-28 | Eastman Kodak Company | Color photographic elements containing a combination of pyrazolone and pyrazoloazole couplers |
EP0631182A1 (en) * | 1993-06-24 | 1994-12-28 | Eastman Kodak Company | Color photographic elements containing a combination of pyrazoloazole couplers |
WO2000038012A1 (en) * | 1998-12-19 | 2000-06-29 | Eastman Kodak Company | Photographic element containing a dir coupler |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2550331B2 (en) * | 1986-11-15 | 1996-11-06 | コニカ株式会社 | Silver halide color photographic material |
EP0889358B1 (en) * | 1997-06-30 | 2002-04-10 | Tulalip Consultoria Comercial Sociedade Unipessoal S.A. | Light-sensitive silver halide color photographic elements containing 2-equivalent 5-pyrazolone magenta couplers |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2250137A1 (en) * | 1973-11-07 | 1975-05-30 | Kodak Pathe | Colour image formation by reversal process - with non diffusable coupler in silver halide layer |
DE2416982A1 (en) * | 1974-04-08 | 1975-10-16 | Agfa Gevaert Ag | Colour photography material with composite layer - consisting of two silver halide layers with same gradation but different sensitivities |
DE2600524A1 (en) * | 1975-01-08 | 1976-07-15 | Fuji Photo Film Co Ltd | COLOR PHOTOGRAPHIC MULTI-LAYER RECORDING MATERIAL |
DE2853362A1 (en) * | 1978-12-11 | 1980-06-12 | Agfa Gevaert Ag | COLOR PHOTOGRAPHIC RECORDING MATERIAL WITH A DIR COUPLER HIGH REACTIVITY |
EP0045427A2 (en) * | 1980-08-01 | 1982-02-10 | Agfa-Gevaert AG | Light-sensitive photographic recording meterial and its use in producing photographic images |
DE3209995A1 (en) * | 1981-03-20 | 1982-09-30 | Konishiroku Photo Industry Co., Ltd., Tokyo | COLOR PHOTOGRAPHIC SILVER HALOGENIDE RECORDING MATERIAL |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2707489C2 (en) * | 1977-02-21 | 1983-10-06 | Agfa-Gevaert Ag, 5090 Leverkusen | Color photographic recording material |
JPS56116029A (en) * | 1980-01-16 | 1981-09-11 | Konishiroku Photo Ind Co Ltd | Silver halide color photographic sensitive material |
JPS58140740A (en) * | 1982-02-15 | 1983-08-20 | Konishiroku Photo Ind Co Ltd | Photosensitive silver halide material |
JPS5960437A (en) * | 1982-09-30 | 1984-04-06 | Fuji Photo Film Co Ltd | Color photographic sensitive silver halide material |
-
1983
- 1983-12-23 DE DE19833346621 patent/DE3346621A1/en not_active Withdrawn
-
1984
- 1984-12-10 US US06/680,154 patent/US4571378A/en not_active Expired - Fee Related
- 1984-12-12 DE DE8484115219T patent/DE3469386D1/en not_active Expired
- 1984-12-12 EP EP84115219A patent/EP0148441B1/en not_active Expired
- 1984-12-21 JP JP59268710A patent/JPS60227256A/en active Pending
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2250137A1 (en) * | 1973-11-07 | 1975-05-30 | Kodak Pathe | Colour image formation by reversal process - with non diffusable coupler in silver halide layer |
DE2416982A1 (en) * | 1974-04-08 | 1975-10-16 | Agfa Gevaert Ag | Colour photography material with composite layer - consisting of two silver halide layers with same gradation but different sensitivities |
DE2600524A1 (en) * | 1975-01-08 | 1976-07-15 | Fuji Photo Film Co Ltd | COLOR PHOTOGRAPHIC MULTI-LAYER RECORDING MATERIAL |
DE2853362A1 (en) * | 1978-12-11 | 1980-06-12 | Agfa Gevaert Ag | COLOR PHOTOGRAPHIC RECORDING MATERIAL WITH A DIR COUPLER HIGH REACTIVITY |
EP0045427A2 (en) * | 1980-08-01 | 1982-02-10 | Agfa-Gevaert AG | Light-sensitive photographic recording meterial and its use in producing photographic images |
DE3209995A1 (en) * | 1981-03-20 | 1982-09-30 | Konishiroku Photo Industry Co., Ltd., Tokyo | COLOR PHOTOGRAPHIC SILVER HALOGENIDE RECORDING MATERIAL |
Cited By (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0220052A3 (en) * | 1985-10-17 | 1989-05-10 | Konishiroku Photo Industry Co. Ltd. | Silver halide color photographic light-sensitive material |
EP0220052A2 (en) * | 1985-10-17 | 1987-04-29 | Konica Corporation | Silver halide color photographic light-sensitive material |
US5118593A (en) * | 1986-01-29 | 1992-06-02 | Fuji Photo Film Co., Ltd. | Method for color image formation |
EP0231870A2 (en) * | 1986-01-29 | 1987-08-12 | Fuji Photo Film Co., Ltd. | Method for color image formation |
EP0231870A3 (en) * | 1986-01-29 | 1989-06-07 | Fuji Photo Film Co., Ltd. | Method for color image formation |
EP0269740A1 (en) * | 1986-03-26 | 1988-06-08 | Konica Corporation | Process for processing silver halide color photographic material involving rapid development |
EP0269740A4 (en) * | 1986-03-26 | 1989-07-26 | Konishiroku Photo Ind | Process for processing silver halide color photographic material involving rapid development. |
US5354646A (en) * | 1986-03-26 | 1994-10-11 | Konishiroku Photo Industry Co., Ltd. | Method capable of rapidly processing a silver halide color photographic light-sensitive material |
EP0317826A2 (en) * | 1987-11-21 | 1989-05-31 | Agfa-Gevaert AG | Negative colour-photographic recording material with DIR compounds |
EP0317826A3 (en) * | 1987-11-21 | 1990-05-09 | Agfa-Gevaert Ag | Negative colour-photographic recording material with dir compounds |
EP0329016A3 (en) * | 1988-02-19 | 1990-08-16 | Agfa-Gevaert Ag | Colour-photographic recording material |
EP0329016A2 (en) * | 1988-02-19 | 1989-08-23 | Agfa-Gevaert AG | Colour-photographic recording material |
EP0377910A2 (en) * | 1989-01-12 | 1990-07-18 | Agfa-Gevaert AG | Colour-photographic negative-recording material |
EP0377910A3 (en) * | 1989-01-12 | 1991-08-14 | Agfa-Gevaert AG | Colour-photographic negative-recording material |
EP0631181A1 (en) * | 1993-06-24 | 1994-12-28 | Eastman Kodak Company | Color photographic elements containing a combination of pyrazolone and pyrazoloazole couplers |
EP0631182A1 (en) * | 1993-06-24 | 1994-12-28 | Eastman Kodak Company | Color photographic elements containing a combination of pyrazoloazole couplers |
WO2000038012A1 (en) * | 1998-12-19 | 2000-06-29 | Eastman Kodak Company | Photographic element containing a dir coupler |
US6346371B1 (en) | 1998-12-19 | 2002-02-12 | Eastman Kodak Company | Photographic element containing a DIR coupler |
Also Published As
Publication number | Publication date |
---|---|
EP0148441B1 (en) | 1988-02-17 |
US4571378A (en) | 1986-02-18 |
EP0148441A3 (en) | 1986-06-25 |
DE3469386D1 (en) | 1988-03-24 |
DE3346621A1 (en) | 1985-07-04 |
JPS60227256A (en) | 1985-11-12 |
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