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
  • G03C7/32—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
• • 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
• • 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
• • 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
• • 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
• • 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.

Landscapes

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

Applications Claiming Priority (2)

Publications (3)

Family

ID=6217827

Family Applications (1)

Country Status (4)

Cited By (10)

Families Citing this family (2)

Family Cites Families (10)

• 1983
  • 1983-12-23 DE DE19833346621 patent/DE3346621A1/de not_active Withdrawn
• 1984
  • 1984-12-10 US US06/680,154 patent/US4571378A/en not_active Expired - Fee Related
  • 1984-12-12 EP EP84115219A patent/EP0148441B1/fr not_active Expired
  • 1984-12-12 DE DE8484115219T patent/DE3469386D1/de not_active Expired
  • 1984-12-21 JP JP59268710A patent/JPS60227256A/ja active Pending

Also Published As

Similar Documents

Legal Events