EP0114306B1 - Multischichtiges farbphotographisches Material mit einer hohen Empfindlichkeit und Entwickelbarkeit - Google Patents

Multischichtiges farbphotographisches Material mit einer hohen Empfindlichkeit und Entwickelbarkeit Download PDF

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Publication number
EP0114306B1
EP0114306B1 EP83112639A EP83112639A EP0114306B1 EP 0114306 B1 EP0114306 B1 EP 0114306B1 EP 83112639 A EP83112639 A EP 83112639A EP 83112639 A EP83112639 A EP 83112639A EP 0114306 B1 EP0114306 B1 EP 0114306B1
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EP
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Prior art keywords
layer
silver
sensitivity
sensitive
group
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EP83112639A
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English (en)
French (fr)
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EP0114306A3 (en
EP0114306A2 (de
Inventor
Marcello Amicucci
Elio De Saraca
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3M Co
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Minnesota Mining and Manufacturing Co
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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
    • G03C7/3029—Materials characterised by a specific arrangement of layers, e.g. unit layers, or layers having a specific function
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/3022—Materials with specific emulsion characteristics, e.g. thickness of the layers, silver content, shape of AgX grains
    • G03C2007/3025—Silver 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
    • G03C2200/00—Details
    • G03C2200/35—Intermediate layer

Definitions

  • the present invention refers to a multilayer color photographic material and in particular to a multilayer color photographic material having high sensitivity and developability and good image quality.
  • a multilayer color photographic material usually consists of a base having coated thereon a red-sensitive emulsion layer containing a cyan-dye forming coupler, a green-sensitive emulsion layer containing a magenta-dye forming coupler, a blue-sensitive emulsion layer containing a yellow-dye forming coupler, intermediate layers, filter layers, an antihalation layer and a protective layer.
  • French patent application 2,379,836 describes the use of DIR compounds included in a light insensitive emulsion layer placed between a high sensitivity red sensitive emulsion layer and a high sensitivity green sensitive emulsion layer to get interimage effects with no significant loss of sensitivity.
  • a technique known to provide high-sensitivity photographic materials is the multilayer technique (described in GB patent 923,045) which consists of using more layers with different sensitivities (also called hemilayers) for the formation of at least one of the three main colors which form a conventional color image (cyan, magenta and yellow).
  • the more sensitive, coarse grain emulsion is used to record low exposures and the less sensitive emulsion is used to record higher intensity exposures.
  • the two emulsions, sensitive to the same region of light and forming the same color are chosen in their sensitometric curves (which define sensitivity, contrast and maximum density), to match and form the desired sensitometric curve, as known in the art. In this sense, we can speak of "matched" hemilayers.
  • the more sensitive emulsion is used in a higher quantity with respect to the less sensitive emulsion but contains a lower proportion of coupler (i.e. a high silver/coupler ratio). This is true also when three emulsions are used respectively to record low, middle and high exposures (as described in US patent 3,843,369).
  • the lowest sensitivity emulsion is used in a lower quantity with respect to the highest sensitivity emulsion or emulsions, but with a relatively higher coupler quantity, i.e. with a lower silver/coupler ratio.
  • a fine grain light insensitive emulsion layer placed between the low sensitivity green sensitive emulsion layer and the high sensitivity red sensitive emulsion layer of a photographic-element including such low sensitivity green sensitive emulsion layer associated with a high sensitivity green sensitive emulsion layer and a DIR compound in said low and high sensitivity green sensitive emulsion layers gives beneficial effects in terms of sensitivity not only to the green but also to the red.
  • Image quality measured as MTF, is improved while higher sensitivity is obtained.
  • a multilayer color photographic material comprising a base having coated thereon at least a red-sensitive emulsion layer containing a cyan-dye forming coupler, a green-sensitive emulsion layer containing a magenta-dye forming coupler, and a blue-sensitive emulsion layer containing a yellow-dye forming coupler, at least one green sensitive layer of which includes a DIR compound, characterized by sequentially including, starting from the base, a low sensitivity red sensitive layer, a high sensitivity red sensitive layer, a light insensitive fine grain emulsion layer coated at a silver coverage of 0.1 to 1 gram for square meter, a low sensitivity green sensitive layer including a DIR compound and a high sensitivity green sensitive layer including a DIR compound.
  • the present invention refers to a multilayer color photographic material as described above, wherein a third red-sensitive middle-sensitivity hemilayer is used in addition to said low and high sensitivity hemilayers.
  • the present invention refers to a multilayer color photographic material as described above which includes layers coated one on the other starting from the base, in the order: red-sensitive low-sensitivity layer, red-sensitive middle-sensitivity layer, red-sensitive high-sensitivity layer, non-sensitive layer, green-sensitive low-sensitivity layer, green-sensitive high-sensitivity layer, yellow filter layer, blue-sensitive low-sensitivity layer, blue-sensitive high-sensitivity layer.
  • the present invention refers to a multilayer color photographic material as described above, wherein said DIR compound is a DIR coupler represented by general formula (I): wherein COUP represents a magenta coupler residue (such as e.g. a .5-pyrazolone coupler, a pyrazolobenzimidazole coupler, a cyanoacetylcumarone coupler and an indazolone coupler) which couples with the oxidation product of a developing agent of the primary aromatic amine type to give a magenta dye and Z represents an organic residue which can be released by (I) during the coupling reaction with the oxidation product of the primary aromatic amine to inhibit development in the silver halide emulsion layer (examples of such organic residue being heterocyclic residues which form 1-triazole or 1-diazole rings, 2-benzotriazole residues, arylmonothio groups and thioetherocyclic groups).
  • a magenta coupler residue such as e.
  • the present invention refers to a multilayer color photographic material as described above wherein said DIR coupler is represented by general formula (II): wherein R represents an aryl group, a heterocyclic group, an alkyl group; R' represents an alkyl group, an alkoxy group, an aryloxy group, an aryl group, a hetereocyclic ring residue, an amino group, an arylamino group, an ureido group; A represents sulfur or selenium and D represents a group which, together with the sulfur or selenium of the thioether or selenoether bond, when such atom is released during coupling, forms a compound exerting a development inhibiting effect.
  • R represents an aryl group, a heterocyclic group, an alkyl group
  • R' represents an alkyl group, an alkoxy group, an aryloxy group, an aryl group, a hetereocyclic ring residue, an amino group, an arylamino group,
  • the present invention preferably refers to a multilayer color photographic material as described above wherein the non light-sensitive silver halide included in the intermediate layer is silver bromo-iodide, more preferably silver bromo-iodide containing from 1 to 4 per cent of silver iodide moles, and the most preferably silver bromo-iodide containing about 2 per cent of silver iodide moles.
  • the present invention refers to a multilayer color photographic material as described above wherein the light insensitive silver halide grains have means sizes lower than 0.2 pm, more preferably lower than 0.1 pm.
  • the DIR compounds used in the practice of the present invention are those compounds which during development release a development inhibiting compound.
  • Compounds of this type are for instance the DIR couplers which release a development inhibiting compound during the reaction with oxidation product of a color developer to form a dye, such as those described e.g. in U.S. patent 3,227,554; the TIMING-DIR couplers which release a development inhibiting compound with the capability of controlling the release time, such as those described e.g.
  • the DIR couplers which are the DIR compounds preferred to the purposes of the present invention, can be represented by the following formula (I): wherein COUP represents a magenta coupler residue which reacts with the oxidation products of a developing agent of the primary aromatic amine type to give a magenta dye and Z represents an organic group which can be released during coupling reaction and inhibits development.
  • couplers are the 5-pyrazolone couplers, the pyrazoloindazole couplers, the cyanoacetylcumarone couplers, the indazolone couplers.
  • groups represented by Z are the heterocyclic residues which form 1-triazole and 1-diazole rings, the 2-benzotriazole residues, the arylmonothio and thioetherocyclic groups, such as those described in US patents 3,617,291; 3,622,328; 3,632,373; 3,620,745; 3,627,747; in GB patents 1,201,110; 1,261,061; 1,269,075 and 1,269,073.
  • the DIR couplers of the present invention are those represented by the following formula (II): wherein R represents an aryl group (e.g. naphthyl, phenyl, 2,4,6-trichlorophenyl, 2-chloro-4,6-dimethylphenyl, 2,6-dichloro-4-methoxyphenyl, 4-methylphenyl, 4-acylaminophenyl, 4-alkylaminophenyl, 4-trifluoromethylphenyl, 3,5-dibromophenyl, etc.), a heterocyclic group (e.g.
  • R represents an aryl group (e.g. naphthyl, phenyl, 2,4,6-trichlorophenyl, 2-chloro-4,6-dimethylphenyl, 2,6-dichloro-4-methoxyphenyl, 4-methylphenyl, 4-acylaminophenyl, 4-alkylaminophenyl, 4-trifluoromethylphenyl, 3,5
  • R' represents a primary, secondary or tertiary alkyl group (e.g. methyl, propyl, n-butyl; tert.-butyl, hexyl, 2-hydroxyethyl, 2-phenylethyl, pentadecyl, etc.), an alkoxy group (e.g. methoxy, ethoxy, benzyloxy, etc.), an aryloxy group (e.g.
  • phenoxy an aryl group (e.g. phenyl, 2,4-ditert.-phenyl, etc.), a heterocyclic ring residue (e.g. quinolinyl, piperidyl, benzofuranyl, oxazolyl, etc.), an amino group (e.g. methylamino, diethylamino, phenylamino, tolylamino, 4-(3-sulfobenzamino)anilino, 2-chloro-5-acylaminoanilino, 2-chloro-5-alkoxycarbonilanilino, etc.), an acylamino group (e.g.
  • alkylcarbonamido such as ethylcarbonamido, etc.
  • arylcarbonamido such as benzothiazolylcarbonamido, sulfonamido, heterocyclic sulfonamido, etc.
  • a ureido group e.g. alkylureido, arylureido, heterocyclic ureido, etc.
  • A represents sulfur or selenium
  • D represents a group which, together with sulfur or selenium of the thioether or selertoether bond, forms a development inhibiting compound which can be released during the coupling reaction.
  • Typical examples of D include an aryl group and a heterocyclic ring.
  • Typical examples of said group, wherein D and sulfur or selenium are linked include, if A is sulfur, a heterocyclic mercapto residue, e.g. a mercaptotetrazole (in particular 1-phenyl-5-mercaptotetrazole, 1-nitrophenyl-5-mercaptotetrazole, 1-naphthyl-5-mercaptotetrazole), a mercaptothiazole (in particular 2-mercaptobenzothiazole, mercaptonaphthothiazole), a mercaptooxadiazole, a mercaptopyrimidine, a mercaptooxazole, a mercaptothiadiazole, a mercaptotriazine and a mercaptotriazole and, as an arylmercapto group residue, include for instance a mercaptobenzene (in particular 1-mercapto-2-benzoic acid, 1-mercapto-2-nitrobenzene
  • A is selenium
  • 1-phenyl-5-selenotetrazole 2-selenobenzoxazole are for instance included and, as the arylseleno group, a selenobenzene [e.g. 4-(4-hydrophenylsulfonyl)selenophenol] is for instance included.
  • a selenobenzene e.g. 4-(4-hydrophenylsulfonyl)selenophenol
  • Concrete exemplification of the DIR coupler used in the present invention and the preparation thereof are for instance described in US patents 3,227,554 and 3,773,201.
  • ballast group In order to render the DIR couplers non diffusible, a group having a hydrophobic residue with about 8 to 32 carbon atoms is introduced into the coupler molecule. Such a residue is called "ballast group".
  • the ballast group is lined to the coupler nucleus directly or through an imino, ether, carbonamido, sulfonamido, ureido, ester, imido, carbamoyl, sulfamoyl, etc., bond. Examples of ballast groups are specifically illustrated in US patent 4,009,038.
  • the magenta-dye forming couplers used in the green sensitive emulsion layer can be 5-pyrazolone couplers, pyrazolotriazole couplers, pyrazolobenzimidazole couplers, cyanoacetylcumarone couplers, indazolone couplers.
  • the couplers represented by the following formula (III) are useful in this invention: wherein Rand R' have the above described meanings and Z' represents a hydrogen atom or a group which can be released during color development, such as thiocyano group, an acyloxy group, an aryloxy group, an alkoxy group, an alkoxycarbonyloxy group, an amino group such as alkylamino, arylamino, alkylsulfonamido, arylsulfonamido, arylamido, cyclic imino, cyclic imido, etc., an arylazo group, an azoheterocyclic group, a heterocyclic group, as descrbed for instance in GB patent 1,603,223 and in US patent 4,262,087.
  • Such couplers are made non diffusible by means of ballasting groups as described above for the DIR couplers.
  • the green-sensitive silver halide emulsion layer for the purposes of the present invention preferably consists of two or more emulsion hemilayers with different sensitivities. These green-sensitive hemilayers can be used in combinations of different silver/coupler ratios and of different color maximum densities.
  • the sensitivity difference between the higher sensitivity layer and the lower sensitivity layer is usefully in the range from 3 to 8 DIN, more preferably from 4 to 6 DIN (the sensitivity in the DIN system is derived from the exposure required to produce a density of 0.1 above fog in the curve of density vs. log ⁇ ⁇ of exposure, as described in P. Glafkidés, Chimie Photographique, 1957, p.
  • the silver/coupler mole ratio of the more sensitive layer is in the range from 30/1 to 100/1, more preferably from 50/1 to 80/1 and the silver/coupler mole ratio of the less sensitive layer is in the range from 5/1 to 20/1, more preferably from 10/1 to 15/1 and that the difference of color maximum density between the lower sensitivity layer and the higher sensitivity layer is in the optical density value range of 0.3 to 0.9, more preferably 0.4 to 0.8.
  • the DIR compounds and the magenta-dye forming couplers can be included in the same green-sensitive silver halide emulsion layer or by separate hemilayers.
  • each of these hemilayers contains the DIR compound in combination with the magenta forming coupler and at least one, and more preferably all of them also contain the so-called masked magenta coupler, i.e. a colored coupler corresponding to the above formula (111), wherein Z' represents an arylazo group or an azoheterocyclic group.
  • masked magenta coupler i.e. a colored coupler corresponding to the above formula (111), wherein Z' represents an arylazo group or an azoheterocyclic group.
  • the total quantity of magenta forming coupler contained in the green-sensitive silver halide emulsion layer or layers is in general in the range from 10 to 50 moles, more preferably from 20 to 40 moles per silver mole and the quantity of DIR coupler included in the layer is in general in the range from 2 to 10 moles, more preferably from 4 to 8 moles per silver halide mole; said DIR couplers is used in combination with the magenta-dye forming coupler in a quantity ranging from 5 to 40 mole per cent, preferably from 10 to 30 mole per cent with respect to the total moles of magenta-dye forming coupler in the green-sensitive layer.
  • said DIR couplers and magenta-dye forming couplers can be included into one or more silver halide emulsion layers which build up the green-sensitive silver halide emulsion layer by various methods known in the photographic art.
  • Couplers having a water-soluble group such as a garboxyl group, a hydroxy group, a sulfonic group or a sulfonamido group, can be added to the emulsion according to the Fisher process, i.e. by dissolving them in an alkaline water solution.
  • Hydrophobic couplers can be added to the silver halide emulsion by dissolving them in a high-boiling solvent and then dispersing them in gelatin as described in US patents 2,322,027 and 2,304,939. Alternatively, it is possible to add at least one coupler according to the Fisher process and the others according to the dispersion method.
  • the blue-sensitive silver halide emulsion layer of the photographic material contains at least a yellow-dye forming coupler of the acylacetanilido type.
  • Particularly useful in this invention are the couplers represented by general formula (IV): wherein R" represents a primary, secondary or tertiary alkyl group (e.g. tert.-butyl, 1,1-dimethylpropyl, 1,1-dimethyl-1-methoxy-fenoxymethyl, etc.), or an aryl group (e.g.
  • phenyl alkylphenyl such as 2-methylphenyl, 3-octadecylphenyl, etc and alkoxyphenyl such as 2-methoxyphenyl, 4-methoxyphenyl, etc., halophenyl, 2-chloro-5-alkylcarbonamidophenyl, 2-chloro-5-[ ⁇ -(2,4-ditert.-aminophenoxy)-butyramido]-phenyl, 2-methoxy-5-alkylamidophenyl, 2-chloro-5-suIfonamidophenyl, etc.); R'" represents a phenyl group (e.g.
  • Z" represents a hydrogen or a group which can be released during color development, such as a halogen atom (in particular fluorine), an acyloxy group, an aryloxy group, an aromatic heterocyclic carbonyloxy group, a sulfimido group, an alkylsulfonyl group, an arylsulfoxy group, a phthalimido group, a dioxyimidazolidinyl group, a dioxyoxazolidinyl group, a dioxythiazolidiny
  • the red-sensitive silver halide emulsion layer of the photographic element contains at least a cyan-dye forming coupler of the napthole or phenole type.
  • couplers useful in this invention are those represented by general formulas (V) and (VI): wherein R ! " represents a substituent used for cyan couplers, such as a carbamyl (e.g. alkylcarbamyl, arylcarbamyl, such as phenylcarbamyl, etc., a heterocyclic carbamyl, such as benzylthiazolylcarbamyl, etc.), a sulfamyl (e.g.
  • R" represents an alkyl group, an aryl group, a heterocyclic group, an amino group (e.g. alkylcarbonamido, arylcarbonamido, etc.), a sulfamido group, a sulfamyl group or a carbamyl group; R"', R"" and R"" !
  • R'" each have the same meaning of R'" and moreover represent a halogen atom or an alkyl group and Z"' represents a hydrogen atom or a group which can be released during color development, such as a halogen atom, a thiocyano group, a cycloamido group (e.g. maleido, sucinimido, 1,2-dicarboxyimido, etc.), an arylazo group or a heterocyclic azo group.
  • a halogen atom e.g. maleido, sucinimido, 1,2-dicarboxyimido, etc.
  • arylazo group e.g. maleido, sucinimido, 1,2-dicarboxyimido, etc.
  • Such yellow-dye and cyan-dye forming couplers are made non-diffusible by means of ballast groups and are introduced into one or more emulsion layers, as described above.
  • the red-sensitive and blue-sensitive silver halide emulsion layers can contain the DIR compounds (such as DIR couplers, TIMING-DIR couplers, DIR hydroquinones or other DIR substances) as said above in association with the cyan and yellow dye forming couplers. Normally, the use of such DIR compounds in these layers does not show significant advantages, but may sometimes be advisable to achieve particular results.
  • DIR compounds such as DIR couplers, TIMING-DIR couplers, DIR hydroquinones or other DIR substances
  • the intermediate layer coated between the red-sensitive silver halide emulsion fayers and the green-sensitive emulsion layers contains fine, light insensitive silver halide grains (light insensitive grains herein mean those grains which upon exposure at the normal employment conditions and development in standard black and white and color developers do not form any image).
  • light insensitive grains herein mean those grains which upon exposure at the normal employment conditions and development in standard black and white and color developers do not form any image.
  • Such silver halide grains are neither physically ripened nor chemically sensitized and have a mean size lower than about 0.2 um, more preferably lower than 0.1 pm.
  • the useful silver halide can be one among silver chloride, silver bromide, silver iodide, silver bromo-iodide, silver chloro-bromide, silver chloro-bromo-iodide, etc., used alone or in combination of two or more of them.
  • silver bromo-iodide having no more than 4% silver iodide moles proved to be very effective in providing the beneficial effects in the green-sensitive silver halide emulsion layer (or layers). Since these silver halide crystals are not to be light sensitive, they must not get bigger during preparation, storage and coating and after the coating itself of the photographic material containing them. In this respect, silver bromo-iodide crystals having from 1 to 4% silver iodide moles were particularly good, in particular when stabilized during the preparation thereof, preferably with triazoindolizine compounds.
  • said fine, light sensitive silver halide crystals have to be a little soluble in the developing solutions to give a contribution to the silver image formation.
  • a part of the image is formed upon chemical development, i.e. upon reduction of the exposed silver halide grains, and a part is formed upon physical development, i.e. upon passage into solution of silver ions from developing or neighbouring grains, then diffusion of such ions to the silver centers (such as those supplied by the latent image or by the chemical development) where they are reduced to silver.
  • the fine light insensitive silver halide grains of the present invention are supposed to act as a source of silver ions which diffuse into adjacent light-sensitive layers to contribute to the silver image formation upon physical development.
  • the amount of such light insensitive silver halide grains useful to obtain the desired effects in the adjacent light-sensitive layers is in the range of about from 0.1 to 1 gram per square meter, preferably from about 0.2 to 0.4 gram per square meter.
  • the intermediate layer comprising the light insensitive silver halide grains of the present invention, can at the same time include other compounds of photographic interest, such as matting agents (e.g. colloidal silica, polymethylmethacrylate, etc.), high-boiling solvents (e.g. tricresylphosphate, dibutylphthalate, etc.), UV-absorbers (e.g. thiazolidone, benzothiazole, acrylonitrile, benzophenone compounds, etc.), antioxidants, ballasted hydroquinone derivatives, surfactants such as coating aids, gelatin hardeners, etc.
  • matting agents e.g. colloidal silica, polymethylmethacrylate, etc.
  • high-boiling solvents e.g. tricresylphosphate, dibutylphthalate, etc.
  • UV-absorbers e.g. thiazolidone, benzothiazole, acrylonitrile, benzophenone compounds, etc.
  • gelatin As a binder for the light insensitive particles, gelatin is used in general, but instead of a part or of whole the gelatin, colloidal albumin, agar, arabic gum, alginic acid, cellulose derivatives such as hydrolized cellulose acetate, carboxymethylcellulose, hydroxyethylcellulose, etc., as well as synthetic binders, for instance polyvinyl alcohol, partially saponified polyvinyl acetate, polyacrylamide, poly-N,N-dimethylacrylamide, poly-N-vinylpyrrolidone, water-soluble polymers, as described in US patents 3,847,620; 3,655,389; 3,341,332; 3,615,424 and 3,860,482, gelatin derivatives, for instance acylated gelatin, phenylcarbamylated gelatin, phthalated gelatin, as described in US patents 2,614,928 and 2,525,753 and a graft polymerization product obtained from a monomer having a polymeriz
  • the silver halide emulsions used in the red-sensitive, green-sensitive and yellow-sensitive layers of the present invention are a fine dispersion of silver chloride, silver bromide, silver chloro-bromide, silver iodo-bromide, silver chloro-iodo-bromide in a hydrophilic polymer.
  • a hydrophilic polymer the conventional polymers used in the photographic art can be advantageously used.
  • the silver halide can have uniform grain sizes or a broader distribution of the grain sizes. Furthermore, the silver halide grain sizes range from about 0.1 pm to about 3 pm.
  • the silver halide emulsion can be prepared by following a single jet, double-jet method or a combination of such methods or can be ripened using for instance an ammonia, a neutralization or an acid method, etc.
  • the silver halide emulsion used as a light-sensitive emulsion layer in this invention can be chemically sensitized such as, for instance, by a gold sensitization method as described in US patents 2,399,083; 3,597,856 and 2,597,915; a reduction sensitization method as described in US patents 2,487,850 and 2,521,925; a sulfur sensitization method as described in US patents 1,623,499 and 2,410,689; a sensitization method using metal ions other than silver as described in US patents 2,566,245 and 2,566,263; or a combination of these methods.
  • the silver halide emulsion can be also sensitized using a spectral sensitization method which is generally employed in producing color photographic materials.
  • a sensitizing dye such as cyanine dye or a merocyanine dye, as described in US patents 2,526,632; 2,503,776; 2,493,748; 3,384,486; 2,933,390 and 2,933,089 can be suitably used.
  • the silver halide emulsion used in this invention can be further contain a stabilizer such as a 4-hydroxy-1,3,3a,7-tetrazaindene derivative, etc., an antifoggant such as mercapto compound and a benzotriazole derivative, a coating aid, a hardening agent, a wetting agent, a sensitizer such as an onium derivative, for instance a quaternary ammonium salt as described in US patents 2,271,623 and 2,288,226 and also a polyalkylene oxide derivative as described in US patents 2,708,162; 2,531,832; 2,533,990; 3,210,191 and 3,158,484.
  • the silver halide emulsion layer further can contain an irradiation preventing dye.
  • the color photographic material of this invention can contain layers such as a filter layer, a mordant dye-containing layer, a colored layer containing a hydrophobic dye, etc.
  • the silver halide emulsions used in this invention can be coated on various supports such as, for instance, a cellulose acetate film, a polyethylene terephthalate film, a polyethylene film, a polypropylene film, a glass plate, a baryta-coated paper, a resin-coated paper or a synthetic paper.
  • the photographic material of this invention is processed with a color developer containing, as a color developing agent, a primary aromatic amine compound such as a p-phenylene diamine derivatives and a p-aminophenol compound.
  • a primary aromatic amine compound such as a p-phenylene diamine derivatives and a p-aminophenol compound.
  • preferred p-phenylene diamine derivatives are p-amino-N- ethyl-N-O-(methanesulfonamidoethyl)-m-toluidine sesquisulfate monohydrate, diethylamino-p-phenylene diamine sesquisulfate, p-amino-N,N-diethyl-m-toluidine hydrochloride, p-amino-N-ethyl-N-p-hydroxyethylaniline sesquisulfate monohydrate, and the like.
  • the color photographic materials of this invention can be developed using developers generally used for developing conventional color photographic negative materials, cine color photographic negative or positive materials, color photographic papers, and instant color photographic materials.
  • developers generally used for developing conventional color photographic negative materials, cine color photographic negative or positive materials, color photographic papers, and instant color photographic materials.
  • the color development processes as described in the specification of GB patent 1,203,316; in US patent 3,695,883; in US patent application S.N. 234,163, filed on Mar. 13, 1972 and S.N. 240,287, filed on Mar. 31, 1972; in H. Gordon, The British journal Of Photography, page 559 et seq., Nov. 15,1954; ibid., page 440 et seq., Sept. 9,1955; and ibid., page 2 et seq., Jan. 6,1956; in S.
  • a multilayer color photographic film (Film A) was prepared by coating on a cellulose triacetate base subbed with gelatin and cellulose diacetate the following layers in the indicated order:
  • a second, third and fourth color photographic films were prepared similarly to film (A) with the only difference that the third layer had the following composition: intermediate layer containing 1.6 g/m 2 of gelatin and 0.25 g/m 2 of the light insensitive silver bromo-iodide emulsion having 2% silver iodide moles and a mean grain size of 0.1 ⁇ m (Film B), 0.6 g/m 2 of gelatin and 0.1 g/m 2 of the above light insensitive silver bromo-iodide emulsion (Film C), 2.6 g/m 2 of gelatin and 0.5 g/m 2 of the above light insensitive silver bromo-iodide emulsion (Film D), all films containing 0.20 g/m 2 of 2,5-diisoctylhydroquinone dispersed in tricresylphosphate.
  • a fifth color photographic film (Film E) was prepared by coating on a subbed cellulose triacetate base the following layers in the indicated order:
  • a sixth color photographic film (Film F) was prepared by coating on a subbed cellulose triacetate base the following layers in the indicated order;
  • a multilayer color photographic film (Film A) was prepared by coating on a subbed cellulose triacetate base the following layers in the indicated order:
  • a second and a third color photographic films were prepared similarly to film (A) with the only difference that the fourth layer thereof had the following composition: intermediate layer of 1.58 g/ m 2 gelatin containing 2,5-diisooctylhydroquinone dspersed in tricresylphosphate and the above light insensitive silver bromo-iodide emulsion (having 2% silver iodide moles and a mean grain size of 0.1 ⁇ m) at a silver coverage respectively of 0.18 (Film B) and 0.36 (Film C) g/m 2 .
  • a multilayer color photographic film (Film A) was prepared by coating on a polyethyleneterephthalate base, subbed with a first methylacrylate-itaconic acid-vinylidene chloride copolymer containing layer and with a second gelatin containing layer, the following layers in the indicated order:
  • a second multilayer color photographic film (Film B) were prepared similarly to film (A) with the only difference that the fifth layer had the following composition: layer of 1.2 g/m 2 of gelatin containing 0.14 g/ m 2 of diisoctylahydroquinone dispersed in tricresylphosphate and the above light insensitive silver bromo- iodide emulsion (i.e. having 2% silver iodide moles and a medium grain size of 0.1 pm) at a silver coverage of 0.25 g /m2.

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

Claims (8)

1. Mehrschichtiges farbphotographisches Material umfassend einen Träger mit wenigstens einer einen Blaugrünkuppler enthaltenden rotempfindlichen Emulsionsschicht, einer einen Purpurkuppler enthaltenden grünempfindlichen Emulsionsschicht, sowie einer einen Gelbkuppler enthaltenden blauempfindlichen Emulsionsschicht, wobei wenigstens eine grünempfindliche Schicht eine DIR-Verbindung enthält, dadurch gekennzeichnet, daß es, ausgehend von Träger, nacheinander eine rotempfindliche Schicht mit geringer Empfindlichkeit, eine rotempfindliche Schicht mit hoher Empfindlichkeit, eine licht-unempfindliche feinkörnige Emulsionsschicht mit einem Silbergehalt von 0,1 bis 1 g/m, eine eine DIR-Verbindung enthaltende grünempfindliche Schicht mit geringer Empfindlichkeit sowie eine eine DIR-Verbindung enthaltende grünempfindliche Schicht mit hoher Empfindlichkeit aufweist.
2. Photographisches Material nach Anspruch 1, dadurch gekennzeichnet, daß es eine dritte angepasste rotempfindliche Halbschicht mittlerer Empfindlichkeit aufweist.
3. Photographisches Material nach Anspruch 2, dadurch gekennzeichnet, daß es, ausgehend vom Träger, aufeinander aufgetragene Schichten in der Reihenfolge rotempfindliche Schicht geringer Empfindlichkeit, rotempfindliche Schicht mittlerer Empfindlichkeit, rotempfindliche Schicht hoher Empfindlichkeit, licht-unempfindliche Schicht, grünempfindliche Schicht geringer Empfindlichkeit, grünempfindliche Schicht hoher Empfindlichkeit, Gelbfilter-Schicht, blauempfindliche Schicht geringer Empfindlichkeit und blauempfindliche Schicht hoher Empfindlichkeit aufweist.
4. Farbphotographisches Material nach Anspruch 1, bei dem die DIR-Verbindung durch die allgemeine Formel (I) dargestellt ist:
Figure imgb0013
wobei COUP einen Purpurkuppler-Rest bedeutet, der mit dem Oxidationsprodukt eines Entwicklers des primären aromatischen Amintyps zur Bildung eines Purpur-Farbstoffs kuppelt, und Z einen organischen Rest darstellt, der während der Kupplungsreaktion mit dem Oxidationsprodukt des Entwicklers des primären aromatischen Amintyps von dem Kuppler freigesetzt wird und die Entwicklung in der Silberhalogenid-Emulsionsschicht hemmt.
5. Farbphotographisches Material nach Anspruch 1, dadurch gekennzeichnet, daß die DIR-Verbindung durch die allgemeine Formel (11) dargestellt wird:
Figure imgb0014
wobei R einen Arylrest, einen heterocyclischen Rest oder einen Alkylrest bedeutet; R' einen Alkyl-, Alkoxy-, Aryloxy- oder Aryl rest, den Rest eines heterocyclischen Rings, eine Amino-, Acylamino- oder Ureidogruppe darstellt; A ein Schwefel- oder Selenatom ist und D eine Gruppe bedeutet, die zusammen mit dem Schwefel- oder Selenatom der Thioäther- oder Selenätherbindung, eine entwicklungshemmende Verbindung bildet, die während der Reaktion mit dem Oxidationsprodukt des Entwicklers des primären aromatischen Amintyps freigesetzt wird.
6. Farbphotographisches Material nach Anspruch 1, wobei die in der Zwischenschicht enthaltene licht-unempfindliche Silberhalogenid-Emulsion eine Silberbromidjodid-Emulsion ist.
7. Farbphotographisches Material nach Anspruch 1, dadurch gekennzeichnet, daß die in der Zwischenschicht befindliche licht-unempfindliche Silberhalogenid-Emulsion eine Silberbromidjodid-Emulsion ist, die 1 bis 4 Mol% Silberjodid enthält.
8. Farbphotographisches Material nach Anspruch 1, dadurch gekennzeichnet, daß das in der Zwischenschicht befindliche Silberhalogenid eine mittlere Korngröße von weniger als 0,2 pm hat.
EP83112639A 1982-12-24 1983-12-15 Multischichtiges farbphotographisches Material mit einer hohen Empfindlichkeit und Entwickelbarkeit Expired EP0114306B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IT6521382 1982-12-24
IT65213/82A IT1218307B (it) 1982-12-24 1982-12-24 Materiale fotografico a colori multistrato ad alta sensibilita e sviluppabilita

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EP0114306A2 EP0114306A2 (de) 1984-08-01
EP0114306A3 EP0114306A3 (en) 1986-06-11
EP0114306B1 true EP0114306B1 (de) 1989-01-18

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JPS6180250A (ja) * 1984-09-28 1986-04-23 Konishiroku Photo Ind Co Ltd ハロゲン化銀カラ−写真感光材料
JP2550331B2 (ja) * 1986-11-15 1996-11-06 コニカ株式会社 ハロゲン化銀カラ−写真感光材料
JPH0830874B2 (ja) * 1988-02-12 1996-03-27 富士写真フイルム株式会社 ハロゲン化銀カラー写真感光材料
FR2664399A1 (fr) * 1990-07-04 1992-01-10 Kodak Pathe Produit inversible pour la photographie en couleurs avec sous-couche a grains fins.

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FR959735A (de) * 1943-05-27 1950-04-04
GB1201110A (en) * 1967-07-18 1970-08-05 Fuji Photo Film Co Ltd Multi-colour photographic elements
JPS593737B2 (ja) * 1973-06-29 1984-01-25 富士写真フイルム株式会社 多層カラ−感光材料
DE2704797C2 (de) * 1977-02-05 1982-05-27 Agfa-Gevaert Ag, 5090 Leverkusen Farbphotographisches Aufzeichnungsmaterial
JPS5614236A (en) * 1979-07-13 1981-02-12 Konishiroku Photo Ind Co Ltd Silver halide multilayer color printing paper
JPS5626013A (en) * 1979-08-10 1981-03-13 Kanai Hiroyuki Ring holder for spinning machine

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BR8307118A (pt) 1984-08-07
EP0114306A3 (en) 1986-06-11
IT1218307B (it) 1990-04-12
IT8265213A0 (it) 1982-12-24
DE3378997D1 (en) 1989-02-23
EP0114306A2 (de) 1984-08-01
JPS59170839A (ja) 1984-09-27
JPH0640208B2 (ja) 1994-05-25

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